Resin composition, wavelength conversion layer, laminate, and display device

Abstract

The present invention can provide a resin composition having excellent viscosity stability after storage and excellent redispersibility.SOLUTION: The above problem can be solved by a polymer composition comprising organic fluorescent particles (A), scattering particles (B), a polymer (C), and a dispersion medium (D), wherein the polymer (C) comprises a polymer (C1) having a basic group. The organic fluorescent particles (A) preferably contain resinous particles (A1) dyed with an organic fluorescent dye. The average particle diameter of the organic fluorescent particle (A) is preferably 0.1 to 5.0 μm.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a wavelength-convertible resin composition. [Background technology]

[0002] LED (light-emitting diode) display devices and OLED (organic light-emitting diode) display devices are display devices that use LEDs or OLEDs as light sources and convert part of the light using a wavelength conversion layer to display full color.

[0003] A wavelength conversion layer is formed using a composition containing a fluorescent compound that absorbs light from a light source and emits light of a desired wavelength. For example, Patent Document 1 discloses a dye dispersion composition containing a fluorescent dye with a solubility of more than 0% but less than 1%, a dispersant with an acid value of 1 to 250 mgKOH / g, and a dispersion solvent. Furthermore, it is known that adding scattering particles increases the optical path length by scattering light within the wavelength conversion layer, improving light absorption, and also improves luminous efficiency by re-scattering light reflected at the interface. For example, Patent Document 2 discloses a self-luminous photosensitive resin composition for forming a color conversion layer, containing a fluorescent dye, a highly refractive material, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 2019-157126 [Patent Document 2] JP 2016-71360 A Summary of the Invention [Problem to be solved by the invention]

[0005] Compositions for forming wavelength conversion layers are typically stored for several weeks to several months after production, depending on demand. As a result, fluorescent compounds and scattering particles settle, requiring redispersion before use. However, conventional compositions have the problem that once particles settle, they cannot be redispersed to the same level as immediately after production.

[0006] An object of the present invention is to provide a resin composition that is excellent in viscosity stability after storage and redispersibility. [Means for solving the problem]

[0007] The present invention provides a resin composition comprising organic fluorescent particles (A), scattering particles (B), a resin (C), and a solvent (D), The resin (C) relates to a resin composition containing a resin (C1) having a basic group. [Effects of the Invention]

[0008] According to the present invention, it is possible to provide a resin composition having excellent viscosity stability after storage and excellent redispersibility. The present invention also provides a wavelength conversion layer, a laminate, and a display device. [Brief explanation of the drawings]

[0009] [Figure 1] FIG. 1 is a schematic cross-sectional view showing an example of the structure of the laminate of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0010] Hereinafter, embodiments for carrying out the resin composition of the present invention will be described in detail. Note that the present invention is not limited to the following embodiments, and can be modified and carried out within a range that can solve the problems.

[0011] In this specification, unless otherwise specified, "(meth)acryloyl," "(meth)acrylic," "(meth)acrylic acid," "(meth)acrylate," or "(meth)acrylamide" means "acryloyl and / or methacryloyl," "acrylic and / or methacrylic," "acrylic acid and / or methacrylic acid," "acrylate and / or methacrylate," or "acrylamide and / or methacrylamide," respectively. Additionally, "CI" means Color Index (CI; published by The Society of Dyers and Colourists). In this specification, the polymerizable unsaturated group is an ethylenically unsaturated double bond. As used herein, a monomer is a compound that forms a resin upon polymerization. A monomer is in an unreacted state, and a monomer unit is a monomer that forms a resin after polymerization. In this specification, the molecular weight of a low-molecular-weight compound that can be determined is a calculated value (formula weight) or a molecular weight measured by ESI-MS (electrospray ionization mass spectrometry), and the molecular weight of a compound having a molecular weight distribution is a weight-average molecular weight in terms of polystyrene measured by gel permeation chromatography using tetrahydrofuran as a solvent. In this specification, a numerical range expressed using "to" means a range that includes the numerical values ​​before and after "to" as the lower and upper limits. In this specification, the average particle size is the average value of the primary particle sizes of 20 particles randomly selected from the images obtained by observing the surface and cross section of a film containing the particles to be measured using a scanning electron microscope. For particles that are not spherical, the average value of the major axis length and minor axis length is calculated and used as the primary particle size.

[0012] <Resin composition> A resin composition according to one embodiment of the present invention is a resin composition comprising organic fluorescent particles (A), scattering particles (B), a resin (C), and a solvent (D), The resin (C) includes a resin (C1) having a basic group.

[0013] The mechanism by which the resin composition having the above-described configuration can solve the problems of the present invention is not clear, but is speculated as follows.

[0014] The organic fluorescent particles (A) and scattering particles (B) are not dissolved in the solvent (D) but exist in a dispersed state. As a result, they settle during storage of the resin composition, and the particles associate and aggregate, making redispersion difficult. However, when a resin (C1) having basic groups is used, it is adsorbed onto the particles, and the presence of the resin (C1) having basic groups between the particles weakens the interactions between the particles, improving viscosity stability and redispersibility.

[0015] The components that are or can be contained in the resin composition of the present invention will be described in detail below.

[0016] [Organic fluorescent particles (A)] The resin composition of the present invention contains organic fluorescent particles (A). The organic fluorescent particles (A) are compounds that absorb light from a light source of a display device and convert it into light of a desired wavelength. By including the organic fluorescent particles (A), the resin composition of the present invention can form a wavelength conversion layer.

[0017] The organic fluorescent particles (A) are not particularly limited, and known organic fluorescent particles can be used. In the present invention, "organic fluorescent particles (A)" means that they are substantially insoluble in propylene glycol monomethyl ether acetate at 25°C and exist in a state having a particle size. "Substantially insoluble" means that the solubility in 100 g of propylene glycol monomethyl ether acetate at 25°C is less than 2 g. The solubility is preferably less than 1 g.

[0018] Examples of the organic fluorescent particles (A) include organic fluorescent pigments such as 2,5-dihydroxyterephthalic acid diethyl, dixanthene, 9,10-dianilinoanthracene, 2-hydroxybenzaldehyde azine, 2-oxynaphthaldazine, 2-anilino-4-(2,5-dichlorobenzoylamino)-1,9-pyrimidoanthrone, and 1,4-bis-(β-cyano-β-carbethoxyvinyl)benzene, and resin particles dyed with organic fluorescent dyes.

[0019] The average particle size of the organic fluorescent particles (A) is preferably from 0.1 to 5.0 μm, more preferably from 0.1 to 4.5 μm, and even more preferably from 0.5 to 3.5 μm, from the viewpoints of viscosity stability and redispersibility.

[0020] The organic fluorescent particles (A) can be used alone or in combination of two or more kinds.

[0021] The content of the organic fluorescent particles (A) is preferably from 20 to 60% by mass, more preferably from 25 to 55% by mass, based on 100% by mass of the nonvolatile content of the resin composition.

[0022] (Resin particles dyed with organic fluorescent dye (A1)) The organic fluorescent particles (A) preferably contain resin particles (A1) dyed with an organic fluorescent dye (hereinafter simply referred to as organic fluorescent resin particles (A1)). By using particles in which an organic fluorescent dye is immobilized in a resin, association and aggregation can be suppressed. Furthermore, elution of the organic fluorescent dye can be suppressed during the development process for forming the wavelength conversion layer, which will be described later.

[0023] [Organic fluorescent dyes] The organic fluorescent dye in the organic fluorescent resin particles (A1) is not particularly limited, and known organic fluorescent dyes can be used.

[0024] Examples of organic fluorescent dyes include compounds having a xanthene, azine, azole, thiazole, azo, diarylmethane, triarylmethane, acridine, anthracene, coumarin, methine, perylene, pyrene, pyrromethene, and cyanine structure. Specifically, CI Basic Red 1, 1:1, 2, 12, 13, 14, 15, 36, CI Basic Orange 15, 22, CI Basic Violet 1, 3, 10, 11, 11:1, 14, 15, 16, 27, CI Basic Yellow 1, 2, 9, 13, 24, 37, 40, 44, 96, CI Basic Blue 1, 3, 7, 9, 45, CI Basic Green 1, CI Basic Black 2; CI Acid Red 51, 52, 57, 77, 87, 89, 92, CI Acid Yellow 3, 7, 23, 73, 87, 184, 245, 250, CI Acid Blue 9; CI Disperse Red 58, 60, 274, 277, 303, CI Disperse Orange 11, 32, CI Disperse Yellow 11, 82, 139, 184, 186, 199, 202, 232, CI Disperse Blue 7; CI Solvent Red 43, 44, 45, 49, 149, 175, 196, 197, CI Solvent Orange 5, 45, 63, 112, 115, CI Solvent Yellow 7, 43, 44, 85, 98, 116, 131, 145, 160:1, 172, 185, 195, 196, CI Solvent Blue 5, CI Solvent Green 5, 7; Examples include CI Direct Red 2, 9, CI Direct Orange 8, CI Direct Yellow 27, 85, 96, CI Direct Blue 22, 199, and CI Direct Green 6. Other examples include coumarin 6, coumarin 7, coumarin 135, 4-dicyanomethylene-2-methyl-6-(p-dimethylaminostyryl)-4H-pyran, 4,4-difluoro-1,3,5,7-tetraphenyl-4-bora-3a, 4a-diaza-s-indacene (IV), and the like.

[0025] The organic fluorescent dye preferably has an emission wavelength in the range of 450 to 800 nm, more preferably in the range of 470 to 750 nm. In this specification, the emission wavelength refers to a value measured by a spectrofluorometer (monochromatic monitor ratio calculation method).

[0026] The organic fluorescent dyes can be used alone or in combination of two or more kinds.

[0027] The content of the organic fluorescent dye is preferably from 0.1 to 40 parts by mass, more preferably from 0.5 to 20 parts by mass, per 100 parts by mass of the resin of the organic fluorescent resin particles (A1).

[0028] 〔resin〕 The resin in the organic fluorescent resin particles (A1) is not particularly limited, and known resins can be used.

[0029] Examples of the resin include (meth)acrylic resins, styrene resins, epoxy resins, urethane resins, polycarbonate resins, polyester resins, polyether resins, benzoguanamine resins, formaldehyde resins, melamine resins, urea resins, urea resins, polyamide resins, polyimide resins, cyclic olefin resins, polysiloxane resins, vinyl chloride resins, vinyl acetate resins, alkyd resins, and composite resins combining these resins. Among these, melamine resins are preferred from the viewpoint of redispersibility.

[0030] The melamine resin is not particularly limited, and any known melamine resin can be used, such as benzoguanamine-melamine resin, melamine-formaldehyde resin, benzoguanamine-melamine-formaldehyde resin, urea-melamine-formaldehyde resin, and urea-melamine resin.

[0031] From the viewpoint of storage stability, the melamine resin preferably has a free formaldehyde content of 0.2% by mass or less. The method for measuring free formaldehyde is not particularly limited, and known methods can be used. Examples include the method described in ISO 14184, the method described in JIS L1041, the hydroxylamine hydrochloride method, the sodium sulfite method, and the ammonium cyanide method.

[0032] The resin preferably has at least one structure selected from the group consisting of an aromatic hydrocarbon ring structure and an aromatic heterocyclic structure, which can suppress dissolution in the solvent (D).

[0033] Examples of the aromatic hydrocarbon ring structure include a benzene ring structure, a naphthalene ring structure, a biphenyl ring structure, an anthracene ring structure, etc. Among these, a benzene ring structure is preferred.

[0034] Examples of the aromatic heterocyclic structure include a furan ring structure, a pyran ring structure, a benzofuran ring structure, a benzopyran ring structure, a pyridine ring structure, a pyrimidine ring structure, an indole ring structure, a quinoline ring structure, an imidazole ring structure, a triazole ring structure, a triazine ring structure, a thiophene ring structure, a dibenzothiophene ring structure, an oxazole ring structure, a benzoxazole ring structure, a benzothiazole ring structure, etc. Among these, a triazine ring structure is preferred. Examples of resins having a triazine ring structure include melamine resins.

[0035] The method for producing the organic fluorescent resin particles (A1) is not particularly limited, and known methods can be used, such as emulsion polymerization, addition condensation bulk resin pulverization, and suspension polymerization. The emulsion polymerization method is a method in which an organic fluorescent dye is added to a monomer having a polymerizable unsaturated group and organic fluorescent resin particles are produced by an emulsion polymerization reaction, or a method in which an organic fluorescent dye is added to emulsion-polymerized resin particles to dye them. The addition condensation bulk resin pulverization method is a method in which an organic fluorescent dye is added during the resin polymerization process or in a dissolved state by heating, solidified, and then finely pulverized to produce organic fluorescent resin particles. The suspension polymerization method is a method in which a monomer having a polymerizable unsaturated group is stirred in a solvent to form a suspension, and an organic fluorescent dye is added during or after the polymerization process to produce organic fluorescent resin particles. Examples of the production method include those described in U.S. Pat. No. 2,938,873, U.S. Pat. No. 3,116,256, Japanese Patent Publication No. 13437 / 1961, Japanese Patent Publication No. 005678 / 1976, Japanese Patent Publication No. 029336 / 1977, Japanese Patent Laid-Open No. 2005-314540, Japanese Patent Laid-Open No. 2001-181544, Japanese Patent Laid-Open No. 2009-161688, Japanese Patent Laid-Open No. 125276 / 1993, Japanese Patent Laid-Open No. 08-048899, and Japanese Patent Laid-Open No. 09-020864.

[0036] Commercially available organic fluorescent resin particles (A1) include, for example, FA-001, 005, 006, 007, 227LF, FZ-247, 277, 3057, 5005, M, and MB manufactured by Shinroihi Corporation.

[0037] [Scattered particles (B)] The resin composition of the present invention contains scattering particles (B). By including the scattering particles (B), for example, the wavelength conversion layer can increase the chance of collision between light from a light source and the organic fluorescent particles (A), thereby improving the wavelength conversion efficiency. Furthermore, although a portion of the light converted by the organic fluorescent particles (A) is reflected at the interface of the wavelength conversion layer and returns to the inside of the layer, the scattering particles (B) change the traveling direction of the light and extract it to the outside, thereby improving the wavelength conversion efficiency.

[0038] The scattering particles (B) are not particularly limited, and known scattering particles can be used. Examples of the scattering particles (B) include inorganic particles, organic particles, and organic-inorganic composite particles.

[0039] The average particle size of the scattering particles (B) is preferably from 0.1 to 1.0 μm, more preferably from 0.2 to 0.8 μm, from the viewpoints of viscosity stability and redispersibility.

[0040] The refractive index of the scattering particles (B) is preferably from 1.7 to 3.0, more preferably from 1.9 to 3.0, from the viewpoint of wavelength conversion efficiency.

[0041] The scattering particles (B) can be used alone or in combination of two or more kinds.

[0042] The content of the scattering particles (B) is preferably from 1 to 20 mass %, more preferably from 5 to 15 mass %, based on 100 mass % of the nonvolatile content of the resin composition.

[0043] The total amount of the organic fluorescent particles (A) and the scattering particles (B) is preferably 30 to 80 mass %, more preferably 40 to 70 mass %, based on 100 mass % of the nonvolatile content of the resin composition. The mass ratio of the organic fluorescent particles (A) to the scattering particles (B) is preferably 95:5 to 50:50, more preferably 95:15 to 75:25.

[0044] (Inorganic particles (B1)) From the viewpoint of wavelength conversion efficiency, the scattering particles (B) preferably contain inorganic particles (B1).

[0045] The inorganic particles (B1) may be in the form of hollow particles or solid particles, of which solid particles are preferred from the viewpoint of wavelength conversion efficiency. Hollow particles are particles that have a cavity inside them. Hollow particles may have a structure consisting of a cavity inside and an outer shell surrounding the cavity. Hollow particles may also have a structure in which multiple cavities exist inside the particle. A solid particle is a particle that is substantially free of voids within the particle, where "substantially free" means that the particle has a void content of less than 5%.

[0046] The inorganic particles (B1) can be used alone or in combination of two or more kinds.

[0047] The content of the inorganic particles (B1) is preferably from 10 to 100% by mass, more preferably from 20 to 100% by mass, based on 100% by mass of the scattering particles (B).

[0048] Examples of inorganic particles (B1) include titanium oxide, zirconium oxide, aluminum oxide, zinc oxide, tin oxide, hafnium oxide, tantalum oxide, calcium oxide, barium oxide, bismuth oxide, magnesium carbonate, barium carbonate, calcium carbonate, aluminum hydroxide, calcium titanate, barium titanate, strontium titanate, silica, kaolin, talc, tungsten, zirconium, titanium, platinum, bismuth, rhodium, palladium, silver, tin, platinum, and gold. Among these, titanium oxide is preferred from the viewpoint of wavelength conversion efficiency.

[0049] [Titanium oxide] The titanium oxide is not particularly limited, and any known titanium oxide can be used.

[0050] The crystal structure of titanium oxide may be anatase or rutile, with the rutile being preferred from the viewpoints of storage stability and wavelength conversion efficiency.

[0051] The shape of titanium oxide may be isotropic (for example, spherical, polyhedral, etc.), anisotropic (for example, needle, rod, plate, etc.), or amorphous.

[0052] From the viewpoint of viscosity stability and redispersibility, it is preferable to use titanium oxide whose surface is at least partially covered with a surface treatment agent such as an inorganic substance such as alumina, silica, zirconia, tin, antimony, titania, etc., or an organic substance such as a polyol, alkanolamine, higher fatty acid, organosilicon compound, organophosphate compound, carboxylic acid, etc. The surface treatment agent can be used alone or in combination of two or more kinds. From the viewpoint of redispersibility, it is more preferable that at least a portion of the surface of the titanium oxide is covered with at least one material selected from the group consisting of alumina, silica, and zirconia.

[0053] The method for treating the surface of titanium oxide is not particularly limited, and known methods can be used, such as wet treatment methods and dry treatment methods.

[0054] Commercially available titanium oxide products include, for example, Typeque R-550, R-580, R-630, R-670, R-680, R-780, R-780-2, R-820, R-830, R-850, R-855, R-930, R-980, CR-50, CR-50-2, CR-57, CR-58, CR-58-2, CR-60, CR-60-2, CR-63, CR-67, CR-Cuper 70, CR-80, CR-85, CR-90, CR-90-2, CR-93, CR-95, CR-953, CR-97, PFC105, PF-736, PF- 737,PF-742,PF-690,PF-691,PF-711,PF-739,PF-740,PFR209,PER210,PC-3,S-305,CR-EL,PT-301,PT-401M,PT-401L,PT-501A,PT-501R,UT771,T TO-51(A),TTO-51(C),TTO-55(A),TTO-55(B),TTO-55(C),TTO-55(D),A-1 00,A-220, R-3L, R-5N, R-7E, R-11P, R-21, R-25, R-32, R-42, R-44 manufactured by Sakai Chemical Industry Co., Ltd. , R-45M, R-62N, R-310, R-650, SR-1, D-918, GTR-100, FTR-700, TCR-52, A-110, A-190, SA-1, SA-1L, STR-100A-LP, STR-100C-LP, TCA-123E, Teika JR, JRNC, JR-301, JR-403, JR-405, JR-600A, JR-600E, JR-603, JR-605, JR-701, JR-800, JR-805, JR-806, JR-1000, MT-01, MT-05, MT-10EX, MT-100S, MT -100TV, MT-100Z, MT-100AQ, MT-100WP, MT-100SA, MT-100HD, MT-150EX, MT-150W, MT-300HD, MT-500B, MT-500SA, MT-500HD, MT-600B, MT-600SA, MT-700B, MT-700BS, MT-700HD, MT-700Z, KR-310, KR-380, KR-380N, ST-485SA15 manufactured by Titanium Industries Co., Ltd., and TR-600, TR-700, TR-750, TR-840, TR-900 manufactured by Fuji Titanium Industries Co., Ltd.

[0055] Titanium oxide can be used alone or in combination of two or more types.

[0056] [Resin (C)] The resin composition of the present invention contains a resin (C).

[0057] Resin (C) used mainly to disperse organic fluorescent particles (A) and scattering particles (B) is called dispersion resin, and resin (C) used mainly to impart resistance to the wavelength conversion layer is called binder resin. One type of resin (C) may function as both dispersion resin and binder resin, but it is preferable that the resin (C) contains both dispersion resin and binder resin. This use of resin (C) is just one example, and it can also be used for other purposes.

[0058] The resin (C) is not particularly limited, and known resins can be used. Examples of the resin (C) include (meth)acrylic resins, styrene resins, styrene / (meth)acrylic resins, epoxy resins, urethane resins, urethane acrylic resins, polycarbonate resins, polyester resins, polyether resins, polyimide resins, polyamideimide resins, polysiloxane resins, and cyclic olefin resins.

[0059] The weight average molecular weight of the resin (C) is preferably from 3,000 to 100,000, more preferably from 4,000 to 80,000.

[0060] The resin (C) can be used alone or in combination of two or more kinds.

[0061] The content of the resin (C) is preferably from 1 to 70 mass %, more preferably from 5 to 60 mass %, based on 100 mass % of the nonvolatile content of the resin composition.

[0062] (Resin (C1) having basic groups) The resin (C) includes a resin (C1) having a basic group. In this specification, the resin (C1) having a basic group refers to a resin in which the amount of basic groups is greater than the amount of acidic groups.

[0063] Examples of the basic group include a primary amino group, a secondary amino group, a tertiary amino group, a quaternary ammonium base, and a group containing a nitrogen atom such as a nitrogen-containing heterocycle.

[0064] The amine value of the resin (C1) having a basic group is preferably 20 to 250 mgKOH / g, more preferably 30 to 150 mgKOH / g, from the viewpoints of viscosity stability and redispersibility. In this specification, the amine value refers to the amine value when a quaternary ammonium salt group is also considered as an amino group, and can be calculated by the method described in paragraphs 0039 to 0040 of WO 2022 / 172607.

[0065] The weight average molecular weight of the resin (C1) having a basic group is preferably from 2,000 to 60,000, more preferably from 4,000 to 50,000.

[0066] The resin (C1) having a basic group can be used alone or in combination of two or more kinds.

[0067] The content of the resin (C1) having a basic group is preferably from 5 to 80 mass %, more preferably from 5 to 70 mass %, in 100 mass % of the resin (C) from the viewpoint of viscosity stability and redispersibility.

[0068] The resin (C1) having a basic group is not particularly limited, and known resins having a basic group can be used. Examples of the resin (C1) having a basic group include salts of long-chain polyaminoamides and high molecular weight acid esters, polyester polyamines, amine salts of copolymers of unsaturated carboxylic acids such as polyacrylic acid, polyethyleneimine compounds, etc. Other examples include resins described in JP 2013-119568 A, JP 2018-203795 A, JP 2019-089953 A, JP 2019-089954 A, and WO 2020 / 031634 A.

[0069] Commercially available dispersion resins (C1) having a basic group include, for example, Disperbyk-108, 109, 161, 162, 164, 167, 168, 182, 184, 185, 2000, 2008, 2013, 2022, 2050, 2055, 2150, 2155, 2163, and BYK-LPN6919 and 21116 manufactured by BYK Japan, and SO Examples of such surfactants include LSPERSE-9000, 13240, 13650, 13940, 17000, 18000, 24000SC, 24000GR, 28000, 31845, 32000, 32500, 34750, 35100, 35200, 36600, and 38500, and Ajisper PA111, PB711, PB821, PB822, and PB824 manufactured by Ajinomoto Fine-Techno Co., Ltd.

[0070] Examples of the structure of the dispersion resin (C1) having a basic group include a random structure, a block structure, a graft structure, a comb structure, and a star structure. Among these, the block structure or the graft structure is preferred from the viewpoints of viscosity stability and redispersibility.

[0071] From the viewpoint of viscosity stability and redispersibility, the dispersing resin (C1) having a basic group preferably contains a resin having, as a basic group, one or more types of monomer units selected from the group consisting of monomer units represented by the following general formulas (1) to (3):

[0072] [ka]

[0073] In general formula (1), R1 to R3 each independently represent a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or an aralkyl group which may have a substituent, and two or more of R1 to R3 may be bonded to each other to form a cyclic structure. R4 represents a hydrogen atom or a methyl group, X1 represents a divalent linking group, and Y1 - represents a counter anion.

[0074] The alkyl groups represented by R1 to R3 in general formula (1) are linear, branched, cyclic, or a combination thereof. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, an octyl group, a cyclohexyl group, and a cyclohexylmethyl group. Among these, a methyl group, an ethyl group, a propyl group, and a butyl group are preferred.

[0075] Examples of the aryl group in R1 to R3 of general formula (1) include a phenyl group, a naphthyl group, a biphenyl group, an anthracenyl group, etc. Among these, a phenyl group is preferred.

[0076] Examples of the aralkyl group in R1 to R3 of general formula (1) include a benzyl group, a phenethyl group, a phenylpropyl group, a phenylbutyl group, a phenylisopropyl group, etc. Among these, a benzyl group and a phenethyl group are preferred.

[0077] When the alkyl group, aryl group, or aralkyl group of R1 to R3 in general formula (1) has a substituent, examples of the substituent include a halogen atom, an alkoxy group, and a benzoyl group.

[0078] Examples of the cyclic structure formed by two or more of R1 to R3 bonding to each other include a 5- to 7-membered nitrogen-containing heterocycle. Examples of the cyclic structure include the following cyclic structures. R in the following formulas is a substituent explained above for R1 to R3.

[0079] [ka]

[0080] These cyclic structures may have a substituent, such as a halogen atom, an alkoxy group, or a hydroxyl group.

[0081] Examples of the divalent linking group X1 in general formula (1) include an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 12 carbon atoms, -CONH-R5-, or -COO-R6- (wherein R5 and R6 are each independently a single bond, an alkylene group having 1 to 10 carbon atoms, or an ether group (alkyloxyalkyl group) having 2 to 10 carbon atoms). Among these, -COO-R6- in which R6 is an alkylene group having 1 to 3 carbon atoms is preferred.

[0082] Counteranion Y1 of general formula (1) - For example, Cl - , Br - , I - , ClO4 - , BF4 - , CH3COO - , PF6 - , SO3 - , aromatic dicarboxylic acid imide anion, aromatic sulfonic acid anion, aromatic phosphonic acid anion, aromatic carboxylic acid anion, etc.

[0083] Examples of the monomer that forms the monomer unit represented by general formula (1) include alkyl (meth)acrylate-based quaternary ammonium salts such as (meth)acryloyloxyethyl trimethyl ammonium chloride, (meth)acryloyloxyethyl triethyl ammonium chloride, (meth)acryloyloxyethyl dimethyl benzyl ammonium chloride, and (meth)acryloyloxyethyl methyl morpholino ammonium chloride; alkyl (meth)acryloylamide-based quaternary ammonium salts such as (meth)acryloylaminopropyl trimethyl ammonium chloride, (meth)acryloylaminoethyl triethyl ammonium chloride, and (meth)acryloylaminoethyl dimethyl benzyl ammonium chloride; dimethyl diallyl ammonium methyl sulfate; and trimethyl vinyl phenyl ammonium chloride.

[0084] In general formula (2), R7 and R8 each independently represent a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted aralkyl group, and R7 and R8 may be bonded to each other to form a cyclic structure. R9 represents a hydrogen atom or a methyl group, and X2 represents a divalent linking group.

[0085] The alkyl groups in R7 and R8 in general formula (2) are linear, branched, cyclic, or a combination thereof. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, an octyl group, a cyclohexyl group, and a cyclohexylmethyl group. Among these, a methyl group, an ethyl group, a propyl group, and a butyl group are preferred.

[0086] Examples of the aryl group in R7 and R8 in general formula (2) include a phenyl group, a naphthyl group, a biphenyl group, an anthracenyl group, etc. Among these, a phenyl group is preferred.

[0087] Examples of the aralkyl group in R7 and R8 in general formula (2) include a benzyl group, a phenethyl group, a phenylpropyl group, a phenylbutyl group, a phenylisopropyl group, etc. Among these, a benzyl group and a phenethyl group are preferred.

[0088] When the alkyl group, aryl group, or aralkyl group of R7 and R8 in general formula (2) has a substituent, examples of the substituent include a halogen atom, an alkoxy group, a benzoyl group, and a hydroxyl group.

[0089] The cyclic structure formed by R7 and R8 bonding to each other includes, for example, a 5- to 7-membered nitrogen-containing heterocycle, such as the following cyclic structures:

[0090] [ka]

[0091] These cyclic structures may have a substituent, such as a halogen atom or an alkoxy group.

[0092] As the divalent linking group X2 in general formula (2), the groups exemplified as the divalent linking group X1 in general formula (1) can be preferably used.

[0093] Examples of the monomer forming the monomer unit represented by general formula (2) include (meth)acrylates having a tertiary amino group, such as N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylate, and N,N-diethylaminopropyl (meth)acrylate; Examples include (meth)acrylamides having a tertiary amino group, such as N,N-dimethylaminoethyl(meth)acrylamide, N,N-diethylaminoethyl(meth)acrylamide, N,N-dimethylaminopropyl(meth)acrylamide, and N,N-diethylaminopropyl(meth)acrylamide.

[0094] In general formula (3), R 10 represents a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, an aralkyl group which may have a substituent, an acyl group, an oxy radical group, or -OR 16 represents R 16 represents a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, an aralkyl group which may have a substituent, or an acyl group. 11 ~R 14 each independently represents a methyl group, an ethyl group, or a phenyl group; R 15 represents a hydrogen atom or a methyl group, and X3 represents a divalent linking group.

[0095] R in general formula (3) 10The alkyl group in the formula (I) is linear, branched, cyclic, or a combination thereof. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, an n-hexyl group, a cyclohexyl group, an n-octyl group, and a hexadecyl group. Among these, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group are preferred.

[0096] R in general formula (3) 10 Examples of the aryl group in the formula (I) include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group.

[0097] R in general formula (3) 10 Examples of the aralkyl group in the formula (I) include a benzyl group, a phenethyl group, a phenylpropyl group, a phenylbutyl group, and a phenylisopropyl group.

[0098] R in general formula (3) 10 Examples of the acyl group include an acetyl group and a benzoyl group.

[0099] R in general formula (3) 10 When the alkyl group, aryl group, or aralkyl group has a substituent, examples of the substituent include a halogen atom, an alkoxy group, and a benzoyl group.

[0100] -OR 16 R 16 is R 10 The groups exemplified as the alkyl group which may have a substituent, the aryl group which may have a substituent, the aralkyl group which may have a substituent, or the acyl group in the above formula can be preferably used.

[0101] As the divalent linking group X3 in general formula (3), the groups exemplified as the divalent linking group X1 in general formula (1) can be preferably used.

[0102] Examples of the monomer that forms the monomer unit represented by general formula (3) include the following monomers: 15represents a hydrogen atom or a methyl group.

[0103] [ka]

[0104] Among the above monomers, 2,2,6,6-tetramethylpiperidyl methacrylate and 1,2,2,6,6-pentamethylpiperidyl methacrylate are preferred, and 1,2,2,6,6-pentamethylpiperidyl methacrylate is more preferred.

[0105] The monomer units represented by the general formulae (1) to (3) may be contained alone or in combination of two or more kinds.

[0106] The total content of the monomer units represented by general formulae (1) to (3) is preferably from 1 to 70 mol %, more preferably from 1 to 60 mol %, of all the structural units of the resin (C1) having a basic group.

[0107] The dispersing resin (C1) having a basic group can contain other monomer units in addition to at least one type of monomer unit selected from the group consisting of monomer units represented by general formulas (1) to (3).

[0108] Other monomer units include, for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2,3-Dihydroxypropyl (meth)acrylate, glycerol mono(meth)acrylate, cyclohexanedimethanol mono(meth)acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-acryloyloxyethyl-2-hydroxyethyl phthalate, 4-vinylphenol, 4-isopropenylphenol, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate (Meth)acrylate, Adamantyl (meth)acrylate, (meth)acrylic acid, Crotonic acid, Propiolic acid, Cinnamic acid, Itaconic acid, Itaconic anhydride, Maleic acid, Monomethyl maleate, Monoethyl maleate, Monoisopropyl maleate, Maleic anhydride, Fumaric acid, 2-Methacryloyloxyethyl succinic acid, 2-Acryloyloxyethyl phthalic acid, 2-Acryloyloxyethyl hexylhydrophthalic acid, p-Styrene sulfonic acid, Vinyl sulfonic acid, 2-Acrylamido-2-methylpropane sulfonic acid, tert-Butyl acrylamide Sulfonic acid, 2-(meth)acryloyloxyethyl acid phosphate, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethanol Oxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, ethylene oxide (EO) modified (meth)acrylate of phenol, EO or propylene oxide (PO) modified (meth)acrylate of nonylphenol, EO or PO modified (meth)acrylate of paracumylphenol, glycidyl (meth)acrylate, 2-methylglycidyl (meth)acrylate, 2-ethylglycidyl (meth)acrylate, 2-oxiranylethyl (meth)acrylate, 2-glycidyloxyethyl (meth)acrylate, 3,4-Epoxycyclohexyl (meth)acrylate, 3,4-Epoxycyclohexylmethyl (meth)acrylate, 3,4-Epoxytricyclo[5.2.1.0, 2,6 ] decan-8-yl (meth)acrylate, 3,4-epoxytricyclo[5.2.1.0 2,6]Decan-9-yl(meth)acrylate, 3-((meth)acryloyloxymethyl)oxetane, 3-((meth)acryloyloxymethyl)-3-ethyloxetane, 3-((meth)acryloyloxymethyl)-2-methyloxetane, 3-((meth)acryloyloxyethyl)-3-ethyloxetane, 2-ethyl-3-((meth)acryloyloxyethyl)oxetane, 3-methyl-3-(meth)acryloyloxymethyloxetane, 3-ethyl-3-(meth)acry methyloxymethyloxetane, 2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl methacrylate (MOI-BP manufactured by Resonac), 2-[O-(1'-methylpropylideneamino)carboxyamino]ethyl methacrylate (MOI-BM manufactured by Resonac), malonic acid-2-[[[[(2-methyl-1-oxo-2-propenyl)oxy]ethyl]amino]carbonyl]-1,3-diethyl ester (KarenzMOI-DEM manufactured by Resonac), 2-(acetamidopropyl)methyl methacrylate (MOI-BP manufactured by Resonac), 2-[O-(1'-methylpropylideneamino)carboxyamino]ethyl methacrylate (MOI-BM manufactured by Resonac), malonic acid-2-[[[[(2-methyl-1-oxo-2-propenyl)oxy]ethyl]amino]carbonyl]-1,3-diethyl ester (KarenzMOI-DEM manufactured by Resonac), (acetoacetoxy)ethyl methacrylate, 2-(acetoacetoxy)ethyl acrylate, 3-methacryloyloxypropylmethyldiethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, styrene, α-methylstyrene, p-vinyltoluene, p-chlorostyrene, vinylnaphthalene, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, vinyl acetate, or vinyl propionate, Examples of monomer units derived from monomers such as dimethyl-2,2'-[oxybis(methylene)]bis-2-propenoate, diethyl-2,2'-[oxybis(methylene)]bis-2-propenoate, di(n-propyl)-2,2'-[oxybis(methylene)]bis-2-propenoate, di(isopropyl)-2,2'-[oxybis(methylene)]bis-2-propenoate, and di(2-ethylhexyl)-2,2'-[oxybis(methylene)]bis-2-propenoate.

[0109] The other monomer unit may be a polymerizable unsaturated group-containing monomer unit. Examples of the polymerizable unsaturated group-containing monomer unit include units synthesized by the following methods (I) to (III).

[0110] <Method (I)> Method (I) involves adding an epoxy group-containing monomer to the carboxyl group of a resin (precursor) having a carboxyl group.

[0111] Examples of epoxy group-containing monomers include oxiranyl(meth)acrylate, glycidyl(meth)acrylate, 2-methylglycidyl(meth)acrylate, 2-ethylglycidyl(meth)acrylate, 2-oxiranylethyl(meth)acrylate, 2-glycidyloxyethyl(meth)acrylate, 3,4-epoxycyclohexyl(meth)acrylate, 3,4-epoxycyclohexylmethyl(meth)acrylate, 2-(3,4-epoxycyclohexyl)ethyl(meth)acrylate, 2-(3,4-epoxycyclohexylmethyloxy)ethyl(meth)acrylate, and 3-(3,4-epoxycyclohexylmethyloxy)propyl(meth)acrylate.

[0112] <Method (II)> Method (II) involves adding a carboxyl group-containing monomer to the epoxy group of a resin (precursor) having an epoxy group.

[0113] Examples of the carboxyl group-containing monomer include (meth)acrylic acid, 2-(meth)acryloyloxyethyl succinate, 2-(meth)acryloyloxyethyl hexyl hydrophthalate, β-carboxyethyl (meth)acrylate, and ω-carboxypolycaprolactone (meth)acrylate.

[0114] <Method (III)> Method (III) involves reacting the hydroxyl groups of a resin (precursor) having hydroxyl groups with the isocyanate groups of an isocyanate group-containing monomer.

[0115] Examples of the isocyanate group-containing monomer include 2-(meth)acryloylethyl isocyanate, 2-(meth)acryloyloxyethyl isocyanate, and 1,1-bis[methacryloyloxy]ethyl isocyanate.

[0116] (Other resins (C2)) From the viewpoint of film durability, the resin (C) preferably contains another resin (C2) other than the resin (C1) having a basic group.

[0117] Examples of the other resin (C2) include (meth)acrylic resin, styrene resin, styrene / (meth)acrylic resin, epoxy resin, urethane resin, urethane acrylic resin, polycarbonate resin, polyester resin, polyether resin, polysiloxane resin, and cyclic olefin resin.

[0118] Examples of the structure of the other resin (C2) include a random structure, a block structure, a graft structure, a comb structure, and a star structure.

[0119] The weight average molecular weight (Mw) of the other resin (C2) is preferably from 3,000 to 60,000, more preferably from 4,000 to 50,000.

[0120] The acid value of the other resin (C2) is preferably from 30 to 200 mgKOH / g, more preferably from 40 to 180 mgKOH / g.

[0121] The other resins (C2) can be used alone or in combination of two or more.

[0122] The content of the other resin (C2) is preferably from 5 to 80 mass %, more preferably from 10 to 70 mass %, in 100 mass % of the resin (C).

[0123] The other resin (C2) is preferably a resin having a polycyclic alicyclic hydrocarbon group-containing monomer unit.

[0124] [Polycyclic / alicyclic hydrocarbon group-containing monomer unit] Examples of the polycyclic alicyclic hydrocarbon group-containing monomer unit include monomer units derived from monomers such as isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, and adamantyl (meth)acrylate. Among these, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, and dicyclopentanyloxyethyl (meth)acrylate are preferred.

[0125] The content of the polycyclic alicyclic hydrocarbon group-containing monomer unit is preferably from 1 to 60 mol %, more preferably from 1 to 50 mol %, of all the monomer units in the resin.

[0126] In addition to the polycyclic alicyclic hydrocarbon group-containing monomer unit, the copolymer may contain, for example, an acidic group-containing monomer unit, a hydroxyl group-containing monomer unit, a thermally crosslinkable group-containing monomer unit, a polymerizable unsaturated group-containing monomer unit, and other monomer units. These monomer units may be contained alone or in combination of two or more types. Among these, it is preferable to contain at least one selected from a thermocrosslinkable group-containing monomer unit and a polymerizable unsaturated group-containing monomer unit.

[0127] [Acidic Group-Containing Monomer Unit] Examples of the acidic group-containing monomer unit include monomer units derived from monomers such as (meth)acrylic acid, crotonic acid, propiolic acid, cinnamic acid, itaconic acid, itaconic anhydride, maleic acid, monomethyl maleate, monoethyl maleate, monoisopropyl maleate, maleic anhydride, fumaric acid, 2-methacryloyloxyethyl succinic acid, 2-acryloyloxyethyl phthalic acid, 2-acryloyloxyethylhexylhydrophthalic acid, p-styrenesulfonic acid, vinylsulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, tert-butylacrylamidosulfonic acid, and 2-(meth)acryloyloxyethyl acid phosphate.

[0128] The content of the acidic group-containing monomer units is preferably from 1 to 40 mol %, more preferably from 5 to 30 mol %, of all the monomer units in the resin.

[0129] The method for introducing the acidic group-containing monomer unit may be a method of copolymerizing a polycyclic alicyclic hydrocarbon group-containing monomer with an acidic group-containing monomer, or a method of adding an acid anhydride (modifying compound) to the hydroxyl groups contained in the resin (precursor). Examples of the acid anhydride include succinic anhydride, phthalic anhydride, and 1,2,3,6-tetrahydrophthalic anhydride.

[0130] [Hydroxyl group-containing monomer unit] Examples of the hydroxyl group-containing monomer unit include monomer units derived from monomers such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2,3-dihydroxypropyl (meth)acrylate, glycerol mono(meth)acrylate, cyclohexanedimethanol mono(meth)acrylate, 2-hydroxy-3-phenoxypropyl acrylate, and 2-acryloyloxyethyl-2-hydroxyethyl phthalate.

[0131] In addition, the method for introducing the hydroxyl group-containing monomer unit may be a method of copolymerizing a polycyclic alicyclic hydrocarbon group-containing monomer with a hydroxyl group-containing monomer, or a method of adding a compound having a carboxyl group (modifying compound) to an epoxy group contained in a resin (precursor), or a method of adding a compound having an epoxy group (modifying compound) to a carboxyl group contained in a resin (precursor).

[0132] [Thermal crosslinkable group-containing monomer unit] The thermally crosslinkable group is a group that undergoes a crosslinking reaction upon heating and crosslinks, and examples thereof include a cyclic ether group, a blocked isocyanate group, an acetoacetoxy group, an alkoxysilyl group, a tertiary alkyl group, and a methylol group.

[0133] Examples of the thermocrosslinkable group-containing monomer unit include monomer units derived from monomers represented by the following general formulas (4) to (9).

[0134] [ka]

[0135] In general formula (4), R 1 represents a hydrogen atom or a methyl group.

[0136] In general formula (4), L 1 represents a single bond or a divalent organic group. Examples of the divalent organic group include an alkylene group having 1 to 20 carbon atoms, and an alkylene group having 1 to 20 carbon atoms having -O- between the carbon-carbon bond. The alkylene group having 1 to 20 carbon atoms is linear or branched, and examples thereof include a methylene group, an ethylene group, an n-propyl group, an n-butylene group, an n-pentylene group, an n-hexylene group, an n-heptylene group, an n-octylene group, an isopropylene group, a 2-methylpropylene group, a 2-methylhexylene group, and a tetramethylethylene group.

[0137] In general formula (4), X 1 represents a cyclic ether group. Examples of the cyclic ether group include an epoxy group and an oxetanyl group. The epoxy group may be an alicyclic epoxy group. The alicyclic epoxy group refers to a group having a cyclic structure in which an epoxy group and a saturated hydrocarbon ring are condensed.

[0138] Examples of the monomer represented by general formula (4) include glycidyl (meth)acrylate, 2-methylglycidyl (meth)acrylate, 2-ethylglycidyl (meth)acrylate, 2-oxiranylethyl (meth)acrylate, 2-glycidyloxyethyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, 3,4-epoxytricyclo[5.2.1.0] 2,6] decan-8-yl (meth)acrylate, 3,4-epoxytricyclo[5.2.1.0 2,6 Examples of the compound include compounds having an epoxy group such as decan-9-yl(meth)acrylate. Examples of compounds having an oxetanyl group include 3-((meth)acryloyloxymethyl)oxetane, 3-((meth)acryloyloxymethyl)-3-ethyloxetane, 3-((meth)acryloyloxymethyl)-2-methyloxetane, 3-((meth)acryloyloxyethyl)-3-ethyloxetane, 2-ethyl-3-((meth)acryloyloxyethyl)oxetane, 3-methyl-3-(meth)acryloyloxymethyloxetane, and 3-ethyl-3-(meth)acryloyloxymethyloxetane.

[0139] [ka]

[0140] In general formula (5), R 1 represents a hydrogen atom or a methyl group.

[0141] In general formula (5), R 2 and R 3 each independently represents an alkyl group having 1 to 10 carbon atoms. The alkyl group having 1 to 10 carbon atoms is linear or branched, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an isopropyl group, an isobutyl group, an amyl group, an isoamyl group, a heptyl group, an octyl group, an isooctyl group, a 2-ethylhexyl group, a nonyl group, a decyl group, etc. Among these, a methyl group, an ethyl group, and an n-propyl group are preferred.

[0142] In general formula (5), L 1 represents a single bond or a divalent organic group. Examples of the divalent organic group include an alkylene group having 1 to 20 carbon atoms, and an alkylene group having 1 to 20 carbon atoms having -O- between the carbon-carbon bond. The alkylene group having 1 to 20 carbon atoms is linear or branched, and examples thereof include a methylene group, an ethylene group, an n-propyl group, an n-butylene group, an n-pentylene group, an n-hexylene group, an n-heptylene group, an n-octylene group, an isopropylene group, a 2-methylpropylene group, a 2-methylhexylene group, a tetramethylethylene group, etc. Among these, a methylene group, an ethylene group, and an n-propylene group are preferred.

[0143] In general formula (5), L 2 represents a single bond or an oxygen atom.

[0144] In general formula (5), L 3 and L 4 each independently represents a single bond or a divalent organic group. The divalent organic group may be an alkylene group having 1 to 20 carbon atoms. The alkylene group having 1 to 20 carbon atoms is L in the general formula (5). 1 The alkylene group has the same meaning as that described above.

[0145] The method for producing the monomer represented by general formula (5) is not particularly limited, and known methods can be used, such as those described in JP-A-10-316643 and WO 2022 / 145298.

[0146] Hereinafter, examples of the monomer represented by general formula (5) include monomers represented by formulas (5-1) to (5-10), but the present invention is not limited thereto.

[0147] [ka]

[0148] [ka]

[0149] In general formula (6), R 1 represents a hydrogen atom or a methyl group.

[0150] In general formula (6), R 4 ~R 6 each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. The alkyl group having 1 to 10 carbon atoms is R 2 and R 3 Among these, R 4 and R 5 is preferably a hydrogen atom, and R 6 is preferably a methyl group, an ethyl group, or an n-propyl group.

[0151] In general formula (6), L 1 represents a single bond or a divalent organic group. Examples of the divalent organic group include an alkylene group having 1 to 20 carbon atoms, and an alkylene group having 1 to 20 carbon atoms having -O- between the carbon-carbon bond. The alkylene group having 1 to 20 carbon atoms is L in the general formula (5). 1 The alkylene group has the same meaning as that described above.

[0152] The method for producing the monomer represented by general formula (6) is not particularly limited, and known methods can be used, such as those described in WO 2022 / 145298.

[0153] Hereinafter, examples of the monomer represented by general formula (6) include monomers represented by formulas (6-1) to (6-6), but the present invention is not limited thereto.

[0154] [ka]

[0155] [ka]

[0156] In general formula (7), R 1 represents a hydrogen atom or a methyl group.

[0157] In general formula (7), R 7 represents an alkyl group having 1 to 10 carbon atoms. The alkyl group having 1 to 10 carbon atoms is R 2 and R 3 It has the same meaning as the alkyl group described above.

[0158] In general formula (7), L 1 represents a single bond or a divalent organic group. Examples of the divalent organic group include an alkylene group having 1 to 20 carbon atoms, and an alkylene group having 1 to 20 carbon atoms having -O- between the carbon-carbon bond. The alkylene group having 1 to 20 carbon atoms is L in the general formula (5). 1 The alkylene group has the same meaning as that described above.

[0159] The method for producing the monomer represented by general formula (7) is not particularly limited, and known methods can be used, such as those described in Witzeman, JS, and Dell Rector, FJ, Coatings Technology, Vol. 62.

[0160] Hereinafter, examples of the monomer represented by general formula (7) include monomers represented by formulas (7-1) to (7-4), but the present invention is not limited thereto.

[0161] [ka]

[0162] [ka]

[0163] In general formula (8), R 1 represents a hydrogen atom or a methyl group.

[0164] In general formula (8), R 8 ~R 10each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms, provided that R 8 ~R 10 At least one of them is an alkoxy group having 1 to 6 carbon atoms. Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a butyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an isopropyl group, and an isobutyl group. Examples of the alkoxy group having 1 to 6 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, an isopropoxy group, etc. Among these, a methoxy group and an ethoxy group are preferred. In general formula (8), R 8 ~R 10 At least two of these are preferably alkoxy groups having 1 to 6 carbon atoms.

[0165] In general formula (8), L 1 represents a single bond or a divalent organic group. Examples of the divalent organic group include an alkylene group having 1 to 20 carbon atoms, and an alkylene group having 1 to 20 carbon atoms having -O- between the carbon-carbon bond. The alkylene group having 1 to 20 carbon atoms is L in the general formula (5). 1 The alkylene group has the same meaning as that described above.

[0166] Hereinafter, examples of the monomer represented by general formula (8) include monomers represented by formulas (8-1) to (8-6), but the present invention is not limited thereto.

[0167] [ka]

[0168] [ka]

[0169] In general formula (9), R 1 represents a hydrogen atom or a methyl group.

[0170] In general formula (9), R 11 ~R 13 each independently represents an alkyl group having 1 to 10 carbon atoms. The alkyl group having 1 to 10 carbon atoms is R 2 and R 3 Among these, a methyl group is preferred.

[0171] In general formula (9), L 1 represents a single bond or a divalent organic group. The divalent organic group may be an alkylene group having 1 to 20 carbon atoms, a group having -NH-, or a combination thereof. The alkylene group having 1 to 20 carbon atoms is L in the general formula (5). 1 The alkylene group has the same meaning as that described above.

[0172] Hereinafter, examples of the monomer represented by general formula (9) include monomers represented by formulas (9-1) to (9-6), but the present invention is not limited thereto.

[0173] [ka]

[0174] [Polymerizable unsaturated group-containing monomer unit (b5)] The polymerizable unsaturated group-containing monomer unit (b5) can be formed, for example, by any of the following methods (i) to (iii).

[0175] <Method (i)> In the method (i), for example, a precursor having an epoxy group is first synthesized, and then an acidic group-containing monomer (carboxyl group-containing monomer) in which the acidic group is a carboxyl group is added to the epoxy group of the precursor.

[0176] Examples of the carboxyl group-containing monomer include (meth)acrylic acid, 2-(meth)acryloyloxyethyl succinate, 2-(meth)acryloyloxyethyl hexyl hydrophthalate, β-carboxyethyl (meth)acrylate, and ω-carboxypolycaprolactone (meth)acrylate.

[0177] The site where the carboxyl group-containing monomer is added to the epoxy group of the precursor can be further reacted with an acid anhydride.

[0178] Examples of the acid anhydride include 1,2,3,6-tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, and maleic anhydride.

[0179] <Method (ii)> In the method (ii), for example, a precursor having a carboxyl group is first synthesized, and then an epoxy group-containing monomer is added to the carboxyl group of the precursor.

[0180] Examples of epoxy group-containing monomers include glycidyl (meth)acrylate, methyl glycidyl (meth)acrylate, 2-glycidoxyethyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, and 3,4-epoxycyclohexyl (meth)acrylate.

[0181] The site where the epoxy group-containing monomer is added to the carboxyl group of the precursor can be further reacted with an acid anhydride.

[0182] <Method (iii)> In the method (iii), for example, a precursor having a hydroxyl group is first synthesized, and then the hydroxyl group of the precursor is reacted with the isocyanate group of an isocyanate group-containing monomer.

[0183] Examples of the isocyanate group-containing monomer include 2-(meth)acryloylethyl isocyanate, 2-(meth)acryloyloxyethyl isocyanate, and 1,1-bis[methacryloyloxy]ethyl isocyanate.

[0184] [Other monomer units] Examples of other monomer units include acrylic acid esters such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, EO-modified (meth)acrylate of phenol, EO- or PO-modified (meth)acrylate of nonylphenol, EO- or PO-modified (meth)acrylate of paracumylphenol, dimethylaminoethyl (meth)acrylate, and diethylaminoethyl (meth)acrylate; Aromatic vinyl compounds such as styrene, α-methylstyrene, p-vinyltoluene, p-chlorostyrene, and vinylnaphthalene; (meth)acrylamides such as (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, diacetone(meth)acrylamide, or acryloylmorpholine; vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, or isobutyl vinyl ether; vinyl fatty acid vinyl compounds such as vinyl acetate or vinyl propionate; Phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimidoethane, 1,6-bismaleimidohexane, 6,7-methylenedioxy-4-methyl-3-maleimidocoumarin, 4,4'-bismaleimidodiphenylmethane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, N,N'-1,3-phenylenedimaleimide, N,N'-1,4-phenylenedimaleimide, N-(1-pyrenyl)maleimide, N-(2,4,6-trichlorophenyl)maleimide, N- N-substituted maleimides such as (4-aminophenyl)maleimide, N-(4-nitrophenyl)maleimide, N-benzylmaleimide, N-bromomethyl-2,3-dichloromaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-3-maleimidopropionate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidohexanoate, N-[4-(2-benzimidazolyl)phenyl]maleimide, and 9-maleimidoacridine; Examples of monomer units include those derived from monomers such as dimethyl-2,2'-[oxybis(methylene)]bis-2-propenoate, diethyl-2,2'-[oxybis(methylene)]bis-2-propenoate, di(n-propyl)-2,2'-[oxybis(methylene)]bis-2-propenoate, di(isopropyl)-2,2'-[oxybis(methylene)]bis-2-propenoate, and di(2-ethylhexyl)-2,2'-[oxybis(methylene)]bis-2-propenoate. These monomers can be used alone or in combination of two or more.

[0185] [Solvent (D)] The resin composition of the present invention contains a solvent (D).

[0186] The solvent (D) is not particularly limited, and known solvents can be used. Examples of the solvent (D) include 1,2,3-trichloropropane, ethyl lactate, methyl lactate, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, and 3-methoxy-3-methylbutylacetate. acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene, N,N-dimethylacetamide, N,N-dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, N-methylpyrrolidone, o-xylene, toluene, o-chlorotoluene, benzene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone ton, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether,Examples of the olefin copolymer include dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone, methylcyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate, dibasic acid esters, and water.

[0187] The solvent (D) can be used alone or in combination of two or more kinds.

[0188] The content of the solvent (D) is preferably an amount such that the nonvolatile content of the resin composition is 5 to 60 mass %.

[0189] (Hansen solubility parameter hydrogen bond term is 10MPa 1 / 2 or more) From the viewpoint of viscosity stability and redispersibility, solvent (D) is selected so that the hydrogen bond term of the Hansen solubility parameter is 10 MPa. 1 / 2 It is preferable that the solvent (D1) (hereinafter, also simply referred to as solvent (D1)) is contained.

[0190] Here, the Hansen solubility parameter is a solubility parameter introduced by Hildebrand, divided into three components: a dispersion term (hereinafter also referred to as δd), a polar term (hereinafter also referred to as δp), and a hydrogen bonding term (hereinafter also referred to as δh), and expressed in three-dimensional space. The dispersion term indicates the effect of dispersion forces, the polar term indicates the effect of dipole-dipole forces, and the hydrogen bonding term indicates the effect of hydrogen bonding forces.

[0191] The definition and calculation of Hansen solubility parameters are described in "Hansen Solubility Parameters: A Users Handbook" by Charles M. Hansen (CRC Press, 2007). Furthermore, Hansen solubility parameters can be calculated from chemical structures using computer software "Hansen Solubility Parameters in Practice (HSPiP)." For the solvent (D1) of the present invention, values ​​from Hansen Solubility Parameters: A Users Handbook, Second Edition are used, and for those not listed, values ​​calculated using "Hansen Solubility Parameters in Practice (HSPiP)" are used.

[0192] The hydrogen bond parameter of the solvent (D1) is 10 to 45 MPa from the viewpoint of viscosity stability and redispersibility. 1 / 2 is preferred.

[0193] Examples of the solvent (D1) include dipropylene glycol monobutyl ether (δh=10.0), diethylene glycol hexyl ether (δh=10.0), butyl lactate (δh=10.2), propylene glycol monoethyl ether (δh=10.5), diethylene glycol monobutyl ether (δh=10.6), diacetone alcohol (δh=10.8), dipropylene glycol monopropyl ether (δh=11.0), dipropylene glycol monomethyl ether (δh=11.2), propylene glycol monomethyl ether (δh=11.6), diethylene glycol monoethyl ether (δh=12.2), and ethylene glycol monobutyl ether (δh=12.3). , 3-methyl-1-butanol (δh = 13.3), ethyl lactate (δh = 12.5), diethylene glycol monomethyl ether (δh = 12.6), cyclohexanol (δh = 13.5), 3-methoxy-1-butanol (δh = 13.6), benzyl alcohol (δh = 13.7), 2-methyl-1-butanol (δh = 14.3), ethylene glycol monoethyl ether (δh = 14.3), 2-butanol (δh = 14.5), methyl lactate (δh = 14.6), furfuryl alcohol (δh = 15.1), 1-butanol (δh = 15.8), ethylene glycol monomethyl ether (δh = 16.4), ethanol (δh = 19.4), water (δh = 42.3), etc. Among these, it is preferable to contain at least one selected from the group consisting of propylene glycol monoethyl ether, propylene glycol monomethyl ether, ethylene glycol monobutyl ether, cyclohexanol, 3-methoxy-1-butanol, ethylene glycol monoethyl ether, and water.

[0194] The content of the solvent (D1) is preferably from 0.01 to 20% by mass, more preferably from 0.05 to 15% by mass, based on 100% by mass of the resin composition. The content of water is preferably 0.01 to 2% by mass, and more preferably 0.05 to 1% by mass, based on 100% by mass of the resin composition.

[0195] (Other solvents (D2)) The solvent (D) may contain a solvent (D2) other than the solvent (D1).

[0196] The other solvent (D2) preferably contains at least one selected from the group consisting of propylene glycol diacetate, 3-methoxybutyl acetate, diethylene glycol dimethyl ether, ethyl 3-ethoxypropionate, cyclopentanone, methyl 3-methoxypropionate, propylene glycol monomethyl ether acetate, cyclohexanone, and butyl acetate.

[0197] From an environmental viewpoint, the resin composition of the present invention preferably does not substantially contain any aromatic hydrocarbon solvents (toluene, xylene, benzene, chlorobenzene, etc.) "Substantially not containing" means that the content of such solvents in the resin composition is 50 ppm by mass or less, preferably 30 ppm by mass or less, and more preferably 10 ppm by mass or less.

[0198] [Polymerizable compound (E)] From the viewpoint of film durability, the resin composition of the present invention preferably contains a polymerizable compound (E).

[0199] The polymerizable compound (E) is not particularly limited, and known polymerizable compounds can be used. Examples of the polymerizable compound (E) include monomers and oligomers having a polymerizable unsaturated group. Examples of the polymerizable unsaturated group include a vinyl group, a (meth)allyl group, a (meth)acryloyl group, and a (meth)acryloyloxy group.

[0200] Examples of the polymerizable compound (E) include lactone-modified polymerizable compounds, polymerizable compounds having an acidic group, polymerizable compounds having a hydroxyl group, polymerizable compounds having a urethane bond, polymerizable compounds having an amine structure, polymerizable compounds having a dendrimer structure or a hyperbranched structure, and other polymerizable compounds.

[0201] (Lactone-modified polymerizable compound) The lactone-modified polymerizable compound is a compound having a lactone-modified structure in the molecule. The lactone-modified polymerizable compound can be obtained by esterifying a polyhydric alcohol such as trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaethylthritol, tripentaerythritol, glycerin, diglycerol, or trimetrolmelamine with (meth)acrylic acid and ε-caprolactone or another lactone compound.

[0202] Examples of commercially available lactone-modified polymerizable compounds include KAYARAD DPCA-20, DPCA-30, and DPCA-60 manufactured by Nippon Kayaku Co., Ltd.

[0203] (Polymerizable compound having an acidic group) Examples of polymerizable compounds having an acidic group include esters of dicarboxylic acids and poly(meth)acrylates containing free hydroxyl groups, which are polyhydric alcohols and (meth)acrylic acid; and esters of polycarboxylic acids and monohydroxyalkyl(meth)acrylates.

[0204] Examples of the polyhydric alcohol include ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, glycerin, trimethylolpropane, ditrimethylolpropane, pentaerythritol, and dipentaerythritol.

[0205] Examples of the dicarboxylic acids include malonic acid, succinic acid, maleic acid, glutaric acid, phthalic acid, itaconic acid, and the like.

[0206] Examples of the polycarboxylic acid include trimellitic acid and pyromellitic acid. Examples of monohydroxyalkyl (meth)acrylates include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, pentaerythritol triacrylate, and 2-hydroxy-3-acryloyloxypropyl methacrylate.

[0207] Commercially available polymerizable compounds having an acidic group include Aronix M-5300, M-5400, M-510, M-520, and M-521 manufactured by Toagosei Co., Ltd., Light Acrylate HOA-MS(N), HOA-HH(N), HOA-MPE(N), and P-1A(N) manufactured by Kyoeisha Chemical Co., Ltd., and β-CEA manufactured by Daicel Allnex Corporation.

[0208] (Polymerizable compound having a hydroxyl group) Examples of the polymerizable compound having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2,3-hydroxypropyl (meth)acrylate, glycerol di(meth)acrylate, cyclohexanedimethanol mono(meth)acrylate, 2-hydroxy-3-phenoxypropyl acrylate, isocyanuric acid EO or PO modified (meth)acrylate, isocyanuric acid EO or PO modified di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, polypentaerythritol penta(meth)acrylate, dipentaerythritol EO or PO modified penta(meth)acrylate and other acrylic acid esters; and epoxy (meth)acrylates obtained by reacting the epoxy group of an epoxy compound with the carboxyl group of (meth)acrylic acid.

[0209] Examples of commercially available polymerizable compounds having a hydroxyl group include KAYARAD R-128H and R-167 manufactured by Nippon Kayaku Co., Ltd.; Blenmar GLM, GLM-R, GMR-M, GMR-R, GAM, GAM-R, and G-FA80 manufactured by NOF Corp.; Aronix M-5700 and M-920 manufactured by Toagosei Co., Ltd.; NK Ester 701A manufactured by Shin-Nakamura Chemical Co., Ltd.; Light Ester HOP(N), HOA(N), HOP-A(N), HOB(N), and G-201P, and Epoxy Ester M-600A, 40EM, 70PA, 200PA, 80MFA, 3002M(N), 3002A(N), and 3000A manufactured by Kyoeisha Chemical Co., Ltd.; and OGSOL GA-5060P and GA-2800 manufactured by Osaka Gas Chemical Co., Ltd.

[0210] (Polymerizable compound having a urethane bond) Examples of the polymerizable compound having a urethane bond include urethane (meth)acrylates obtained by reacting a hydroxyl group-containing (meth)acrylate with a polyfunctional isocyanate, and urethane (meth)acrylates obtained by reacting a polyhydric alcohol with a polyfunctional isocyanate and then reacting the resulting mixture with a hydroxyl group-containing (meth)acrylate.

[0211] Examples of the hydroxyl group-containing (meth)acrylate include 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol EO-modified penta(meth)acrylate, dipentaerythritol PO-modified penta(meth)acrylate, dipentaerythritol caprolactone-modified penta(meth)acrylate, glycerol dimethacrylate, 2-hydroxy-3-acryloylpropyl methacrylate, a reaction product of an epoxy group-containing compound and a carboxy(meth)acrylate, and a hydroxyl group-containing polyol polyacrylate.

[0212] Examples of the polyfunctional isocyanate include aromatic diisocyanates such as tolylene diisocyanate, diphenylmethylene diisocyanate, and xylene diisocyanate; aliphatic diisocyanates such as trimethylene diisocyanate, tetramethylene diisocyanate, and hexamethylene diisocyanate; and alicyclic diisocyanate such as isophorone diisocyanate; as well as biuret derivatives, isocyanurates, and trimethylolpropane adducts thereof.

[0213] From the viewpoint of developability, the polymerizable compound having a urethane bond may further have an acidic group. Examples of the acidic group include a sulfonic acid group, a carboxyl group, and a phosphate group. Among these, a carboxyl group is preferred.

[0214] The acidic group can be introduced into a polymerizable compound having a urethane bond by, for example, first reacting the hydroxyl group-containing (meth)acrylate with the polyfunctional isocyanate, and then adding a mercapto compound having a carboxyl group to the product.

[0215] Examples of the mercapto compound having a carboxyl group include mercaptoacetic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, o-mercaptobenzoic acid, 2-mercaptonicotinic acid, and mercaptosuccinic acid.

[0216] Another method is to react the polyfunctional isocyanate with a diol compound having a carboxy group to synthesize a precursor having isocyanate groups at both ends, and then to react the precursor with the hydroxyl group-containing (meth)acrylate.

[0217] Examples of the diol compound having a carboxy group include 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, 2,2-dimethylolpentanoic acid, and 2,2-dimethylolhexanoic acid.

[0218] Examples of commercially available polymerizable compounds having a urethane bond include AH-600, UA-306H, UA-306T, UA-306I, UA-510H, and UF-8001G manufactured by Kyoeisha Chemical Co., Ltd., UA-1100H, U-6LPA, UA-33H, U-10HA, and U-15HA manufactured by Shin-Nakamura Chemical Co., Ltd., and EBECRYL1290 and KRM8452 manufactured by Daicel-Allnex Corporation.

[0219] (Polymerizable compound having an amine structure) The amine structure of the polymerizable compound having an amine structure may be any of a primary amine, secondary amine, and tertiary amine structure, but is preferably a secondary amine or tertiary amine. However, the amine structure of the polymerizable compound having an amine structure does not include an amide structure, an imide structure, or a urethane structure in which a carbonyl group is directly bonded to a nitrogen atom.

[0220] Examples of the polymerizable compound having an amine structure include tris(acryloyloxyethyl)amine, tris(methacryloyloxyethyl)amine, tris(2-hydroxy-3-methacryloyloxypropyl)amine, and a Michael addition reaction product of a (meth)acrylate compound (X) and an amine compound (Y).

[0221] Examples of the (meth)acrylate compound (X) include glycerin tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and diglycerides thereof. Examples of the alkylene oxide-modified tri(meth)acrylate include lin tri(meth)acrylate, diglycerin tetra(meth)acrylate, trimethylolpropane alkylene oxide-modified tri- and tetra(meth)acrylate, ditrimethylolpropane alkylene oxide-modified tri- and tetra(meth)acrylate, pentaerythritol alkylene oxide-modified tri- and tetra(meth)acrylate, diglycerin alkylene oxide-modified tri- and tetra(meth)acrylate, and dipentaerythritol alkylene oxide-modified tetra-, penta-, and hexa(meth)acrylate. Examples of the alkylene oxide unit in the alkylene oxide modification include ethylene oxide, propylene oxide, and butylene oxide. The (meth)acrylate compound (X) also includes a (meth)acrylate compound having an acidic group.

[0222] The (meth)acrylate compound (X) can be used alone or in combination of two or more kinds.

[0223] Examples of the amine compound (Y) include primary amines such as n-propylamine, n-butylamine, n-hexylamine, benzylamine, aminocaproic acid, monoethanolamine, 2-(2-aminoethoxy)ethanol, o-aminophenol, m-aminophenol, and p-aminophenol; Examples of the secondary amines include dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, cyclohexylamine, morpholine, piperidine, 1-methylpiperazine, proline, N-merylethanolamine, N-acetylethanolamine, diethanolamine, 3-anilinephenol, and 4-anilinephenol.

[0224] The amine compound (Y) can be used alone or in combination of two or more kinds.

[0225] The method for producing the Michael addition reaction product of the (meth)acrylate compound (X) and the amine compound (Y) is not particularly limited, and known methods can be used, such as those described in International Publication No. 2006 / 075754, JP-A No. 2008-545859, and JP-A No. 2017-066347.

[0226] The polymerizable compound having an amine structure may have an acidic group and / or a hydroxyl group. Examples of methods for introducing the acidic group and / or the hydroxyl group include a method of using a compound having an acidic group and / or a hydroxyl group in the (meth)acrylate compound (X) or the amine compound (Y), and a method of adding an acid anhydride after a Michael addition reaction.

[0227] Examples of commercially available polymerizable compounds having an amine structure include Aronix MT-3041 and 3042 manufactured by Toagosei Co., Ltd., EBECRYL80 and 7100 manufactured by Daicel-Allnex Co., Ltd., and CN371NS, 372, 374, 383, and 386 manufactured by Arkema.

[0228] The polymerizable compound having an amine structure may further contain a urethane bond. This forms a chemical crosslinked structure through polymerization as well as a physical crosslinked structure through intermolecular hydrogen bonds between the urethane bonds and between the urethane bonds and the functional groups of the substrate. The molecular cohesive energy of the intermolecular hydrogen bonds at the urethane bond sites is greater than the cohesive energy of other organic structures such as ether bonds. Therefore, the film becomes flexible and strong due to the interaction between the urethane bonds, and resistance is likely to be improved.

[0229] The urethane bond can be introduced, for example, by a method of producing the polymer by a urethane reaction between a Michael addition reaction product (precursor) of the above-mentioned (meth)acrylate compound (X) and the above-mentioned amine compound (Y) having a hydroxyl group, and a polyisocyanate compound (Z).

[0230] Examples of the polyisocyanate compound (Z) include polyisocyanate compounds having an aliphatic structure, such as butane-1,4-diisocyanate, hexamethylene diisocyanate, isopropylene diisocyanate, methylene diisocyanate, and 2,2,4-trimethylhexamethylene diisocyanate; Polyisocyanate compounds having an alicyclic structure, such as cyclohexane-1,4-diisocyanate, isophorone diisocyanate, dimethylcyclohexyl diisocyanate, methylcyclohexyl diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 1,3-bis(isocyanatemethyl)cyclohexane, methylcyclohexane diisocyanate, norbornane diisocyanate, and bis(isocyanatemethyl)cyclohexane; Examples of the polyisocyanate compound include polyisocyanate compounds having an aromatic structure, such as 1,5-naphthylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-dibenzyl isocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, xylylene diisocyanate, m-tetramethylxylylene diisocyanate, 4,4-diphenylmethane diisocyanate, tolylene diisocyanate, bischloromethyldiphenylmethane diisocyanate, 2,6-diisocyanate-benzyl chloride, and bis(isocyanatomethyl)benzene. Further, biuret, isocyanurate, adduct, allophanate and the like of these compounds may also be used.

[0231] The polyisocyanate compounds (Z) can be used alone or in combination of two or more kinds.

[0232] The method for the urethane reaction between the precursor and the polyisocyanate compound (Z) is not particularly limited, and known methods can be used, such as those described in JP-A-2018-517797.

[0233] An example of a commercially available product in which a urethane bond has been introduced into a polymerizable compound having an amine structure is CN9906NS manufactured by Arkema.

[0234] (Polymerizable compound having a dendrimer structure or a hyperbranched structure) A polymerizable compound with a dendrimer structure has a chemical structure in which branches are regularly repeated outward from a chemical structure constituting a core (hereinafter also referred to as the core portion), and polymerizable unsaturated groups are bonded to the ends of the branches, and has a spherical, highly controlled chemical structure and molecular weight. The hyperbranched structure has a chemical structure similar to that of a dendrimer structure.

[0235] Commercially available polymerizable compounds having a dendrimer structure or a hyperbranched structure include, for example, Viscoat #1000LT (dendrimer structure, average number of acryloyl groups: 14) manufactured by Osaka Organic Chemical Industry Co., Ltd., Miramer SP-1106 (dendrimer structure, average number of acryloyl groups: 18) and Miramer SP-1108 (dendrimer structure, average number of acryloyl groups: 13) manufactured by Miwon Specialty Chemical Co., Ltd., CN2301 (hyperbranched structure, average number of acryloyl groups: 9), CN2302 (hyperbranched structure, average number of acryloyl groups: 16), CN2303 (hyperbranched structure, average number of acryloyl groups: 6), and CN2304 (hyperbranched structure, average number of acryloyl groups: 18) manufactured by SARTOMER Co., Ltd., and Eternal Examples include Etercure 6361-100 (hyperbranched structure, average number of acryloyl groups: 8), Etercure 6362-100 (hyperbranched structure, average number of acryloyl groups: 12), Etercure 6363 (hyperbranched structure, average number of acryloyl groups: 16), and Etercure DR-E522 (hyperbranched structure, average number of acryloyl groups: 15), all manufactured by Materials Corporation.

[0236] (Other polymerizable compounds) Other polymerizable compounds include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, cyclohexyl (meth)acrylate, polyethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, triethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, phenoxytetraethylene glycol (meth)acrylate, phenoxyhexaethylene glycol (meth)acrylate, glycerol tri(meth)acrylate, trimethylolpropane PO-modified tri(meth)acrylate, trimethylolpropane E Examples of the methacrylate include O-modified or PO-modified tri(meth)acrylate, isocyanuric acid EO-modified or PO-modified tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol EO- or PO-modified hexa(meth)acrylate, tricyclodecanyl (meth)acrylate, (meth)acrylic acid ester of methylolated melamine, styrene, vinyl acetate, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth)acrylamide, N-vinylformamide, and acrylonitrile.

[0237] Other commercially available polymerizable compounds include, for example, KAYARAD NPGDA, PEG400DA, FM-400, HX-200, HX-620, R-551, R-712, R-604, R-684, GPOD-303, TMPTA, T-1420(T), RP-1040, DPEA-12, and D-310 manufactured by Nippon Kayaku Co., Ltd.; Aronix M-101A, M-102, M-111, M-113, M-120, M-140, M-208, and M-211B manufactured by Toagosei Co., Ltd.; M-220, M-225, M-270, M-240, M-309, M-310, M-321, M-350, M-360, M-408, M-460, M-930, Viscoat #150, #155, #160, #192, #MTG, #200, #196, #195, #230, #260, #310, #700HV, #295 manufactured by Osaka Organic Chemical Industry Co., Ltd., and OGSOL manufactured by Osaka Gas Chemicals Co., Ltd. EA-0200, EA-0300, Miramer HR6060, 6100, 6200 manufactured by Miwon Specialty Chemical Co., Ltd., and NK Ester A-HD-N, A-NPG, A-200, A-400, APG-200, APG-400, A-DCP, ABE-300, A-BPE-4, A-BPE-10, A-TMPT, A-TMPT-9EO, A-GLY-3E, A-GLY-9E, A-TMMT, ATM-35E, AD-TMP manufactured by Shin-Nakamura Chemical Co., Ltd.

[0238] The polymerizable compound (E) can be used alone or in combination of two or more kinds.

[0239] The content of the polymerizable compound (E) is preferably from 1 to 70 mass %, more preferably from 5 to 60 mass %, based on 100 mass % of the nonvolatile content of the resin composition.

[0240] [Polymerization initiator (F)] From the viewpoint of film durability, the resin composition of the present invention preferably contains a polymerization initiator (F).

[0241] The polymerization initiator (F) is not particularly limited, and known polymerization initiators can be used. Examples of the polymerization initiator (F) include compounds that generate radicals by the action of light or heat, thereby initiating or promoting a radical polymerization reaction. The polymerization initiator that generates radicals by light (hereinafter also simply referred to as a photopolymerization initiator) is preferably a compound that generates radicals in response to light in the ultraviolet to visible region. The polymerization initiator that generates radicals by heat (hereinafter also simply referred to as a thermal polymerization initiator) may be a compound that generates radicals by the action of heat and light.

[0242] Examples of the photopolymerization initiator include α-hydroxyketone compounds such as 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methylpropiophenone, and 2-hydroxy-1-[4-(2-hydroxyethoxy)phenyl]-2-methyl-1-propanone; α-aminoketone compounds such as 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-(dimethylamino)-4'-morpholinobutyrophenone, and 2-dimethylamino-2-(4-methylbenzyl)-1-[4-(morpholinophenyl)-butan-1-one; acylphosphine compounds such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and diphenyl-2,4,6-trimethylbenzoylphosphine oxide; Oxime compounds such as 1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)], ethanol, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime); triazine-based compounds such as 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-piperonyl-4,6-bis(trichloromethyl)-s-triazine, 2,4-bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxy-naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-trichloromethyl-(piperonyl)-6-triazine, and 2,4-trichloromethyl-(4'-methoxystyryl)-6-triazine; Examples include quinone compounds such as 9,10-phenanthrenequinone, camphorquinone, and ethylanthraquinone.

[0243] Commercially available products include Omnirad 127, 184, 1173, and 2959 manufactured by IGM Resins as α-hydroxyketone compounds, Omnirad 907, 369E, and 379EG manufactured by IGM Resins as α-aminoketone compounds, Omnirad 819 and TPO manufactured by IGM Resins as acylphosphine compounds, IRGACURE OXE-01, 02, 03, 04, and 05 manufactured by BASF Japan, Adeka Arcure N-1919T, NCI-730, 831E, and 930 manufactured by ADEKA, TRONLY TR-PBG-301, 304, 305, 309, 314, 345, 358, 380, 365, 610, 3054, and 3057 manufactured by Changzhou Strong New Materials Co., Ltd., and IGM Examples include Omnirad 1312, 1314, and 1316 manufactured by Resins, SPI-02, 03, 04, 05, 06, and 07 manufactured by Samyang Corporation, and DFI-020, 306, and EOX-01 manufactured by Daito Chemiks. Further, compounds described in JP 2007-210991 A, JP 2009-179619 A, JP 2010-037223 A, JP 2010-215575 A, JP 2011-020998 A, WO 2015 / 036910, JP 2019-507108 A, JP 2019-528331 A, WO 2021 / 175855, JP 2022-5115524 A, etc., compounds described in WO 2023 / 085056, etc., can also be mentioned.

[0244] Examples of the thermal polymerization initiator include benzopinacol, 1,2-dimethoxy-1,1,2,2-tetraphenylethane, 1,2-dimethoxy-1,1,2,2-tetraphenylethane, 1,2-diphenoxy-1,1,2,2-tetraphenylethane, 1,2-dimethoxy-1,1,2,2-tetraphenylethane, 1,2-dimethoxy-1,1,2,2-tetra(4-methylphenyl)ethane, 1,2-diphenoxy-1,1,2,2-tetra(4-methoxyphenyl)ethane, and 1,2-bis(trimethylsiloxy)-1,1,2,2-tetraphenylethane. pinacol-based compounds such as silane, 1,2-bis(triethylsiloxy)-1,1,2,2-tetraphenylethane, 1,2-bis(tert-butyldimethylsiloxy)-1,1,2,2-tetraphenylethane, 1-hydroxy-2-trimethylsiloxy-1,1,2,2-tetraphenylethane, 1-hydroxy-2-triethylsiloxy-1,1,2,2-tetraphenylethane, and 1-hydroxy-2-tert-butyldimethylsiloxy-1,1,2,2-tetraphenylethane; azo compounds such as 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), dimethyl-2,2'-azobis(2-methylpropionate), 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis(cyclohexane-1-carbonitrile), 2,2'-azobis[N-(2-propenyl)2-methylpropionamide], 1-[(1-cyano-1-methylethyl)azo]formamide, 2,2'-azobis(N-butyl-2-methylpropionamide), and 2,2'-azobis(N-cyclohexyl-2-methylpropionamide); Examples of the organic peroxide include methyl ethyl ketone peroxide, cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, methylcyclohexanone peroxide, acetylacetone peroxide, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(tert-butylperoxy)cyclohexane, 2,2-bis(tert-butylperoxy)butane, succinic peroxide, and benzoyl peroxide. Further examples include oxime sulfonate compounds described in WO 2012 / 101245, WO 2016 / 030790, etc.

[0245] The polymerization initiator (F) can be used alone or in combination of two or more kinds.

[0246] The content of the polymerization initiator (F) is preferably from 0.1 to 20 mass %, more preferably from 0.3 to 10 mass %, based on 100 mass % of the nonvolatile content of the resin composition.

[0247] (The absorption coefficient of light at a wavelength of 365 nm in propylene glycol monomethyl ether acetate is 5.0 × 10 3 L / mol cm or more polymerization initiator (F1)) The polymerization initiator (F) has an absorption coefficient of 5.0 × 10 for light with a wavelength of 365 nm in propylene glycol monomethyl ether acetate. 3 It is preferable that the polymerization initiator (F1) (hereinafter, simply referred to as polymerization initiator (F1)) has a viscosity of 1000 MPa (1000 MPa) or more.

[0248] The absorption coefficient of the polymerization initiator (F1) in propylene glycol monomethyl ether acetate at a wavelength of 365 nm is 5.0 x 10 3 ~5.0×10 4 mL / gcm is preferred, 1.0 x 10 4 ~4.0×10 4 L / mol·cm is more preferred.

[0249] Specific examples of the polymerization initiator (F1) are shown below, but the present invention is not limited to these.

[0250] [ka]

[0251] [ka]

[0252] Among the above compounds, it is particularly preferable to include at least one compound selected from the group consisting of (F1-1) to (F1-6).

[0253] The polymerization initiator (F1) can be used alone or in combination of two or more kinds.

[0254] The content of the polymerization initiator (F1) is preferably from 10 to 100% by mass, more preferably from 20 to 100% by mass, based on 100% by mass of the polymerization initiator (F).

[0255] [Sensitizer (G)] The resin composition of the present invention may contain a sensitizer (G).

[0256] The sensitizer (G) is not particularly limited, and known sensitizers can be used. Examples of the sensitizer (G) include chalcone compounds, unsaturated ketones typified by dibenzalacetone, 1,2-diketone compounds typified by benzil and camphorquinone, benzoin compounds, fluorene compounds, naphthoquinone compounds, anthraquinone compounds, xanthene compounds, thioxanthene compounds, xanthone compounds, thioxanthone compounds, coumarin compounds, ketocoumarin compounds, cyanine compounds, merocyanine compounds, and polymethine dyes such as oxonol compounds, acridine compounds, azine compounds, thiazine compounds, oxazine compounds, indoline compounds, azulene compounds, and azulenium compounds. compounds, squarylium compounds, porphyrin compounds, tetraphenylporphyrin compounds, triarylmethane compounds, tetrabenzoporphyrin compounds, tetrapyrazinoporphyrazine compounds, phthalocyanine compounds, tetraazaporphyrazine compounds, tetraquinoxalylporphyrazine compounds, naphthalocyanine compounds, subphthalocyanine compounds, pyrylium compounds, thiopyrylium compounds, tetraphyrin compounds, annulene compounds, spiropyran compounds, spirooxazine compounds, thiospiropyran compounds, metal arene complexes, organic ruthenium complexes, and benzophenone compounds.

[0257] The sensitizer (G) can be used alone or in combination of two or more kinds.

[0258] The content of the sensitizer (G) is preferably from 5 to 200 parts by mass, more preferably from 10 to 150 parts by mass, relative to 100 parts by mass of the polymerization initiator (F).

[0259] [Thermal crosslinkable compound (H)] The resinous composition of the present invention may contain a thermally crosslinkable compound (H).

[0260] The thermally crosslinkable compound (H) is not particularly limited, and known thermally crosslinkable compounds can be used. Examples of the thermally crosslinkable compound (H) include epoxy compounds, oxetane compounds, benzoguanamine compounds, rosin-modified maleic acid compounds, rosin-modified fumaric acid compounds, melamine compounds, urea compounds, phenol compounds, and blocked isocyanate compounds. Among these, epoxy compounds, oxetane compounds, melamine compounds, and blocked isocyanate compounds are preferred.

[0261] (epoxy compounds) The epoxy compound is not particularly limited, and known epoxy compounds can be used, such as polyglycidyl ether compounds of bisphenols, such as bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, and hydrogenated bisphenol F diglycidyl ether; Polyglycidyl ether compounds of polyhydric alcohols such as 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, and polypropylene glycol diglycidyl ether; Polyglycidyl ether compounds of polyether polyols obtained by adding alkylene oxides to polyhydric alcohols such as ethylene glycol, propylene glycol, and glycerin; 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-1-methylcyclohexyl-3,4-epoxy-1-methylhexanecarboxylate, 6-methyl-3,4-epoxycyclohexylmethyl-6-methyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-3-methylcyclohexylmethyl-3,4-epoxy-3-methylcyclohexanecarboxylate, 3,4-epoxy-5-methylcyclohexylmethyl-3,4-epoxy-5-methylcyclohexanecarboxylate, 2-(3,4-epoxycyclohexyl) compounds having two or more 3,4-epoxycyclohexyl groups in the molecule, such as bis(3,4-epoxycyclohexylmethyl)-5,5-spiro-3,4-epoxy)cyclohexane-metadioxane, bis(3,4-epoxycyclohexylmethyl)adipate, 3,4-epoxy-6-methylcyclohexylcarboxylate, methylenebis(3,4-epoxycyclohexane), ethylenebis(3,4-epoxycyclohexanecarboxylate), dioctyl epoxyhexahydrophthalate, 1-epoxyethyl-3,4-epoxycyclohexane, butanetetracarboxylic acid tetra(3,4-epoxycyclohexylmethyl)-modified ε-caprolactone; Examples include 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol.

[0262] Commercially available epoxy compounds include, for example, Epicoat 807, 815, 825, 827, 828, 190P, and 191P manufactured by Yuka Shell Epoxy Co., Ltd., and TECHMORE manufactured by Mitsui Chemicals, Inc. VG3101L, EPPN-201, 501H, 502H, EOCN-102S, 103S, 104S, 1020 manufactured by Nippon Kayaku Co., Ltd., Epicoat 1004, 1256, JER1032H60, 157S65, 157S70, 152, 154 manufactured by Japan Epoxy Resins Co., Ltd., Celloxide 2021, EHPE-3150, Epolead GT401 manufactured by Daicel Chemical Industries, Ltd., Denacol EX-211, 212, 252, 313, 314, 321, 411, 421, 512, 521, 611, 612, 614, 614B, 622, 711, 721 manufactured by Nagase ChemteX Corporation, TEPIC-L, H, S manufactured by Nissan Chemical Industries, Ltd., and EPICLON manufactured by DIC Corporation Examples include 830, 840, 850, 860, 1050, 3050, 4050, N-660, N-670, N-740, N-770, N865, HP-7200, HP-4700, HP-4770, HP-5000, HP-6000, and HP-9500.

[0263] The epoxy compound is preferably a compound having 2 to 50 epoxy groups in the molecule.

[0264] The epoxy equivalent of the epoxy compound is preferably 50 to 400 g / eq, more preferably 100 to 200 g / eq. The epoxy equivalent is defined as the mass of an epoxy compound containing one equivalent of epoxy groups.

[0265] (Oxetane compounds) The oxetane compound is not particularly limited, and known oxetane compounds can be used. Examples of the oxetane compound include (3-ethyloxetan-3-yl)methyl acrylate, (3-ethyloxetan-3-yl)methyl methacrylate, 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-(phenoxymethyl)oxetane, 3-ethyl-3-(2-methacryloxymethyl)oxetane, 3-ethyl-3-{ [3-(triethoxysilyl)propoxy]methyl}oxetane, 4,4'-bis[(3-ethyl-3-oxetanyl)methoxymethyl]biphenyl), 1,4-bis[(3-ethyl-3-oxetanyl)methoxymethyl]benzene, 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene, di[1-ethyl(3-oxetanyl)]methyl ether, di[1-ethyl(3-oxetanyl)]methyl ether, bis(3-ethyl-3-oxetanylmethyl) ether, 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-(2-phenoxymethyl)oxetane, 3,7-bis(3-oxetanyl)-5-oxa-nonane, 1,2-bis[(3-ethyl-3-oxetanylmethoxy)methyl]ethane, 1,3-bis[(3-ethyl-3-oxetanylmethoxy)methyl]propane, ethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, dicyclopentenyl bis(3-ethyl-3-oxetanylmethyl)ether, triethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, tetraethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, 1,4-bis(3-ethyl-3-oxetanylmethoxy)butane, 1,6-bis(3-ethyl-3-oxetanylmethoxy)hexane, polyethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether, ethylene oxide (EO) modified bisphenol A bis(3-ethyl-3-oxetanylmethyl) ether, propylene oxide (PO) modified bisphenol A bis(3-ethyl-3-oxetanylmethyl) ether, EO modified hydrogenated bisphenol A bis(3-ethyl-3-oxetanylmethyl) ether, PO modified hydrogenated bisphenol A bis(3-ethyl-3-oxetanylmethyl) ether, EO modified bisphenol F(3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tris(3-ethyl-3-oxetanylmethyl) dipentaerythritol hexa(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol pentakis(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol hexa(3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol pentakis(3-ethyl-3-oxetanylmethyl) ether, ditrimethylolpropane tetrakis(3-ethyl-3-oxetanylmethyl) ether, etc.

[0266] Examples of commercially available oxetane compounds include OXE-10 and 30 manufactured by Osaka Organic Chemical Industry Co., Ltd., OXT-101, 121, 212 and 221 manufactured by Toagosei Co., Ltd., and OXBP and OXTP manufactured by Ube Industries, Ltd.

[0267] (melamine compounds) The melamine compound is a compound having a melamine ring structure, and is preferably a compound having a methylol group.

[0268] Examples of commercially available melamine compounds include Nikalac MW-30HM, MW-390, MW-100LM, MX-750LM, MW-30M, MW-30, MW-22, MS-21, MS-11, MW-24X, MS-001, MX-002, MX-730, MX-750, MX-708, MX-706, MX-042, MX-45, MX-500, MX-520, MX-43, MX-417, and MX-410 manufactured by Sanwa Chemical Co., Ltd., and Cymel 232, 235, 236, 238, 285, 300, 301, 303, 350, and 370 manufactured by Nippon Cytec Industries Co., Ltd.

[0269] (Blocked isocyanate compounds) A blocked isocyanate compound can be synthesized by reacting a compound having two or more isocyanate groups in the molecule with a blocking agent.

[0270] Examples of compounds having two or more isocyanate groups in the molecule include compounds having an aliphatic structure such as butane-1,4-diisocyanate, hexamethylene diisocyanate, isopropylene diisocyanate, methylene diisocyanate, and 2,2,4-trimethylhexamethylene diisocyanate; Compounds having an alicyclic structure, such as cyclohexane-1,4-diisocyanate, isophorone diisocyanate, dimethylcyclohexyl diisocyanate, methylcyclohexyl diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 1,3-bis(isocyanatemethyl)cyclohexane, methylcyclohexane diisocyanate, norbornane diisocyanate, and bis(isocyanatemethyl)cyclohexane; Examples of the aromatic isocyanate include 1,5-naphthylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-dibenzyl isocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, xylylene diisocyanate, m-tetramethylxylylene diisocyanate, 4,4-diphenylmethane diisocyanate, tolylene diisocyanate, bischloromethyldiphenylmethane diisocyanate, 2,6-diisocyanate-benzyl chloride, and compounds having an aromatic structure such as bis(isocyanatomethyl)benzene. Further, biuret, isocyanurate, adduct, allophanate and the like of these compounds may also be used.

[0271] Examples of the blocking agent include oxime compounds such as formaldoxime, acetaldoxime, acetoxime, methyl ethyl ketoxime, methyl isobutyl ketoxime, cyclohexanone oxime, and benzophenone oxime; Lactam compounds such as ε-caprolactam, δ-valerolactam, γ-butyrolactam, and β-propiolactam; Phenolic compounds such as phenol, cresol, 2,6-xylenol, 3,5-xylenol, ethylphenol, p-tert-butylphenol, nonylphenol, methyl 2-hydroxybenzoate, methyl 4-hydroxybenzoate, p-naphthol, and p-nitrophenol; alcohol compounds such as methanol, ethanol, propanol, butanol, ethylene glycol, methyl cellosolve, butyl cellosolve, methyl carbitol, benzyl alcohol, phenyl cellosolve, and furfuryl alcohol; Amine compounds such as diphenylamine, phenylnaphthylamine, aniline, and carbazole; Active methylene compounds such as dimethyl malonate, diethyl malonate, methyl acetoacetate, ethyl acetoacetate, and acetylacetone; pyrazole compounds such as pyrazole, methylpyrazole, and 3,5-dimethylpyrazole; Mercaptan compounds such as butyl mercaptan, thiophenol, and tert-dodecyl mercaptan; imidazole compounds such as imidazole, 2-methylimidazole, 2-ethylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, and 1-benzyl-2-phenylimidazole; Imide compounds such as succinimide, maleimide, maleimide, and phthalimide; urea compounds such as urea, thiourea, and ethylene urea; Imine compounds such as ethyleneimine and polyethyleneimine; Examples of the blocking agent include bisulfite compounds such as sodium bisulfite and potassium bisulfite. Among these, the blocking agent is preferably at least one selected from the group consisting of oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, pyrazole compounds, mercaptan compounds, imidazole compounds, and imide compounds.

[0272] Commercially available blocked isocyanate compounds include, for example, Duranate SBN-70D, SBB-70P, SBF-70E, TPA-B80E, 17B-60P, MF-B60B, E402-B80B, and MF-K60B manufactured by Asahi Kasei Corporation; Takenate B-882, B-830, B-815N, and B-846 manufactured by Mitsui Chemicals, Inc.; Coronate BI-301, 2507, and 2554 manufactured by Tosoh Corporation; and BI7960, BI7961, BI7982, BI7991, BI7992, BI7950, BI7951, and BI7990 manufactured by Baxenden.

[0273] The thermally crosslinkable compound (H) can be used alone or in combination of two or more kinds.

[0274] The content of the thermally crosslinkable compound (H) is preferably from 0.5 to 40 mass %, more preferably from 1 to 30 mass %, based on 100 mass % of the nonvolatile content of the resin composition.

[0275] [Thiol-based chain transfer agents (I)] The resin composition of the present invention may contain a thiol-based chain transfer agent (I).

[0276] The thiol chain transfer agent (I) is not particularly limited, and known thiol chain transfer agents can be used. Examples of the thiol chain transfer agent (I) include monofunctional thiol compounds such as thiophenol, 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercapto-5-methoxybenzothiazole, 2-mercapto-5-benzimidazole, butanethiol, octanethiol, 1-dodecanethiol, methyl 3-mercaptopropionate, ethyl 3-mercaptopropionate, octyl 3-mercaptopropionate, and 2-ethylhexyl 3-mercaptopropionate; Monofunctional thiol compounds having a hydroxyl group or an acidic group, such as 2-mercaptoethanol, 1-thioglycerol, thioglycolic acid, 2-mercaptobenzoic acid, 3-mercaptobenzoic acid, 4-mercaptonicotinic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 4-mercaptobutanoic acid, octyl thioglycolate, mercaptosuccinic acid, 11-mercaptoundecanoic acid, and 2-mercaptoethanesulfonic acid; Examples of polyfunctional thiol compounds include hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakis thioglycolate, pentaerythritol tetrakis(3-mercaptopropionate), trimercaptopropionic acid tris(2-hydroxyethyl)isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, and 2-(N,N-dibutylamino)-4,6-dimercapto-s-triazine.

[0277] The thiol chain transfer agent (I) can be used alone or in combination of two or more kinds.

[0278] The content of the thiol chain transfer agent (I) is preferably 0.5 to 10% by mass based on 100% by mass of the nonvolatile content of the resin composition.

[0279] [Silane coupling agent (J)] The resin composition of the present invention may contain a silane coupling agent (J).

[0280] The silane coupling agent (J) is a compound having a hydrolyzable group. The hydrolyzable group is a group that is directly bonded to a silicon atom and generates a siloxane bond by at least one of a hydrolysis reaction and a condensation reaction. Examples of the hydrolyzable group include a halogen atom, an alkoxy group, and an acyloxy group. Among these, an alkoxy group is preferred. From the viewpoint of reactivity, a methoxy group or an ethoxy group is preferred as the alkoxy group. The silane coupling agent (J) may also have a functional group other than the hydrolyzable group, such as an epoxy group, an amino group, a vinyl group, a (meth)acryloyl group, an isocyanate group, an isocyanurate group, a mercapto group, an oxetanyl group, a styryl group, or a ureido group.

[0281] Commercially available silane coupling agents (J) include, for example, KBM-302, KBM-402, KBM-403, KBE-402, KBE-403, KBM-4803, KBM-602, KBM-603, KBM-903, KBE-9103P, KBM-573, KBM-6803, KBM-1003, KBE-1003, and KBM-5 manufactured by Shin-Etsu Chemical Co., Ltd. 02, KBM-503, KBE-502, KBE-503, KBM-5803, X-12-1048, X-12-1050, KBE-9007N, KBM-9659, KBM-802, KBM-803, KBM-1043, KBM-3086, KBE-585A, X-12-1048, X-12-50, X-12-5263HP, etc.

[0282] The silane coupling agent (J) may also be a polymer type, such as a polysiloxane type or an organic polymer type.

[0283] The polysiloxane type is a compound in which the hydrolyzable group and other functional groups are bonded to a polymer having a polysiloxane skeleton in the main chain. Commercially available polysiloxane type products include KR-513, KR-516, KR-517, X-41-1805, and X-41-1810 manufactured by Shin-Etsu Chemical Co., Ltd.

[0284] The organic polymer type is a silane coupling agent (J) in which the hydrolyzable group and other functional groups are bonded to an organic polymer whose main chain has an organic structure. Commercially available organic polymer type products include X-12-9815, X-12-9845, X-12-1154, X-12-972F, and X-12-1159L manufactured by Shin-Etsu Chemical Co., Ltd.

[0285] The silane coupling agent (J) can be used alone or in combination of two or more kinds.

[0286] The content of the silane coupling agent (J) is preferably 0.1 to 10 mass % in 100 mass % of the nonvolatile content of the resin composition.

[0287] [Polymerization inhibitor (K)] The resin composition of the present invention may contain a polymerization inhibitor (K).

[0288] The polymerization inhibitor (K) is not particularly limited, and known polymerization inhibitors can be used. Examples of the polymerization inhibitor (K) include alkyl catechol compounds such as catechol, resorcinol, 1,4-hydroquinone, 2-methyl catechol, 3-methyl catechol, 4-methyl catechol, 2-ethyl catechol, 3-ethyl catechol, 4-ethyl catechol, 2-propyl catechol, 3-propyl catechol, 4-propyl catechol, 2-n-butyl catechol, 3-n-butyl catechol, 4-n-butyl catechol, 2-tert-butyl catechol, 3-tert-butyl catechol, 4-tert-butyl catechol, and 3,5-di-tert-butyl catechol; 2-methyl resorcinol, 4-methyl resorcinol, 2-ethyl resorcinol, 4-ethyl resorcinol, 2-propyl resorcinol, 4-propyl resorcinol, and 2-n alkylresorcinol compounds such as 1-n-butylresorcinol, 4-n-butylresorcinol, 2-tert-butylresorcinol, and 4-tert-butylresorcinol; alkylhydroquinone compounds such as methylhydroquinone, ethylhydroquinone, propylhydroquinone, tert-butylhydroquinone, and 2,5-di-tert-butylhydroquinone; phosphine compounds such as tributylphosphine, trioctylphosphine, tricyclohexylphosphine, triphenylphosphine, and tribenzylphosphine; phosphine oxide compounds such as trioctylphosphine oxide and triphenylphosphine oxide; phosphite compounds such as triphenylphosphite and trisnonylphenylphosphite; pyrogallol; and phloroglucinol.

[0289] The polymerization inhibitor (K) can be used alone or in combination of two or more kinds.

[0290] The content of the polymerization inhibitor (K) is preferably 0.01 to 0.5% by mass in 100% by mass of the nonvolatile content of the resin composition.

[0291] [Ultraviolet absorber (L)] The resin composition of the present invention may contain an ultraviolet absorber (L).

[0292] The ultraviolet absorber (L) is not particularly limited, and known ultraviolet absorbers can be used. Examples of the ultraviolet absorber (L) include benzotriazole-based organic compounds, triazine-based organic compounds, benzophenone-based organic compounds, salicylic acid ester-based organic compounds, cyanoacrylate-based organic compounds, and salicylate-based organic compounds.

[0293] Commercially available benzotriazole compounds include, for example, TINUVIN P, PS, 234, 326, 329, 384-2, 900, 928, 99-2, and 1130 manufactured by BASF Japan Ltd., ADK STAB LA-29, LA-31RG, LA-32, and LA-36 manufactured by ADEKA Corporation, KEMISORB71, 73, 74, 79, and 279 manufactured by Chemipro Chemical Co., Ltd., and RUVA-93 manufactured by Otsuka Chemical Co., Ltd.

[0294] Commercially available triazine compounds include, for example, KEMISORB102 manufactured by Chemipro Chemicals, TINUVIN 400, 405, 460, 477, 479, and 1577ED manufactured by BASF Japan, ADK STAB LA-46 and LA-F70 manufactured by ADEKA, and CYASORB UV-1164 manufactured by Sun Chemical.

[0295] Commercially available benzophenone compounds include, for example, KEMISORB10, 11, 11S, 12, and 111 manufactured by Chemipro Chemicals, SEESORB 101 and 107 manufactured by Shipro Chemicals, Adekastab 1413 manufactured by ADEKA, and UV-12 manufactured by Sun Chemical.

[0296] Examples of salicylate compounds include phenyl salicylate, p-octylphenyl salicylate, and p-tert-butylphenyl salicylate.

[0297] The ultraviolet absorbers (L) can be used alone or in combination of two or more kinds.

[0298] The content of the ultraviolet absorber (L) is preferably 0.1 to 5.0% by mass relative to 100% by mass of the nonvolatile content of the resin composition.

[0299] [Antioxidant (M)] The resin composition of the present invention may contain an antioxidant (M).

[0300] The antioxidant (M) is not particularly limited, and known antioxidants can be used. Examples of the antioxidant (M) include hindered phenol-based, hindered amine-based, phosphorus-based, sulfur-based, and hydroxylamine-based compounds. Among these, hindered phenol-based antioxidants, hindered amine-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants are preferred.

[0301] Examples of commercially available hindered phenol antioxidants include ADK STAB AO-20, AO-30, AO-40, AO-50, AO-60, AO-80, and AO-330 manufactured by ADEKA Corporation; KEMINOX 101, 179, 76, and 9425 manufactured by Chemipro Corporation; IRGANOX 1010, 1035, 1076, 1098, 1135, 1330, 1726, 1425WL, 1520L, 245, 259, 3114, 5057, and 565 manufactured by BASF Japan Ltd.; and Cyanox CY-1790 and CY-2777 manufactured by Sun Chemical Company.

[0302] Examples of commercially available hindered amine antioxidants include ADK STAB LA-52, LA-57, LA-63P, LA-68, LA-72, LA-77Y, LA-77G, LA-81, LA-82, LA-87, LA-402F, and LA-502XP manufactured by ADEKA CORPORATION; KAMISTAB 29, 62, 77, and 94 manufactured by Chemipro Chemicals; Tinuvin 111FDL, 123, 144, 249, 292, and 5100 manufactured by BASF Japan Ltd.; and Cyasorb UV-3346, UV-3529, and UV-3853 manufactured by Sun Chemical Company.

[0303] Commercially available phosphorus-based antioxidants include, for example, Adeka STAB PEP-36, PEP-8, HP-10, 2112, 1178, 1500, C, 135A, 3010, and TPP manufactured by ADEKA CORPORATION, IRGAFOS168 manufactured by BASF Japan Ltd., and HostanoxP-EPQ manufactured by Clariant Chemicals.

[0304] Examples of commercially available sulfur-based antioxidants include Adekastab AO-412S and AO-503 manufactured by ADEKA Corporation, and KEMINOXPLS manufactured by Chemipro Chemicals.

[0305] The antioxidant (M) can be used alone or in combination of two or more kinds.

[0306] The content of the antioxidant (M) is preferably 0.1 to 5.0% by mass relative to 100% by mass of the nonvolatile content of the resin composition.

[0307] [Leveling Agent (N)] The resin composition of the present invention may contain a leveling agent (N).

[0308] The leveling agent (N) is not particularly limited, and any known leveling agent can be used. Examples of the leveling agent (N) include silicone-based leveling agents, fluorine-based leveling agents, acrylic-based leveling agents, and acetylene diol-based leveling agents.

[0309] Commercially available silicone leveling agents include, for example, BYK-300, 306, 310, 313, 315N, 320, 322, 323, 330, 331, 333, 342, 345, 346, 347, 348, 349, 370, 377, 378, 3455, UV3510, and 3570 manufactured by BYK-Chemie Co., Ltd.; FZ-7002, 2110, 2122, 2123, 2191, and 5609 manufactured by Toray Dow Corning Co., Ltd.; Examples of such products include X-22-4952, X-22-4272, X-22-6266, KF-351A, KF-354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-4515, KF-6004, and KP-341 manufactured by Gakushu Kogyosha; TegoGlide 432, 440, and 450, TegoWet 250, 260, 265, 270, and 280 manufactured by Evonik; and MEGAFACE EFS-131, EFS-321, EFS-521, and EFS-801 manufactured by DIC Corporation.

[0310] Commercially available fluorine-based leveling agents include Surflon S-242, 243, 420, 611, 651, and 386 manufactured by AGC Seimi Chemical Co., Ltd.; Megafac F-253, 477, 551, 552, 554, 555, 556, 558, 559, 560, 561, 570, 575, 576, R-01, R-40, R-40-LM, R-41, and RS-72-K manufactured by DIC Corporation; FC-4430 and 4432 manufactured by Sumitomo 3M Limited; EF-PP31N09, EF-PP33G1, and EF-PP32C1 manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.; and Ftergent 602A manufactured by Neos Corporation.

[0311] Examples of commercially available acrylic leveling agents include BYK-350, 352, 354, 355, 358, 380, 381, 392, and 394 manufactured by BYK-Chemie, and Polyflow 57, 77, and 95 manufactured by Kyoeisha Chemical.

[0312] Commercially available acetylene diol leveling agents include, for example, Surfynol 420, 440, 465, 485, SE, DF110D, DE85, and Olfine E1004 and 1010 manufactured by Nissin Chemical Industry Co., Ltd.

[0313] The leveling agent (N) can be used alone or in combination of two or more kinds.

[0314] The content of the leveling agent (N) is preferably from 0.001 to 2.0 mass %, more preferably from 0.005 to 1.0 mass %, based on 100 mass % of the nonvolatile content of the resin composition.

[0315] [Storage stabilizer (O)] The resin composition of the present invention may contain a storage stabilizer (O).

[0316] The storage stabilizer (O) is not particularly limited, and known storage stabilizers can be used. Examples of the storage stabilizer (O) include quaternary ammonium chlorides such as benzyl trimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid and their methyl ethers, organic phosphines such as tert-butylpyrocatechol, tetraethylphosphine and tetraphenylphosphine, and phosphites.

[0317] The content of the storage stabilizer (O) is preferably 0.05 to 5.0% by mass relative to 100% by mass of the nonvolatile content of the resin composition.

[0318] [Other ingredients (P)] The resin composition of the present invention can contain components other than those described above (hereinafter also referred to as other components (P)). Examples of other components (P) include colorants, near-infrared absorbers, fluorescent compounds other than the organic fluorescent particles (A) (e.g., organic fluorescent dyes, inorganic fluorescent pigments, quantum dots, quantum dots, etc.), dye derivatives, curing catalysts, acid generators, salt generators, etc. The content of other components (P) can be appropriately set within a range that does not impair the effects of the present invention.

[0319] [Specific metal element content] The resin composition of the present invention preferably contains Li, Na, K, Mg, Ca, Fe, and Cr (hereinafter also referred to as specific metal elements) in a total content of 500 mass ppm or less.

[0320] A resin composition in which the total amount of the specific metal elements is within the above range has excellent stability even after storage over time. The content of the specific metal elements can be measured by inductively coupled plasma atomic emission spectroscopy (ICP).

[0321] [Method of producing resin composition] The resin composition of the present invention can be prepared by mixing the above-mentioned components. When preparing the resin composition, the components may be mixed together or may be dissolved or dispersed in the solvent (D) and then mixed successively. For example, organic fluorescent particles (A) and scattering particles (B) are each added to a resin (C1) having a basic group and a solvent (D) and a dispersion treatment is carried out to produce a dispersion. Then, the dispersions are mixed together to produce the dispersion. The timing of blending each material is optional. The dispersion process can also be carried out multiple times.

[0322] Examples of dispersing machines for carrying out the dispersion treatment include a two-roll mill, a three-roll mill, a ball mill, a horizontal sand mill, a vertical sand mill, an annular bead mill, and an attritor.

[0323] The resin composition of the present invention is preferably used for forming a wavelength conversion layer. The resin composition of the present invention is preferably used for forming a pattern by photolithography, although the present invention is not limited thereto.

[0324] <Wavelength conversion layer> The wavelength converting layer of the present invention is formed using the resin composition of the present invention. The wavelength converting layer is preferably a patterned wavelength converting layer, but can also be used as a flat layer without patterning.

[0325] [Method of manufacturing wavelength conversion layer] The method for producing the wavelength conversion layer is not particularly limited, and any known method can be used. For example, the wavelength conversion layer can be produced through the following steps.

[0326] [Coating process] The resin composition is applied onto a substrate. Examples of the substrate include those made of glass, resin, silicone, and the like. The glass may be colorless and transparent, or colored glass such as blue glass may be used depending on the application. Examples of the resin include polyester-based resins such as polyester terephthalate, polyolefin-based resins such as polypropylene and polyethylene, polycarbonate resins, and epoxy resins. The thickness of the substrate is preferably 0.01 to 10 mm. A light source may be formed on the substrate, and an undercoat layer may be provided on the substrate, if necessary, to improve adhesion with an upper layer, prevent diffusion of substances, and flatten the surface.

[0327] Any known coating method can be used, including, for example, a dropping method, a slit coating method, a spray method, a roll coating method, a spin coating method, a cast coating method, an inkjet method, flexographic printing, screen printing, gravure printing, and offset printing.

[0328] The thickness of the wavelength conversion layer is preferably from 1 to 50 μm, more preferably from 3 to 20 μm.

[0329] [Drying process] The resin composition applied to the substrate can be dried by any known method without any particular limitation, such as reduced pressure drying using a vacuum drying device, heat drying using a hot plate, an IR oven, a convection oven, or the like, or a combination of these methods.

[0330] The drying temperature and time can be adjusted as appropriate. The drying temperature is preferably about 50 to 130°C, and the drying time is preferably about 5 seconds to 5 minutes.

[0331] Next, a pattern is formed. Examples of a method for forming a pattern include photolithography and dry etching. Among these, photolithography is preferred. When used as a flat layer, the step of forming a pattern is not necessary, and the layer is simply dried or exposed after coating.

[0332] The method of forming a pattern by photolithography will be described in detail below. In the photolithography method, the resin composition of the present invention is coated on a substrate, dried, and then exposed to light in a pattern through a mask (exposure step), and the unexposed portions are removed by alkaline development (development step), after which the pattern is heat-treated (post-bake step).

[0333] [Exposure process] In the exposure step, for example, an exposure device such as a stepper is used to expose a specific pattern through a mask. This allows the exposed portion to be cured. Examples of active energy rays used for exposure include ultraviolet rays such as g-rays (wavelength 436 nm), h-rays (wavelength 405 nm), and i-rays (wavelength 365 nm). Light with a wavelength of 300 nm or less can also be used. Examples of light with a wavelength of 300 nm or less include KrF rays (wavelength 248 nm) and ArF rays (wavelength 193 nm). Furthermore, the exposure may be performed by continuous irradiation with light, or by repeating irradiation and pauses of light in short cycles (for example, milliseconds or less) (pulse exposure). In addition, a plurality of active energy rays may be used in combination or may be exposed in several separate steps.

[0334] [Development process] Next, by treating with an alkaline developer, the unexposed portions are dissolved in the alkaline developer, leaving only the hardened portions to obtain a pattern. Examples of alkaline developers include alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, and 1,8-diazabicyclo-[5.4.0]-7-undecene. The concentration of the alkaline developer is preferably 0.001 to 10% by mass, more preferably 0.01 to 1% by mass. The pH of the alkaline developer is preferably 11 to 13, more preferably 11.5 to 12.5. When used at an appropriate pH, pattern roughening and peeling are suppressed, and the remaining film rate after development is improved. Examples of the developing method include a dipping method, a spraying method, a puddling method, etc. The developing temperature is preferably 15 to 40° C. After the alkaline development, it is preferable to wash with pure water and then dry.

[0335] [Post-baking process] After development, a heat treatment (post-baking) is performed. Post-baking improves the durability of the wavelength conversion layer. The temperature is preferably 80 to 260°C. The time is preferably about 2 minutes to 2 hours. When a material with low heat resistance is used for the substrate, when a substrate having an organic electroluminescence element is used, or from an environmental viewpoint, the temperature is preferably 180°C or less.

[0336] <Laminate> The laminate of the present invention has the wavelength conversion layer and a color filter layer. The color filter layer is not particularly limited, but preferably has a black matrix and at least one pixel selected from the group consisting of red pixels, green pixels, blue pixels, and yellow pixels. These pixels are known pixels.

[0337] <Display device> The display device of the present invention includes the laminate. The form of the display device is not particularly limited as long as it functions as a display device, and examples thereof include a liquid crystal display and an organic EL display.

[0338] For example, they are described in "Next Generation Liquid Crystal Display Technology" (by Uchida Tatsuo, published by Kogyo Chosakai Co., Ltd. in 1994), "Electronic Display Devices" (by Sasaki Akio, published by Kogyo Chosakai Co., Ltd. in 1990), and "Display Devices" (by Ibuki Nobuaki, published by Sangyo Tosho Co., Ltd. in 1989). [Example]

[0339] The present invention will be described in more detail below with reference to examples. However, the present invention is not limited to these examples. Note that "parts" means "parts by mass" and "%" means "% by mass."

[0340] Before describing the examples, each measurement method will be explained.

[0341] The weight average molecular weight (Mw) of the resin, the number average molecular weight (Mn) of the resin, the acid value (mgKOH / g) of the resin, the amine value (mgKOH / g) of the resin, and the extinction coefficient (L / mol cm) of the polymerization initiator were measured as follows.

[0342] (Molecular Weight of Resin) Number-average molecular weight (Mn) and weight-average molecular weight (Mw) were measured using gel permeation chromatography (GPC) equipped with an RI detector. The instrument used was an HLC-8220GPC (manufactured by Tosoh Corporation). Two separation columns were connected in series, with both columns packed with "TSK-GEL SUPER HZM-N" in series. Measurements were performed at an oven temperature of 40°C, a tetrahydrofuran (THF) solution as the eluent, and a flow rate of 0.35 ml / min. The sample was dissolved in a solvent consisting of 1% by mass of the above eluent, and 20 microliters was injected. The molecular weight is expressed in terms of polystyrene.

[0343] (resin acid value) 80 ml of acetone and 10 ml of water were added to 0.5 to 1 g of sample solution, and the mixture was stirred to dissolve uniformly. The solution was titrated using an automatic titrator ("COM-555" manufactured by Hiranuma Sangyo Co., Ltd.) with a 0.1 mol / L KOH aqueous solution as the titrant, and the acid value (mgKOH / g) was measured. The acid value per unit of nonvolatile content was calculated from the acid value of the solution and the concentration of nonvolatile content in the solution.

[0344] (Amine value of resin) The amine value of a resin is the total amine value (mgKOH / g) measured in accordance with the method of ASTM D 2074 and converted into nonvolatile content. In this specification, the amine value refers to the amine value when quaternary ammonium salt groups are also considered as amino groups.

[0345] (Absorption coefficient of polymerization initiator) A 0.1% by mass measurement solution was prepared by dissolving 0.001 g of polymerization initiator in 0.01 L of propylene glycol monomethyl ether acetate. The resulting 0.1% by mass measurement solution was then diluted with propylene glycol monomethyl ether acetate to prepare 0.01% and 0.001% by mass measurement solutions. The absorbance of each concentration of the measurement solution was measured at 365 nm using a spectrophotometer (Hitachi High-Technologies Corporation, U-3010). The extinction coefficient (L / mol cm) was calculated from the slope of the plot, with the horizontal axis representing molar concentration and the vertical axis representing absorbance.

[0346] <Production of Resin (C)> (Solution of resin (C1-1) having basic groups) A reactor equipped with a gas inlet tube, condenser, stirring blade, and thermometer was charged with 40.0 parts of methyl methacrylate, 10.0 parts of n-butyl methacrylate, and 13.2 parts of tetramethylethylenediamine as a catalyst. The mixture was stirred at 50 °C for 1 hour while flowing nitrogen, and the atmosphere inside the reactor was replaced with nitrogen. Next, 9.3 parts of ethyl bromoisobutyrate as a polymerization initiator, 5.6 parts of cuprous chloride as a catalyst, and 100 parts of propylene glycol monomethyl ether acetate (PGMAc) were charged. The temperature was raised to 110 °C under a nitrogen stream to initiate polymerization of the first block (B block). After 4 hours of polymerization, the polymerization solution was sampled and the nonvolatile content was measured. Based on the nonvolatile content, it was confirmed that the polymerization conversion was 98% or higher. Next, 50 parts of PGMAc, 40.0 parts of dimethylaminoethyl methacrylate as the second block (A block) monomer, and 10.0 parts of methacryloyloxyethyl benzyldimethylammonium chloride were added to the reactor, and the reaction was continued with stirring while maintaining the temperature at 110°C under a nitrogen atmosphere. Two hours after addition, a sample of the polymerization solution was taken and the nonvolatile content was measured. Based on the nonvolatile content, the polymerization conversion of the second block (A block) was confirmed to be 98% or higher. After cooling, PGMAc was added to achieve a nonvolatile content of 30% by mass, thereby preparing a resin (C1-1) solution having a block structure with basic groups and monomer units represented by general formula (1) and general formula (2). The amine value was 169.8 mg KOH / g.

[0347] (Resin (C1-2) solution having basic groups) A reactor equipped with a gas inlet tube, condenser, stirring blade, and thermometer was charged with 250 parts of tetrahydrofuran and 5.8 parts of dimethylketene methyltrimethylsilyl acetal as a polymerization initiator, and the reactor was purged with nitrogen. 0.5 parts of a 1 mol / L acetonitrile solution of tetrabutylammonium m-chlorobenzoate as a catalyst was injected using a syringe, and 19.7 parts of 2-hydroxyethyl methacrylate, 7.5 parts of 2-ethylhexyl methacrylate, 12.9 parts of n-butyl methacrylate, 10.7 parts of benzyl methacrylate, and 30.9 parts of methyl methacrylate were added dropwise over 60 minutes using a dropping funnel to conduct the reaction. During the reaction, the temperature was maintained below 40°C by cooling the reaction vessel in an ice bath. After 1 hour, 18.3 parts of dimethylaminopropyl methacrylamide were added dropwise over 20 minutes. After 1 hour of reaction, 1.0 part of methanol was added to terminate the reaction. The resulting copolymer was reprecipitated in hexane, filtered, and vacuum dried for purification. Next, 15.0 parts of the obtained copolymer were dissolved in 35 parts of PGMAc in a 100 mL round-bottom flask, and 1.1 parts of phenylphosphinic acid (0.5 molar equivalents relative to dimethylaminopropylmethacrylamide), a salt-forming component, was added, followed by stirring for 20 hours at a reaction temperature of 30° C. PGMAc was added so that the nonvolatile content was 30%, to prepare a resin (C1-2) solution having a basic group with a block structure containing monomer units represented by general formula (1) and general formula (2).

[0348] (Resin (C1-3) solution having basic groups) A reactor equipped with a gas inlet tube, condenser, stirring blade, and thermometer was charged with 30.0 parts of methyl methacrylate, 30.0 parts of n-butyl methacrylate, 20.0 parts of hydroxyethyl methacrylate, and 13.2 parts of tetramethylethylenediamine. The mixture was stirred at 50 °C for 1 hour while flowing nitrogen, and the atmosphere inside the reactor was purged with nitrogen. Next, 9.3 parts of ethyl bromoisobutyrate, 5.6 parts of cuprous chloride, and 133 parts of PGMAC were charged. The mixture was heated to 110 °C under a nitrogen stream to initiate polymerization of the first block (B block). After 4 hours of polymerization, the polymerization solution was sampled and the nonvolatile content was measured. Based on the nonvolatile content, a polymerization conversion of 98% or more was confirmed. Next, 61 parts of PGMAc and 20.0 parts of 1,2,2,6,6-pentamethylpiperidyl methacrylate (Hitachi Chemical Co., Ltd., Fancryl FA-711MM) as the second block (A block) monomer were added to the reactor, and the reaction was continued with stirring at 110°C under a nitrogen atmosphere. Two hours after the addition of 1,2,2,6,6-pentamethylpiperidyl methacrylate, a sample of the polymerization solution was taken and the nonvolatile content was measured. Based on the nonvolatile content, a polymerization conversion rate of the second block (A block) of 98% or higher was confirmed. The reaction solution was then cooled to room temperature to terminate the polymerization. PGMAc was added to adjust the nonvolatile content to 30%, yielding a solution of a resin (C1-3) with a block structure containing a monomer unit represented by general formula (3) and basic groups. The amine value was 57 mg KOH / g.

[0349] (Resin (C1-4) solution having basic groups) According to Synthesis Example 5 of JP 2021-167893 A, a resin (C1-4) having a basic group with a graft structure having a monomer unit represented by general formula (2) was synthesized, and PGMAc was added so that the nonvolatile content was 30% by mass. The amine value was 105 mg KOH / g and the weight-average molecular weight was 10,500.

[0350] (Resin (C1-5) solution having basic groups) A resin (C1-5) having a basic group and a block structure containing monomer units represented by general formula (2) was synthesized according to Example A3 of WO 2022 / 172607. PGMAc was added to the resin to achieve a nonvolatile content of 30% by mass. The amine value was 67 mg KOH / g and the weight-average molecular weight was 5,600.

[0351] (Resin (C1-6) solution having basic groups) A resin (C1-6) having a basic group and a block structure containing monomer units represented by general formula (2) was synthesized according to Synthesis Example c3 of WO 2023 / 119898. PGMAc was added to the resin to achieve a nonvolatile content of 30% by mass. The amine value was 70 mgKOH / g and the weight-average molecular weight was 5,500.

[0352] (Resin (C1-7) solution having basic groups) A resin (C1-7) having a basic group and a block structure containing monomer units represented by general formula (2) was synthesized according to Example 15 of WO 2018 / 159458. PGMAc was added to the resin to achieve a nonvolatile content of 30% by mass. The resin had an amine value of 95 mg KOH / g and a weight-average molecular weight of 7,730.

[0353] (Other resin (C2-1) solution) A reaction vessel equipped with a thermometer, reflux condenser, nitrogen gas inlet, and stirrer was charged with 10 parts methacrylic acid, 90 parts methyl methacrylate, 50 parts ethyl acrylate, 50 parts tert-butyl acrylate, and 50 parts PGMAc, and the atmosphere was purged with nitrogen gas. The reaction vessel was heated to 50°C, and 12 parts 3-mercapto-1,2-propanediol was added while stirring. The temperature was raised to 90°C, and a solution of 2,2'-azobisisobutyronitrile (polymerization initiator) in PGMAc was added while the reaction was continued for 7 hours. Measurement of the nonvolatile content confirmed that more than 95% had reacted. Next, 19 parts pyromellitic dianhydride, 50 parts PGMAc, and 0.4 parts 1,8-diazabicyclo[5.4.0]-7-undecene (catalyst) were added, and the reaction was continued for 7 hours at 100°C. Acid value measurement confirmed that more than 98% of the acid anhydride had been half-esterified, and the reaction was terminated. After cooling, PGMAc was added so that the nonvolatile content was 30% by mass, to prepare a solution of other resin (C2-1). The acid value was 70 mgKOH / g and the weight-average molecular weight was 9,000.

[0354] (Other resin (C2-2) solution) A flask equipped with a stirrer, dropping funnel, condenser, thermometer, and gas inlet tube was charged with 100 parts of PGMAc, and the mixture was stirred while purging with nitrogen and heated to 78°C. Next, a mixture of 25.2 parts of Karenz MOI-DEM (2-[[[[(2-methyl-1-oxo-2-propenyl)oxy]ethyl]amino]carbonyl]-1,3-diethyl malonate, manufactured by Resonac Corporation), 31.2 parts of 2-hydroxyethyl methacrylate, 37.5 parts of dicyclopentanyl methacrylate, 20.7 parts of methacrylic acid, and 27.0 parts of methyl methacrylate, and a mixture of 12.0 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) (polymerization initiator) dissolved in 50 parts of PGMAc were added dropwise from the dropping funnel to the flask. After the dropwise addition, the mixture was stirred at 78°C for 3 hours to react. Thereafter, PGMAc was added so that the nonvolatile content became 40% by mass, to prepare a solution of other resin (C2-2).The acid value was 74 mgKOH / g and the weight-average molecular weight was 8,000.

[0355] (Other resin (C2-3) solution) A four-neck flask equipped with a stirrer, thermometer, dropping funnel, and reflux condenser was charged with 190.2 parts of diethyl malate, 0.17 parts of 2,6-di-tert-butyl-4-methylphenol, and 0.33 parts of dibutyltin dilaurate, and the mixture was stirred and cooled to 15-20°C. Then, while maintaining the temperature at 15-20°C and stirring, 141.1 parts of 2-acryloyloxyethyl isocyanate was added dropwise from the dropping funnel. After the dropwise addition was completed, the mixture was stirred and reacted at 25°C for 13 hours, yielding compound a. Next, 150 parts of PGMAc were placed in a flask equipped with a stirrer, dropping funnel, condenser, thermometer, and gas inlet tube, and the mixture was stirred while purging with nitrogen and heated to 78 ° C. 48.8 parts of compound a, 10.0 parts of Karenz MOI-BP (2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl methacrylate manufactured by Resonac), 14.7 parts of dicyclopentanyl methacrylate, 25.5 parts of 2-hydroxyethyl methacrylate, 8.6 parts of 2-ethylhexyl acrylate, and 17.4 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) (polymerization initiator) were mixed and added dropwise to the flask from the dropping funnel. After the addition was completed, the mixture was stirred at 78 ° C for 3 hours to react, and then 0.2 parts of 1,8-diazabicyclo[5.4.0]-undecene-7 was added and stirred at 78 ° C for an additional 30 minutes. Next, 9.9 parts of succinic anhydride and 0.5 parts of lithium naphthenate (catalyst) were added, and the mixture was stirred for 1 hour at 78° C. This caused a reaction between some of the hydroxyl groups of 2-hydroxyethyl methacrylate and succinic anhydride. Thereafter, PGMAc was added so that the nonvolatile content was 40% by mass, to prepare a solution of other resin (C2-3).The acid value was 44 mgKOH / g and the weight-average molecular weight was 12,500.

[0356] (Other resin (C2-4) solution) A flask equipped with a stirrer, dropping funnel, condenser, thermometer, and gas inlet tube was charged with 100 parts of PGMAc, which was then stirred while purging with nitrogen and heated to 90°C. Next, a mixture of 30.0 parts of 2-(acetoacetoxy)ethyl methacrylate, 26.4 parts of methacrylic acid, 21.7 parts of 2-hydroxyethyl methacrylate, 54.4 parts of dicyclopentanyl methacrylate, and 19.1 parts of n-butyl methacrylate, and a mixture of 5.0 parts of 2,2'-azobis(isobutyrate)dimethyl ester dissolved in 30 parts of PGMAc were each added dropwise from the dropping funnel to the flask. After the addition was completed, the mixture was stirred at 90°C for 6 hours to react. Thereafter, PGMAc was added so that the nonvolatile content was 40% by mass, to prepare a solution of other resin (C2-4).The acid value was 98 mgKOH / g and the weight-average molecular weight was 14,300.

[0357] (Other resin (C2-5) solution) 200 parts of PGMAc was added to a flask equipped with a stirrer, dropping funnel, condenser, thermometer, and gas inlet tube, and the mixture was stirred while purging with nitrogen and heated to 105°C. Next, a mixture of 130.2 parts of 3-methacryloyloxypropylmethyldiethoxysilane, 17.2 parts of methacrylic acid, 26.0 parts of 2-hydroxyethyl methacrylate, and 22.0 parts of dicyclopentanyl methacrylate, plus 30.3 parts of 2,2'-azobis(isobutyrate)dimethyl, was added dropwise from the dropping funnel to the flask. After the addition was complete, the mixture was allowed to react for 2 hours with stirring at 105°C. Thereafter, PGMAc was added so that the nonvolatile content became 40% by mass, and a solution of other resin (C2-5) was prepared. The acid value was 50 mgKOH / g and the weight-average molecular weight was 5,100.

[0358] (Other resin (C2-6) solution) A flask equipped with a stirrer, dropping funnel, condenser, thermometer, and gas inlet tube was charged with 100 parts of PGMAc, which was then stirred while purging with nitrogen and heated to 90°C. Next, a mixture of 35.0 parts of tert-butyl methacrylate, 5.0 parts of 2-(acetoacetoxy)ethyl methacrylate, 10.0 parts of N-benzylmaleimide, 20.0 parts of 2-hydroxyethyl methacrylate, 17.1 parts of methacrylic acid, and 2.0 parts of tert-butyl peroxy-2-ethylhexanoate (polymerization initiator) and a mixture of 0.6 parts of n-dodecyl mercaptan and 20 parts of PGMAc were each added dropwise from the dropping funnel to the flask. After the addition was completed, the mixture was maintained at 90°C for 30 minutes, then heated to 115°C, and stirred for 90 minutes to react. Thereafter, PGMAc was added so that the nonvolatile content was 40% by mass, to prepare a solution of other resin (C2-6).The acid value was 98 mgKOH / g and the weight-average molecular weight was 19,500.

[0359] (Other resin (C2-7) solution) A flask equipped with a stirrer, dropping funnel, condenser, thermometer, and gas inlet tube was charged with 100 parts of PGMAc. The mixture was stirred while purging with nitrogen and heated to 120°C. Next, a mixture of 76.8 parts of glycidyl methacrylate, 66.1 parts of dicyclopentanyl methacrylate, and 16.7 parts of styrene and a mixture of 5.5 parts of azobisisobutyronitrile as a polymerization initiator dissolved in PGMAc were added dropwise from the dropping funnel to the flask over 2.5 hours. After the addition was complete, the mixture was stirred for an additional 2 hours at 120°C. Next, the atmosphere in the flask was purged with air, and 38.9 parts of acrylic acid, 0.3 parts of tris(dimethylaminomethyl)phenol, and 0.3 parts of hydroquinone were added and reacted at 120°C for 5 hours. This resulted in the reaction of all of the epoxy groups of the glycidyl methacrylate with the carboxyl groups of the acrylic acid. Next, 40.0 parts of succinic anhydride and 0.5 parts of triethylamine were added and reacted for 4 hours at 120° C. This allowed some of the hydroxyl groups generated by cleavage of the epoxy groups of glycidyl methacrylate to react with succinic anhydride. Thereafter, PGMAc was added so that the nonvolatile content was 40% by mass, to prepare a solution of another resin (C2-7).The acid value was 95 mgKOH / g and the weight-average molecular weight was 9,000.

[0360] <Production of organic fluorescent particle dispersion (MA)> (Organic fluorescent particle dispersion (MA-1)) The following raw materials were mixed and stirred until uniform, and then dispersed in an Eiger mill (Eiger Japan "Mini Model M-250 MKII") using zirconia beads with a diameter of 0.5 mm so that the resin particles (A1-1) dyed with an organic fluorescent dye had an average particle diameter of 2.50 μm, producing an organic fluorescent particle dispersion (MA-1). The nonvolatile content was 52.0 mass%. Resin particles dyed with organic fluorescent dye (A1-1): 40.00 parts Resin (C1-1) solution having basic groups: 40.00 parts Other solvents (D2-1): 20.00 parts

[0361] (Organic fluorescent particle dispersions (MA-2) to (MA-20)) The dispersion time was changed so that the average particle diameter (μm) of the organic fluorescent particles (A) would be the values ​​shown in Tables 1-1 and 1-2, and organic fluorescent particle dispersions (MA-2) to (MA-20) were produced.

[0362] [Table 1-1]

[0363] [Table 1-2]

[0364] The components listed in Tables 1-1 and 1-2 are as follows. In the tables, resin particles (A1) are resin particles (A1) dyed with an organic fluorescent dye. Organic fluorescent particles (A2) are organic fluorescent particles (A2) other than resin particles (A1) dyed with an organic fluorescent dye.

[0365] [Organic fluorescent particles (A)] (Resin particles dyed with organic fluorescent dye (A1)) A1-1: SHNLOIHI COLOR FA-006 (Melamine resin particles dyed with an organic fluorescent dye with an emission wavelength of 574 nm and containing 0.2% or less of free formaldehyde by mass, manufactured by SHNLOIHI) A1-2: SHNLOIHI COLOR FA-227LF (Melamine resin particles dyed with an organic fluorescent dye with an emission wavelength of 626 nm and containing 0.2% or less of free formaldehyde by mass, manufactured by SHNLOIHI) A1-3: SHNLOIHI COLOR FZ-277 (Melamine resin particles dyed with an organic fluorescent dye with an emission wavelength of 626 nm and containing 0.2% or less of free formaldehyde by mass, manufactured by SHNLOIHI) A1-4: SHNLOIHI COLOR FA-005 (Melamine resin particles dyed with an organic fluorescent dye with an emission wavelength of 523 nm and containing 0.2% or less of free formaldehyde by mass, manufactured by SHNLOIHI) A1-5: SHNLOIHI COLOR FA-5005 (Melamine resin particles dyed with an organic fluorescent dye with an emission wavelength of 517 nm and containing 0.2% or less of free formaldehyde by mass, manufactured by SHNLOIHI)

[0366] (Organic fluorescent particles (A2) other than resin particles (A1) dyed with an organic fluorescent dye) A2-1: Compound of the following structure

[0367] [ka]

[0368] [Resin (C)] (Other resin (C2) solution) C2-8: DISPERBYK-111 (manufactured by BYK-Chemie, phosphate ester resin, acid value 129 mg KOH / g, non-volatile content 95% by mass)

[0369] [Solvent (D)] (Other solvents (D2)) D2-1: Propylene glycol monomethyl ether acetate

[0370] <Production of scattering particle dispersion (MB)> (Scattering particle dispersion (MB-1)) The following raw materials were mixed and stirred until uniform, and then dispersed in an Eiger mill (Eiger Japan "Mini Model M-250 MKII") using zirconia beads with a diameter of 0.5 mm so that the inorganic particles (B1-1) had an average particle size of 0.25 μm, to produce a scattering particle dispersion (MB-1). The nonvolatile content was 46.0 mass%. Inorganic particles (B1-1): 40.00 parts Resin (C1-1) solution having basic groups: 20.00 parts Other solvents (D2-1): 40.00 parts

[0371] (Scattering particle dispersion (MB-2)~(MB-10)) The dispersion time was changed so that the average particle diameter (μm) of the scattering particles (B) would be the value shown in Table 2, and scattering particle dispersions (MB-2) to (MB-10) were produced.

[0372] [Table 2]

[0373] The components listed in Table 2 are as follows: In the table, scattering particles (B2) are scattering particles (B2) other than inorganic particles (B1).

[0374] [Scattered particles (B)] (Inorganic particles (B1)) B1-1: CR-50 (Ishihara Sangyo Kaisha, alumina-treated rutile titanium dioxide, refractive index 2.72) B1-2: CR-90 (Ishihara Sangyo Kaisha, Ltd., alumina / silica-treated rutile titanium dioxide, refractive index 2.72) B1-3: R-980 (Ishihara Sangyo Kaisha, alumina / organic treated rutile titanium dioxide, refractive index 2.72) B1-4: R-38L (Sakai Chemical Co., Ltd., alumina / zirconia-treated rutile titanium dioxide, refractive index 2.72) B1-5: A-190 (Sakai Chemical Co., Ltd., alumina-treated anatase titanium dioxide, refractive index 2.52) B1-6: Advanced Alumina AA-04 (Sumitomo Chemical Co., Ltd., aluminum oxide, refractive index 1.76) B1-7: Seahoster KE-P50 (Nippon Shokubai Co., Ltd., silica, refractive index 1.43)

[0375] (Scattering particles (B2) other than inorganic particles (B1)) B2-1: Eposter S12 (Nippon Shokubai Co., Ltd., melamine-formaldehyde resin, refractive index 1.66)

[0376] [Resin (C)] (Other resin (C2) solution) C2-8: DISPERBYK-111 (manufactured by BYK-Chemie, phosphate ester resin, acid value 129 mg KOH / g, non-volatile content 95% by mass)

[0377] [Solvent (D)] (Other solvents (D2)) D2-1: Propylene glycol monomethyl ether acetate

[0378] <Production of inorganic fluorescent particle dispersion (MP)> (Inorganic fluorescent particle dispersion (MP-1)) The following raw materials were mixed and stirred until uniform, and then dispersed in an Eiger mill (Eiger Japan "Mini Model M-250 MKII") using zirconia beads with a diameter of 0.5 mm so that the inorganic fluorescent particles (P-1) had an average particle diameter of 1.00 μm, producing inorganic fluorescent particle dispersion (MP-1). The nonvolatile content was 52.0 mass%. Inorganic fluorescent particles (P-1): 40.00 parts Resin (C1-1) solution having basic groups: 40.00 parts Other solvents (D2-1): 20.00 parts

[0379] Inorganic fluorescent particles (P-1) were D3450 (YAlO 12 :Ce). The other solvent (D2-1) is propylene glycol monomethyl ether acetate.

[0380] <Production of Resin Composition> [Example 1] (Resin composition 1) The following raw materials were mixed and stirred to produce Resin Composition 1. The nonvolatile content was 41.0 mass %. Organic fluorescent particle dispersion (MA-1): 45.00 parts Scattering particle dispersion (MB-1): 10.25 parts Other resin (C2-2) solution: 10.00 parts Other resin (C2-7) solution: 8.94 parts Solvent (D1-2): 5.00 parts Other solvents (D2-1): 10.50 parts Other solvents (D2-2): 5.00 parts Polymerizable compound (E-1): 3.60 parts Polymerizable compound (E-2): 1.00 parts Polymerizable compound (E-3): 0.30 part Polymerization initiator (F1-1): 0.20 parts Polymerization initiator (F1-2): 0.20 parts Leveling agent (N-1): 0.01 parts

[0381] [Examples 2 to 45 and Comparative Example 1] (Resin composition 2~46) Resin compositions 2 to 46 were produced in the same manner as in Example 1, except that the raw materials and amounts were changed to those shown in Tables 3-1 to 3-5.

[0382] [Table 3-1]

[0383] [Table 3-2]

[0384] [Table 3-3]

[0385] [Table 3-4]

[0386] [Table 3-5]

[0387] The raw materials listed in Tables 3-1 to 3-5 are as follows:

[0388] [Solvent (D)] (Solvent (D1)) D1-1: Propylene glycol monoethyl ether (δh = 10.5) D1-2: Propylene glycol monomethyl ether (δh = 11.6) D1-3: Ethylene glycol monobutyl ether (δh=12.3) D1-4: Cyclohexanol (δh = 13.5) D1-5: 3-methoxy-1-butanol (δh = 13.6) D1-6: Ethylene glycol monoethyl ether (δh=14.3) D1-7: Water (δh=42.3)

[0389] (Other solvents (D2)) D2-1: Propylene glycol monomethyl ether acetate D2-2: Ethyl 3-ethoxypropionate

[0390] [Polymerizable compound (E)] E-1: Aronix M-403 (manufactured by Toagosei Co., Ltd., a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate) E-2: KAYARAD DPEA-12 (manufactured by Nippon Kayaku Co., Ltd., dipentaerythritol EO-modified hexaacrylate) E-3: CN9906NS (Arkema, multifunctional acrylate with an amine structure)

[0391] [Polymerization initiator (F)] (Polymerization initiator (F1)) F1-1: The above compound (F1-1) (absorption coefficient of light at a wavelength of 365 nm is 13,410 L / mol cm) F1-2: The above compound (F1-2) (absorption coefficient of light at a wavelength of 365 nm is 14,214 L / mol cm)

[0392] [Leveling Agent (N)] N-1: Block copolymer having the following structure (n:m=50:50 (mol %))

[0393] [ka]

[0394] <Evaluation of Resin Composition> The resulting resin compositions 1 to 46 were evaluated as follows. The evaluation results are shown in Table 4.

[0395] [Viscosity stability evaluation] The obtained resin composition was placed in a sealed container and subjected to 10 cycles of temperature increase and decrease, with 12 hours at 40°C and 12 hours at -10°C. The rate of change in viscosity before and after storage was calculated and evaluated using the following formula (1). The viscosity was measured using an E-type viscometer ("ELD-type viscometer" manufactured by Toki Sangyo Co., Ltd.) at 25°C and a rotation speed of 50 rpm. The evaluation criteria are as follows, with a score of 3 or higher being considered practical. Formula (1): Rate of change = |(initial viscosity - viscosity over time) / initial viscosity| x 100 5: The rate of change was less than 3%. 4: The rate of change was 3% or more but less than 6%. 3: The rate of change was 6% or more but less than 9%. 2: The rate of change was 9% or more but less than 12%. 1: The rate of change was 12% or more.

[0396] [Redispersibility evaluation] The resin composition for which the nonvolatile content immediately after production (initial nonvolatile content) was measured was placed in a sealed container and centrifuged at 10,000 rpm for 30 minutes. It was then placed in a shaker and shaken at 1,500 rpm for 10 minutes. Approximately 1 g of the resin composition was then sampled from the upper portion using a dropper, and the nonvolatile content (nonvolatile content after centrifugation) was measured. Approximately 1 g of the resin composition was dried at 110°C for 3 hours, and the nonvolatile content was calculated from the change in mass before and after drying. The evaluation criteria are as follows, with a score of 3 or higher being considered practical. 5: The nonvolatile content after centrifugation was 99% or more of the initial nonvolatile content. 4: The nonvolatile content after centrifugation was 98% or more but less than 99% of the initial nonvolatile content. 3: The nonvolatile content after centrifugation was 97% or more and less than 98% of the initial nonvolatile content. 2: The nonvolatile content after centrifugation was 96% or more and less than 97% of the initial nonvolatile content. 1: The nonvolatile content after centrifugation was less than 96% of the initial nonvolatile content.

[0397] [Table 4] [Explanation of symbols]

[0398] 10 TFT substrate 11 Light source (blue LED) 12 wavelength conversion layers (12RCC, 12GCC, 12YCC) 13 Transparent layer 14 Bulkhead 15 Color filter layer (15RCF: red pixel, 15GCF: green pixel, 15BCF: blue pixel, 15YCF: yellow pixel) 16 boards

Claims

1. A resin composition comprising organic fluorescent particles (A), scattering particles (B), a resin (C), and a solvent (D), The resin composition, wherein the resin (C) comprises a resin (C1) having a basic group.

2. The resin composition according to claim 1 , wherein the organic fluorescent particles (A) include resin particles (A1) dyed with an organic fluorescent dye.

3. 2. The resin composition according to claim 1, wherein the organic fluorescent particles (A) have an average particle size of 0.1 to 5.0 μm.

4. The resin composition according to claim 1, wherein the scattering particles (B) have an average particle size of 0.1 to 1.0 μm.

5. The resin composition according to claim 1, wherein the mass ratio of the organic fluorescent particles (A) to the scattering particles (B) is 95:5 to 50:

50.

6. The resin composition according to claim 1, wherein the resin (C1) having a basic group is a resin having one or more monomer units selected from the group consisting of monomer units represented by the following general formulas (1) to (3): 【Chemistry 20】 (In general formula (1), R １ ~R ３ each independently represents a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or an aralkyl group which may have a substituent; R １ ~R ３ Two or more of R may be bonded to each other to form a cyclic structure. ４ represents a hydrogen atom or a methyl group, and X １ represents a divalent linking group, Y １ － represents a counter anion. In general formula (2), R ７ and R ８ each independently represents a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or an aralkyl group which may have a substituent; R ７ and R ８ may be bonded to each other to form a cyclic structure. ９ represents a hydrogen atom or a methyl group, and X ２ represents a divalent linking group. In general formula (3), R １０ represents a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, an aralkyl group which may have a substituent, an acyl group, an oxy radical group, or —OR １６ represents R １６ represents a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, an aralkyl group which may have a substituent, or an acyl group. １１ ~R １４ each independently represents a methyl group, an ethyl group, or a phenyl group; R １５ represents a hydrogen atom or a methyl group, and X ３ represents a divalent linking group.

7. The resin composition according to claim 1 , further comprising a polymerizable compound (E) and a polymerization initiator (F).

8. A wavelength conversion layer formed from the resin composition according to any one of claims 1 to 7.

9. A laminate comprising the wavelength conversion layer according to claim 8 and a color filter layer.

10. A display device comprising the laminate according to claim 9 .

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