Cured film and display device

Abstract

To provide a cured film of a curable composition containing a light scattering agent and a resin which has less variations in restoration easiness in a film plane after deformation of the film, and a display device including the cured film.SOLUTION: A cured film of a curable composition containing a light scattering agent (B) and a resin (C) has Martens hardness of 5 MPa or more and 120 MPa or less. A ratio Ra / t of surface roughness Ra (mm) of the cured film to film thickness t (μm) of the cured film is 0.80 (nm / μm) or more.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a cured film and a display device including the cured film.

Background Art

[0002] Patent Document 1 discloses a cured film of a curable composition containing a light scattering agent (A) and a photopolymerizable compound (B), wherein the Martens hardness of the cured film is 0.10 GPa or more.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] In a cured film of a curable composition containing a light scattering agent and a resin, when a load is applied to the film, if the ease of return after deformation of the film varies greatly within the film surface, internal stress may be generated and cracks may occur, which is not preferable.

[0005] Therefore, an object of the present invention is to provide a cured film of a curable composition containing a light scattering agent and a resin, in which the variation in the ease of return after deformation within the film surface of the film is small, and a display device including the cured film.

Means for Solving the Problems

[0006] The present invention that has achieved the above problems is as follows. [1] A cured film of a curable composition containing a light scattering agent (B) and a resin (C), wherein the Martens hardness is 5 MPa or more and 120 MPa or less, and the ratio of the surface roughness Ra (nm) of the cured film to the film thickness t (μm) of the cured film: Ra / t is 0.80 (nm / μm) or more. The cured film according to [1], wherein the acid value of the resin (C) is 150 mg-KOH / g or less. The cured film according to [1] or [2], wherein the mass ratio (C / B) of the resin (C) to the light scattering agent (B) is 16 or more. The cured film according to any one of [1] to [3], wherein the curable composition further contains a polymerizable compound (D). The cured film according to [4], wherein the polymerizable compound (D) contains a polymerizable compound having one or more cyclic hydrocarbon groups and two ethylenically unsaturated bonds in one molecule. The cured film according to any one of [1] to [5], wherein the cured film contains no semiconductor particles (A) or contains them in an amount of less than 1% by mass, and contains no colored colorant (K) or contains it in an amount of less than 1% by mass. A display device including the cured film according to any one of [1] to [6]. [Effects of the Invention]

[0007] According to the present invention, there can be provided a cured film of a curable composition containing a light scattering agent and a resin, the cured film having a small variation in the ease of return after deformation of the film within the film surface, and a display device including the cured film. [Embodiments for Carrying Out the Invention]

[0008] [[Cured Film]] The cured film of the curable composition containing a light-scattering agent (B) and a resin (C) according to the present invention is a white (transparent, achromatic) cured film, for example, a cured pattern, and emits colored light such as red and green light when light from a light source (for example, a blue light source) is incident thereon. It is preferably substantially free of a colorant (semiconductor particles (A) such as quantum dots that absorb primary light and emit light having a wavelength different from that of the primary light, and a colored colorant (K) such as a pigment and a dye)). That is, the cured film according to the present invention usually scatters and emits light having the same or substantially the same wavelength as the incident light. Substantially free of the semiconductor particles (A) and the colored colorant (K) means that the amount of the semiconductor particles (A) in the cured film is less than 1% by mass (including 0% by mass), and the amount of the colored colorant (K) in the cured film is less than 1% by mass (including 0% by mass). The amounts of the semiconductor particles (A) and the colored colorant (K) in the cured film are preferably both 0.1% by mass or less (including 0% by mass).

[0009] The cured film of the present invention has a Martens hardness of 5 MPa or more and 120 MPa or less, and is a cured film in which the ratio of the surface roughness Ra (nm) of the cured film to the film thickness t (μm) of the cured film: Ra / t is 0.80 (nm / μm) or more. By having a relatively low Martens hardness as described above and a ratio of surface roughness to film thickness of a predetermined value or more, it is possible to suppress the in-plane variation in the elastic deformation work rate, which is an index of the ease of return after deformation of the film.

[0010] The martensite hardness is preferably 110 MPa or less, more preferably 100 MPa or less. Also, the martensite hardness may be 15 MPa or more, may be 30 MPa or more, or may be 40 MPa or more. When the martensite hardness is a predetermined value or more, deformation or damage of the cured film can be prevented. If the martensite hardness of the cured film is excessively large, when the cured film is used as a white (transparent) pattern, the emitted light intensity may decrease. The decrease in the emitted light intensity is considered to be caused by, for example, the aggregation and proximity of the light scattering agent (B) in the cured film due to the shrinkage of the cured film, resulting in light scattering in the cured film and a decrease in the light extraction efficiency. In addition, the cured film having the martensite hardness in the above range has an advantage that since it has excellent flexibility, when laminated with other layers, it can easily follow the shape of the other layer, so the adhesion at the interface can be improved.

[0011] The ratio of the surface roughness Ra (nm) of the cured film to the film thickness t (μm) of the cured film: Ra / t is preferably 1.0 or more, more preferably 1.2 or more, still more preferably 1.4 or more, and the upper limit is not particularly limited, but may be 2.5 or less, for example.

[0012] The surface roughness Ra of the cured film is, for example, 1.5 nm or more, preferably 2 nm or more, more preferably 3 nm or more, and the upper limit is not particularly limited, but may be 15 nm or less. The film thickness t of the cured film is, for example, 0.5 μm or more and 10 μm or less, preferably 1 μm or more and 9 μm or less, more preferably 1.5 μm or more and 7 μm or less, and still more preferably 2 μm or more and 5 μm or less.

[0013] The cured film of the present invention can reduce the standard deviation σ of the elastic deformation work rate (%) in the plane. For example, when the film thickness t of the cured film is 4 μm or more, the standard deviation σ can be less than 0.68%, preferably 0.6% or less, more preferably 0.4% or less, and the lower limit is not particularly limited but may be 0.1%. When the film thickness t of the cured film is less than 4 μm, the standard deviation σ can be less than 1.26%, preferably less than 1%, more preferably 0.8% or less, still more preferably 0.6% or less, and the lower limit is not particularly limited but may be 0.1%. The average value of the elastic deformation work rate in the plane is, for example, 25% or more and 35% or less.

[0014] <<Curing composition>> The curing composition preferably contains at least one selected from a polymerizable compound (D), a polymerization initiator (E), a light stabilizer (F), a leveling agent (H), and a solvent (J), in addition to a light scattering agent (B) and a resin (C). In addition, in order to satisfy the function of scattering light that is substantially the same as the incident light, the curing composition preferably does not substantially contain semiconductor particles (A) such as quantum dots that absorb primary light and emit light having a wavelength different from that of the primary light, and a colored colorant (K) such as a pigment or a dye. By "not substantially containing" either the semiconductor particles (A) or the colored colorant (K), it means that the amount in the curing composition is less than 1% by mass (including 0% by mass). The amount in the curing composition is preferably 0.1% by mass or less. The amounts of the semiconductor particles (A) and the colored colorant (K) in the curing composition described above are preferably the amounts in 100% by mass of the solid content of the curing composition.

[0015] In the present specification, the compounds exemplified as each component can be used alone or in combination of two or more, unless otherwise specified. When a plurality of types of each component are used, the content can be adjusted by the total amount of the plurality of types, unless otherwise specified.

[0016] <Light scattering agent (B)> The cured film formed from the curable composition containing the light scattering agent (B) can scatter and emit light having the same or almost the same wavelength as the light incident on the cured film. Further, by incorporating the light scattering agent (B) into the cured film, the light transmittance and viewing angle characteristics of the cured film can be controlled, or the emitted light intensity of the cured film can be improved.

[0017] Examples of the light scattering agent (B) include inorganic particles such as metal or metal oxide particles and glass particles. Since it is preferable to have no absorption due to coloring and only have a scattering effect, it is preferably metal oxide particles. Examples of the metal oxide include TiO2, SiO2, BaTiO3, ZnO, etc. Since it scatters light efficiently, it is preferably TiO2 particles. Generally, since the above inorganic particles are difficult to disperse in a solvent as they are, a dispersant described later is usually used. The light scattering agent (B) may contain two or more kinds of particles.

[0018] The average particle diameter of the light scattering agent (B) is, for example, about 0.03 μm or more and 20 μm or less. From the viewpoint of enhancing the light scattering ability and the dispersibility in the curable composition, it is preferably 0.05 μm or more and 1 μm or less, more preferably 0.05 μm or more and 0.5 μm or less, and still more preferably 0.05 μm or more and 0.35 μm or less. The average particle diameter of the light scattering agent (B) can be measured as the volume-based median diameter (D50) by measuring the particle diameter distribution using a centrifugal sedimentation type dispersion stability particle diameter distribution apparatus.

[0019] As the light scattering agent (B), those in which the light scattering agent is preliminarily dispersed in part or all of the solvent (J) using the dispersant (I) may be used. Commercially available products can be used as the dispersant (I). Examples of commercially available products include DISPERBYK-101, 102, 103, 106, 107, 108, 109, 110, 111, 116, 118, 130, 140, 154, 161, 162, 163, 164, 165, 166, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 192, 2000, 2001, 2020, 2025, 2050, 2070, 2095, 2150, 2155 manufactured by Big Chemie Japan Co., Ltd.; ANTI-TERRA-U, U100, 203, 204, 250; BYK-P104, P104S, P105, 220S, 6919; BYK-LPN6919, 21116; LACTIMON, LACTIMON-WS; Bykumen, etc.; SOLSPERSE-3000, 9000, 13000, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 76500, etc. manufactured by Lubrizol Japan Co., Ltd.; EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc. manufactured by BASF; Examples include Ajisper PA111, PB711, PB821, PB822, PB824, etc. manufactured by Ajinomoto Fine-Techno Co., Inc.

[0020] The content rate of the light scattering agent (B) in the curable composition is, for example, 0.001 mass% or more and 50 mass% or less with respect to the total amount of the solid content of the curable composition. From the viewpoints of the developability of the cured film, enhancing the light scattering ability, and improving the emission light intensity of the cured film, it is preferably 0.5 mass% or more and 30 mass% or less, more preferably 1 mass% or more and 10 mass% or less, and still more preferably 2 mass% or more and 7 mass% or less.

[0021] In this specification, the total amount of the solid content in the composition means the total of the components contained in the composition excluding the solvent (J). The content rate in the solid content of the composition can be measured by known analysis means such as liquid chromatography or gas chromatography. The content rate of each component in the solid content of the composition may be calculated from the formulation at the time of preparing the composition.

[0022] <Resin (C)> Examples of the resin (C) include the following resins [K1] to [K6] and the like.

[0023] Resin [K1]; A copolymer having a structural unit derived from at least one (a) selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides (hereinafter also referred to as "(a)"), and a structural unit derived from a monomer (c) copolymerizable with (a) (however, different from (a)) (hereinafter also referred to as "(c)"); Resin [K2]; A copolymer having a structural unit derived from the above (a), a structural unit derived from the above (c), and a structural unit derived from 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)"); Resin [K3]; A copolymer having a structural unit obtained by adding the above (b) to the structural unit derived from the above (a) and a structural unit derived from the above (c); Resin [K4]: A copolymer having a structural unit obtained by adding the above (b) to the structural unit derived from the above (a) and further ester-bonding a carboxylic acid anhydride, and a structural unit derived from the above (c). Resin [K5]; a copolymer having a structural unit obtained by adding the component (a) to the structural unit derived from the component (b) and a structural unit derived from the component (c); Resin [K6]; a copolymer having a structural unit obtained by adding the component (a) to the structural unit derived from the component (b) and further ester-bonding a carboxylic anhydride, and a structural unit derived from the component (c).

[0024] Examples of the component (a) include unsaturated monocarboxylic acids such as (meth)acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid; unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyltetrahydrophthalic acid, 1,4-cyclohexenedicarboxylic acid; bicyclic unsaturated compounds containing a carboxy group such as methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene, 5-carboxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-ethylbicyclo[2.2.1]hept-2-ene; 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; unsaturated mono[(meth)acryloyloxyalkyl] esters of polyvalent carboxylic acids having two or more valences such as succinic acid mono[2-(meth)acryloyloxyethyl], phthalic acid mono[2-(meth)acryloyloxyethyl]; Unsaturated (meth)acrylates containing a hydroxy group and a carboxy group in the same molecule, such as α-(hydroxymethyl)(meth)acrylic acid and the like can be mentioned.

[0025] Among these, from the viewpoints of copolymerization reactivity and the like, (meth)acrylic acid, succinic acid mono[2-(meth)acryloyloxyethyl], maleic anhydride and the like are preferable.

[0026] In this specification, (meth)acrylic acid means acrylic acid and / or methacrylic acid. The same applies to "(meth)acryloyl", "(meth)acrylate" and the like.

[0027] (b) is, for example, a monomer having a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one selected from the group consisting of an oxirane ring, an oxetane ring and a tetrahydrofuran ring) and an ethylenically unsaturated bond. (b) is preferably a monomer having a cyclic ether structure having 2 to 4 carbon atoms and a (meth)acryloyloxy group.

[0028] Examples of (b) include a monomer (b1) having an oxiranyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b1)"), a monomer (b2) having an oxetanyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b2)"), a monomer (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b3)") and the like.

[0029] Examples of (b1) include a monomer (b1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized (hereinafter sometimes referred to as "(b1-1)"), and a monomer (b1-2) having a structure in which an alicyclic unsaturated hydrocarbon is epoxidized (hereinafter sometimes referred to as "(b1-2)").

[0030] Examples of (b1-1) include glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, β-ethylglycidyl (meth)acrylate, glycidyl vinyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl-m-vinylbenzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-bis(glycidyloxymethyl)styrene, 2,4-bis(glycidyloxymethyl)styrene, 2,5-bis(glycidyloxymethyl)styrene, 2,6-bis(glycidyloxymethyl)styrene, 2,3,4-tris(glycidyloxymethyl)styrene, 2,3,5-tris(glycidyloxymethyl)styrene, 2,3,6-tris(glycidyloxymethyl)styrene, 3,4,5-tris(glycidyloxymethyl)styrene, 2,4,6-tris(glycidyloxymethyl)styrene, and the like.

[0031] Examples of (b1-2) include vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane (e.g., Celloxide 2000; manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl (meth)acrylate (e.g., Cyclomer A400; manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl (meth)acrylate (e.g., Cyclomer M100; manufactured by Daicel Corporation), the compound represented by formula (BI), the compound represented by formula (BII), and the like.

[0032] [Chemical formula]

[0033] [In formula (BI) and formula (BII), R e and R f each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted with a hydroxy group. X e and X fis a single bond, *-R g -, *-R g -O-, *-R g -S- or *-R g -NH-. R g represents an alkanediyl group having 1 to 6 carbon atoms. * represents a bond to O.]

[0034] Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group and the like. Examples of the alkyl group in which a hydrogen atom is substituted with hydroxy include a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, a 1-hydroxypropyl group, a 2-hydroxypropyl group, a 3-hydroxypropyl group, a 1-hydroxy-1-methylethyl group, a 2-hydroxy-1-methylethyl group, a 1-hydroxybutyl group, a 2-hydroxybutyl group, a 3-hydroxybutyl group, a 4-hydroxybutyl group and the like. R e and R f are preferably a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, more preferably a hydrogen atom, a methyl group.

[0035] Examples of the alkanediyl group include a methylene group, an ethylene group, a propane-1,2-diyl group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, a hexane-1,6-diyl group and the like. X e and X f are preferably a single bond, a methylene group, an ethylene group, *-CH2-O- and *-CH2CH2-O-, more preferably a single bond, *-CH2CH2-O- (* represents a bond to O).

[0036] Examples of the compound represented by formula (BI) include compounds represented by any of formula (BI-1) to formula (BI-15). Among them, compounds represented by formula (BI-1), formula (BI-3), formula (BII-5), formula (BI-7), formula (BI-9) or formula (BI-11) to formula (BI-15) are preferred, and compounds represented by formula (BI-1), formula (BI-7), formula (BI-9) or formula (BI-15) are more preferred.

[0037]

Chemical formula

[0038] Examples of the compound represented by formula (BII) include compounds represented by any of formula (BII-1) to formula (BII-15). Among them, compounds represented by formula (BII-1), formula (BII-3), formula (BII-5), formula (BII-7), formula (BII-9) or formula (BII-11) to formula (BII-15) are preferred, and compounds represented by formula (BII-1), formula (BII-7), formula (BII-9) or formula (BII-15) are more preferred.

[0039]

Chemical formula

[0040] The compound represented by formula (BI) and the compound represented by formula (BII) may be used alone or in combination of two or more. When the compound represented by formula (BI) and the compound represented by formula (BII) are used in combination, their content ratios [compound represented by formula (BI): compound represented by formula (BII)] are preferably 5:95 to 95:5, more preferably 20:80 to 80:20 on a molar basis.

[0041] As (b2), monomers having an oxetanyl group and a (meth)acryloyloxy group are more preferable. Examples of (b2) include 3-methyl-3-methacryloyloxymethyloxetane, 3-methyl-3-acryloyloxymethyloxetane, 3-ethyl-3-methacryloyloxymethyloxetane, 3-ethyl-3-acryloyloxymethyloxetane, 3-methyl-3-methacryloyloxyethyloxetane, 3-methyl-3-acryloyloxyethyloxetane, 3-ethyl-3-methacryloyloxyethyloxetane, 3-ethyl-3-acryloyloxyethyloxetane and the like.

[0042] As (b3), monomers having a tetrahydrofuryl group and a (meth)acryloyloxy group are more preferable. Specifically, examples of (b3) include tetrahydrofurfuryl acrylate (for example, Biscoat V#150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate and the like.

[0043] As (b), being (b1) is preferable in terms of being able to further improve the reliability such as chemical resistance.

[0044] Since the reactivity during the production of resins [K3] to [K6] is high and unreacted (b) is less likely to remain, as (b), monomers having an oxirane ring and an ethylenically unsaturated bond are preferable.

[0045] Examples of (c) include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0 2,6Decan-8-yl (meth)acrylate (in the art, it is commonly referred to as "dicyclopentanyl (meth)acrylate". It may also be referred to as "tricyclodecyl (meth)acrylate".), tricyclo[5.2.1.0 2,6 Decen-8-yl (meth)acrylate (in the art, it is commonly referred to as "dicyclopentenyl (meth)acrylate".), dicyclopentanyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, allyl (meth)acrylate, propargyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, benzyl (meth)acrylate and other (meth)acrylic acid esters; Hydroxy group-containing (meth)acrylic acid esters such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate; Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, and diethyl itaconate; Bicyclo[2.2.1]hept-2-ene, 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxybicyclo[2.2.1]hept-2-ene, 5-hydroxymethylbicyclo[2.2.1]hept-2-ene, 5-(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5-methoxybicyclo[2.2.1]hept-2-ene, 5-ethoxybicyclo[2.2.1]hept-2-ene, 5,6-dihydroxybicyclo[2.2.1]hept-2-ene, 5,6-di(hydroxymethyl)bicyclo[2.2.1]hept-2-ene, 5,6-di(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5,6-dimethoxybicyclo[2.2.1]hept-2-ene, 5,6-diethoxybicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxymethyl-5-methylbicyclo[2.2.1]hept-2-ene, 5-tert-butoxycarbonylbicyclo[2.2.1]hept-2-ene, 5-cyclohexyloxycarbonylbicyclo[2.2.1]hept-2-ene, 5-phenoxycarbonylbicyclo[2.2.1]hept-2-ene, 5,6-bis(tert-butoxycarbonyl)bicyclo[2.2.1]hept-2-ene, 5,6-bis(cyclohexyloxycarbonyl)bicyclo[2.2.1]hept-2-ene and other bicyclic unsaturated compounds; Dicarbonylimide derivatives such as N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl 3-maleimidobenzoate, N-succinimidyl 4-maleimidobutyrate, N-succinimidyl 6-maleimidocaproate, N-succinimidyl 3-maleimidopropionate, N-(9-acridinyl)maleimide; 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. can be mentioned.

[0046] Among the above, from the viewpoint of copolymerization reactivity, methyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, styrene, vinyltoluene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo[2.2.1]hept-2-ene, etc. are preferable.

[0047] In resin [K1], the ratio of the structural units derived from each is among all the structural units constituting resin [K1], (a) the structural unit derived from; 2 mol% or more and 60 mol% or less (c) the structural unit derived from; 40 mol% or more and 98 mol% or less it is preferably, (a) the structural unit derived from; 10 mol% or more and 50 mol% or less (c) the structural unit derived from; 50 mol% or more and 90 mol% or less it is more preferably.

[0048] When the ratio of the structural units of resin [K1] is within the above range, there is a tendency to be excellent in storage stability and solvent resistance.

[0049] Resin [K1] can be produced, for example, with reference to the method described in the literature "Experimental Methods of Polymer Synthesis" (written by Takayuki Otsu, published by Kagaku Dojin Publishing Co., Ltd., 1st edition, 1st printing, issued on March 1, 1972) and the cited references described in the literature.

[0050] Specifically, a method includes putting predetermined amounts of (a) and (c), a polymerization initiator, a solvent, etc. into a reaction vessel, replacing oxygen with nitrogen, for example, to create a deoxygenated atmosphere, and heating and maintaining the temperature while stirring.

[0051] The polymerization initiator, solvent, etc. used are not particularly limited, and those commonly used in the art can be used. For example, as the polymerization initiator, azo compounds (2,2’-azobisisobutyronitrile, 2,2’-azobis(2,4-dimethylvaleronitrile), etc.) and organic peroxides (benzoyl peroxide, t-butyl peroxy-2-ethylhexanoate, etc.) can be mentioned. As the solvent, any solvent that can dissolve each monomer may be used, and examples include the solvents described later as solvent (J).

[0052] The obtained copolymer may be used as the reaction solution as it is, or a concentrated or diluted solution may be used, or a solid (powder) taken out by a method such as reprecipitation may be used. If the solvent (J) described later is used as the solvent during polymerization, the reaction solution can be used as it is for the preparation of the composition, so the manufacturing process of the composition can be simplified.

[0053] In resin [K2], the ratio of the structural units derived from each is among all the structural units constituting resin [K2], Structural unit derived from (a); 2 to 45 mol% Structural unit derived from (b); 2 to 95 mol% Structural unit derived from (c); 1 to 65 mol% It is preferably as follows, Structural unit derived from (a); 5 to 40 mol% Structural unit derived from (b); 5 to 80 mol% Structural unit derived from (c); 5 to 60 mol% More preferably, it is as follows.

[0054] When the ratio of the structural units of resin [K2] is within the above range, the storage stability of the curable composition and the developability when forming a coloring pattern tend to be excellent.

[0055] Resin [K2] can be produced in the same manner as the method described, for example, as the production method of resin [K1].

[0056] Resin [K3] can be produced by adding the cyclic ether having 2 to 4 carbon atoms that (b) has to the carboxylic acid and / or carboxylic anhydride that (a) has in the copolymer of (a) and (c).

[0057] First, a copolymer of (a) and (c) is produced in the same manner as the method described as the production method of resin [K1]. In this case, the ratio of the structural units derived from each is preferably the same as the ratio described for resin [K1].

[0058] Next, a cyclic ether having 2 to 4 carbon atoms that (b) has is reacted with a part of the carboxylic acid and / or carboxylic anhydride derived from (a) in the copolymer.

[0059] Following the production of the copolymer of (a) and (c), the atmosphere in the flask is replaced from nitrogen to air, and in the presence of (b), a reaction catalyst for the carboxylic acid or carboxylic anhydride and the cyclic ether (for example, an organic phosphorus compound, a metal complex, an amine compound, etc.) and a polymerization inhibitor (for example, hydroquinone, methoxyquinone, etc.), etc., for example, at 60 °C or higher and 130 °C or lower, and reacting for 1 hour or more and 10 hours or less, resin [K3] can be produced.

[0060] The usage amount of (b) is preferably 5 mol or more and 80 mol or less, more preferably 10 mol or more and 75 mol or less, per 100 mol of (a). By setting it within this range, in the mode of producing a cured film by thermally curing after the steps of pre-baking and exposing the coating film of the curable composition (and further developing if necessary), the pre-baking and thermosetting temperatures can be lowered, and the Martens hardness and the value of Ra / t can be appropriately adjusted, and as a result, the variation in the elastic deformation work rate in the plane can be suppressed.

[0061] Examples of the organic phosphorus compound as the reaction catalyst include triphenylphosphine and the like. As the amine compound as the reaction catalyst, for example, an aliphatic tertiary amine compound or an aliphatic quaternary ammonium salt compound can be used. Specific examples thereof include tris(dimethylaminomethyl)phenol, triethylamine, tetrabutylammonium bromide, tetrabutylammonium chloride and the like. The reaction catalyst is preferably an organic phosphorus compound.

[0062] The amount of the reaction catalyst used is preferably 0.001 part by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the total amount of (a), (b) and (c).

[0063] The amount of the polymerization inhibitor used is preferably 0.001 part by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the total amount of (a), (b) and (c).

[0064] The charging method, reaction conditions such as reaction temperature and time can be appropriately adjusted in consideration of the production equipment, the heat generation amount due to polymerization, etc. Note that, similar to the polymerization conditions, the charging method and reaction temperature can be appropriately adjusted in consideration of the production equipment, the heat generation amount due to polymerization, etc.

[0065] Resin [K4] is a resin obtained by further reacting resin [K3] with a carboxylic anhydride. The carboxylic anhydride is reacted with the hydroxy group generated by the reaction of the carboxylic acid or carboxylic anhydride with the cyclic ether. Examples of the carboxylic anhydride include succinic anhydride, maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride and the like. The amount of the carboxylic anhydride used is preferably 0.5 mol or more and 1 mol or less with respect to 1 mol of the amount of (b) used.

[0066] As a first step, the resin [K5] is obtained in the same manner as the method for producing the resin [K1] described above, to obtain a copolymer of (b) and (c). Similarly to the above, the resulting copolymer may be used as the solution after the reaction as it is, or a concentrated or diluted solution may be used, or a solid (powder) taken out by a method such as reprecipitation may be used.

[0067] (b) and the ratio of the structural units derived from (c) are, respectively, based on the total number of moles of all the structural units constituting the copolymer, Structural units derived from (b); 5 mol% or more and 95 mol% or less Structural units derived from (c); 5 mol% or more and 95 mol% or less it is preferably that, Structural units derived from (b); 10 mol% or more and 90 mol% or less Structural units derived from (c); 10 mol% or more and 90 mol% or less it is more preferably that.

[0068] The resin [K5] can be obtained by reacting the carboxylic acid or carboxylic anhydride of (a) with the cyclic ether derived from (b) that the copolymer of (b) and (c) has under the same conditions as the method for producing the resin [K3].

[0069] The amount of (a) used for the reaction with the copolymer is preferably 5 mol or more and 120 mol or less, more preferably 20 mol or more and 110 mol or less, per 100 mol of (b).

[0070] The resin [K6] is a resin obtained by further reacting the resin [K5] with a carboxylic anhydride. The carboxylic anhydride is reacted with the hydroxy group generated by the reaction of the cyclic ether and the carboxylic acid or carboxylic anhydride.

[0071] Examples of the carboxylic acid anhydride include succinic anhydride, maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride, and the like.

[0072] The amount of the carboxylic acid anhydride used is preferably 0.05 to 1 mol, more preferably 0.1 to 0.8 mol, and still more preferably 0.15 to 0.6 mol, per 1 mol of the amount of (a) used.

[0073] Examples of the resins [K1], [K2], [K3], [K4], [K5], and [K6] include resin [K1] such as benzyl (meth)acrylate / (meth)acrylic acid copolymer, styrene / (meth)acrylic acid copolymer, (meth)acrylic acid / succinic acid mono[2-(meth)acryloyloxyethyl] / dicyclopentanyl (meth)acrylate / methyl (meth)acrylate copolymer; resin [K2] such as glycidyl (meth)acrylate / benzyl (meth)acrylate / (meth)acrylic acid copolymer, glycidyl (meth)acrylate / styrene / (meth)acrylic acid copolymer, 3,4-epoxytricyclo[5.2.1.0 2,6 decyl acrylate / (meth)acrylic acid / methyl (meth)acrylate copolymer, 3,4-epoxytricyclo[5.2.1.0 2,6 decyl acrylate / (meth)acrylic acid / N-cyclohexylmaleimide copolymer, 3,4-epoxytricyclo[5.2.1.0 2,6 decyl acrylate / (meth)acrylic acid / benzyl (meth)acrylate copolymer; Resins such as a resin obtained by adding glycidyl (meth)acrylate to a benzyl (meth)acrylate / (meth)acrylic acid copolymer, a resin obtained by adding glycidyl (meth)acrylate to a tricyclodecyl (meth)acrylate / styrene / (meth)acrylic acid copolymer, and a resin obtained by adding glycidyl (meth)acrylate to a tricyclodecyl (meth)acrylate / benzyl (meth)acrylate / (meth)acrylic acid copolymer [K3]; Resins such as a resin obtained by further ester-bonding tetrahydrophthalic anhydride or succinic anhydride to a resin obtained by adding glycidyl (meth)acrylate to a dicyclopentanyl (meth)acrylate / methyl (meth)acrylate / (meth)acrylic acid copolymer, and a resin obtained by further ester-bonding tetrahydrophthalic anhydride or succinic anhydride to a resin obtained by adding glycidyl (meth)acrylate to a dicyclopentanyl (meth)acrylate / 2-ethylhexyl (meth)acrylate / (meth)acrylic acid copolymer [K4]; Resins such as a resin obtained by adding (meth)acrylic acid to a copolymer of tricyclodecyl (meth)acrylate / glycidyl (meth)acrylate, and a resin obtained by adding (meth)acrylic acid to a copolymer of tricyclodecyl (meth)acrylate / styrene / glycidyl (meth)acrylate [K5]; Examples thereof include resins such as a resin obtained by further ester-bonding tetrahydrophthalic anhydride or succinic anhydride to a resin obtained by adding (meth)acrylic acid to a copolymer of tricyclodecyl (meth)acrylate / glycidyl (meth)acrylate, and a resin obtained by further ester-bonding tetrahydrophthalic anhydride or succinic anhydride to a resin obtained by adding (meth)acrylic acid to a copolymer of dicyclopentanyl (meth)acrylate / 2-ethylhexyl (meth)acrylate / glycidyl (meth)acrylate [K6], etc.

[0074] The resin (C) contained in the curable composition preferably contains at least one selected from the group consisting of resin [K1], resin [K2], resin [K3], resin [K4], resin [K5] and resin [K6], more preferably contains at least one selected from the group consisting of resin [K3], resin [K4], resin [K5] and resin [K6], still more preferably contains at least one selected from the group consisting of resin [K4] and resin [K6], and resin [K6] is particularly preferred.

[0075] As a further example of the resin (C), the resin described in JP-A-2018-123274 can be mentioned. As the resin, a polymer having a double bond in the side chain and containing a structural unit (α) represented by the following formula (I) and a structural unit (β) represented by the following formula (II) in the main chain and further containing an acid group (hereinafter, also referred to as "resin (Ca)") can be mentioned.

[0076] The acid group can be introduced into the resin, for example, by the resin (Ca) containing a structural unit (γ) derived from an acid group-containing monomer (for example, (meth)acrylic acid, etc.). The resin (Ca) preferably contains the structural units (α), (β) and (γ) in the main chain skeleton.

[0077] [Chemical formula]

[0078] [In the formula, R A and R B represent the same or different hydrogen atoms or hydrocarbon groups having 1 to 25 carbon atoms. n represents the average number of repeating units of the structural unit represented by formula (I) and is a number of 1 or more. ]

[0079] [Chemical formula]

[0080] [In the formula, R C represent the same or different hydrogen atoms or methyl groups. R Dis the same or different and represents a linear or branched hydrocarbon group having 4 to 20 carbon atoms. m represents the average number of repeating units of the structural unit represented by formula (II) and is a number of 1 or more. In the resin (Ca), from the viewpoint of the storage stability of the resin (Ca), the content ratio of the structural unit (α) is, for example, 0.5% by mass or more and 50% by mass or less, preferably 1% by mass or more and 40% by mass or less, more preferably 5% by mass or more and 30% by mass or less, based on 100% by mass of the total amount of all monomer units giving the main chain skeleton of the resin (Ca). n in formula (I) represents the average number of repeating units of the structural unit (α) in the resin (Ca), and n can be set so that the content ratio of the structural unit (α) is within the above range.

[0081] From the viewpoint of solvent resistance, the content ratio of the structural unit (β) is, for example, 10% by mass or more and 90% by mass or less, preferably 20% by mass or more and 80% by mass or less, more preferably 30% by mass or more and 75% by mass or less, based on 100% by mass of the total amount of all monomer units giving the main chain skeleton of the resin (Ca). m in formula (II) represents the average number of repeating units of the structural unit (β) in the resin (Ca), and m can be set so that the content ratio of the structural unit (β) is within the above-described range.

[0082] From the viewpoints such as the solubility of the resin (Ca) in the solvent (J), the content ratio of the structural unit (γ) is, for example, 0.5% by mass or more and 50% by mass or less, preferably 2% by mass or more and 50% by mass or less, more preferably 5% by mass or more and 45% by mass or less, based on 100% by mass of the total amount of all monomer units giving the main chain skeleton of the resin (Ca).

[0083] The resin (C) has a weight average molecular weight Mw in terms of standard polystyrene measured by GPC of, for example, 1,000 or more and 100,000 or less, and from the viewpoints of the developability and the emitted light intensity of the curable composition, it is preferably 2,000 or more and 50,000 or less, more preferably 3,000 or more and 20,000 or less, and still more preferably 5,000 or more and 8,000 or less. The Mw of the resin (C) can be adjusted by appropriately combining the selection of the raw materials used, the charging method, the reaction temperature and time, and other reaction conditions. The Mw of the resin (C) can be measured according to the measurement method described in the column of Examples below. Alternatively, for the resin (C) contained in the curable composition, the Mw may be measured using GPC.

[0084] From the viewpoints of the developability and solvent resistance of the curable composition, the acid value of the resin (C) is preferably 150 mg-KOH / g or less, more preferably 110 mg-KOH / g or less, still more preferably 80 mg-KOH / g or less, and preferably 20 mg-KOH / g or more, more preferably 30 mg-KOH / g or more. The acid value of the resin (C) can be adjusted by the content of the monomer component having an acid group (for example, the above (a)) and the content of the carboxylic acid anhydride.

[0085] The acid value of the resin (C) 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 an aqueous potassium hydroxide solution. Specifically, it can be measured according to the measurement method described in the column of Examples below. Alternatively, for the resin (C) contained in the composition, the acid value may be determined, for example, by performing its structural analysis.

[0086] The resin (C) preferably contains a resin having a double bond equivalent of 500 g / eq or less, more preferably contains a resin having a double bond equivalent of 450 g / eq or less. In a preferred embodiment, the lower limit of the double bond equivalent of these resins contained may be 200 g / eq in each case. When the double bond equivalent is within the above range, in the mode of producing a cured film by pre-baking and exposing a coating film of the curable composition (and further developing if necessary) and then thermally curing, the pre-baking and thermosetting temperatures can be lowered, the variation in the elastic deformation work rate of the cured film in the plane can be suppressed, and also, even if the pre-baking temperature is low, film sagging during development can be suppressed. Examples of the resin having the above-described double bond equivalent include (meth)acrylic resins. The resin (C) preferably consists of a (meth)acrylic resin.

[0087] The content of the resin (C) in the curable composition is, for example, 5% by mass or more and 80% by mass or less, preferably 20% by mass or more and 75% by mass or less, more preferably 35% by mass or more and 73% by mass or less, still more preferably 40% by mass or more and 70% by mass or less, based on the total amount of the solid content of the curable composition. When the content of the resin (C) is within the above range, the pre-baking and thermosetting temperatures of the coating film of the curable composition can be lowered, and the variation in the elastic deformation work rate of the cured film in the plane can be suppressed.

[0088] The mass ratio (C / B) of the resin (C) to the light scattering agent (B) is preferably 16 or more, more preferably 18 or more, still more preferably 20 or more. The upper limit is not particularly limited and may be 35 or less. When the mass ratio (C / B) of the resin (C) to the light scattering agent (B) is within the above range, the light scattering agent (B) is likely to be dispersed, and the variation in the elastic deformation work rate of the cured film in the plane is likely to be small.

[0089] <Polymerizable compound (D)> The polymerizable compound (D) is a compound that can be polymerized by active radicals, acids, etc. generated from a polymerization initiator (E) described later. Examples of the polymerizable compound (D) include photopolymerizable compounds such as compounds having an ethylenically unsaturated bond, for example, (meth)acrylic acid ester compounds. Another example of the polymerizable compound (D) is a thermopolymerizable compound. The curable composition may contain two or more kinds of the polymerizable compound (D).

[0090] Examples of the polymerizable compound (D) include a photopolymerizable compound (Dα) having two ethylenically unsaturated bonds in the molecule and a photopolymerizable compound (Dβ) having three or more ethylenically unsaturated bonds in the molecule. In the photopolymerizable compounds (Dα) and (Dβ), the number of ethylenically unsaturated bonds in the molecule is preferably 6 or less. The ethylenically unsaturated bond is preferably a (meth)acryloyloxy group. The weight average molecular weight of the polymerizable compound (D) is preferably 150 or more and 2900 or less, more preferably 250 or more and 1500 or less. The polymerizable compound (D) preferably contains one or more selected from the photopolymerizable compound (Dα) and the photopolymerizable compound (Dβ), and more preferably contains one or more of the photopolymerizable compound (Dβ). The photopolymerizable compound (D) may contain one or more of the photopolymerizable compound (Dα) and one or more of the photopolymerizable compound (Dβ).

[0091] Examples of the photopolymerizable compound (Dα) having two ethylenically unsaturated bonds in the molecule include bifunctional (meth)acrylic compounds, for example, alkylene glycol di(meth)acrylate, polyoxyalkylene glycol di(meth)acrylate, halogen-substituted alkylene glycol di(meth)acrylate, di(meth)acrylate of aliphatic polyol, di(meth)acrylate of hydrogenated dicyclopentadiene or tricyclodecane dialkanol, di(meth)acrylate of dioxane glycol or dioxane dialkanol, di(meth)acrylate of an alkylene oxide adduct of bisphenol A or bisphenol F, epoxy di(meth)acrylate of bisphenol A or bisphenol F, and the like.

[0092] More specific examples of the above bifunctional (meth)acrylic compounds include ethylene glycol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol di(meth)acrylate, ditrimethylolpropane di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polytetramethylene glycol di(meth)acrylate, di(meth)acrylate of hydroxypivalic acid neopentyl glycol ester, 2,2-bis[4-(meth)acryloyloxyethoxyethoxyphenyl]propane, 2,2-bis[4-(meth)acryloyloxyethoxyethoxycyclohexyl]propane, hydrogenated dicyclopentadienyl di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, 1,3-dioxane-2,5-diyl di(meth)acrylate [alias: dioxane glycol di(meth)acrylate], di(meth)acrylate of an acetal compound of hydroxypivalaldehyde and trimethylolpropane [chemical name: 2-(2-hydroxy-1,1-dimethylethyl)-5-ethyl-5-hydroxymethyl-1,3-dioxane], tris(hydroxyethyl)isocyanurate di(meth)acrylate, di(meth)acrylate of ethoxylated bisphenol A, di(meth)acrylate of propoxylated bisphenol A, di(meth)acrylate of ethoxylated bisphenol F, di(meth)acrylate of propoxylated bisphenol F, and the like.

[0093] The photopolymerizable compound (Dα) having two ethylenically unsaturated bonds in the molecule is preferably a photopolymerizable compound (Dα1) having one or more cyclic hydrocarbon groups and two ethylenically unsaturated bonds in one molecule, and it is preferable that the polymerizable compound (D) contains one or more of the photopolymerizable compounds (Dα1). In the photopolymerizable compound (Dα1), the cyclic hydrocarbon group is preferably an aromatic hydrocarbon group, and the aromatic hydrocarbon group is more preferably a phenylene group. Also, in the photopolymerizable compound (Dα1), the number of cyclic hydrocarbon groups in one molecule is preferably two. Specific examples of the photopolymerizable compound (Dα1) include di(meth)acrylates of ethoxylated bisphenol A, di(meth)acrylates of propoxylated bisphenol A, di(meth)acrylates of ethoxylated bisphenol F, di(meth)acrylates of propoxylated bisphenol F, and the like.

[0094] Examples of the polymerizable compound (Dβ) having three or more ethylenically unsaturated bonds in the molecule include a compound (Dβ1) having three or more (meth)acryloyloxy groups and an acidic functional group in the molecule, and a compound (Dβ2) having three or more (meth)acryloyloxy groups and no acidic functional group in the molecule. The polymerizable compound (D) preferably contains at least one of the compounds (Dβ1) and (Dβ2), and more preferably contains at least one of the compounds (Dβ1). Examples of the above acidic functional group include a carboxy group, a sulfonic acid group, a phosphoric acid group, and the like. Among them, the acidic functional group is preferably a carboxy group.

[0095] The number of (meth)acryloyloxy groups in one molecule of the compound (Dβ1) is, for example, 3 or more and 6 or less, preferably 3 or more and 5 or less, and more preferably 3. The number of acidic functional groups in one molecule of the compound (Dβ1) is 1 or more, and preferably 1. When having two or more acidic functional groups, the respective acidic functional groups may be different or the same, but it is preferable to have at least one carboxy group.

[0096] Examples of the compound (Dβ1) include compounds obtained by esterifying a compound having three or more (meth)acryloyloxy groups and hydroxy groups, such as pentaerythritol tri(meth)acrylate or dipentaerythritol penta(meth)acrylate, with a dicarboxylic acid or dicarboxylic anhydride. Examples of such compounds include a compound obtained by monoesterifying pentaerythritol tri(meth)acrylate with succinic acid, a compound obtained by monoesterifying dipentaerythritol penta(meth)acrylate with succinic acid, a compound obtained by monoesterifying pentaerythritol tri(meth)acrylate with maleic acid, and a compound obtained by monoesterifying dipentaerythritol penta(meth)acrylate with maleic acid. Among them, a compound obtained by monoesterifying pentaerythritol tri(meth)acrylate with succinic acid is preferred.

[0097] The number of (meth)acryloyloxy groups in the compound (Dβ2) is preferably 3 to 6, more preferably 4 to 6.

[0098] Examples of the compound (Dβ2) include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol octa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, tetrapentaerythritol deca(meth)acrylate, tetrapentaerythritol nona(meth)acrylate, tris(2-(meth)acryloyloxyethyl) isocyanurate, ethylene glycol-modified pentaerythritol tetra(meth)acrylate, ethylene glycol-modified dipentaerythritol hexa(meth)acrylate, propylene glycol-modified pentaerythritol tetra(meth)acrylate, propylene glycol-modified dipentaerythritol hexa(meth)acrylate, caprolactone-modified pentaerythritol tetra(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate, and the like. Among them, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and the like are preferable.

[0099] Examples of the commercially available products of the compound (Dβ1) include "Aronix M-510" manufactured by Toagosei Co., Ltd., which contains a dibasic acid anhydride adduct of pentaerythritol tri(meth)acrylate as the main component, and "Aronix M-520D" manufactured by Toagosei Co., Ltd., which contains a dibasic acid anhydride adduct of dipentaerythritol penta(meth)acrylate as the main component. These commercially available products have a carboxy group as an acidic functional group.

[0100] In the curable composition, the polymerizable compound (D) preferably contains the compound (Dα) (particularly the compound (Dα1)) because it can lower the pre-baking and thermosetting temperatures of the coating film of the curable composition, can suppress the in-plane variation in the elastic deformation work rate of the cured film, and can reduce the residue after development of the curable composition. Further, when the polymerizable compound (D) contains the compound (Dβ), it can lower the pre-baking and thermosetting temperatures of the coating film of the curable composition, can suppress the in-plane variation in the elastic deformation work rate of the cured film, can improve the curability during exposure and the patterning property during development, can further improve the dispersibility of the light scattering agent (B), and thereby can improve the emitted light intensity of the cured film, which is preferable.

[0101] In 100% by mass of the polymerizable compound (D) contained in the curable composition, the compound (Dα) (particularly the compound (Dα1)) is preferably 30% by mass or more, more preferably 40% by mass or more, still more preferably 50% by mass or more, and may be 70% by mass or less. In 100% by mass of the polymerizable compound (D) contained in the curable composition, the compound (Dβ) is preferably 20% by mass or more, more preferably 30% by mass or more, still more preferably 40% by mass or more, and may be 100% by mass or 60% by mass or less.

[0102] When the polymerizable compound (D) in the curable composition contains both the compound (Dα) and the compound (Dβ), it preferably contains the compounds (Dα1) and (Dβ1). The total content of the compounds (Dα1) and (Dβ1) with respect to 100% by mass of the polymerizable compound (D) is preferably 70% by mass or more, more preferably 85% by mass or more, and may be 100% by mass. The content of the compound (Dα1) with respect to 100% by mass of the total amount of the compounds (Dα1) and (Dβ1) is preferably more than 50% by mass, more preferably 53% by mass or more, still more preferably 55% by mass or more, and may be 70% by mass or less.

[0103] When the polymerizable compound (D) in the curable composition contains both the compound (Dβ1) and the compound (Dβ2), the total content of the compound (Dβ1) and the compound (Dβ2) relative to 100% by mass of the polymerizable compound (D) is preferably 70% by mass or more, more preferably 85% by mass or more, and may be 100% by mass. The content of the compound (Dβ2) relative to 100% by mass of the total amount of the compound (Dβ1) and the compound (Dβ2) is preferably more than 50% by mass, more preferably 53% by mass or more, still more preferably 55% by mass or more, and may be 70% by mass or less.

[0104] The content of the polymerizable compound (D) in the curable composition (when there are multiple types, the total amount) is preferably 3% by mass or more and 40% by mass or less, more preferably 8% by mass or more and 30% by mass or less, still more preferably 10% by mass or more and 25% by mass or less, based on 100% by mass of the total solid content of the curable composition. When the content of the polymerizable compound (D) is within the above range, the pre-baking and thermosetting temperatures of the coating film of the curable composition can be lowered, and the variation in the elastic deformation work rate of the cured film within the plane can be suppressed.

[0105] <Polymerization initiator (E)> The polymerization initiator (E) is a compound that can generate active radicals, acids, etc. by the action of light or heat and initiate the polymerization of the polymerizable compound (D). The curable composition can contain one or more polymerization initiators (E).

[0106] Examples of the polymerization initiator (E) include compounds represented by the formula (EA). By including a compound represented by the formula (EA) as the polymerization initiator (E), the pre-baking and thermosetting temperatures of the coating film of the curable composition can be lowered, and the variation in the elastic deformation work rate of the cured film within the plane can be suppressed. Also, by including a compound represented by the formula (EA), the Martens hardness can be made a predetermined value or more (for example, 40 MPa or more).

[0107] [Chemical formula] [In the formula, Rea1 represents a branched hydrocarbon group having 3 to 20 carbon atoms which may have a substituent. R ea2 ~R ea5 each independently represents a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. n represents any integer from 0 to 4. -CH2- contained in the hydrocarbon group may be replaced by -O-, -S-, -CO- or -OCO-.

[0108] R ea1 Examples of the branched hydrocarbon group having 3 to 20 carbon atoms represented by R include a branched saturated hydrocarbon group having 3 to 20 carbon atoms, a branched unsaturated hydrocarbon group having 3 to 20 carbon atoms, and the like.

[0109] R ea1Examples of the branched saturated hydrocarbon group having 3 to 20 carbon atoms represented by include a 1-methylethyl group (isopropyl group), a 1-methylpropyl group (sec-butyl group), a 2-methylpropyl group (isobutyl group), a 1,1-dimethylethyl group (tert-butyl group), a 1,1-dimethylpropyl group, a 2,2-dimethylpropyl group, a 1,2-dimethylpropyl group, a 1-ethylpropyl group, a 1-methylbutyl group, a 2-methylbutyl group, a 3-methylbutyl group, a 1,1-dimethylbutyl group, a 2,2-dimethylbutyl group, a 3,3-dimethylbutyl group, a 1,2-dimethylbutyl group, a 1,3-dimethylbutyl group, a 2,3-dimethylbutyl group, a 1-ethylbutyl group, a 2-ethylbutyl group, a 1-methylpentyl group, a 2-methylpentyl group, a 3-methylpentyl group, a 4-methylpentyl group, a 1,1-dimethylpentyl group, a 2,2-dimethylpentyl group, a 3,3-dimethylpentyl group, a 1,2-dimethylpentyl group, a 1,3-dimethylpentyl group, a 2,3-dimethylpentyl group, a 1-ethylpentyl group, a 2-ethylpentyl group, a 3-ethylpentyl group, a 1-methylhexyl group, a 2-methylhexyl group, a 3-methylhexyl group, a 4-methylhexyl group, a 1,1-dimethylhexyl group, a 2,2-dimethylhexyl group, a 3,3-dimethylhexyl group, a 1,2-dimethylhexyl group, a 1,3-dimethylhexyl group, a 2,3-dimethylhexyl group, a 1-ethylhexyl group, a 2-ethylhexyl group, a 3-ethylhexyl group, a 1-methylheptyl group, a 2-methylheptyl group, a 3-methylheptyl group, a 4-methylheptyl group, a 1,1-dimethylheptyl group, a 2,2-dimethylheptyl group, a 3,3-dimethylheptyl group, a 1,2-dimethylheptyl group, a 1,3-dimethylheptyl group, a 2,3-dimethylheptyl group, a 1-ethylheptyl group, a 2-ethylheptyl group, a 3-ethylheptyl group, a 1-methyloctyl group, a 2-methyloctyl group, a 3-methyloctyl group, a 4-methyloctyl group, a 1,1-dimethyloctyl group, a 2,2-dimethyloctyl group, a 3,3-dimethyloctyl group, a 1,2-dimethyloctyl group, a 1,3-dimethyloctyl group, 2,Branched alkyl groups such as 3-dimethyloctyl group, 1-ethyloctyl group, 2-ethyloctyl group, 3-ethyloctyl group, 1-methylnonyl group, 2-methylnonyl group, 3-methylnonyl group, 4-methylnonyl group, dimethylnonyl group, ethylnonyl group, methyldecyl group, dimethyldecyl group, ethyldecyl group, methylundecyl group, dimethylundecyl group, ethylundecyl group, methyldodecyl group, etc.; may be mentioned. R ea1 The branched alkyl group represented by may be any of a primary branched alkyl group, a secondary branched alkyl group, or a tertiary branched alkyl group. R ea1 The number of carbon atoms of the branched saturated hydrocarbon group represented by is preferably 4 or more, more preferably 5 or more, preferably 16 or less, more preferably 12 or less, and even more preferably 10 or less.

[0110] R ea1 Examples of the branched unsaturated hydrocarbon group represented by include groups in which at least one carbon-carbon single bond contained in the branched saturated hydrocarbon group represented by the aforementioned R ea1 is replaced by a carbon-carbon double bond or a carbon-carbon triple bond, and the like. R ea1 Examples of the branched unsaturated hydrocarbon group represented by include alkenyl groups such as isopropenyl group, isobutenyl group, isopentenyl group, isohexenyl group, isoheptenyl group, isooctenyl group, isononyl group, isodecenyl group; alkynyl groups such as isopropynyl group, isobutinyl group, isopentynyl group, isohexynyl group, isoheptynyl group, isooctynyl group, isononynyl group, isodecynyl group; and the like. R ea1 The number of carbon atoms of the branched unsaturated hydrocarbon group represented by is preferably 4 or more, more preferably 5 or more, preferably 16 or less, more preferably 12 or less, and even more preferably 10 or less.

[0111] R ea2 R ea3 R ea4 and R ea5Examples of the hydrocarbon group having 1 to 20 carbon atoms represented by [ [ are a saturated hydrocarbon group having 1 to 20 carbon atoms, an unsaturated hydrocarbon group having 2 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, and the like. R ea2 , R ea3 , R ea4 and R ea5 The hydrocarbon groups represented by may be the same or different from each other.

[0112] Examples of the saturated hydrocarbon group having 1 to 20 carbon atoms include linear alkyl groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, hexadecyl group, icosyl group, etc.; branched-chain alkyl groups such as isopropyl group, isobutyl group, isopentyl group, neopentyl group, 2-ethylhexyl group, etc.; and alicyclic saturated hydrocarbon groups having 3 to 20 carbon atoms such as cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, tricyclodecyl group, etc. The number of carbon atoms of the saturated hydrocarbon group is preferably 1 to 18, more preferably 1 to 15, still more preferably 1 to 10, and even more preferably 1 to 8.

[0113] Examples of the unsaturated hydrocarbon group having 2 to 20 carbon atoms include alkenyl groups such as vinyl group, allyl group, butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, nonenyl group, decenyl group, undecenyl group, dodecenyl group, hexadecenyl group, octadecenyl group, icosenyl group, etc.; alkynyl groups such as ethynyl group, propynyl group, hexynyl group, decynyl group, icosenyl group, etc.; cycloalkenyl groups such as cyclopentenyl group, cyclohexenyl group, cycloheptenyl group, etc. The number of carbon atoms of the unsaturated hydrocarbon group is preferably 2 to 18, more preferably 2 to 15, and still more preferably 2 to 10.

[0114] Examples of the aromatic hydrocarbon group having 6 to 20 carbon atoms include phenyl group, xylyl group, trimethylphenyl group, dipropylphenyl group, bis(2,2-dimethylpropyl)phenyl group, naphthyl group, benzyl group, phenylethyl group, phenylbutyl group and the like. The number of carbon atoms of the aromatic hydrocarbon group is preferably 6 to 18, more preferably 6 to 15, still more preferably 6 to 12.

[0115] R ea1 , R ea2 , R ea3 , R ea4 and R ea5 Examples of the substituent which the hydrocarbon group represented by may have include halogen atom, cyano group and nitro group. The halogen atom is preferably a fluorine atom, a bromine atom, a chlorine atom or an iodine atom.

[0116] -CH2- contained in the hydrocarbon group may be replaced by -O-, -S-, -CO- or -OCO-, and adjacent -CH2- is not simultaneously replaced by the same kind of group, and terminal -CH2- is not replaced.

[0117] n represents any integer from 0 to 4, preferably an integer from 0 to 3, more preferably an integer from 0 to 2, still more preferably an integer of 0 or 1, and even more preferably 0.

[0118] *-OCO-R ea4 The bonding position of the group (* represents a bond to the phenyl group.) may be any of the 2-position, 3-position or 4-position of the phenyl group to which the *-OCO-R ea4 group is bonded, preferably the 3-position or 4-position, more preferably the 4-position.

[0119] R ea1 The branched hydrocarbon group having 3 to 20 carbon atoms represented by is preferably a branched saturated hydrocarbon group having 3 to 20 carbon atoms, more preferably a branched-chain alkyl group having 3 to 20 carbon atoms, still more preferably a branched-chain alkyl group having 3 to 10 carbon atoms, One or more selected from the group consisting of 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 1-ethylpentyl group, 2-ethylpentyl group, 3-ethylpentyl group, 1-methylhexyl group, 2-methylhexyl group, 3-methylhexyl group, 1-ethylhexyl group, 2-ethylhexyl group, 3-ethylhexyl group, 1-methylheptyl group, 2-methylheptyl group, 3-methylheptyl group, 1-ethylheptyl group, 2-ethylheptyl group and 3-ethylheptyl group are preferred.

[0120] R ea2 , R ea3 , R ea4 and R ea5 The hydrocarbon group having 1 to 20 carbon atoms represented by A saturated hydrocarbon group having 1 to 20 carbon atoms and an unsaturated hydrocarbon group having 2 to 20 carbon atoms are preferred. A saturated hydrocarbon group having 1 to 20 carbon atoms is more preferred. A linear saturated hydrocarbon group having 1 to 10 carbon atoms is even more preferred. A linear alkyl group having 1 to 8 carbon atoms is even more preferred. R ea2 is preferably a linear alkyl group having 1 to 8 carbon atoms, and more preferably a linear alkyl group having 1 to 6 carbon atoms. R ea3 is preferably a linear alkyl group having 1 to 8 carbon atoms, and more preferably a linear alkyl group having 1 to 3 carbon atoms. R ea4 is preferably a linear alkyl group having 1 to 8 carbon atoms, and more preferably a linear alkyl group having 1 to 3 carbon atoms. R ea5 is preferably a linear or branched alkyl group having 1 to 8 carbon atoms, and more preferably a linear or branched alkyl group having 1 to 6 carbon atoms.

[0121] Further, as the polymerization initiator (E), a compound represented by the formula (EB) can be mentioned. By including the compound represented by the formula (EB) as the polymerization initiator (E), the pre-baking and thermosetting temperatures of the coating film of the curable composition can be lowered, and the in-plane variation of the elastic deformation work rate of the cured film can be suppressed.

[0122] [Chemical formula] [In the formula, R eb1 represents a branched hydrocarbon group having 3 to 20 carbon atoms which may have a substituent. R eb2 ~R eb4 each independently represents a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. m represents any integer from 0 to 4. The -CH2- contained in the hydrocarbon group may be replaced by -O-, -S-, -CO- or -OCO-.

[0123] R eb1 Examples of the branched hydrocarbon group having 3 to 20 carbon atoms represented by include a branched saturated hydrocarbon group having 3 to 20 carbon atoms, a branched unsaturated hydrocarbon group having 3 to 20 carbon atoms, and the like.

[0124] R eb1 Examples of the branched saturated hydrocarbon group having 3 to 20 carbon atoms represented by include those similar to those exemplified above for the branched saturated hydrocarbon group having 3 to 20 carbon atoms represented by R ea1 . R eb1 The branched alkyl group represented by may be any of a primary branched alkyl group, a secondary branched alkyl group, or a tertiary branched alkyl group. R eb1 The number of carbon atoms of the branched saturated hydrocarbon group represented by is preferably 4 or more, more preferably 5 or more, preferably 16 or less, more preferably 12 or less, and even more preferably 10 or less.

[0125] R eb1 Examples of the branched unsaturated hydrocarbon group represented by include groups in which at least one carbon-carbon single bond contained in the branched saturated hydrocarbon group represented by the aforementioned R eb1 is replaced by a carbon-carbon double bond or a carbon-carbon triple bond. R eb1Examples of the branched unsaturated hydrocarbon group represented by the formula (I) include alkenyl groups such as an isopropenyl group, an isobutenyl group, an isopentenyl group, an isohexenyl group, an isoheptenyl group, an isooctenyl group, an isononyl group, and an isodecenyl group; and alkynyl groups such as an isopropynyl group, an isobutynyl group, an isopentynyl group, an isohexynyl group, an isoheptynyl group, an isooctynyl group, an isononynyl group, and an isodecynyl group. R eb1 The branched unsaturated hydrocarbon group represented by the formula (I) has preferably 4 or more, more preferably 5 or more, and preferably 16 or less, more preferably 12 or less, and further preferably 10 or less.

[0126] R eb2 , R eb3 and R eb4 Examples of the hydrocarbon group having 1 to 20 carbon atoms represented by the formula (I) include a saturated hydrocarbon group having 1 to 20 carbon atoms, an unsaturated hydrocarbon group having 2 to 20 carbon atoms, and an aromatic hydrocarbon group having 6 to 20 carbon atoms. eb2 , R eb3 and R eb4 The hydrocarbon groups represented by the following formula may be the same or different.

[0127] Examples of the saturated hydrocarbon group having 1 to 20 carbon atoms include linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, hexadecyl, and icosyl groups; branched alkyl groups such as isopropyl, isobutyl, isopentyl, neopentyl, and 2-ethylhexyl groups; and alicyclic saturated hydrocarbon groups having 3 to 20 carbon atoms such as cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and tricyclodecyl groups. The number of carbon atoms in the saturated hydrocarbon group is preferably 1 to 18, more preferably 1 to 15, even more preferably 1 to 10, and even more preferably 1 to 8.

[0128] Examples of the unsaturated hydrocarbon group having 2 to 20 carbon atoms include alkenyl groups such as vinyl group, allyl group, butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, nonenyl group, decenyl group, undecenyl group, dodecenyl group, hexadecenyl group, octadecenyl group, and icosenyl group; alkynyl groups such as ethynyl group, propynyl group, hexynyl group, decynyl group, and icosenyl group; cycloalkenyl groups such as cyclopentenyl group, cyclohexenyl group, and cycloheptenyl group; etc. The number of carbon atoms in the unsaturated hydrocarbon group is preferably 2 to 18, more preferably 2 to 15, and even more preferably 2 to 10.

[0129] Examples of the aromatic hydrocarbon group having 6 to 20 carbon atoms include a phenyl group, a xylyl group, a trimethylphenyl group, a dipropylphenyl group, a di(2,2-dimethylpropyl)phenyl group, a naphthyl group, a benzyl group, a phenylethyl group, a phenylbutyl group, etc. The number of carbon atoms in the aromatic hydrocarbon group is preferably 6 to 18, more preferably 6 to 15, and further preferably 6 to 12.

[0130] R eb1 , R eb2 , R eb3 and R eb4 Examples of the substituent that the hydrocarbon group represented by the formula (I) may have include a halogen atom, a cyano group, and a nitro group. The halogen atom is preferably a fluorine atom, a bromine atom, a chlorine atom, or an iodine atom, and more preferably a fluorine atom.

[0131] The -CH2- contained in the hydrocarbon group may be replaced by -O-, -S-, -CO- or -OCO-, in particular may be replaced by -O-, provided that adjacent -CH2- are not simultaneously replaced by the same group, and the terminal -CH2- is not replaced.

[0132] m represents an integer of 0 to 4, preferably an integer of 1 to 3, more preferably an integer of 2 or 3, and further preferably 3.

[0133] If m is 1 or more, then *-R eb4At least one of the 2-, 4- and 6-positions of the phenyl group to which is bonded, *-R eb4 (* represents a bond to a phenyl group) is preferably bonded, and *-R eb4 At least two of the 2-, 4-, and 6-positions of the phenyl group to which *-R is bonded eb4 is more preferably bonded, and *-R eb4 *-R is attached to all of the 2nd, 4th and 6th positions of the phenyl group to which eb4 It is more preferred that

[0134] R eb1 The branched hydrocarbon group having 3 to 20 carbon atoms represented by the formula: A branched saturated hydrocarbon group having 3 to 20 carbon atoms is preferred. A branched alkyl group having 3 to 20 carbon atoms is more preferable. A branched alkyl group having 3 to 10 carbon atoms is more preferable. It is preferable that the alkyl group is one or more selected from the group consisting of a 1-methylpentyl group, a 2-methylpentyl group, a 3-methylpentyl group, a 1-ethylpentyl group, a 2-ethylpentyl group, a 3-ethylpentyl group, a 1-methylhexyl group, a 2-methylhexyl group, a 3-methylhexyl group, a 1-ethylhexyl group, a 2-ethylhexyl group, a 3-ethylhexyl group, a 1-methylheptyl group, a 2-methylheptyl group, a 3-methylheptyl group, a 1-ethylheptyl group, a 2-ethylheptyl group, and a 3-ethylheptyl group.

[0135] R eb2 The hydrocarbon group having 1 to 20 carbon atoms represented by the formula (I) is preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, more preferably an aromatic hydrocarbon group having 6 to 17 carbon atoms, still more preferably an aromatic hydrocarbon group having 7 to 15 carbon atoms, and particularly preferably an aromatic hydrocarbon group having 8 to 13 carbon atoms. In any of these preferred embodiments, it is preferable that the hydrocarbon group has 1 to 8 (particularly 1 to 5) fluorine atoms as a substituent and has 1 or more -CH2-, with 1 to 2 -CH2- being replaced by -O-.

[0136] R eb2In a preferred embodiment, the aromatic hydrocarbon group having 8 to 13 carbon atoms is preferably any one of the following (eb2-1) to (eb2-6).

[0137] [Chemical formula]

[0138] R eb3 and R eb4 The hydrocarbon groups having 1 to 20 carbon atoms represented by are each independently preferably a saturated hydrocarbon group having 1 to 20 carbon atoms or an unsaturated hydrocarbon group having 2 to 20 carbon atoms,[ more preferably a saturated hydrocarbon group having 1 to 20 carbon atoms,[ even more preferably a linear saturated hydrocarbon group having 1 to 10 carbon atoms,[ even more preferably a linear alkyl group having 1 to 8 carbon atoms, and particularly preferably a linear alkyl group having 1 to 3 carbon atoms.[

[0139] In addition, when -CH2- contained in the hydrocarbon group in formula (EB) is replaced by -O-, -S-, -CO- or -OCO-, the carbon number of the replaced part shall be counted as the carbon number of -CH2- before replacement.[

[0140] Examples of the polymerization initiator (E) other than the compound represented by formula (EA) include oxime compounds (excluding the compounds represented by formula (EA) and formula (EB)), alkylphenone compounds, biimidazole compounds, triazine compounds, and acylphosphine compounds, etc., which are photoinitiators, and azo compounds and organic peroxides, etc., which are thermal polymerization initiators.[

[0141] An example of the oxime compound (excluding the compounds represented by formula (EA) and formula (EB)) 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)".[

[0142] [Chemical formula]

[0143] Including the oxime compound (1) as the polymerization initiator (E) can be advantageous from the viewpoint of improving the emitted light intensity. One of the reasons for such an effect is that due to the specific molecular structure of the oxime compound (1), when the oxime compound (1) initiates photopolymerization, the absorption wavelength of the oxime compound (1) before and after cleavage (decomposition) of the oxime compound (1) required for the initiation of photopolymerization changes significantly. Therefore, it is presumed that the oxime compound (1) has a high ability to initiate photoradical polymerization.

[0144] In formula (1), R 1 represents R 11 , OR 11 , COR 11 , SR 11 , CONR 12 R 13 or CN.

[0145] 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.

[0146] R 11 , R 12 or R 13 The hydrogen atom of the group represented by is OR 21 , COR 21 , SR 21 , NR 22 R 23 , CONR 22 R 23 , -NR 22 -OR 23 , -N(COR 22 )-OCOR 23 , -C(=N-OR 21 )-R 22 , -C(=N-OCOR 21 )-R 22 , CN, a halogen atom, or COOR 21 may be substituted.

[0147] 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.

[0148] R 21 , R 22 or R 23 The hydrogen atom of the group represented by the formula (I) may be substituted by CN, a halogen atom, a hydroxy group or a carboxy group.

[0149] R 11 , R 12 , R 13 , R 21 , R 22 or R 23 When the group represented by the formula (I) has an alkylene portion, the alkylene portion is preferably -O-, -S-, -COO-, -OCO-, -NR 24 -, -NR 24 CO-, -NR 24 COO-, -OCONR 24 It may be interrupted 1 to 5 times by -, -SCO-, -COS-, -OCS- or -CSO-.

[0150] R 24 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms.

[0151] R 11 , R 12 , R 13 , R 21 , R 22 or R 23 When the group represented by R 12 and R 13 and R 22 and R 23 may be joined together to form a ring.

[0152] * represents a bond with a second molecular structure, which is a molecular structure other than the first molecular structure possessed by the oxime compound (1).

[0153] R in formula (1) 11 R 12 R 13 R 21 R 22 R 23 and R 24 Examples of the alkyl group having 1 to 20 carbon atoms represented by R, R, R, R, R, R, and R include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, tert-pentyl group, hexyl group, heptyl group, octyl group, isooctyl group, 2-ethylhexyl group, tert-octyl group, nonyl group, isononyl group, decyl group, isodecyl group, undecyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group, icosyl group, cyclopentyl group, cyclohexyl group, cyclohexylmethyl group, cyclohexylethyl group, etc.

[0154] R in formula (1) 11 R 12 R 13 R 21 R 22 R 23 and R 24 Examples of the aryl group having 6 to 30 carbon atoms represented by R, R, R, R, R, R, and R include phenyl group, tolyl group, xylyl group, ethylphenyl group, naphthyl group, anthryl group, phenanthryl group, phenyl group substituted with one or more of the above alkyl groups, biphenylyl group, naphthyl group, anthryl group, etc.

[0155] R in formula (1) 11 R 12 R 13 R 21 R 22 R 23 and R 24 Examples of the aralkyl group having 7 to 30 carbon atoms represented by R, R, R, R, R, R, and R include benzyl group, α-methylbenzyl group, α,α-dimethylbenzyl group, phenylethyl group, etc.

[0156] R in formula (1) 11 , R 12 , R 13 , R 21 , R 22 , R 23 and R 24 Examples of the heterocyclic group having 2 to 20 carbon atoms represented by include a pyridyl group, a pyrimidyl group, a furyl group, a thienyl group, a tetrahydrofuryl group, a dioxolanyl group, a benzoxazol-2-yl group, a tetrahydropyranyl group, a pyrrolidyl group, an imidazolidyl group, a pyrazolidyl group, a thiazolidyl group, an isothiazolidyl group, an oxazolidyl group, an isoxazolidyl group, a piperidyl group, a piperazinyl group, a morpholinyl group, etc. Preferably, it is a 5- to 7-membered heterocycle.

[0157] R in formula (1) 12 and R 13 and R 22 and R 23 each may together form a ring, which means that R 12 and R 13 and R 22 and R 23 each may together form a ring with the connecting nitrogen atom, carbon atom or oxygen atom.

[0158] R in formula (1) 12 and R 13 and R 22 and R 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, etc. Preferably, it is a 5- to 7-membered ring.

[0159] R in formula (1) 11 , R 12 , R 13 , R 21 , R 22 and R 23 Examples of the halogen atom that may be possessed as a substituent include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

[0160] R in formula (1) 1 is preferably R 11 and more preferably an alkyl group having 1 to 20 carbon atoms, still more preferably an alkyl group having 1 to 10 carbon atoms, and even more preferably an alkyl group having 1 to 6 carbon atoms.

[0161] An example of the second molecular structure linked to the first molecular structure represented by formula (1) is the structure represented by the following formula (2). The second molecular structure means another molecular structure part other than the above first molecular structure that the oxime compound (1) has.

[0162] In formula (2), the bond represented by "*" is directly bonded to the bond represented by "*" in formula (1). That is, when the second molecular structure is the structure represented by formula (2), the benzene ring having "-*" in formula (2) and the carbonyl group having "-*" in formula (1) are directly bonded.

[0163] [Chemical formula]

[0164] In formula (2), R 2 and R 3 each independently represent R 11 , OR 11 , SR 11 , COR 11 , CONR 12 R 13 , NR 12 , COR 11 , OCOR 11 , COOR 11 , SCOR 11 , OCSR 11 , COSR 11 , CSOR 11 , CN or a halogen atom.

[0165] When there are a plurality of Rs 2 they may be the same or different.

[0166] R 3 When there are a plurality of them, they may be the same or different.

[0167] R 11 、R 12 and R 13 have the same meaning as described above.

[0168] s and t each independently represent an integer from 0 to 4.

[0169] L represents a sulfur atom, CR 31 R 32 , CO or NR 33 .

[0170] R 31 、R 32 and R 33 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an aralkyl group having 7 to 30 carbon atoms.

[0171] R 31 、R 32 or R 33 When the group represented by has an alkyl moiety, the alkyl moiety may be branched or cyclic, and R 31 、R 32 and R 33 may each independently form a ring together with either adjacent benzene ring.

[0172] R 4 is a hydroxy group, a carboxy group or the following formula (2-1)

[0173]

Chemical formula

[0174] (In formula (2-1), L 1 represents -O-, -S-, -NR 22 -, -NR 22 CO-, -SO2-, -CS-, -OCO- or -COO-.

[0175] R 22 represents the same meaning as described above.

[0176] L 2 represents a group obtained by removing v hydrogen atoms from an alkyl group having 1 to 20 carbon atoms, a group obtained by removing v hydrogen atoms from an aryl group having 6 to 30 carbon atoms, a group obtained by removing v hydrogen atoms from an aralkyl group having 7 to 30 carbon atoms, or a group obtained by removing v hydrogen atoms from a heterocyclic group having 2 to 20 carbon atoms.

[0177] L 2 When the group represented by has an alkylene moiety, the alkylene moiety may be interrupted 1 to 5 times by -O-, -S-, -COO-, -OCO-, -NR 22 -, -NR 22 COO-, -OCONR 22 -, -SCO-, -COS-, -OCS- or -CSO-, and the alkylene moiety may be branched or cyclic.

[0178] R 4a is OR 41 , SR 41 , CONR 42 R 43 , NR 42 COR 43 , OCOR 41 , COOR 41 , SCOR 41 , OCSR 41 , COSR 41 , CSOR 41 , CN or a halogen atom.

[0179] R 4a When a plurality of them exist, they may be the same or different.

[0180] 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, R 41 R 42 and R43 When the group represented by has an alkyl moiety, the alkyl moiety may be branched or cyclic, and R 42 and R 43 may combine together to form a ring.

[0181] v represents an integer from 1 to 3.) represents a group represented by.

[0182] * represents a bond with the first molecular structure of the oxime compound (1).

[0183] 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, aryl group having 6 to 30 carbon atoms, and aralkyl group having 7 to 30 carbon atoms represented by are the same as the examples for R 11 , R 12 , R 13 , R 21 , R 22 , R 23 and R 24 in formula (1).

[0184] 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 the heterocyclic group having 2 to 20 carbon atoms represented by are the same as the examples for R 11 , R 12 , R 13 , R 21 , R 22 , R 23 and R24 It is the same as the example for

[0185] R in formula (2) 31 , R 32 and R 33 may each independently form a ring together with either adjacent benzene ring, which means that R 31 , R 32 and R 33 may each independently form a ring together with either adjacent benzene ring and the nitrogen atom connecting therewith.

[0186] R in formula (2) 31 , R 32 and R 33 Examples of the ring that may be formed together with either adjacent benzene ring are the same as the examples of the ring that may be formed by R 12 and R 13 and R 2 and R 23 in formula (1).

[0187] L in the above formula (2-1) 2 represents a group obtained by removing v hydrogen atoms from an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms.

[0188] Examples of the group obtained by removing v hydrogen atoms from an alkyl group having 1 to 20 carbon atoms include, for example, when v is 1, methylene group, ethylene group, propylene group, methylethylene group, butylene group, 1-methylpropylene group, 2-methylpropylene group, 1,2-dimethylpropylene group, 1,3-dimethylpropylene group, 1-methylbutylene group, 2-methylbutylene group, 3-methylbutylene group, 4-methylbutylene group, 2,4-dimethylbutylene group, 1,3-dimethylbutylene group, pentylene group, hexylene group, heptylene group, octylene group, nonylene group, decylene group, dodecylene group, tridecylene group, tetradecylene group, pentadecylene group, ethane-1,1-diyl group, propane-2,2-diyl group and other alkylene groups.

[0189] Examples of the group obtained by removing v hydrogen atoms from an aryl group having 6 to 30 carbon atoms include, when v = 1, an arylene group such as 1,2-phenylene group, 1,3-phenylene group, 1,4-phenylene group, 2,6-naphthylene group, 1,4-naphthylene group, 2,5-dimethyl-1,4-phenylene group, diphenylmethane-4,4'-diyl group, 2,2-diphenylpropane-4,4'-diyl group, diphenylsulfide-4,4'-diyl group, diphenylsulfone-4,4'-diyl group, etc.

[0190] Examples of the group obtained by removing v hydrogen atoms from an aralkyl group having 7 to 30 carbon atoms include, when v = 1, the group represented by the following formula (a) and the group represented by the following formula (b), etc.

[0191]

Chemical formula

[0192] [In formulas (a) and (b), L 3 and L 5 represent an alkylene group having 1 to 10 carbon atoms, and L 4 and L 6 represent a single bond or an alkylene group having 1 to 10 carbon atoms.] Examples of the alkylene group having 1 to 10 carbon atoms include, for example, methylene group, ethylene group, propylene group, methylethylene group, butylene group, 1-methylpropylene group, 2-methylpropylene group, 1,2-dimethylpropylene group, 1,3-dimethylpropylene group, 1-methylbutylene group, 2-methylbutylene group, 3-methylbutylene group, 4-methylbutylene group, 2,4-dimethylbutylene group, 1,3-dimethylbutylene group, pentylene group, hexylene group, heptylene group, octylene group, nonylene group, decylene group, etc.

[0193] Examples of the group obtained by removing v hydrogen atoms from a complex ring group having 2 to 20 carbon atoms include, for example, when v is 1, divalent complex ring groups such as 2,5-pyridinediyl group, 2,6-pyridinediyl group, 2,5-pyrimidinediyl group, 2,5-thiophenediyl group, 3,4-tetrahydrofuranediyl group, 2,5-tetrahydrofuranediyl group, 2,5-furandiyl group, 3,4-thiazolediy group, 2,5-benzofurandiyl group, 2,5-benzothiophenediyl group, N-methylindole-2,5-diyl group, 2,5-benzothiazolediy group, 2,5-benzoxazolediy group, etc.

[0194] R in formula (2) 2 and R 3 , and also R in the above formula (2-1) 4a Examples of the halogen atom represented by include fluorine atom, chlorine atom, bromine atom and iodine atom.

[0195] From the viewpoints of solubility in the solvent (J) and / or developability of the curable composition, a preferable example of the structure represented by formula (2) is the structure represented by the following formula (2a).

[0196]

Chemical formula

[0197] [In formula (2a), L'represents a sulfur atom or NR 50 , R 50 represents a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, and R 2 , R 3 , R 4 , s and t represent the same meanings as described above.] From the same viewpoints as above, another preferable example of the structure represented by formula (2) is the structure represented by the following formula (2b).

[0198]

Chemical formula

[0199] [In formula (2b), R 44 represents a hydroxy group, a carboxy group, or the following formula (2-2)

[0200] [Chemical formula]

[0201] (In formula (2-2), L 11 represents *-O- or *-OCO-, where * represents the bond with L 12 and L 12 represents an alkylene group having 1 to 20 carbon atoms, and the alkylene group may be interrupted by 1 to 3 -O-'s. R 44a represents OR 55 or COOR 55 and R 55 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.) represents a group represented by) R 44 is preferably a group represented by formula (2-2). In this case, it is advantageous in terms of the solubility of the oxime compound (1) in the solvent (J) and the developability of the curable composition.

[0202] The number of carbon atoms of the alkylene group represented by L 12 is preferably 1 to 10, more preferably 1 to 4.

[0203] R 44a is preferably a hydroxy group or a carboxy group, more preferably a hydroxy group.

[0204] The method for producing the oxime compound (1) having the second molecular structure represented by formula (2) is not particularly limited, but for example, it can be produced by the method described in JP-A-2011-132215.

[0205] Another example of the second molecular structure linked to the first molecular structure represented by formula (1) is a structure represented by the following formula (3).

[0206] In formula (3), the bond represented by "*" is directly bonded to the bond represented by "*" in formula (1). That is, when the second molecular structure is the structure represented by formula (3), the benzene ring having "-*" in formula (3) and the carbonyl group having "-*" in formula (1) are directly bonded.

[0207]

Chemical formula

[0208] In formula (3), R 5 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms.

[0209] R 5 When the group represented by has an alkyl moiety, the alkyl moiety may be branched or cyclic.

[0210] R 5 The hydrogen atom of the group represented by is R 21 , OR 21 , COR 21 , SR 21 , NR 22 R 23 , CONR 22 R 23 , -NR 22 -OR 23 , -N(COR 22 )-OCOR 23 , NR 22 COR 21 , OCOR 21 , COOR 21 , -C(=N-OR 21 )-R 22 , -C(=N-OCOR 21 )-R 22 , SCOR 21 , OCSR 21 , COSR 21 , CSOR 21 , a hydroxyl group, a nitro group, CN, a halogen atom, or COOR 21 and may be substituted.

[0211] R 21 、R 22 and R 23 have the same meaning as described above.

[0212] R 21 、R 22 or R 23 The hydrogen atom of the group represented by may be substituted with a CN, a halogen atom, a hydroxy group or a carboxy group.

[0213] R 21 、R 22 and R 23 When the group represented by has an alkylene moiety, the alkylene moiety may be interrupted 1 to 5 times by -O-, -S-, -COO-, -OCO-, -NR 24 -, -NR 24 CO-, -NR 24 COO-, -OCONR 24 -, -SCO-, -COS-, -OCS- or -CSO-.

[0214] R 24 has the same meaning as described above.

[0215] R 21 、R 22 and R 23 When the group represented by has an alkyl moiety, the alkyl moiety may be branched, may be cyclic, and also, R 22 and R 23 may combine together to form a ring.

[0216] 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 , represents a hydroxyl group, nitro group, CN or halogen atom.

[0217] R 61 , R 62 , R 63 , R 64 and R 65 each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or a heterocyclic group having 2 to 20 carbon atoms.

[0218] R 61 , R 62 , R 63 , R 64 or R 65 The hydrogen atom of the group represented by is OR 21 , COR 21 , SR 21 , NR 22 R 23 , CONR 22 R 23 , -NR 22 -OR 23 , -N(COR 22 )-OCOR 23 , -C(=N-OR 21 )-R 22 , -C(=N-OCOR 21 )-R 22 , CN, halogen atom, or COOR 21 may be substituted.

[0219] R 6 and R 7 , R 7 and R 8 and R 8 and R 9 may together form a ring.

[0220] * represents a bond with the first molecular structure possessed by the oxime compound (1).

[0221] 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, aryl group having 6 to 30 carbon atoms, aralkyl group having 7 to 30 carbon atoms, and heterocyclic group having 2 to 20 carbon atoms represented by are the same as the examples for R 11 , R 12 , R 13 , R 21 , R 22 , R 23 and R 24 are the same as those for.

[0222] R in formula (3) 22 and R 23 may together form a ring, which means that R 22 and R 23 may together form a ring with the connecting nitrogen atom, carbon atom or oxygen atom.

[0223] R in formula (3) 22 and R 23 Examples of the ring that can be formed together are the same as those for the ring that can be formed together by R 12 and R 13 and R 22 and R 23 are the same as those for.

[0224] R in formula (3) 6 , R 7 , R 8 and R 9 Examples of the halogen atom represented by, R 5 , R 21 , R 22 , R 23 , R 61 , R 62 , R 63 , R 64 and R 65 Examples of the halogen atom that may substitute the hydrogen atom of include fluorine atom, chlorine atom, bromine atom and iodine atom.

[0225] From the viewpoints of solubility in the solvent (J) and / or developability of the curable composition, in one preferred embodiment, R 5 is a group represented by the following formula (3-1).

[0226] [Chemical formula]

[0227] [In formula (3-1), Z represents a group obtained by removing one hydrogen atom from an alkyl group having 1 to 20 carbon atoms, a group obtained by removing one hydrogen atom from an aryl group having 6 to 30 carbon atoms, a group obtained by removing one hydrogen atom from an aralkyl group having 7 to 30 carbon atoms, or a group obtained by removing one hydrogen atom from a heterocyclic group having 2 to 20 carbon atoms. When the group represented by Z has an alkylene moiety, the alkylene moiety may be interrupted 1 to 5 times by -O-, -S-, -COO-, -OCO-, -NR -, -NR 24 -, -NR 24 COO-, -OCONR 24 -, -SCO-, -COS-, -OCS- or -CSO-, and the alkylene moiety may be branched or cyclic. R R 21 , R 22 and R 24 represent the same meaning as described above.] From the same viewpoints as above, in formula (3-1), Z is preferably a methylene group, an ethylene group or a phenylene group.

[0228] In formula (3-1), R 21 and R 22 are preferably an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 30 carbon atoms from the same viewpoints as above, and more preferably a methyl group, an ethyl group or a phenyl group.

[0229] From the same viewpoints as above, in another preferred embodiment, R 7 is a nitro group.

[0230] The production method of the oxime compound (1) having the second molecular structure represented by the formula (3) is not particularly limited. For example, it can be produced by the methods described in JP-A-2000-80068 and JP-A-2011-178776.

[0231] Still another example of the second molecular structure linked to the first molecular structure represented by the formula (1) is the structure represented by the following formula (4).

[0232] In the formula (4), the bond represented by "*" is directly bonded to the bond represented by "*" in the formula (1). That is, when the second molecular structure is the structure represented by the formula (4), the benzene ring having "-*" in the formula (4) and the carbonyl group having "-*" in the formula (1) are directly bonded.

[0233]

Chemical formula

[0234] In the formula (4), R 71 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms.

[0235] When the group represented by R 71 has an alkyl moiety, the alkyl moiety may be branched or cyclic.

[0236] The hydrogen atom of the group represented by R 71 is R 21 , OR 21 , COR 21 , SR 21 , NR 22 R 23 , CONR 22 R 23 , -NR 22 -OR 23 , -N(COR 22 )-OCOR 23 , NR 22 COR 21 , OCOR 21, COOR 21 , -C(=N-OR 21 )-R 22 , -C(=N-OCOR 21 )-R 22 , SCOR 21 , OCSR 21 , COSR 21 , CSOR 21 , a hydroxyl group, a nitro group, CN, a halogen atom, or COOR 21 may be substituted therewith.

[0237] R 21 , R 22 and R 23 represent the same meaning as described above.

[0238] R 21 , R 22 or R 23 The hydrogen atom of the group represented by may be substituted with CN, a halogen atom, a hydroxy group or a carboxy group.

[0239] R 21 , R 22 and R 23 When the group represented by has an alkylene moiety, the alkylene moiety may be interrupted 1 to 5 times by -O-, -S-, -COO-, -OCO-, -NR 24 -, -NR 24 CO-, -NR 24 COO-, -OCONR 24 -, -SCO-, -COS-, -OCS- or -CSO-.

[0240] R 24 represents the same meaning as described above.

[0241] R 21 , R 22 and R 23 When the group represented by has an alkyl moiety, the alkyl moiety may be branched or cyclic, and R 22 and R 23 may together form a ring.

[0242] R72 , R 73 and three Rs 74 are each independently R 61 , OR 61 , SR 61 , COR 62 , CONR 63 R 64 , NR 65 COR 61 , OCOR 61 , COOR 62 , SCOR 61 , OCSR 61 , COSR 62 , CSOR 61 , represent a hydroxyl group, nitro group, CN or halogen atom.

[0243] R 61 , R 62 , R 63 , R 64 and R 65 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or a heterocyclic group having 2 to 20 carbon atoms.

[0244] R 61 , R 62 , R 63 , R 64 or R 65 The hydrogen atom of the group represented by is OR 21 , COR 21 , SR 21 , NR 22 R 23 , CONR 22 R 23 , -NR 22 -OR 23 , -N(COR 22 )-OCOR 23 , -C(=N-OR 21 )-R 22 , -C(=N-OCOR 21 )-R 22 , CN, halogen atom, or COOR 21 and may be substituted.

[0245] R 72 and R73 and two Rs 74 may together form a ring.

[0246] * represents a bond with the first molecular structure of the oxime compound (1).

[0247] 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, aryl group having 6 to 30 carbon atoms, aralkyl group having 7 to 30 carbon atoms, and heterocyclic group having 2 to 20 carbon atoms represented by R 11 R 12 R 13 R 21 R 22 R 23 and R 24 are the same as the examples for R

[0248] R in formula (4) 22 and R 23 may together form a ring means that R 22 and R 23 may together form a ring with the nitrogen atom, carbon atom or oxygen atom to which they are connected.

[0249] R in formula (4) 22 and R 23 Examples of the ring that can be formed together by R 12 and R 13 and R 22 and R 23 are the same as the examples for the ring that can be formed together by R

[0250] R in formula (4) 72 R 73 and R 74 represent a halogen atom, R 71 R 21 R22 , R 23 , R 61 , R 62 , R 63 , R 64 and R 65 Examples of the halogen atom that may substitute the hydrogen atom of R include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0251] The method for producing the oxime compound (1) having the second molecular structure represented by the formula (4) is not particularly limited, and for example, it can be produced by the methods described in International Publication No. 2017 / 051680 and International Publication No. 2020 / 004601.

[0252] Still another example of the second molecular structure linked to the first molecular structure represented by the formula (1) is a structure represented by the following formula (5).

[0253] In the formula (5), the bond represented by "*" is directly bonded to the bond represented by "*" in the formula (1). That is, when the second molecular structure is a structure represented by the formula (5), the pyrrole ring having "-*" in the formula (5) and the carbonyl group having "-*" in the formula (1) are directly bonded.

[0254]

Chemical formula

[0255] In the formula (5), R 81 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms.

[0256] R 81 When the group represented by has an alkyl moiety, the alkyl moiety may be branched or cyclic.

[0257] R 81 The hydrogen atom of the group represented by is R 21 , OR 21 , COR 21, SR 21 , NR 22 R 23 , CONR 22 R 23 , -NR 22 , -OR 23 , -N(COR 22 )-OCOR 23 , NR 22 COR 21 , OCOR 21 , COOR 21 , -C(=N-OR 21 )-R 22 , -C(=N-OCOR 21 )-R 22 , SCOR 21 , OCSR 21 , COSR 21 , CSOR 21 , a hydroxyl group, a nitro group, CN, a halogen atom, or COOR 21 may be substituted.

[0258] R 21 , R 22 and R 23 have the same meaning as described above.

[0259] R 21 , R 22 or R 23 The hydrogen atom of the group represented by may be substituted with CN, a halogen atom, a hydroxy group or a carboxy group.

[0260] R 21 , R 22 and R 23 If the group represented by has an alkylene moiety, the alkylene moiety may be interrupted 1 to 5 times by -O-, -S-, -COO-, -OCO-, -NR 24 -, -NR 24 CO-, -NR 24 COO-, -OCONR 24 -, -SCO-, -COS-, -OCS- or -CSO-.

[0261] R 24 has the same meaning as described above.

[0262] R 21 、R 22 and R 23 when the group represented by 23 has an alkyl moiety, the alkyl moiety may be branched or cyclic, and R 22 and R 23 may combine together to form a ring.

[0263] R 82 、R 83 、R 84 、R 85 and R 86 each independently represent R 61 、OR 61 、SR 61 、COR 62 、CONR 63 R 64 、NR 65 COR 61 、OCOR 61 、COOR 62 、SCOR 61 、OCSR 61 、COSR 62 、CSOR 61 、a hydroxyl group, a nitro group, CN or a halogen atom.

[0264] R 61 、R 62 、R 63 、R 64 and R 65 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or a heterocyclic group having 2 to 20 carbon atoms.

[0265] R 61 、R 62 、R 63 、R 64 or R 65 the hydrogen atom of the group represented by 65 is OR 21 、COR 21 、SR 21 、NR 22 R 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, a halogen atom, or COOR 21 may be substituted.

[0266] R 83 and R 84 , R 84 and R 85 and R 85 and R 86 may together form a ring.

[0267] * represents a bond to the first molecular structure of the oxime compound (1).

[0268] 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, aryl group having 6 to 30 carbon atoms, aralkyl group having 7 to 30 carbon atoms, and heterocyclic group having 2 to 20 carbon atoms represented by are the same as the examples for R 11 , R 12 , R 13 , R 21 , R 22 , R 23 and R 24 in formula (1).

[0269] R in formula (5) 22 and R 23 may together form a ring means that R 22 and R 23 may together form a ring with the connecting nitrogen atom, carbon atom or oxygen atom.

[0270] R in formula (5)22 and R 23 Examples of rings that R 12 and R 13 and R 22 and R 23 can form together are the same as the examples of rings that can be formed by combining them together.

[0271] R 82 , R 83 , R 84 , R 85 and R 86 represented by the halogen atoms, R 81 , R 21 , R 22 , R 23 , R 61 , R 62 , R 63 , R 64 and R 65 Examples of halogen atoms that may substitute the hydrogen atoms of are fluorine atom, chlorine atom, bromine atom and iodine atom.

[0272] The method for producing the oxime compound (1) having the second molecular structure represented by the formula (5) is not particularly limited, and for example, it can be produced by the methods described in International Publication No. 2017 / 051680 and International Publication No. 2020 / 004601.

[0273] Still another example of the second molecular structure linked to the first molecular structure represented by the formula (1) is the structure represented by the following formula (6).

[0274] In the formula (6), the bond represented by "*" is directly bonded to the bond represented by "*" in the formula (1). That is, when the second molecular structure is the structure represented by the formula (6), the benzene ring having "-*" in the formula (6) and the carbonyl group having "-*" in the formula (1) are directly bonded.

[0275]

Chemical formula

[0276] In formula (6), the four Rs 91 , R 92 , R 93 , R 94 , R 95 , R 96 and R 97 are each independently R 61 , OR 61 , SR 61 , COR 62 , CONR 63 R 64 , NR 65 COR 61 , OCOR 61 , COOR 62 , SCOR 61 , OCSR 61 , COSR 62 , CSOR 61 , a hydroxyl group, a nitro group, CN or a halogen atom.

[0277] R 61 , R 62 , R 63 , R 64 and R 65 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or a heterocyclic group having 2 to 20 carbon atoms.

[0278] R 61 , R 62 , R 63 , R 64 or R 65 represented by the group, the hydrogen atom is OR 21 , COR 21 , SR 21 , NR 22 R 23 , CONR 22 R 23 , -NR 22 -OR 23 , -N(COR 22 )-OCOR 23 , -C(=N-OR 21 )-R 22 , -C(=N-OCOR 21 )-R 22 , CN, a halogen atom, or COOR 21may be replaced.

[0279] R 21 、R 22 and R 23 represent the same meaning as described above.

[0280] R 92 and R 93 、R 94 and R 95 、R 95 and R 96 and R 96 and R 97 may together form a ring.

[0281] * represents a bond with the first molecular structure of the oxime compound (1).

[0282] R in formula (6) 21 、R 22 、R 23 、R 61 、R 62 、R 63 、R 64 and R 65 Examples of the alkyl group having 1 to 20 carbon atoms, aryl group having 6 to 30 carbon atoms, aralkyl group having 7 to 30 carbon atoms, and heterocyclic group having 2 to 20 carbon atoms represented by are the same as the examples for R in formula (1) 11 、R 12 、R 13 、R 21 、R 22 and R 23 is the same.

[0283] R in formula (6) 22 and R 23 may together form a ring means that R 22 and R 23 may together form a ring with the connecting nitrogen atom, carbon atom or oxygen atom.

[0284] R in formula (6) 22 and R 23 Examples of the ring that can be formed together are the same as those of R in formula (1) 12 and R 13and R 22 and R 23 is the same as the example of the ring that can be formed together with

[0285] R in formula (6) 91 、R 92 、R 93 、R 94 、R 95 、R 96 and R 97 The halogen atoms represented by 21 、R 22 、R 23 、R 61 、R 62 、R 63 、R 64 and R 65 Examples of the halogen atoms that may substitute the hydrogen atoms of

[0286] The method for producing the oxime compound (1) having the second molecular structure represented by formula (6) is not particularly limited. For example, it can be produced by the methods described in International Publication No. 2017 / 051680 and International Publication No. 2020 / 004601.

[0287] Examples of the oxime compound other than the compound represented by formula (EA) and other than the oxime compound (1) include oxime compounds having a partial structure represented by the following formula (d1). * represents a bond.

[0288]

Chemical formula

[0289] Examples of the oxime compound having the partial structure represented by the formula (d1) include N-benzoyloxy-1-(4-phenylsulfanylphenyl)butane-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)octane-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)-3-cyclopentylpropane-1-one-2-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl-2,4-dioxacyclopentanylmethyloxy)benzoyl}-9H-carbazol-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-3-cyclopentylpropane-1-imine, N-benzoyloxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-3-cyclopentylpropane-1-one-2-imine; compounds described in JP-A-2011-132215, WO 2008 / 78678, WO 2008 / 78686, WO 2012 / 132558, etc. may be mentioned. Commercially available products such as Irgacure OXE01 (N-benzoyloxy-1-(4-phenylsulfanylphenyl)octane-1-one-2-imine), OXE02 (N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethane-1-imine) (both manufactured by BASF), N-1919 (manufactured by ADEKA), etc. may also be used.

[0290] Among them, the oxime compound having the partial structure represented by the formula (d1) is preferably at least one selected from the group consisting of N-benzoyloxy-1-(4-phenylsulfanylphenyl)butane-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)octane-1-one-2-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethane-1-imine, and N-benzoyloxy-1-(4-phenylsulfanylphenyl)-3-cyclopentylpropane-1-one-2-imine, and more preferably N-benzoyloxy-1-(4-phenylsulfanylphenyl)octane-1-one-2-imine or N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethane-1-imine.

[0291] 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. * represents a bond.

[0292]

Chemical formula

[0293] Examples of the compound having the structure represented by the formula (d2) include 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl)propan-1-one, 2-dimethylamino-1-(4-morpholinophenyl)-2-benzylbutan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]butan-1-one, and the like. Commercially available products such as OMNIRAD (registered trademark) 369, 907, 379 (manufactured by IGM Resins) may also be used.

[0294] Examples of the compound having the structure represented by the formula (d3) include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexyl phenyl ketone, oligomers of 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propan-1-one, α,α-diethoxyacetophenone, benzyldimethyl ketal, and the like.

[0295] In terms of sensitivity, as the alkylphenone compound, a compound having the structure represented by the formula (d2) is preferable.

[0296] Examples of the biimidazole compound include, for example, the compound represented by the formula (d5).

[0297] [Chemical formula]

[0298] [In the formula (d5), R E ~R J each represents an aryl group having 6 to 10 carbon atoms which may have a substituent.] Examples of the aryl group having 6 to 10 carbon atoms include a phenyl group, a toluyl group, a xylyl group, an ethylphenyl group, a naphthyl group, etc., and a phenyl group is preferable.

[0299] Examples of the substituent include a halogen atom, an alkoxy group having 1 to 4 carbon atoms, etc. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and a chlorine atom is preferable. Examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, etc., and a methoxy group is preferable.

[0300] Examples of the biimidazole compounds include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (see, for example, JP-A-6-75372 and JP-A-6-75373), 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(dialkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(trialkoxyphenyl)biimidazole (see, for example, JP-B-48-38403 and JP-A-62-174204), biimidazole compounds in which the phenyl groups at the 4,4',5,5'-positions are substituted with carboxyalkoxy groups (see, for example, JP-A-7-10913), and the like. Among them, compounds represented by the following formula or mixtures thereof are preferable.

[0301]

Chemical formula

[0302] Examples of the triazine compound include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2-yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-dimethylamino-2-methylphenyl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)ethenyl]-1,3,5-triazine, etc. Among them, 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-triazine is preferable.

[0303] Examples of the acylphosphine compound include bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, (2,4,6-trimethylbenzoyl)diphenylphosphine oxide, etc.

[0304] Another example of the photopolymerization initiator includes, for example, benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether; benzophenone compounds such as benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone, 4,4'-bis(diethylamino)benzophenone; quinone compounds such as 9,10-phenanthrenequinone, 2-ethylanthraquinone, camphorquinone; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, titanocene compounds, etc.

[0305] The content of the polymerization initiator (E) in the curable composition is preferably 0.1 part by mass or more and 300 parts by mass or less, more preferably 0.1 part by mass or more and 200 parts by mass or less, based on 100 parts by mass of the polymerizable compound (D). Further, the content of the polymerization initiator (E) in the curable composition is preferably 0.1 part by mass or more and 30 parts by mass or less, more preferably 0.5 part by mass or more and 20 parts by mass or less, based on 100 parts by mass of the total amount of the resin (C) and the polymerizable compound (D). When the content of the polymerization initiator (E) is within the above range, the pre-baking and thermosetting temperatures of the coating film of the curable composition can be lowered, and the variation in the elastic deformation work rate of the cured film within the plane can be suppressed.

[0306] The content ratio of the polymerization initiator (E) in the curable composition is, for example, 0.01% by mass or more and 20% by mass or less, preferably 0.1% by mass or more and 15% by mass or less, more preferably 0.5% by mass or more and 10% by mass or less, still more preferably 1% by mass or more and 8% by mass or less, and even more preferably 1.5% by mass or more and 5% by mass or less, based on the total amount of the solid content of the curable composition.

[0307] The polymerization initiator (E) preferably contains at least one of the compound represented by the formula (EA) and the compound represented by the formula (EB), and more preferably contains at least one of the compounds represented by the formula (EA). As described above, both the compound represented by the formula (EA) and the compound represented by the formula (EB) can lower the pre-baking and thermosetting temperatures of the coating film of the curable composition, and can suppress the variation in the elastic deformation work rate of the cured film within the plane. The compound represented by the formula (EA) can further increase the martens hardness of the cured film to a predetermined value or more. The content ratio of the compound represented by the formula (EA) is preferably 50% by mass or more, more preferably 80% by mass or more, and still more preferably 100% by mass (that is, the polymerization initiator (E) contains the compound represented by the formula (EA) and does not contain the compound represented by the formula (EB)), based on 100% by mass of the total amount of the compound represented by the formula (EA) and the compound represented by the formula (EB).

[0308] When the polymerization initiator (E) contains at least one of the compound represented by formula (EA) and the compound represented by formula (EB), the total content of the compound represented by formula (EA) and the compound represented by formula (EB) in the polymerization initiator (E) is preferably 30 mass% or more and 100 mass% or less, more preferably 50 mass% or more and 100 mass% or less, even more preferably 70 mass% or more and 100 mass% or less, still more preferably 80 mass% or more and 100 mass% or less, especially preferably 90 mass% or more and 100 mass% or less, particularly preferably 95 mass% or more and 100 mass% or less, and may be 100 mass%.

[0309] <Light stabilizer (F)> The light stabilizer (F) may be any additive that has the effect of stabilizing components against light, including known light stabilizers (Fa), and the light stabilizer (F) of the present invention also includes an antioxidant (Fb) and an ultraviolet absorber (Fc) that absorbs light and renders it harmless. The curable composition may contain two or more types of light stabilizers (F).

[0310] <Light stabilizer (Fa)> Examples of the light stabilizer (Fa) include hindered amine-based light stabilizers, acrylate-based light stabilizers, nickel-based light stabilizers, and oxamide-based light stabilizers.

[0311] <Antioxidants (Fb)> The antioxidant (Fb) is not particularly limited as long as it is an antioxidant generally used industrially, and may be a phenol-based antioxidant, a phosphorus-based antioxidant, a phosphorus / phenol complex type antioxidant, a sulfur-based antioxidant, etc. The curable composition may contain two or more types of antioxidants (Fb).

[0312] The phosphorus / phenol complex type antioxidant is, for example, a compound having one or more phosphorus atoms and one or more phenol structures in the molecule. Among them, from the viewpoints of the developability and emitted light intensity of the curable composition, it is preferable that the antioxidant (Fb) contains a phosphorus / phenol complex type antioxidant.

[0313] Examples of phenolic antioxidants include Irganox (registered trademark) 1010 (Irganox 1010: pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], manufactured by BASF Corporation), 1076 (Irganox 1076: octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, manufactured by BASF Corporation), 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), 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), 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), 1035 (Irganox 1035: thiodiethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], manufactured by BASF Corporation), 1135 (Irganox 1135: 3,5-bis(1,1-dimethylethyl)-4-hydroxy-C7-C9 branched alkyl ester of benzenepropanoic acid, manufactured by BASF Corporation), 1520L (Irganox 1520L: 4,6-bis(octylthiomethyl)-o-cresol, manufactured by BASF Corporation), 3125 (Irganox 3125, manufactured by BASF Corporation), 565 (Irganox 565: 2,4-bis(n-octylthio)-6-(4-hydroxy-3’,5’-di-tert-butylanilino)-1,3,5-triazine, manufactured by BASF Corporation), AdekaStab (registered trademark) AO-80 (AdekaStab AO-80: 3,9-bis(2-(3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy)-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro(5,5) Undecane (manufactured by ADEKA CORPORATION), Sumilizer (registered trademark) BHT, GA-80, GS (above, manufactured by Sumitomo Chemical Co., Ltd.), CyanoGuard (registered trademark) 1790 (Cyanox 1790, manufactured by Saitex Corporation), Vitamin E (manufactured by Eisai Co., Ltd.), etc.

[0314] Examples of phosphorus-based antioxidants include Irgafos (registered trademark) 168 (Irgafos 168: Tris(2,4-di-tert-butylphenyl) phosphite, manufactured by BASF SE), Irgafos 12 (Irgafos 12: Tris[2-[[2,4,8,10-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphin-6-yl]oxy]ethyl]amine, manufactured by BASF SE), Irgafos 38 (Irgafos 38: Bis(2,4-bis(1,1-dimethylethyl)-6-methylphenyl) ethyl ester phosphite, manufactured by BASF SE), AdekaStab (registered trademark) 329K, PEP36, PEP-8 (above, manufactured by ADEKA CORPORATION), Sandstab P-EPQ (manufactured by Clariant), Weston (registered trademark) 618, Weston 619G (above, manufactured by GE), Ultranox626 (manufactured by GE), etc.

[0315] Examples of phosphorus / phenol composite antioxidants 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]dioxaphosphepine) (manufactured by Sumitomo Chemical Co., Ltd.), etc.

[0316] Examples of sulfur-based antioxidants include dialkyl thiodipropionate compounds such as dilauryl, dimyristyl or distearyl thiodipropionate, and polyol β-alkyl mercaptopropionate ester compounds such as tetrakis[methylene(3-dodecylthio)propionate]methane.

[0317] <Ultraviolet Absorber (Fc)> Examples of the ultraviolet absorber (Fc) include benzotriazole compounds such as 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole and 2-(2,4-dihydroxyphenyl)-2H-benzotriazole; benzophenone compounds such as 2-hydroxy-4-octyloxybenzophenone; benzoate compounds such as 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate; triazine compounds such as 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-hexyloxyphenol; and the like.

[0318] The content of the light stabilizer (F) in the curable composition (total amount in the case of multiple types) is, for example, 1 part by mass or more and 40 parts by mass or less with respect to 100 parts by mass of the resin (C). From the viewpoint of the emitted light intensity, it is preferably 2 parts by mass or more and 30 parts by mass or less, more preferably 3 parts by mass or more and 20 parts by mass or less.

[0319] When the curable composition contains the light stabilizer (F), the light stabilizer (F) is preferably an antioxidant (Fb) and / or an ultraviolet absorber (Fc).

[0320] <Leveling agent (H)> Examples of the leveling agent (H) include silicone surfactants, fluorine surfactants, and silicone surfactants having fluorine atoms. These may have a polymerizable group in the side chain. The leveling agent (H) preferably contains a silicone surfactant. The curable composition may contain two or more kinds of the leveling agent (H).

[0321] Examples of silicone surfactants include surfactants having a siloxane bond in the molecule. Specifically, examples include Toray Silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH8400 (trade name: manufactured by Toray Dow Corning Co., Ltd.), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452, and TSF4460 (manufactured by Momentive Performance Materials Japan LLC).

[0322] Examples of fluorosurfactants include surfactants having a fluorocarbon chain in the molecule. Specifically, examples include Fluorad (registered trademark) FC430, FC431 (manufactured by Sumitomo 3M Limited), Megafac (registered trademark) F142D, F171, F172, F173, F177, F183, F554, F575, R30, RS-718-K (manufactured by DIC Corporation), F-Top (registered trademark) EF301, EF303, EF351, EF352 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), Surflon (registered trademark) S381, S382, SC101, SC105 (manufactured by Asahi Glass Co., Ltd.), and E5844 (manufactured by Daikin Fine Chemical Research Institute Co., Ltd.).

[0323] Examples of silicone surfactants having a fluorine atom include surfactants having a siloxane bond and a fluorocarbon chain in the molecule. Specifically, examples include Megafac (registered trademark) R08, BL20, F475, F477, and F443 (manufactured by DIC Corporation).

[0324] When the curable composition contains a leveling agent (H), the content of the leveling agent (H) in the curable composition is, for example, 0.001% by mass or more and 1.0% by mass or less, preferably 0.005% by mass or more and 0.75% by mass or less, more preferably 0.01% by mass or more and 0.5% by mass or less, based on the total amount of the curable composition. When the content of the leveling agent (H) is within the above range, the flatness of the cured film can be made better.

[0325] <Solvent (J)> The solvent (J) dissolves the resin (C), and the polymerizable compound (D) and the polymerization initiator (E) used in a preferred embodiment. Examples of the solvent (J) include ester solvents (solvents containing -COO- in the molecule and not containing -O-), ether solvents (solvents containing -O- in the molecule and not containing -COO-), ether ester solvents (solvents containing -COO- and -O- in the molecule), ketone solvents (solvents containing -CO- in the molecule and not containing -COO-), alcohol solvents (solvents containing OH in the molecule and not containing -O-, -CO- and COO-), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide, and the like.

[0326] Examples of the ester solvent include methyl lactate, ethyl lactate, n-butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl formate, isopentyl acetate, n-butyl propionate, isopropyl butyrate, ethyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexyl acetate, and γ-butyrolactone.

[0327] Examples of ether solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenetole, and methyl anisole, etc.

[0328] Examples of ether ester solvents include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 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, etc.

[0329] 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.

[0330] Examples of the alcohol solvent include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, and glycerin.

[0331] Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, and mesitylene.

[0332] Examples of the amide solvent include N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.

[0333] The solvent (J) preferably contains one or more selected from the group consisting of propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, cyclohexyl acetate, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 4-hydroxy-4-methyl-2-pentanone, and aromatic hydrocarbon solvents.

[0334] The solvent (J) is preferably propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, cyclohexyl acetate, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 4-hydroxy-4-methyl-2-pentanone or toluene, or a mixture of two or more thereof.

[0335] The solvent (J) is a component other than the solid content, and for example, a solvent contained in a solution of the resin (C) is also included in the solvent (J).

[0336] The content rate of the solvent (J) in the curable composition is the ratio of the total mass of all solvents contained in the curable composition to the total amount of the curable composition, and is, for example, 40% by mass or more and 95% by mass or less, preferably 50% by mass or more and 90% by mass or less with respect to the total amount of the curable composition. In other words, the solid content of the curable composition is, for example, 5% by mass or more and 60% by mass or less, preferably 10% by mass or more and 50% by mass or less. When the content rate of the solvent (J) is within the above range, the flatness of the curable composition layer during coating becomes better, and it tends to be easily controlled to an appropriate thickness.

[0337] <Other components> The curable composition may further contain additives known in the art, such as a polymerization inhibitor, a filler, other polymer compounds, an adhesion promoter, a chain transfer agent, etc., as necessary. From the viewpoint of enhancing the dispersibility of the light scattering agent (B), the curable composition may contain an organic compound having at least one kind of group selected from the group consisting of a thiol group (-SH), a carboxyl group (-COOH), and an amino group (-NH2).

[0338] <<Method for producing curable composition>> The curable composition can be produced by a method including a step of mixing predetermined components and other components used as necessary. The method for producing the curable composition may further include a step of preparing the resin (C). Among the components contained in the curable composition, the light scattering agent (B) may be mixed with a part or all of the solvent (J) in advance and then mixed with other components.

[0339] <<Method for producing cured film>> The cured film according to the present invention can be produced by a production method including a step of applying a curable composition containing a light scattering agent (B) and a resin (C), and a thermal curing step of thermally curing the coating film of the curable composition (hereinafter also referred to as "composition layer"). It is preferable to include an exposure step of irradiating light to the coating film of the curable composition after the step of applying the curable composition, and it is more preferable to carry out the thermal curing step after the exposure step.

[0340] The method for manufacturing a cured film may include other steps than the above steps. Examples of other steps include a drying step of drying the composition layer formed by the coating step, a developing step performed on the composition layer after the exposure step, and the like. The cured film may be formed over the entire surface of the substrate, or may be formed as a cured pattern on a part of the substrate surface. In this specification, the cured pattern is one aspect of the cured film and refers to a cured film formed in a pattern shape.

[0341] The curable composition used for forming the cured film contains a light scattering agent (B) and a resin (C), and examples thereof are the curable compositions described in the above <Curable Composition>.

[0342] The coating step is a step of coating a curable composition on a substrate to form a composition layer. Examples of the coating method include a spin coating method, a slit coating method, a slit and spin coating method, a printing method, and the like. In the printing method, the curable composition is coated through a mask provided on the substrate, and after the mask is peeled off from the substrate, the composition layer formed by the coating step is cured, whereby a cured film can be formed as a cured pattern on a part of the substrate surface.

[0343] Examples of the substrate include glass plates such as quartz glass, borosilicate glass, aluminosilicate glass, and soda lime glass with a silica-coated surface, resin plates such as polycarbonate, polymethyl methacrylate, and polyethylene terephthalate, silicon, and those having an aluminum, silver, silver / copper / palladium alloy thin film or the like formed on the above substrate. The substrate is preferably a glass plate, a silicon substrate, or the like.

[0344] The substrate may be one that has been subjected to a pretreatment capable of adjusting the wettability of the substrate surface. Examples of the pretreatment include solvent cleaning with alcohol, acetone, or the like, acid treatment, alkali treatment, plasma treatment, corona treatment, and the like. By selecting an appropriate pretreatment for the substrate on which the cured film is to be laminated, the coatability of the curable composition can be improved compared to an untreated substrate.

[0345] When the curable composition contains the solvent (J), it is preferable to carry out a drying step of removing volatile components such as the solvent (J) from the composition layer after the coating step. The drying step may include a heat drying (pre-baking) treatment, a reduced pressure drying treatment, or both of these. When performing heat drying, the temperature is preferably 30°C or higher and lower than 100°C, more preferably 50°C or higher and 95°C or lower. The heating time is preferably 10 seconds or longer and 60 minutes or shorter, more preferably 30 seconds or longer and 30 minutes or shorter. When performing reduced pressure drying, it is preferably carried out under a pressure of 50 Pa or higher and 150 Pa or lower in a temperature range of 20°C or higher and 25°C or lower.

[0346] The film thickness of the composition layer after the coating step or the drying step is not particularly limited and may be appropriately selected according to the film thickness of the target cured film. For example, it is 0.5 μm or more and 10 μm or less, preferably 1 μm or more and 9 μm or less, more preferably 1.5 μm or more and 7 μm or less, and still more preferably 2 μm or more and 5 μm or less. The film thickness of the finally obtained cured film may be the same as above.

[0347] Next, it is preferable to carry out an exposure step on the composition layer after the coating step or the drying step. The exposed composition layer cures by polymerization of the polymerizable compound (D) and the like contained in the composition layer including the preferred embodiments. As the light source used for exposure, a light source that generates light with a wavelength of 250 nm or more and 450 nm or less is preferable. When the curable composition contains a photoinitiator (E), light near 436 nm, near 408 nm, or near 365 nm may be selectively extracted from the light of the above wavelength by a band-pass filter according to the absorption wavelength of the photoinitiator (E). Specific examples of the light source include a mercury lamp, a light-emitting diode, a metal halide lamp, and a halogen lamp.

[0348] The exposure amount X in the exposure step is preferably 50 mJ / cm 2 or more, more preferably 80 mJ / cm 2 or more, still more preferably 100 mJ / cm 2More preferably, it is 150 mJ / cm or more. 2 or more. The exposure dose X is usually 1000 mJ / cm or less, 2 preferably 800 mJ / cm or less, 2 more preferably 700 mJ / cm or less. 2 When the exposure dose X in the exposure process is 1000 mJ / cm or less, 2 it is possible to prevent the cured film from shrinking too much, so that the proximity of the light scattering agent (B) in the film due to the shrinkage of the cured film can be prevented, and the decrease in the emitted light intensity can be prevented. The exposure dose X is the exposure dose based on a wavelength of 365 nm and can be measured using an ultraviolet integrated light meter (UIT-250, manufactured by USHIO INC.).

[0349] As an example of a method for forming a cured pattern, which is one aspect of the cured film, a photolithography method can be mentioned. The photolithography method is a method of exposing and developing a composition layer through a photomask for forming a target cured pattern. In this case, since it is possible to irradiate the entire exposure surface with parallel light rays uniformly or to perform accurate alignment between the photomask and the substrate on which the composition layer is formed, it is preferable to use an exposure apparatus such as a mask aligner and a stepper.

[0350] By subjecting the composition layer after the exposure process to a development process in which the composition layer is brought into contact with a developer and developed, the unexposed portion of the composition layer is dissolved and removed by the developer, and a pattern is imparted to the composition layer. Examples of the developer include aqueous solutions of alkaline compounds such as potassium hydroxide, sodium hydrogen carbonate, sodium carbonate, and tetramethylammonium hydroxide, and organic solvents. The concentration in the aqueous solution of the alkaline compound is preferably 0.01% by mass or more and 10% by mass or less, more preferably 0.03% by mass or more and 5% by mass or less. Examples of the organic solvent include the same ones as the above-mentioned solvent (J). The developer may contain a surfactant. The development method may be any of a paddle method, a dipping method, a spray method, etc. Further, the substrate may be tilted at an arbitrary angle during development.

[0351] The composition layer after the exposure process or the development process is thermally cured (post-baked) in the thermal curing process. By the thermal curing process, the polymerization of the resin (C), the polymerizable compound (D), etc. including the preferred embodiments can be further advanced, and the resistance to the solvent is improved as compared with that before the post-baking.

[0352] The thermal curing temperature in the thermal curing process carried out after the exposure process or the development process is preferably 150°C or lower, more preferably 120°C or lower, still more preferably less than 100°C, and particularly preferably 95°C or lower. By setting such a temperature range, the hardness of the cured film can be made soft, and the ratio of the surface roughness Ra (nm) of the cured film to the film thickness t (μm) of the cured film: Ra / t can be made equal to or more than a predetermined value. The thermal curing temperature is preferably 70°C or higher, more preferably 80°C or higher, and still more preferably 85°C or higher from the viewpoint of ensuring that the hardness of the film is equal to or more than a predetermined value.

[0353] The thermal curing time in the thermal curing process is preferably 0.1 hr or more, more preferably 0.2 hr or more, still more preferably 0.4 hr or more, and even more preferably 0.5 hr or more. The thermal curing time is usually 2 hr or less, preferably 1.5 hr or less, and more preferably 1.2 hr or less.

[0354] The thermal curing process can be carried out in an air atmosphere, or can also be carried out in a vacuum atmosphere from the viewpoints of ensuring that the martensitic hardness of the obtained cured film is equal to or more than a predetermined value and increasing the emitted light intensity of the cured film. The vacuum atmosphere means a pressure range of 150 Pa or lower, preferably 120 Pa or lower, more preferably 100 Pa or lower, and may be 50 Pa or more.

[0355] The temperatures in the above-described drying process (particularly heat drying) and the thermal curing process are both preferably less than 100°C, and more preferably both are 95°C or lower.

[0356] <<Display device>> The display device according to the present invention includes at least a light source and the above-mentioned cured film. Examples of the display device include a liquid crystal display device, an organic EL display device, or an inorganic EL display device. Specifically, the display devices described in JP-A-2006-309219, JP-A-2006-310303, JP-A-2013-15812, JP-A-2009-251129, JP-A-2014-2363, etc. can be mentioned.

[0357] In the display device, the cured film according to the present invention is used as the above-mentioned white (transparent, achromatic) pattern, and usually a pixel is formed in combination with a colored pattern. This colored pattern has a function of converting the wavelength of the incident light and emitting it, and may be a cured pattern of a curable composition containing a colorant (quantum dots, pigments, dyes, etc.). The display device according to an embodiment of the present invention includes a backlight which is a blue light source, and a plurality of patterns provided on the viewing side of the backlight. The patterns include a red pattern, a green pattern, and a white (transparent, achromatic) pattern which is the cured film according to the present invention. Light having a wavelength emitted from the blue light source is emitted from the white pattern.

Example

[0358] Hereinafter, the present invention will be described in more detail with reference to examples. In the examples, “%” and “parts” are mass % and parts by mass, respectively, unless otherwise specified.

[0359] [Measurement of Martens hardness and elastic deformation work rate of cured film] For the cured film formed on the substrate, a Vickers indenter was attached to a ultra-micro hardness tester (manufactured by Fischer Instruments, FISCHERSCOPE HM2000), and a load-unload test was performed in accordance with ISO 14577 to measure the load-indentation curve. The measurement temperature was room temperature. Here, the maximum test load was 0.5 mN, the holding time was 30 seconds, and the load was unloaded to 0 mN. The measurement data was processed by WIN-HCU (manufactured by Fischer Instruments) to obtain the Martens hardness (MPa) and the elastic deformation work rate (ηIT). The measurements were carried out at three arbitrary locations. For the martensite hardness, the arithmetic mean value of the martensite hardness at the three locations was determined. For the elastic deformation work rate, the standard deviation σ of the elastic deformation work rate measured at the three locations was determined.

[0360] [Surface roughness of the cured film] For the cured film formed on the substrate, the arithmetic mean roughness Ra was determined in accordance with JIS B0601.

[0361] [Thickness of the cured film] It was measured with a film thickness measuring device (DEKTAKXT; manufactured by Bruker).

[0362] [Weight-average molecular weight] The measurement of the weight-average molecular weight (Mw) of resin (C) was carried out under the following conditions by the GPC method. Apparatus: K2479 (manufactured by Shimadzu Corporation) Column: SHIMADZU Shim-pack GPC-80M Column temperature: 40 °C Solvent: Tetrahydrofuran Flow rate: 1.0 mL / min Detector: RI Standard substance for calibration: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Corporation)

[0363] [Acid value] 3 g of the resin (C) solution was precisely weighed, dissolved in a mixed solvent of 90 g of acetone and 10 g of water, and using a 0.1 N aqueous KOH solution as the titrant, the acid value of the resin (C) solution was measured with an automatic titrator (manufactured by Hiranuma Sangyo Co., Ltd., trade name: COM-555), and the acid value per gram of solid content (AV) was determined from the acid value of the solution and the solid content of the solution.

[0364] [Double bond equivalent] The double bond equivalent was determined by dividing the total mass of the curable resin by the number of moles of radically polymerizable double bonds introduced into the curable resin.

[0365] [Solid content] Weighed approximately 1 g of the resin (C) solution into an aluminum cup, dried it at 180 °C for 1 hour, and then measured its mass. From the mass reduction, the solid content (mass %) of the resin (C) solution was calculated.

[0366] (Synthesis Example 1: Synthesis of Resin (C1)) 276.8 g of propylene glycol monomethyl ether acetate was placed in a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer, and a gas inlet tube, and stirred while purging with nitrogen and heated to 120 °C. Next, a monomer mixture consisting of 92.4 g of 2-ethylhexyl acrylate, 184.9 g of glycidyl methacrylate, and 12.3 g of dicyclopentanyl methacrylate, to which 35.3 g of t-butyl peroxy-2-ethylhexanoate (polymerization initiator) was added, was dropped into the flask from the dropping funnel over 2 hours. After completion of the dropping, stirring was continued at 120 °C for an additional 30 minutes to conduct a copolymerization reaction to produce an addition copolymer.

[0367] Thereafter, the inside of the flask was replaced with air, 93.7 g of acrylic acid, 1.5 g of triphenylphosphine (catalyst), and 0.8 g of methoquinone (polymerization inhibitor) were added to the above addition copolymer solution, and the reaction was continued at 110 °C for 10 hours. The epoxy group derived from glycidyl methacrylate reacted with acrylic acid to cleave the epoxy group and at the same time introduce a polymerizable unsaturated bond into the side chain of the polymer. Next, 24.2 g of succinic anhydride was added to the reaction system, and the reaction was continued at 110 °C for 1 hour. The hydroxyl group generated by the cleavage of the epoxy group was reacted with succinic anhydride to introduce a carboxyl group into the side chain, and a polymer (resin C1) was obtained.

[0368] Finally, 383.3 g of propylene glycol monomethyl ether acetate was added to the reaction solution to obtain a resin (C1) solution with a polymer solid content of 40%.

[0369] The weight average molecular weight Mw of the produced copolymer was 6.2×10 3 , the acid value in terms of solid content was 35 mg-KOH / g, and the double bond equivalent was 313 g / eq.

[0370] (Preparation Example 1: Preparation of Dispersion Liquid c of Light Scattering Agent (B)) To 70 parts of titanium oxide nanoparticles (B1) (average particle diameter: about 0.2 μm), 3 parts of BYK-LPN21116 (manufactured by BYK-Chemie Japan) in terms of solid content and propylene glycol monomethyl ether acetate (hereinafter referred to as "PGMEA") were added so that the total amount became 100 parts, and then the mixture was stirred with a paint shaker until it was sufficiently dispersed to obtain a dispersion liquid c of light scattering agent (B1) (solid content: 73%).

[0371] (Preparation Example 2: Preparation of Curable Compositions 1 to 4) The dispersion liquid c of light scattering agent (B1) and each component were mixed to prepare curable compositions 1 to 4 having the compositions shown in Table 1. In Table 1, the number of parts of components other than the solvent (J) indicates the value in terms of solid content.

[0372]

Table 1

[0373] Polymerizable compound (D1): Carboxy group-containing polyfunctional (meth)acrylate (trade name "Aronix (registered trademark) M-510" manufactured by Toagosei Co., Ltd.) Polymerizable compound (D2): Ethylene oxide-modified bisphenol diacrylate, average molecular weight Mw is 512 Polymerizable compound (D3): Dipentaerythritol polyacrylate (5 to 6 functional groups) Polymerization initiator (E1): Compound represented by the following formula (EA-1)

[0374]

Chemical formula

[0375] Polymerization initiator (E2): Compound represented by the following formula (EB-1)

[0376]

Chemical formula

[0377] Ultraviolet absorber (Fc1): "DAINSORB T-0" manufactured by Daiwa Kasei Co., Ltd. (2-(2,4-dihydroxyphenyl)-2H-benzotriazole) Leveling agent (H1): Polyether-modified silicone oil (trade name "Toray Silicone SH8400" manufactured by Toray Dow Corning Co., Ltd.) Dispersant (I1): BYK-LPN21116 (manufactured by BYK-Chemie Japan) Solvent (J1): PGMEA (propylene glycol monomethyl ether acetate)

[0378] [Example 1] On a 5 cm square glass substrate (Eagle 2000; manufactured by Corning), the curable composition 1 obtained in Preparation Example 2 was applied by spin coating so that the film thickness after post-baking would be 5 μm, and then a drying step (pre-bake) at 70 °C for 1 minute was performed to form a film of the curable composition 1. After cooling, using an exposure machine (UPE-1255MA; manufactured by USHIO Lighting Co., Ltd.), in an air atmosphere, light irradiation was performed at an exposure dose of 200 mJ / cm 2 (based on 365 nm) to carry out the exposure step, and a heat curing treatment (post-bake) at 95 °C for 30 minutes was performed to carry out the heat curing step, obtaining a substrate having a cured film.

[0379] [Examples 2 to 8, Comparative Examples 1 to 5] Except that the film thickness (μm) of the cured film, the drying temperature (°C) of the drying step, and the heat curing temperature (°C) in the heat curing step were as shown in Tables 2 and 3, the drying step, the exposure step, and the heat curing step were carried out in the same manner as in Example 1 to obtain a substrate having a cured film.

[0380] The measurement results are shown in Tables 2 and 3.

[0381]

Table 2

[0382]

Table 3

[0383] When comparing the examples and comparative examples in the case where the film thickness is 5 μm, by comparing Example 1 and Comparative Example 1, Example 2 and Comparative Example 2, Example 3 and Comparative Example 3, and Example 4 and Comparative Example 4 respectively, it can be seen that the standard deviation of the elastic deformation work rate in the examples can be reduced to about half compared to the comparative examples. Similarly, when comparing Example 5 and Comparative Example 5 (both with a film thickness of 2 μm) in the case where the film thickness is 2 μm, it can be seen that the standard deviation of the elastic deformation work rate can be reduced to about half.

Claims

1. A cured film of a curable composition containing a light scattering agent (B) and a resin (C), having a Martens hardness of 5 MPa or more and 120 MPa or less, and a ratio of the surface roughness Ra (nm) of the cured film to the film thickness t (μm) of the cured film: Ra / t is 0.80 (nm / μm) or more.

2. The cured film according to Claim 1, wherein the acid value of the resin (C) is 150 mg-KOH / g or less.

3. The cured film according to Claim 1, wherein the mass ratio (C / B) of the resin (C) to the light scattering agent (B) is 16 or more.

4. The cured film according to Claim 1, wherein the curable composition further contains a polymerizable compound (D).

5. The cured film according to Claim 4, wherein the polymerizable compound (D) contains a polymerizable compound having one or more cyclic hydrocarbon groups and two ethylenically unsaturated bonds in one molecule.

6. The cured film according to Claim 1, wherein the cured film does not contain semiconductor particles (A) or contains them in an amount of less than 1% by mass, and does not contain a colored colorant (K) or contains it in an amount of less than 1% by mass.

7. A display device including the cured film according to any one of Claims 1 to 6.

Images