Wavelength conversion photosensitive composition, wavelength conversion layer, laminate, and display device

Abstract

To provide a wavelength conversion photosensitive composition which is superior in terms of developability, pattern formability, and wavelength conversion efficiency.SOLUTION: A wavelength conversion photosensitive composition is provided, comprising organic fluorescent particles (A), resin (B), polymerizable compound (C), and polymerization initiator (D), where the resin (B) comprises a resin (B1) having an aromatic carboxylic group.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] Embodiments of the present invention relate to a wavelength-converting photosensitive composition, a wavelength-converting layer, a laminate, and a display device. [Background technology]

[0002] In recent years, in the field of display devices such as televisions, smartphones, and tablets, there has been a demand for higher brightness and wider color gamuts from the viewpoints of energy conservation and color reproducibility. For example, LED (light-emitting diode) display devices and OLED (organic light-emitting diode) display devices equipped with wavelength conversion layers have attracted attention. These display devices use LEDs or OLEDs as light sources and convert part of the light emitted by the wavelength conversion layer to produce a full-color display, and are excellent in color reproducibility, contrast, and brightness.

[0003] The wavelength conversion layer contains a fluorescent material that absorbs light from a light source and emits light of a desired wavelength, and fluorescent dyes, quantum dots, and the like have been considered as typical fluorescent materials.

[0004] For example, Patent Document 1 discloses a composition for forming a color conversion layer, which contains a fluorescent dye, a highly refractive material, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent. Patent Document 2 discloses a self-luminous photosensitive resin composition, which contains quantum dots, a scatterer, an alkali-soluble resin, a photopolymerizable compound, a curing accelerator, and a solvent. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] JP 2016-71360 A [Patent Document 2] Japanese Patent Publication No. 2021-128343 Summary of the Invention [Problem to be solved by the invention]

[0006] However, typical conventional fluorescent dyes have poor light resistance and alkaline developer resistance, and are not fully satisfactory in terms of wavelength conversion efficiency. Furthermore, conventional quantum dots are susceptible to the effects of oxygen and moisture, and there is room for improvement in terms of pattern formation in photolithography.

[0007] Therefore, an object of the present invention is to provide a wavelength conversion photosensitive composition that is excellent in developability and pattern formability, and also in wavelength conversion efficiency. [Means for solving the problem]

[0008] The embodiments of the present invention include the following: However, the present invention is not limited to the following embodiments and includes various embodiments. [1] A composition comprising organic fluorescent particles (A), a resin (B), a polymerizable compound (C), and a polymerization initiator (D), The wavelength-converting photosensitive composition, wherein the resin (B) comprises a resin (B1) having an aromatic carboxyl group.

[0009] [2] The wavelength-converting photosensitive composition according to the above [1], wherein the content of the organic fluorescent particles (A) is 20 to 60 mass % based on the total mass of the non-volatile content of the wavelength-converting photosensitive composition.

[0010] [3] The wavelength-converting photosensitive composition according to the above [1] or [2], wherein the organic fluorescent particles (A) comprise resin particles (A1) dyed with an organic fluorescent dye.

[0011] [4] The wavelength-converting photosensitive composition according to any one of the above [1] to [3], wherein the resin (B1) having an aromatic carboxyl group comprises a resin having a repeating unit represented by the following formula (1):

[0012] [ka] [In formula (1), Ar1 represents a group having an aromatic carboxyl group, L1 represents -COO- or -CONH-, L2 represents a trivalent linking group, P1 represents a polymer chain, and n is an integer of 2 or more.]

[0013] [5] The polymerization initiator (D) has an absorption coefficient of 5.0 × 10 at a wavelength of 365 nm in propylene glycol monomethyl ether acetate. 3 The wavelength-converting photosensitive composition according to any one of the above [1] to [4], which contains a polymerization initiator (D1) having a viscosity of at least L / mol·cm.

[0014] [6] The wavelength-converting photosensitive composition according to any one of the above [1] to [5], further comprising scattering particles (F).

[0015] [7] A wavelength-converting layer formed from the wavelength-converting photosensitive composition according to any one of the above [1] to [6].

[0016] [8] A laminate comprising the wavelength conversion layer according to [7] above and a color filter layer.

[0017] [9] A display device having the laminate according to [8] above. [Effects of the Invention]

[0018] The present invention provides a wavelength-converting photosensitive composition that has excellent developability, pattern formability, and wavelength conversion efficiency. Furthermore, the wavelength-converting photosensitive composition can be used to provide a wavelength-converting layer, a laminate, and a display device. [Brief explanation of the drawings]

[0019] [Figure 1] FIG. 1 is a schematic cross-sectional view showing an example of the configuration of a display device according to one embodiment of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0020] DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described in detail below with reference to the following preferred embodiments. However, the present invention is not limited to the following preferred embodiments, and modifications can be made within the scope of the present invention.

[0021] 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).

[0022] In this specification, the polymerizable unsaturated group is an ethylenically unsaturated double bond.

[0023] 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).The molecular weight of a compound with a molecular weight distribution is a weight-average molecular weight in terms of polystyrene measured by gel permeation chromatography using tetrahydrofuran as a solvent.

[0024] 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.

[0025] In this specification, the average particle size is the average value of the primary particle diameters 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 this is taken as the primary particle size.

[0026] <Photosensitive composition for wavelength conversion> A wavelength-converting photosensitive composition according to one embodiment of the present invention (hereinafter also referred to as the wavelength-converting photosensitive composition of the present embodiment) comprises organic fluorescent particles (A), a resin (B), a polymerizable compound (C), and a polymerization initiator (D), and the resin (B) comprises a resin (B1) having an aromatic carboxyl group.

[0027] The mechanism by which the wavelength-converting photosensitive composition having the above-described configuration can solve the problems of the present invention is not clear, but is speculated as follows.

[0028] The organic fluorescent particles (A) are not dissolved in the wavelength conversion photosensitive composition and exist in a state of particle size. Therefore, compared with organic fluorescent dyes, they are less likely to dissolve in an alkaline aqueous solution during pattern formation, and are expected to have excellent wavelength conversion efficiency. However, on the other hand, the organic fluorescent particles (A) are prone to association and aggregation, which may result in a decrease in pattern formability. In contrast, in an embodiment of the present invention, by using a resin (B1) having aromatic carboxyl groups as the resin (B), the aromatic carboxyl groups in the resin act on the organic fluorescent particles (A), suppressing particle association and aggregation, and improving pattern formability. Furthermore, aromatic carboxyl groups, which are acidic groups, have excellent solubility in alkaline aqueous solutions. Therefore, it is believed that the presence of a resin having aromatic carboxyl groups in the wavelength-converting photosensitive composition suppresses residues during development and improves pattern formability.

[0029] The components constituting the wavelength conversion photosensitive composition of this embodiment, and the components that may be optionally contained, will be described in detail below.

[0030] [Organic fluorescent particles (A)] The wavelength-converting photosensitive composition of this embodiment contains organic fluorescent particles (A).

[0031] The organic fluorescent particles (A) are not particularly limited, and known compounds can be used. In this specification, "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.

[0032] The organic fluorescent particles (A) may include, for example, one or more selected from the group consisting of diethyl 2,5-dihydroxyterephthalate, dixanthene, 9,10-dianilinoanthracene, 2-hydroxybenzaldehyde azine, 2-oxynaphthaldazine, 2-anilino-4-(2,5-dichlorobenzoylamino)-1,9-pyrimidoanthrone, 1,4-bis-(β-cyano-β-carbethoxyvinyl)benzene, and resin particles dyed with an organic fluorescent dye.

[0033] The average particle size of the organic fluorescent particles (A) is preferably from 0.1 to 4.5 μm, more preferably from 0.5 to 3.5 μm, from the viewpoints of pattern formability and wavelength conversion efficiency.

[0034] From the viewpoints of pattern formability and wavelength conversion efficiency, the content of the organic fluorescent particles (A) is preferably 20 to 60 mass %, more preferably 25 to 55 mass %, based on the total mass of the nonvolatile components of the wavelength conversion photosensitive composition.

[0035] (Resin particles dyed with organic fluorescent dye (A1)) In some embodiments, from the viewpoint of wavelength conversion efficiency, the organic fluorescent particles (A) preferably contain resin particles dyed with an organic fluorescent dye (hereinafter simply referred to as organic fluorescent resin particles (A1)). The organic fluorescent resin particles (A1) are particles in which an organic fluorescent dye is immobilized in a resin. The use of such resin particles can suppress the elution of the organic fluorescent dye into the alkaline aqueous solution (hereinafter also referred to as alkaline developer) used during development. As a result, it is easy to improve wavelength conversion efficiency and film resistance to alkaline developer.

[0036] In view of the above, in some embodiments, the content of the organic fluorescent resin particles (A1) may be preferably 60% by mass or more, more preferably 70% by mass or more, and even more preferably 80% by mass or more, based on the total mass of the organic fluorescent particles (A). The content of the organic fluorescent resin particles (A1) may be 100% by mass.

[0037] [Organic fluorescent dyes] The organic fluorescent dye in the organic fluorescent resin particles (A1) is not particularly limited, and known compounds can be used.

[0038] 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.

[0039] Specific examples of organic fluorescent dyes include: 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, CI Direct Green 6, etc. 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, and 4a-diaza-s-indacene (IV). The present invention is not limited to these. The organic fluorescent dyes can be used alone or in combination of two or more.

[0040] Although not particularly limited, organic fluorescent dyes having an emission wavelength (maximum peak) in the range of 450 to 800 nm can be preferably used. The emission wavelength range may more preferably be 470 to 750 nm, and even more preferably be 500 to 650 nm. In this specification, the emission wavelength refers to a value measured by a spectrofluorometer (monochromatic monitor ratio calculation method). 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).

[0041] 〔resin〕 The resin in the organic fluorescent resin particles (A1) is not particularly limited, and known compounds can be used.

[0042] 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.

[0043] Among these, in some embodiments, the resin preferably includes a melamine-based resin. In this specification, the melamine-based resin refers to a resin having a structure derived from a triazine compound. Examples of the triazine compound include melamine, benzoguanamine, and acetoguanamine. In some embodiments, the melamine-based resin may be a condensation product of a triazine compound with another compound, such as an aldehyde compound or a urea compound. Examples of aldehyde compounds include formaldehyde, paraformaldehyde, and acetaldehyde. Examples of urea compounds include urea, thiourea, and ethylene urea.

[0044] Specific examples of melamine-based resins include benzoguanamine-melamine resin, melamine-formaldehyde resin, benzoguanamine-melamine-formaldehyde resin, urea-melamine-formaldehyde resin, urea-melamine resin, etc. However, the melamine-based resin is not limited to these, and known resins can be used.

[0045] In some embodiments, from the viewpoint of the storage stability of the wavelength conversion photosensitive composition, the melamine resin preferably has a free formaldehyde content of 0.2 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.

[0046] From the viewpoint of pattern formation, 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 facilitates interaction with the aromatic carboxyl groups of the resin (B1) having aromatic carboxyl groups, making it easier to suppress association and aggregation of the organic fluorescent resin particles (A1).

[0047] 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.

[0048] 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, and a benzothiazole ring structure. Among these, a triazine ring structure is preferable. An example of a resin having a triazine ring structure is a melamine-based resin. The details of the melamine-based resin are as described above.

[0049] 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 compound (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 is stirred in a solvent to form a suspended state, and an organic fluorescent dye is added during or after the polymerization process to produce organic fluorescent resin particles.

[0050] Specific examples include methods described in U.S. Pat. No. 2,938,873, U.S. Pat. No. 3,116,256, Japanese Patent Publication Nos. 1961-13437, 1976-005678, 1977-029336, JP-A-2005-314540, 2001-181544, 2009-161688, JP-A-05-125276, JP-A-08-048899, JP-A-09-020864, ​​and the like.

[0051] The organic fluorescent resin particles (A1) are commercially available. Examples include FA-001, 005, 006, 007, 227LF, FZ-247, 277, 3057, 5005, M, and MB from the SHNLOIHI COLOR series manufactured by SHNLOIHI Co., Ltd. Among these, FA-006, FA-227LF, FZ-277, FA-005, and FA-5005 are particularly suitable for use in some embodiments. These are a type of organic fluorescent resin particle in which an organic fluorescent dye is fixed to a resin containing a melamine resin.

[0052] [Resin (B)] The wavelength-converting photosensitive composition of this embodiment contains a resin (B).

[0053] Regarding the resin (B), the resin (B) used mainly to disperse the organic fluorescent particles (A) is also called a dispersion resin, and the resin (B) used mainly to impart resistance to the wavelength conversion layer is also called a binder resin. Although one type of resin (B) may function as both a dispersion resin and a binder resin, it is preferable that the resin (B) contains both a dispersion resin and a binder resin. The above-described use of the resin (B) is merely an example, and the resin (B) can also be used for other purposes.

[0054] The resin (B) is not particularly limited, and known resins can be used. The resin (B) can be used alone or in combination of two or more. For example, in some embodiments, resin (B) may include one or more selected from the group consisting of (meth)acrylic resin, styrene resin, styrene / (meth)acrylic resin, epoxy resin, urethane resin, urethane(meth)acrylic resin, polycarbonate resin, polyester resin, polyether resin, polyimide resin, polyamideimide resin, polysiloxane resin, and cyclic olefin resin.

[0055] The weight average molecular weight of the resin (B) is preferably from 3,000 to 100,000, more preferably from 4,000 to 80,000.

[0056] The content of the resin (B) is preferably from 1 to 70 mass %, more preferably from 5 to 60 mass %, based on the total mass of the nonvolatile components of the wavelength-converting photosensitive composition.

[0057] (Resin (B1) having an aromatic carboxyl group) In some embodiments, the resin (B) preferably includes a resin (B1) having an aromatic carboxyl group.

[0058] In this specification, the aromatic carboxyl group refers to a group having a structure in which one or more carboxyl groups are directly bonded to an aromatic ring. In some embodiments, the number of carboxyl groups bonded to the aromatic ring in the aromatic carboxyl group is preferably 1 to 4.

[0059] The acid value of the resin (B1) having an aromatic carboxyl group is preferably 20 to 250 mgKOH / g, more preferably 30 to 200 mgKOH / g. In some embodiments, the acid value of the resin (B1) may be preferably 40 to 150, more preferably 50 to 120.

[0060] The weight average molecular weight of the resin (B1) having an aromatic carboxyl group is preferably 3,000 to 50,000, more preferably 4,000 to 40,000. In some embodiments, the weight average molecular weight of the resin may be preferably 4,500 to 30,000, more preferably 5,000 to 25,000.

[0061] The resin (B1) having an aromatic carboxyl group can be used alone or in combination of two or more.

[0062] The content of the resin (B1) having an aromatic carboxyl group is preferably from 5 to 100% by mass, more preferably from 10 to 85% by mass, based on the total mass of the resin (B).

[0063] [Resin having a repeating unit represented by formula (1)] From the viewpoint of developability and pattern formability, the resin (B1) having an aromatic carboxyl group preferably contains a resin having a repeating unit represented by the following formula (1).

[0064] [ka]

[0065] In formula (1), Ar1 represents a group having an aromatic carboxyl group, L1 represents -COO- or -CONH-, L2 represents a trivalent linking group, and P1 represents a polymer chain.

[0066] A resin having a repeating unit represented by formula (1) can be obtained, for example, by forming a moiety containing an aromatic carboxylic acid ester structure (the -Ar1-L1-L2- moiety in formula 1) through a reaction between an aromatic compound having two or more acid anhydride groups and a compound having two or more hydroxyl groups, and then forming a moiety (the P1 moiety in formula 1) through polymerization of a polymerizable compound. This will be explained in more detail below.

[0067] In formula (1), the group having an aromatic carboxyl group in Ar1 includes a structure derived from an aromatic tricarboxylic acid anhydride and a structure derived from an aromatic tetracarboxylic acid anhydride. Examples of the aromatic tricarboxylic acid anhydride and aromatic tetracarboxylic acid anhydride include compounds of the following formulae (2) to (7).

[0068] [ka]

[0069] In formula (4) and formula (7), Q1 represents a single bond, -O-, -CO-, -COOCH2CH2OCO-, -SO2-, -C(CF3)2-, a group represented by the following formula (Q1-1), or a group represented by the following formula (Q1-2).

[0070] [ka]

[0071] Specific examples of the aromatic tricarboxylic acid anhydride include 1,2,3-benzenetricarboxylic acid anhydride, 1,2,4-benzenetricarboxylic acid anhydride, 1,2,4-naphthalenetricarboxylic acid anhydride, 1,4,5-naphthalenetricarboxylic acid anhydride, 2,3,6-naphthalenetricarboxylic acid anhydride, 1,2,8-naphthalenetricarboxylic acid anhydride, 3,4,4'-benzophenonetricarboxylic acid anhydride, 3,4,4'-biphenylethertricarboxylic acid anhydride, 3,4,4'-biphenyltricarboxylic acid anhydride, 2,3,2'-biphenyltricarboxylic acid anhydride, and 3,4,4'-biphenylmethanetricarboxylic acid anhydride.

[0072] Specific examples of the aromatic tetracarboxylic acid anhydride include pyromellitic dianhydride, ethylene glycol ditrimellitic anhydride, propylene glycol ditrimellitic anhydride, butylene glycol ditrimellitic anhydride, 3,3',4,4'-benzophenone tetracarboxylic acid dianhydride, 3,3',4,4'-biphenylsulfone tetracarboxylic acid dianhydride, 1,4,5,8-naphthalene tetracarboxylic acid dianhydride, and 2,3,6,7-naphthalene tetracarboxylic acid dianhydride. tetracarboxylic acid dianhydride, 3,3',4,4'-biphenylethertetracarboxylic acid dianhydride, 3,3',4,4'-dimethyldiphenylsilanetetracarboxylic acid dianhydride, 3,3',4,4'-tetraphenylsilanetetracarboxylic acid dianhydride, 1,2,3,4-furantetracarboxylic acid dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfone dianhydride 4,4'-bis(3,4-dicarboxyphenoxy)diphenylpropane dianhydride, 3,3',4,4'-perfluoroisopropylidenediphthalic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, bis(phthalic acid)phenylphosphine oxide dianhydride, p-phenylene-bis(triphenylphthalic) dianhydride, m-phenylene-bis(triphenylphthalic) dianhydride, bis(triphenylphthalic)-4,4'-diphenyl ether tert-butyl ether dianhydride, bis(triphenylphthalic)-4,4'-diphenylmethane dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, 9,9-bis[4-(3,4-dicarboxyphenoxy)phenyl]fluorene dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride, and 3,4-dicarboxy-1,2,3,4-tetrahydro-6-methyl-1-naphthalene succinic dianhydride.

[0073] Specific examples of the group having an aromatic carboxyl group in Ar1 include groups represented by the following formula (Ar1-1), groups represented by the following formula (Ar1-2), and groups represented by the following formula (Ar1-3).

[0074] [ka]

[0075] In the formulae (Ar1-1) to (Ar1-3), Q2 has the same meaning as Q1 in the formula (7), *1 is a bond, and *1 is a bond to L1 in the formula (1).

[0076] L1 in formula (1) represents -COO- or -CONH-, and among these, -COO- is preferred.

[0077] Examples of the trivalent linking group in L2 in formula (1) include hydrocarbon groups, -O-, -CO-, -COO-, -OCO-, -NH-, -S-, and combinations thereof. Examples of the hydrocarbon group include an aliphatic hydrocarbon group and an aromatic hydrocarbon group. The aliphatic hydrocarbon group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms. The aliphatic hydrocarbon group may be linear, branched, cyclic, or a combination thereof. The aromatic hydrocarbon group preferably has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms. The hydrocarbon group may have a substituent, and examples of the substituent include a hydroxyl group and a halogen atom.

[0078] The trivalent linking group in L2 is preferably a group represented by the following formula (L2-1).

[0079] [ka]

[0080] In formula (L2-1), L3 represents a trivalent linking group, * represents a bond, *2 represents a bond to L1 in formula (1), and *3 represents a bond to P1 in formula (1).

[0081] The trivalent linking group for L3 in formula (L2-1) includes hydrocarbon groups, -O-, -CO-, -COO-, -OCO-, -NH-, and combinations thereof. Among these, hydrocarbon groups are preferred. The hydrocarbon group has the same meaning as the hydrocarbon group for L2 in formula (1).

[0082] In formula (1), P1 represents a polymer chain, which preferably contains at least one structure selected from the group consisting of a poly(meth)acrylic structure, a polyether structure, a polyester structure, and a polyurethane structure.

[0083] The polymer chain more preferably contains a repeating unit represented by the following formula (P1-1).

[0084] [ka]

[0085] In formula (P1-1), R1 represents a hydrogen atom or a methyl group, L4 represents a single bond or a divalent linking group, and X1 represents a hydrogen atom or a substituent.

[0086] Examples of the divalent linking group for L4 in formula (P1-1) include an alkylene group having 1 to 20 carbon atoms which may have a substituent, an arylene group having 6 to 20 carbon atoms which may have a substituent, -NH-, -SO-, -SO2-, -CO-, -O-, -COO-, -OCO-, -S-, -NHCO-, -CONH-, and combinations thereof. The alkylene group having 1 to 20 carbon atoms, which may have a substituent, may be linear, branched, cyclic, or a combination thereof. Examples of the substituents of the alkylene group having 1 to 20 carbon atoms which may have a substituent and the arylene group having 6 to 20 carbon atoms which may have a substituent include a hydroxyl group and a halogen atom.

[0087] Examples of the substituent in X1 of formula (P1-1) include a hydroxyl group, a carboxyl group, an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, an epoxy group, an oxetanyl group, an acetoacetoxy group, an alkoxysilyl group, a blocked isocyanate group, and a polymerizable unsaturated group. A blocked isocyanate group is a group in which an isocyanate group is protected with a compound (hereinafter also referred to as a blocking agent) that is released by heat. Examples of blocking agents include oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, pyrazole compounds, mercaptan compounds, imidazole compounds, imide compounds, urea compounds, imine compounds, and bisulfite compounds. Among these, a compound that is released at 60 to 160°C is preferred as the blocking agent. Examples of the polymerizable unsaturated group include a vinyl group, a (meth)allyl group, a (meth)acryloyl group, a (meth)acryloyloxy group, and a (meth)acryloylamide group.

[0088] Specifically, the repeating unit represented by formula (P1-1) may include repeating units derived from the compounds exemplified below. 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, cyclohexanedimethanol mono(meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 2-(meth)acryloyloxyethyl-2-hydroxyethyl phthalate, (meth)acrylic acid, 2-(meth)acryloyloxy Ethyl succinate, 2-(meth)acryloyloxyethylhexylhydrophthalate, β-carboxyethyl (meth)acrylate, ω-carboxypolycaprolactone (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, adamantyl (meth)acrylate, 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, tridecyl (meth)acrylate, isomyristyl (meth)acrylate, stearyl (meth)acrylate, or isostearyl (meth)acrylate, cyclohexyl (meth)acrylate, tert-butyl cyclo Hexyl (meth)acrylate, methoxyethyl (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, methoxypolytetramethylene glycol (meth)acrylate, methoxypolyethylene glycol polypropylene glycol (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (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, tetrahydrofurfuryl (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, 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)acryloyloxymethyloxetane, 2-(acetoacetoxy)ethyl (meth)acrylate, 3-(meth)acryloyloxypropylmethyldimethoxysilane, 3-(meth)acryloyloxypropyl ethyl ethyldimethoxysilane, 3-(meth)acryloyloxypropylmethyldiethoxysilane, 3-(meth)acryloyloxypropylethyldiethoxysilane, 3-(meth)acryloyloxypropyltrimethoxysilane, 3-(meth)acryloyloxypropyltriethoxysilane, 8-(meth)acryloyloxyoctyltrimethoxysilane, malonic acid-2-[[[[(2-methyl-1-oxo-2-propenyl)oxy]ethyl]amino]carbonyl]-1,3-diethyl ester, 2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl (meth)acrylate, 2-[O-(1'-methylpropylideneamino)carboxyamino]ethyl (meth)acrylate, and the like.

[0089] Furthermore, examples of the repeating unit in which X1 in formula (P1-1) is a polymerizable unsaturated group include repeating units obtained by reacting one or more of a hydroxyl group, a carboxyl group, and an epoxy group present in a polymer chain with a compound having a functional group reactive with these groups and a polymerizable unsaturated group. Examples of the compound having a functional group and a polymerizable unsaturated group include 2-(meth)acryloyloxyethyl isocyanate, 2-(2-(meth)acryloyloxyethyloxy)ethyl isocyanate, 1,1-bis[methacryloyloxy]ethyl isocyanate, (meth)acrylic acid, 2-(meth)acryloyloxyethyl succinic acid, 2-(meth)acryloyloxyethylhexylhydrophthalic acid, β-carboxyethyl (meth)acrylate, ω-carboxypolycaprolactone (meth)acrylate, glycidyl (meth)acrylate, 2-methylglycidyl (meth)acrylate, and 2-ethylglycidyl (meth)acrylate.

[0090] The polymer chain may contain repeating units other than the repeating unit represented by formula (P1-1). The repeating units other than the repeating unit represented by formula (P1-1) may include, for example, repeating units derived from the compounds exemplified below. Styrene, α-methylstyrene, p-vinyltoluene, p-chlorostyrene, vinylnaphthalene, crotonic acid, propiolic acid, cinnamic acid, itaconic acid, itaconic anhydride, maleic acid, monomethyl maleate, monoethyl maleate, monoisopropyl maleate, maleic anhydride, fumaric acid, 2-methacryloyloxyethyl succinate, 2-acryloyloxyethyl phthalate, 2-acryloyloxyethyl hexylhydrophthalic acid, p-styrenesulfonic acid, vinylsulfonic acid, 2-acrylamido-2-methylpropional Pansulfonic acid, tert-butylacrylamidosulfonic acid, 2-(meth)acryloyloxyethyl acid phosphate, 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-phenyl Dimaleimide, N-(1-pyrenyl)maleimide, N-(2,4,6-trichlorophenyl)maleimide, N-(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-benzyl)maleimide] [(2-benzoimidazolyl)phenyl]maleimide, 9-maleimidoacridine, 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, di(2-ethylhexyl)-2,2'-[oxybis(methylene)]bis-2-propenoate, and the like.

[0091] From the viewpoint of durability, the polymer chain preferably contains a repeating unit having a thermally crosslinkable group and / or a polymerizable unsaturated group. Examples of the thermally crosslinkable group include a hydroxyl group, an epoxy group, an oxetanyl group, an acetoacetoxy group, an alkoxysilyl group, a tertiary alkyl group, and a blocked isocyanate group. Examples of the polymerizable unsaturated group include a vinyl group, a (meth)allyl group, a (meth)acryloyl group, a (meth)acryloyloxy group, and a (meth)acryloylamide group. The total content of the repeating units having a thermally crosslinkable group and the repeating units having a polymerizable unsaturated group is preferably 1 to 80 mol %, more preferably 1 to 70 mol %, of all the repeating units constituting the polymer chain.

[0092] From the viewpoint of developability, the polymer chain preferably has a repeating unit having an acidic group, such as a carboxyl group, a phosphate group, or a sulfo group. The repeating unit having an acidic group preferably accounts for 1 to 50 mol %, more preferably 1 to 40 mol %, of all repeating units constituting the polymer chain.

[0093] The weight average molecular weight of the polymer chain is preferably from 500 to 30,000, more preferably from 700 to 20,000, from the viewpoint of pattern formability.

[0094] The resin having the repeating unit represented by formula (1) can be synthesized, for example, by the following two methods.

[0095] <Synthesis method (i)> This method involves radically polymerizing a monomer in the presence of a compound having two or more hydroxyl groups to produce a polymer having two hydroxyl groups at one end, which is then reacted with an aromatic tricarboxylic acid anhydride and / or an aromatic tetracarboxylic acid anhydride.

[0096] <Synthesis method (ii)> A method in which a compound having two or more hydroxyl groups is reacted with an aromatic tricarboxylic acid anhydride and / or an aromatic tetracarboxylic acid anhydride, and then the monomer is radically polymerized in the presence of the reaction product.

[0097] The synthesis method (i) will be explained below. [ka]

[0098] In the above reaction formula, X represents a portion of an aromatic tetracarboxylic acid anhydride, Z represents a portion of a compound having two hydroxyl groups, and R represents a portion of a monoalcohol.

[0099] The compound having two or more hydroxyl groups is preferably a compound having two hydroxyl groups and one thiol group in the molecule. Examples of the compound having two hydroxyl groups and one thiol group in the molecule include 1-mercapto-1,1-methanediol, 1-mercapto-1,1-ethanediol, 3-mercapto-1,2-propanediol (thioglycerin), 2-mercapto-1,2-propanediol, 2-mercapto-2-methyl-1,3-propanediol, 2-mercapto-2-ethyl-1,3-propanediol, 1-mercapto-2,2-propanediol, 2-mercaptoethyl-2-methyl-1,3-propanediol, and 2-mercaptoethyl-2-ethyl-1,3-propanediol.

[0100] The temperature of the synthesis reaction (a) is preferably 40 to 150° C., more preferably 50 to 110° C. If the temperature is 40° C. or higher, the polymerization proceeds easily, and if the temperature is 150° C. or lower, it is easy to control the molecular weight.

[0101] In the synthesis reaction (a), a polymerization initiator can be used in an amount of 0.001 to 5% by mass relative to the total mass of the monomers. Examples of the polymerization initiator include azo compounds and organic peroxides. Examples of azo compounds include 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis(cyclohexane-1-carbonitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethyl-4-methoxyvaleronitrile), dimethyl 2,2'-azobis(2-methylpropionate), 4,4'-azobis(4-cyanovaleric acid), 2,2'-azobis(2-hydroxymethylpropionitrile), and 2,2'-azobis[2-(2-imidazolin-2-yl)propane]. Examples of organic peroxides include benzoyl peroxide, tert-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di(2-ethoxyethyl)peroxydicarbonate, t-butyl peroxyneodecanoate, tert-butyl peroxypivalate, (3,5,5-trimethylhexanoyl)peroxide, dipropionyl peroxide, and diacetyl peroxide. The polymerization initiators can be used alone or in combination of two or more.

[0102] The synthesis reaction (a) is preferably carried out by bulk polymerization or solution polymerization. Examples of polymerization solvents for solution polymerization include ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, xylene, acetone, hexane, methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, and diethylene glycol monobutyl ether acetate. These polymerization solvents can be used alone or in combination of two or more.

[0103] For the synthesis reaction (b), solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, toluene, xylene, acetonitrile, and propylene glycol monomethyl ether acetate can be used.

[0104] A reaction catalyst can be used in the synthesis reaction (b). The reaction catalyst is preferably a tertiary amine compound. Examples of the tertiary amine compound include triethylamine, triethylenediamine, N,N-dimethylbenzylamine, N-methylmorpholine, 1,8-diazabicyclo-[5.4.0]-7-undecene, and 1,5-diazabicyclo-[4.3.0]-5-nonene.

[0105] The temperature of the synthesis reaction (b) is preferably 50 to 180°C, more preferably 80 to 140°C.

[0106] In the synthesis reaction (b), the molar ratio of the acid anhydride groups in the aromatic tetracarboxylic anhydride to the hydroxyl groups in the compound having two or more hydroxyl groups (acid anhydride groups / hydroxyl groups) is preferably 0.5 to 1.5 moles.

[0107] When the terminal of a resin having a repeating unit represented by formula (1) is an acid anhydride group, it may be reacted with a monoalcohol (synthesis reaction (c)). The acid anhydride group undergoes ring-opening with the monoalcohol to produce an alcohol ester and a carboxyl group. This improves the solubility in alkaline developers. Alternatively, a monoamine may be used instead of the monoalcohol.

[0108] Examples of the monoalcohol include methanol, ethanol, 1-butanol, 2-butanol, isobutanol, tert-butanol, 1-pentanol, isopentyl alcohol, tert-pentyl alcohol, cyclopentanol, 1-hexanol, cyclohexanol, 1-heptanol, 1-octanol, 2-ethyl-1-hexanol, isononyl alcohol, 1-nonyl alcohol, amyl alcohol, lauryl alcohol, n-butyl alcohol, isobutyl alcohol, cyclohexanol, benzyl alcohol, and methylcyclohexanol; Monoalcohols having an ether group, such as 3-methoxy-3-methyl-1-butanol, 3-methoxybutanol, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monotertiary butyl ether, ethylene glycol monobutyl ether, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol monophenyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monopropyl ether, and propylene glycol monomethyl ether; Examples include monoalcohols having a carbonyl group such as methyl lactate, ethyl lactate, and diacetone alcohol. Among these, from the viewpoint of developability, compounds having an ether group or a carbonyl group are preferred, and 3-methoxybutanol, propylene glycol monomethyl ether, and diacetone alcohol are more preferred. The monoalcohols can be used alone or in combination of two or more.

[0109] The amount of monoalcohol used relative to the acid anhydride group is preferably 1 to 30 equivalents, more preferably 1.5 to 20 equivalents, per equivalent of the acid anhydride group.

[0110] The acid value of the resin having the repeating unit represented by formula (1) is preferably 20 to 250 mgKOH / g, more preferably 30 to 200 mgKOH / g. In some embodiments, the acid value of the resin may be preferably 35 to 150 mgKOH / g, more preferably 35 to 120 mgKOH / g.

[0111] The weight average molecular weight of the resin having a repeating unit represented by formula (1) is preferably 2,000 to 40,000, more preferably 4,000 to 30,000. In some embodiments, the weight average molecular weight of the resin may be preferably 4,500 to 25,000, more preferably 5,000 to 20,000.

[0112] The resin having the repeating unit represented by formula (1) can be used alone or in combination of two or more kinds.

[0113] From the viewpoint of pattern formability, the content of the resin having the repeating unit represented by formula (1) is preferably 30% by mass or more, more preferably 50% by mass or more, based on the total mass of the resin (B1) having an aromatic carboxyl group. The content of the resin having the repeating unit represented by formula (1) may preferably be 100% by mass.

[0114] In some embodiments, a resin containing a structure derived from pyromellitic dianhydride can be suitably used as the resin (B1) having an aromatic carboxyl group. For example, a resin produced by combining the compounds described below as resin raw materials can be suitably used. The resin can be produced according to the synthesis method described above, but the resins (b1-1) to (b1-5) described below can be more specifically produced by the method described in the Examples below. Resin (b1-1): A resin having a structure derived from methacrylic acid, methyl methacrylate, ethyl acrylate, tert-butyl acrylate, 3-mercapto-1,2-propanediol, and pyromellitic dianhydride. In some embodiments, the resin may have an acid value of 35 to 120 mg KOH / g and a weight average molecular weight of 5,000 to 25,000.

[0115] Resin (b1-2): A resin having a structure derived from pyromellitic dianhydride, 3-mercapto-1,2-propanediol, tert-butyl acrylate, tert-butyl methacrylate, (3-ethyloxetan-3-yl)methyl methacrylate, methyl methacrylate, methacrylic acid, and 2-hydroxyethyl methacrylate. In some embodiments, the acid value of the resin may be 35 to 120 mg KOH / g, and the weight average molecular weight may be 5,000 to 25,000.

[0116] Resin (b1-3): A resin having a structure derived from 3-mercapto-1,2-propanediol, pyromellitic dianhydride, 2-hydroxypropyl methacrylate, ethyl acrylate, tert-butyl acrylate, 2-methoxyethyl acrylate, methyl acrylate, methacrylic acid, and 2-methacryloyloxyethyl isocyanate. In some embodiments, the acid value of the resin may be 35 to 120 mgKOH / g, and the weight average molecular weight may be 5,000 to 25,000.

[0117] Resin (b1-4): a resin having a structure derived from tert-butyl acrylate, methyl methacrylate, ethyl acrylate, methacrylic acid, 3-mercapto-1,2-propanediol, pyromellitic dianhydride, and 3-methoxybutanol. In one embodiment, the acid value of the resin may be 70 to 150 mgKOH / g, and the weight average molecular weight may be 7,000 to 15,000.

[0118] Resin (b1-5): A resin having a structure derived from 1-dodecanol, ε-caprolactone, and pyromellitic dianhydride. In one embodiment, the acid value of the resin may be 35 to 80 mgKOH / g, and the weight average molecular weight may be 2,500 to 10,000.

[0119] (Resin (B2) having no aromatic carboxyl group) From the viewpoint of pattern formability and durability, the resin (B) preferably contains, as a binder resin, a resin (B2) having no aromatic carboxyl group in addition to the resin (B1) having an aromatic carboxyl group.

[0120] The resin (B2) having no aromatic carboxyl group is not particularly limited as long as it is the resin (B1) having no aromatic carboxyl group, and known resins can be used, such as (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.

[0121] The resin (B2) without an aromatic carboxyl group is preferably a resin having a repeating unit derived from a polycyclic alicyclic hydrocarbon group-containing compound and a repeating unit derived from an acidic group-containing compound (however, the acidic group excludes aromatic carboxyl groups). Homopolymers of polycyclic alicyclic hydrocarbon group-containing compounds have a high glass transition temperature and improved resistance. Therefore, it is presumed that chipping and peeling during development with an alkaline developer are suppressed, improving pattern formability. Furthermore, the presence of an acidic group improves developability.

[0122] Examples of resins having a repeating unit derived from a polycyclic alicyclic hydrocarbon group-containing compound and a repeating unit derived from an acidic group-containing compound include copolymers of a polycyclic alicyclic hydrocarbon group-containing compound and an acidic group-containing compound, and copolymers of a polycyclic alicyclic hydrocarbon group-containing compound, an acidic group-containing compound, and another compound copolymerizable with them.

[0123] [Repeating units derived from polycyclic alicyclic hydrocarbon group-containing compounds] Examples of polycyclic alicyclic hydrocarbon group-containing compounds include isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, adamantyl (meth)acrylate, etc. These can be used alone or in combination of two or more. Among these, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, and dicyclopentanyloxyethyl (meth)acrylate are preferred.

[0124] The content of repeating units derived from polycyclic alicyclic hydrocarbon group-containing compounds is preferably from 1 to 60 mol %, more preferably from 1 to 50 mol %, of all repeating units in the resin.

[0125] [Repeating units derived from acidic group-containing compounds] Examples of acidic group-containing compounds (excluding compounds having an aromatic carboxyl group) include (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-acryloyloxyethylhexahydrophthalic acid, vinyl sulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, tert-butylacrylamidosulfonic acid, and 2-(meth)acryloyloxyethyl acid phosphate. These can be used alone or in combination of two or more.

[0126] The repeating unit derived from the acidic group-containing compound also includes a structure in which an acid anhydride (modified compound) is added to a hydroxyl group contained in the resin. Examples of the acid anhydride include succinic anhydride, phthalic anhydride, and 1,2,3,6-tetrahydrophthalic anhydride. Another example is a structure in which an unsaturated monobasic acid (modifying compound) is added to an epoxy group contained in a resin, and an acid anhydride (modifying compound) is added to the resulting hydroxyl group.

[0127] The content of repeating units derived from the acidic group-containing compound is preferably from 1 to 40 mol %, more preferably from 5 to 30 mol %, of all repeating units in the resin.

[0128] [Repeating unit having a polymerizable unsaturated group] From the viewpoint of pattern formability, it is more preferable that the resin having a repeating unit derived from a polycyclic alicyclic hydrocarbon group-containing compound and a repeating unit derived from an acidic group-containing compound further contains a repeating unit having a polymerizable unsaturated group. It is presumed that the polymerizable unsaturated group forms a crosslinked structure in the exposure step, suppresses chipping and peeling during development with an alkaline developer, and improves pattern formability. Examples of the polymerizable unsaturated group include a vinyl group, a (meth)allyl group, a (meth)acryloyl group, a (meth)acryloyloxy group, and a (meth)acryloylamide group.

[0129] Examples of repeating units having a polymerizable unsaturated group include those obtained by reacting a hydroxyl group, a carboxyl group, or an epoxy group present in a resin with a compound having a functional group reactive with these groups and a polymerizable unsaturated group. Examples of the compound having a functional group and a polymerizable unsaturated group include 2-(meth)acryloyloxyethyl isocyanate, 2-(2-(meth)acryloyloxyethyloxy)ethyl isocyanate, 1,1-bis[methacryloyloxy]ethyl isocyanate, (meth)acrylic acid, 2-(meth)acryloyloxyethyl succinic acid, 2-(meth)acryloyloxyethylhexylhydrophthalic acid, β-carboxyethyl (meth)acrylate, ω-carboxypolycaprolactone (meth)acrylate, glycidyl (meth)acrylate, 2-methylglycidyl (meth)acrylate, and 2-ethylglycidyl (meth)acrylate.

[0130] The content of the repeating unit having a polymerizable unsaturated group is preferably from 5 to 80 mol %, more preferably from 10 to 70 mol %, of all repeating units in the resin.

[0131] As described above, the resin (B2) having no aromatic carboxyl group has a repeating unit derived from a polycyclic alicyclic hydrocarbon group-containing compound and a repeating unit derived from an acidic group-containing compound, and more preferably a repeating unit having a polymerizable unsaturated group. When the resin (B2) has a repeating unit derived from an acidic group-containing compound and a repeating unit having a polymerizable unsaturated group, the acidic group and the polymerizable unsaturated group may be contained in the same repeating unit. In some embodiments, the resin (B2) having no aromatic carboxyl group may further contain a repeating unit (other repeating unit) different from the various repeating units described above.

[0132] For example, the other repeating units may include repeating units derived from the compounds exemplified below. 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, 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)acryloyloxymethyloxetane, 2-(acetoacetoxy)ethyl (meth)acrylate, 3-(meth)acrylo Acryloyloxypropylmethyldimethoxysilane, 3-(meth)acryloyloxypropylethyldimethoxysilane, 3-(meth)acryloyloxypropylmethyldiethoxysilane, 3-(meth)acryloyloxypropylethyldiethoxysilane, 3-(meth)acryloyloxypropyltrimethoxysilane, 3-(meth)acryloyloxypropyltriethoxysilane, 8-(meth)acryloyloxyoctyltrimethoxysilane, Malonic acid-2-[[[[(2-methyl-1-oxo-2-propenyl)oxy]ethyl]amino]carbonyl]-1,3-diethyl ester, 2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl (meth)acrylate, 2-[O-(1'-methylpropylideneamino)carboxyamino]ethyl (meth)acrylate, 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, 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, methoxyethyl (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, Toxic polytetramethylene glycol (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, styrene, α-methylstyrene, p-vinyltoluene, p-chlorostyrene, vinylnaphthalene, (meth)acrylamide, N,N-dimethyl (meth)acrylamide, N,N-diethyl (meth)acrylamide, N-isopropyl (meth)acrylamide, diacetone (meth)acrylamide, acryloylmorpholine, ethyl vinyl ether, n-propyl vinyl ether, isopropyl alcohol Propyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, 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-(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 Imide, 9-maleimidoacridine, 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, di(2-ethylhexyl)-2,2'-[oxybis(methylene)]bis-2-propenoate, etc.

[0133] The acid value of the resin (B2) having no aromatic carboxyl group is preferably 20 to 250 mgKOH / g, more preferably 30 to 200 mgKOH / g. In some embodiments, the acid value of the resin (B2) may be preferably 35 to 180 mgKOH / g, more preferably 40 to 160 mgKOH / g.

[0134] The weight average molecular weight of the resin (B2) having no aromatic carboxyl group is preferably 3,000 to 60,000, more preferably 3,500 to 50,000. In some embodiments, the weight average molecular weight of the resin (B2) may be preferably 4,000 to 40,000, more preferably 4,500 to 30,000.

[0135] The resin (B2) having no aromatic carboxyl group can be used alone or in combination of two or more kinds. The content of the resin (B2) having no aromatic carboxyl group is preferably from 15 to 95 mass %, more preferably from 20 to 90 mass %, based on the total mass of the resin (B).

[0136] In some embodiments, the mass ratio of the resin (B1) having an aromatic carboxyl group to the resin (B2) not having an aromatic carboxyl group is preferably 90:10 to 10:90, more preferably 85:15 to 15:85.

[0137] In some embodiments, the resin (B2) not having an aromatic carboxyl group preferably contains a repeating unit derived from a polycyclic alicyclic hydrocarbon group-containing compound and a repeating unit derived from an acidic group-containing compound. In other embodiments, the resin (B2) preferably contains, in addition to the repeating unit, a repeating unit having a polymerizable unsaturated group. For example, resins produced by combining the compounds described below as resin raw materials can be suitably used. The resins can be produced according to the synthesis method described above, but the resins (b2-1) to (b2-6) described below can be more specifically produced by the method described in the Examples below.

[0138] Resin (b2-1): A resin having a structure derived from styrene / dicyclopentanyl methacrylate / glycidyl methacrylate+acrylic acid / glycidyl methacrylate+acrylic acid+succinic anhydride, as shown below. In one embodiment, the resin may have an acid value of 40 to 160 mgKOH / g and a weight-average molecular weight of 3,000 to 30,000.

[0139] [ka]

[0140] Resin (b2-2): A resin having a structure derived from 2-ethylhexyl acrylate / dicyclopentanyl methacrylate / glycidyl methacrylate+acrylic acid / glycidyl methacrylate+acrylic acid+tetrahydrophthalic anhydride, as shown below. In one embodiment, the acid value of the resin may be 20 to 140 mgKOH / g, and the weight average molecular weight may be 4,000 to 25,000.

[0141] [ka]

[0142] Resin (b2-3): A resin having a structure derived from benzyl methacrylate / dicyclopentanyl methacrylate / methacrylic acid / methacrylic acid+glycidyl methacrylate, as shown below. In one embodiment, the acid value of the resin may be 40 to 160 mgKOH / g, and the weight average molecular weight may be 4,000 to 25,000.

[0143] [ka]

[0144] Resin (b2-4): A resin having a structure derived from benzyl methacrylate / dicyclopentanyl methacrylate / methacrylic acid, as shown below. In one embodiment, the resin may have an acid value of 40 to 160 mgKOH / g and a weight average molecular weight of 4,000 to 25,000.

[0145] [ka]

[0146] Resin (b2-5): A resin having a structure derived from Karenz MOI-DEM / 2-hydroxyethyl methacrylate / dicyclopentanyl methacrylate / methyl methacrylate / methacrylic acid, as shown below. In one embodiment, the acid value of the resin may be 40 to 160 mg KOH / g, and the weight average molecular weight may be 4,000 to 25,000.

[0147] [ka]

[0148] Resin (b2-6): A resin having a structure derived from 2-hydroxyethyl methacrylate / Aronix M-110 / n-butyl methacrylate / benzyl methacrylate / methacrylic acid, as shown below. In some embodiments, the acid value of the resin may be 60 to 180 mg KOH / g, and the weight average molecular weight may be 10,000 to 35,000.

[0149] [ka]

[0150] [Polymerizable compound (C)] The wavelength-converting photosensitive composition of this embodiment contains a polymerizable compound (C).

[0151] The polymerizable compound (C) is not particularly limited, and may be any known compound. For example, a monomer or oligomer having a polymerizable unsaturated group may be used. Examples of the polymerizable unsaturated group include a vinyl group, a (meth)allyl group, a (meth)acryloyl group, and a (meth)acryloyloxy group.

[0152] Examples of the polymerizable compound (C) 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.

[0153] (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.

[0154] Examples of commercially available lactone-modified polymerizable compounds include KAYARAD DPCA-20, DPCA-30, and DPCA-60 manufactured by Nippon Kayaku Co., Ltd.

[0155] (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.

[0156] Examples of the polyhydric alcohol include ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, glycerin, trimethylolpropane, ditrimethylolpropane, pentaerythritol, and dipentaerythritol.

[0157] Examples of the dicarboxylic acids include malonic acid, succinic acid, maleic acid, glutaric acid, phthalic acid, itaconic acid, and the like.

[0158] 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.

[0159] 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.

[0160] (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.

[0161] 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.

[0162] (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.

[0163] 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.

[0164] 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.

[0165] 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.

[0166] 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.

[0167] 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.

[0168] Alternatively, the polyfunctional isocyanate may be reacted with a diol compound having a carboxyl group to synthesize a precursor having isocyanate groups at both ends, followed by reacting the precursor with the hydroxyl group-containing (meth)acrylate.

[0169] Examples of the diol compound having a carboxyl group include 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, 2,2-dimethylolpentanoic acid, and 2,2-dimethylolhexanoic acid.

[0170] 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.

[0171] (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 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.

[0172] 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).

[0173] 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.

[0174] The (meth)acrylate compound (X) can be used alone or in combination of two or more kinds.

[0175] 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.

[0176] The amine compound (Y) can be used alone or in combination of two or more kinds.

[0177] 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.

[0178] 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.

[0179] 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.

[0180] 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 its durability is easily improved.

[0181] 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).

[0182] 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.

[0183] The polyisocyanate compounds (Z) can be used alone or in combination of two or more.

[0184] The method for the urethane reaction between the precursor and the polyisocyanate compound (Z) is not particularly limited, and any known method can be used, such as the method described in JP-A-2018-517797.

[0185] 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.

[0186] (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.

[0187] 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.

[0188] (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.

[0189] 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.

[0190] The polymerizable compound (C) can be used alone or in combination of two or more kinds.

[0191] The content of the polymerizable compound (C) is preferably from 1 to 70 mass %, more preferably from 5 to 60 mass %, based on the total mass of the nonvolatile components of the wavelength-converting photosensitive composition.

[0192] [Polymerization initiator (D)] The wavelength-converting photosensitive composition of this embodiment contains a polymerization initiator (D).

[0193] The polymerization initiator (D) is not particularly limited, and known compounds can be used, such as compounds that generate radicals by the action of light or heat to initiate or promote 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.

[0194] 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.

[0195] 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.

[0196] 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.

[0197] The polymerization initiator (D) can be used alone or in combination of two or more kinds.

[0198] The content of the polymerization initiator (D) is preferably from 0.1 to 20 mass %, more preferably from 0.3 to 10 mass %, based on the total mass of the nonvolatile components of the wavelength-converting photosensitive composition.

[0199] (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 (D1) From the viewpoint of pattern formation, the polymerization initiator (D) is selected from those having an absorption coefficient of 5.0×10 in propylene glycol monomethyl ether acetate at a wavelength of 365 nm. 3 It is preferable that the wavelength conversion layer contains a polymerization initiator (D1) (hereinafter simply referred to as polymerization initiator (D1)) with a viscosity of L / mol cm or more. The polymerization initiator (D1) facilitates photoreaction and hardens even at the bottom of the wavelength conversion layer. This is thought to prevent chipping and peeling during development with an alkaline developer, improving pattern formability.

[0200] The absorption coefficient of the polymerization initiator (D1) in propylene glycol monomethyl ether acetate at a wavelength of 365 nm is 5.0 × 10 3 ~5.0×10 4 mL / mol cm is preferred, 1.0 × 10 4~4.0×10 4 L / mol·cm is more preferred.

[0201] The polymerization initiator (D1) preferably contains one or more compounds selected from the group consisting of an oxime compound having a benzofuran structure, an oxime compound having a carbazole structure, and an oxime compound having an indole structure, and more preferably contains an oxime compound having a carbazole structure.

[0202] Specific examples of the polymerization initiator (D1) are shown below, but the present invention is not limited to these.

[0203] [ka] [ka]

[0204] [ka] [ka]

[0205] Among the above compounds, it is more preferable to include at least one compound selected from the group consisting of (D1-1) to (D1-6), and it is particularly preferable to include at least two compounds. In some embodiments, it is preferable to use (D1-1) and (D1-2) in combination.

[0206] The content of the polymerization initiator (D1) is preferably from 10 to 100 mass %, more preferably from 20 to 100 mass %, based on the total mass of the polymerization initiator (D).

[0207] [Scattered particles (E)] From the viewpoint of wavelength conversion efficiency, the wavelength conversion photosensitive composition of this embodiment preferably contains scattering particles (E). This increases the chance of collision between light from the light source and the organic fluorescent particles (A), thereby improving wavelength conversion efficiency. Furthermore, although a portion of the light converted by the organic fluorescent particles (A) is reflected at the interface with the wavelength conversion layer and returns to the inside of the layer, the scattering particles (E) change the traveling direction of the light and extract it to the outside, thereby improving wavelength conversion efficiency.

[0208] The scattering particles (E) are not particularly limited, and known compounds can be used. Examples of the scattering particles (E) include inorganic particles, organic particles, and organic-inorganic composite particles.

[0209] The average particle size of the scattering particles (E) is preferably from 0.1 to 1.0 μm, more preferably from 0.2 to 0.8 μm, from the viewpoint of pattern formability and wavelength conversion efficiency.

[0210] The refractive index of the scattering particles (E) is preferably from 1.7 to 3.0, more preferably from 1.9 to 3.0, from the viewpoint of wavelength conversion efficiency.

[0211] The scattering particles (E) can be used alone or in combination of two or more kinds.

[0212] From the viewpoints of pattern formability and wavelength conversion efficiency, the content of the scattering particles (E) is preferably 1 to 20 mass %, more preferably 5 to 15 mass %, based on the total mass of the nonvolatile components of the wavelength conversion photosensitive composition.

[0213] From the viewpoints of pattern formability and wavelength conversion efficiency, the wavelength conversion photosensitive composition of this embodiment preferably has a total amount of the organic fluorescent particles (A) and the scattering particles (E) of 30 to 80 mass %, more preferably 40 to 70 mass %, based on the total mass of the nonvolatile components of the wavelength conversion photosensitive composition. The mass ratio of the organic fluorescent particles (A) to the scattering particles (E) is preferably from 95:5 to 60:40, more preferably from 90:10 to 75:25, from the viewpoints of pattern formability and wavelength conversion efficiency.

[0214] (Inorganic particles (E1)) From the viewpoint of wavelength conversion efficiency, the wavelength conversion photosensitive composition of this embodiment more preferably contains inorganic particles (E1) as the scattering particles (E).

[0215] Examples of inorganic particles (E1) 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, gold, etc. Among these, titanium oxide is preferred from the viewpoint of wavelength conversion efficiency.

[0216] The inorganic particles (E1) may be either hollow particles or solid particles, but from the viewpoint of wavelength conversion efficiency, solid particles are preferred. Hollow particles refer to 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. By "substantially free," we mean that the void content of the particle is less than 5%.

[0217] The inorganic particles (E1) can be used alone or in combination of two or more kinds.

[0218] The content of the inorganic particles (E1) is preferably from 10 to 100 mass %, more preferably from 20 to 100 mass %, based on the total mass of the scattering particles (E).

[0219] [Titanium oxide] The titanium oxide is not particularly limited, and known compounds can be used.

[0220] The crystal structure of titanium oxide may be either anatase type or rutile type, but from the viewpoints of stability and wavelength conversion efficiency, the rutile type is preferred.

[0221] The shape of titanium oxide may be isotropic (for example, spherical, polyhedral, etc.), anisotropic (for example, needle, rod, plate, etc.), or amorphous.

[0222] Titanium oxide can be used in which at least a portion of the surface is 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, organic silicon compound, organic phosphoric acid compound, carboxylic acid, etc. The surface treatment agent can be used alone or in combination of two or more types. From the viewpoint of weather resistance and pattern formability, it is 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.

[0223] 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.

[0224] Commercially available titanium oxide products include, for example: Ishihara Sangyo Co., Ltd. Typepaque 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-Cuper70, CR-80, CR-85, CR-90, CR-90-2, CR-93, CR-95, CR-953, CR-9 7,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, TTO-51(A), TTO-51(C), TTO-55(A), TTO-55(B), TTO-55(C), TTO-55(D), A-100, A-220, Sakai Chemical Industry Co., Ltd.'s R-3L, R-5N, R-7E, R-11P, R-21, R-25, R-32, R-42, R-44, 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's 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-1 00Z,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, Titanium Industries KR-310, KR-380, KR-380N, ST-485SA15, Examples include TR-600, TR-700, TR-750, TR-840, and TR-900 manufactured by Fuji Titanium Industry Co., Ltd.

[0225] Titanium oxide can be used alone or in combination of two or more types.

[0226] [Sensitizer (F)] The wavelength-converting photosensitive composition of this embodiment can contain a sensitizer (F).

[0227] The sensitizer (F) is not particularly limited, and known compounds can be used. For example, polymethine dyes such as 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 oxonol compounds, acridine compounds, azine compounds, thiazine compounds, oxazine compounds, indoline compounds, azulene compounds, azulenium compounds, sucrose compounds, and the like. Examples of the compound include allylium-based compounds, porphyrin-based compounds, tetraphenylporphyrin-based compounds, triarylmethane-based compounds, tetrabenzoporphyrin-based compounds, tetrapyrazinoporphyrazine-based compounds, phthalocyanine-based compounds, tetraazaporphyrazine-based compounds, tetraquinoxalylporphyrazine-based compounds, naphthalocyanine-based compounds, subphthalocyanine-based compounds, pyrylium-based compounds, thiopyrylium-based compounds, tetraphyrin-based compounds, annulene-based compounds, spiropyran-based compounds, spirooxazine-based compounds, thiospiropyran-based compounds, metal arene complexes, organic ruthenium complexes, and benzophenone-based compounds.

[0228] The sensitizer (F) can be used alone or in combination of two or more kinds.

[0229] The content of the sensitizer (F) is preferably from 5 to 200 parts by mass, more preferably from 10 to 150 parts by mass, based on 100 parts by mass of the polymerization initiator (D).

[0230] [Thermal crosslinkable compound (G)] The wavelength-converting photosensitive composition of this embodiment can contain a thermally crosslinkable compound (G).

[0231] The thermally crosslinkable compound (G) is not particularly limited as long as it is a compound having a thermally crosslinkable group, and known compounds can be used. Examples 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.

[0232] (epoxy compounds) The epoxy compound is not particularly limited, and known compounds can be used, for example, 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.

[0233] 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.

[0234] The epoxy compound is preferably a compound having 2 to 50 epoxy groups in the molecule.

[0235] 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.

[0236] (Oxetane compounds) The oxetane compound is not particularly limited, and known compounds can be used. For example, (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-(triethyl)oxetane] 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 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.

[0237] 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.

[0238] (melamine compounds) The melamine compound is a compound having a melamine ring (triazine ring) structure, and is preferably a compound having a methylol group.

[0239] 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.

[0240] (Blocked isocyanate compounds) A blocked isocyanate compound is a compound obtained by reacting a compound having two or more isocyanate groups in the molecule with a blocking agent.

[0241] 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.

[0242] Examples of the blocking agent include the compounds described above. Among these, 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 is preferred.

[0243] Examples of commercially available products include 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.

[0244] The thermally crosslinkable compound (G) can be used alone or in combination of two or more kinds.

[0245] The content of the thermally crosslinkable compound (G) is preferably from 0.5 to 40 mass %, more preferably from 1 to 30 mass %, based on the total mass of the nonvolatile components of the wavelength-converting photosensitive composition.

[0246] [Thiol-based chain transfer agents (H)] The wavelength-converting photosensitive composition of this embodiment can contain a thiol-based chain transfer agent (H).

[0247] The thiol chain transfer agent (H) is not particularly limited, and known compounds can be used, such as 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.

[0248] The thiol chain transfer agent (H) can be used alone or in combination of two or more kinds.

[0249] The content of the thiol chain transfer agent (H) is preferably 0.5 to 10% by mass based on the total mass of the nonvolatile components of the wavelength-converting photosensitive composition.

[0250] [Silane coupling agent (I)] The wavelength-converting photosensitive composition of this embodiment can contain a silane coupling agent (I).

[0251] The silane coupling agent (I) 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 (I) 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.

[0252] The silane coupling agent (I) is not particularly limited, and known compounds can be used. For example, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, vinyltrimethoxysilane, vinyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, silane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, tris-(trimethoxysilylpropyl)isocyanurate, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, p-styryltrimethoxysilane, 3-ureidopropyltrialkoxysilane, N,N-bis[3-(trimethoxysilyl)propyl]ethylenediamine, bis(3-triethoxysilyl)propyl)tetrasulfide, 1,6-bis(trimethoxysilyl)hexane, 1,8-bis(trimethoxysilyl)octane, tris(trimethoxysilylpropyl)isocyanate, and the like.

[0253] Commercially available silane coupling agents (I) 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.

[0254] The silane coupling agent (I) may also be a polymer type, such as a polysiloxane type or an organic polymer type.

[0255] 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.

[0256] The organic polymer type is a silane coupling agent (I) 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.

[0257] The silane coupling agent (I) can be used alone or in combination of two or more kinds.

[0258] The content of the silane coupling agent (I) is preferably 0.1 to 10 mass % based on the total mass of the nonvolatile components of the wavelength-converting photosensitive composition.

[0259] [Polymerization inhibitor (J)] The wavelength-converting photosensitive composition of this embodiment may contain a polymerization inhibitor (J).

[0260] The polymerization inhibitor (J) is not particularly limited, and known compounds can be used. For example, 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-butyl resorcinol; alkylresorcinol compounds such as resorcinol, 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.

[0261] The polymerization inhibitor (J) can be used alone or in combination of two or more kinds.

[0262] The content of the polymerization inhibitor (J) is preferably 0.01 to 0.5% by mass relative to the total mass of the nonvolatile components of the wavelength-converting photosensitive composition.

[0263] [Ultraviolet absorber (K)] The wavelength-converting photosensitive composition of this embodiment can contain an ultraviolet absorber (K).

[0264] The ultraviolet absorber (K) is not particularly limited, and known compounds can be used, such as 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.

[0265] Examples of benzotriazole compounds include 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-(2-hydroxy-5-tert-butylphenyl)-2H-benzotriazole, 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole, 2-(3-tert-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole, a mixture of 5% 2-methoxy-1-methylethyl acetate and 95% benzenepropanoic acid, 3-(2H-benzotriazol-2-yl)-(1,1-dimethylethyl)-4-hydroxy, C7-9 side chain and linear alkyl esters, 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, 2-(2H-benzotriazol-2-yl) -4-(1,1,3,3-tetramethylbutyl)phenol, 2,2'-methylenebis[6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol], 2-(2H-benzotriazol-2-yl)-p-cresol, 2-(5-chloro-2H-benzotriazol-2-yl)-6-tert-butyl-4-methylphenol, 2-(3,5-di-tert-amyl-2-hydroxyphenyl)benzo triazole, 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole, octyl-3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl]propionate, 2-ethylhexyl-3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl]propionate.

[0266] Examples of commercially available products include 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.

[0267] Examples of triazine compounds include 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-n-octyloxyphenyl)-1,3,5-triazine, 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-[3-(dodecyloxy)-2-hydroxypropoxy]phenol, and the reaction product of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine with (2-ethylhexyl)-glycidic acid ester. Examples of such compounds include 2,4-bis[2-hydroxy-4-butoxyphenyl]-6-(2,4-dibutoxyphenyl)-1,3,5-triazine, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-(hexyloxy)phenol, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]phenol, and 2,4,6-tris(2-hydroxy-4-hexyloxy-3-methylphenyl)-1,3,5-triazine.

[0268] Examples of commercially available products include 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.

[0269] Examples of benzophenone compounds include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid-3-oxide, 2-hydroxy-4-n-octoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, and 2-hydroxy-4-methoxy-2'-carboxybenzophenone.

[0270] Examples of commercially available products include 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.

[0271] Examples of salicylate compounds include phenyl salicylate, p-octylphenyl salicylate, and p-tert-butylphenyl salicylate.

[0272] The ultraviolet absorbers (K) can be used alone or in combination of two or more.

[0273] The content of the ultraviolet absorber (K) is preferably 0.1 to 5.0% by mass relative to the total mass of the nonvolatile components of the wavelength conversion photosensitive composition.

[0274] [Antioxidant (L)] The wavelength-converting photosensitive composition of this embodiment can contain an antioxidant (L).

[0275] The antioxidant (L) is not particularly limited, and known compounds can be used. Examples 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.

[0276] Examples of hindered phenol antioxidants include 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 1,1,3-tris-(2'-methyl-4'-hydroxy-5'-tert-butylphenyl)-butane, 4,4'-butylidene-bis-(2-tert-butyl-5-methylphenol), 3-(3,5-di-tert-butyl-4-hydroxyphenyl)stearyl propionate, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 3,9-bis[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]Undecane, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylmethyl)-2,4,6-trimethylbenzene, 1,3,5-tris(3-hydroxy-4-tert-butyl-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 2,2'-methylenebis(6-tert-butyl-4-ethylphenol), 2,2'-thiodiethylbis(3,5-di-t tert-butyl-4-hydroxyphenyl)-propionate, N,N-hexamethylenebis(3,5-di-tert-butyl-4-hydroxy-hydrocinnamamide), iso-octyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 4,6-bis(dodecylthiomethyl)-o-cresol, calcium salt of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid monoethyl ester , 4,6-bis(octylthiomethyl)-o-cresol, bis[3-(3-methyl-4-hydroxy-5-tert-butylphenyl)propionic acid]ethylenebisoxybisethylene, 1,6-hexanediol bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-tert-butylanilino)-1,3,5-triazine , 2,2'-thio-bis-(6-tert-butyl-4-methylphenol), 2,5-di-tert-amyl-hydroquinone, 2,6-di-tert-butyl-4-nonylphenol, 2,2'-isobutylidene-bis-(4,6-dimethyl-phenol), 2,2'-methylene-bis-(6-(1-methyl-cyclohexyl)-p-cresol), 2,4-dimethyl-6-(1-methyl-cyclohexyl)-phenol, etc.

[0277] Examples of commercially available products 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.

[0278] Examples of the hindered amine antioxidant include tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)1,2,3,4-butanetetracarboxylate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1-undecanoxy-2,2,6,6-tetramethylpiperidin-4-yl)carbonate, 1,2,2,6,6-pentamethyl-4-piperidyl tetramethyl-4-piperidyl methacrylate, 2,2,6,6-tetramethyl-4-piperidyl methacrylate, polycondensate of dimethyl succinate and 1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine, poly[[6-[(1,1,3,3-tetramethylbutyl)amino]-s-triazine-2,4-diyl]-[(2,2,6,6-tetramethyl-4-piperidyl)imino]-hexamethylene-[(2,2,6,6-tetramethyl-4-piperidyl)imino]], 4-hydroxy-2,2,6,6-tetramethyl-1- Ester of piperidineethanol and 3,5,5-trimethylhexanoic acid, N,N'-4,7-tetrakis[4,6-bis{N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino}-1,3,5-triazin-2-yl]-4,7-diazadecane-1,10-diamine, decanedioic acid bis(2,2,6,6-tetramethyl-1-(octyloxy)-4-piperidinyl) ester, reaction products of 1,1-dimethylethyl hydroperoxide with octane, bis(1,2,2,6,6-pentamethyl-4-pyridyl)[[3,5-bi N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,6,6-tetramethyl-4-piperidyl-C12-21 and C18 unsaturated fatty acid esters, N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,6,6-tetramethyl-4-piperidyl ...Examples include 6-hexamethylenediamine and 2-methyl-2-(2,2,6,6-tetramethyl-4-piperidyl)amino-N-(2,2,6,6-tetramethyl-4-piperidyl)propionamide.

[0279] Examples of commercially available products 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; and Cyasorb UV-3346, UV-3529, and UV-3853 manufactured by Sun Chemical Company.

[0280] Examples of the phosphorus-based antioxidant include di(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, 2,2'-methylenebis(4,6-di-tert-butylphenyl)2-ethylhexyl phosphite, tris(2,4-di-tert-butylphenyl)phosphite, tris(nonylphenyl)phosphite, tetra(C12 to C15 alkyl)-4,4'-isopropylidene diphenyl diphosphite, diphenyl mono (2-ethylhexyl) phosphite, diphenyl isodecyl phosphite, tris(isodecyl) phosphite, triphenyl phosphite, tetrakis(2,4-di-tert-butylphenyl)-4,4-biphenyl diphosphonate, tris(tridecyl) phosphite, phenyl isooctyl phosphite, phenyl isodecyl phosphite, phenyl di(tridecyl) phosphite, diphenyl isooctyl phosphite, diphenyl tridecyl phosphite, 4,4'-isopropylidenediphenone tris(di-tert-butylphenyl)pentaerythritol diphosphite, tris(nonylphenyl) phosphite, tris(biphenyl) phosphite, di(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, di(nonylphenyl)pentaerythritol diphosphite, phenyl bisphenol A pentaerythritol diphosphite, tetratridecyl 4,4'-butylidenebis(3-methyl-6-tert-butylphenol) diphosphite, hexatridecyl 1,1,3-tri Examples of suitable phosphate compounds include bis(2-methyl-4-hydroxy-5-tert-butylphenyl)butane triphosphite, 3,5-di-tert-butyl-4-hydroxybenzyl phosphite diethyl ester, sodium bis(4-tert-butylphenyl)phosphite, sodium-2,2-methylene-bis(4,6-di-tert-butylphenyl)-phosphite, 1,3-bis(diphenoxyphosphonyloxy)-benzene, and ethyl bis(2,4-di-tert-butyl-6-methylphenyl)phosphite.

[0281] Examples of commercially available products include 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, and HostanoxP-EPQ manufactured by Clariant Chemicals.

[0282] Examples of sulfur-based antioxidants include 2,2-bis{[3-(dodecylthio)-1-oxopropoxy]methyl}propane-1,3-diylbis[3-(dodecylthio)propionate], ditridecyl 3,3'-thiobispropionate, 2,2-thio-diethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2,4-bis[(octylthio)methyl]-o-cresol, and 2,4-bis[(laurylthio)methyl]-o-cresol.

[0283] Examples of commercially available products include Adekastab AO-412S and AO-503 manufactured by ADEKA Corporation, and KEMINOXPLS manufactured by Chemipro Chemicals.

[0284] The antioxidant (L) can be used alone or in combination of two or more kinds.

[0285] The content of the antioxidant (L) is preferably 0.1 to 5.0% by mass relative to the total mass of the nonvolatile components of the wavelength conversion photosensitive composition.

[0286] [Leveling agent (M)] The wavelength-converting photosensitive composition of this embodiment can contain a leveling agent (M).

[0287] The leveling agent (M) is not particularly limited, and known compounds can be used, such as silicone-based leveling agents, fluorine-based leveling agents, acrylic-based leveling agents, and acetylene diol-based leveling agents.

[0288] Examples of commercially available silicone leveling agents include the following: BYK-Chemie BYK-300, 306, 310, 313, 315N, 320, 322, 323, 330, 331, 333, 342, 345, 346, 347, 348, 349, 370, 377, 378, 3455, UV3510, 3570, FZ-7002, 2110, 2122, 2123, 2191, 5609 manufactured by Toray Dow Corning Co., Ltd. Shin-Etsu Chemical Co., Ltd.'s 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; Evonik's TegoGlide 432, 440, and 450; TegoWet 250, 260, 265, 270, and 280; MEGAFACE EFS-131, EFS-321, EFS-521, EFS-801, etc. manufactured by DIC Corporation.

[0289] Commercially available fluorine-based leveling agents include, for example: AGC Seimi Chemical's Surflon S-242, 243, 420, 611, 651, 386, DIC 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, RS-72-K, Sumitomo 3M FC-4430, 4432, Mitsubishi Materials Electronics Co., Ltd. EF-PP31N09, EF-PP33G1, EF-PP32C1, Examples include Futergent 602A manufactured by Neos Corporation.

[0290] 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.

[0291] 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.

[0292] The leveling agent (M) can be used alone or in combination of two or more kinds.

[0293] The content of the leveling agent (M) is preferably from 0.001 to 2.0 mass %, more preferably from 0.005 to 1.0 mass %, based on the total mass of the nonvolatile components of the wavelength conversion photosensitive composition.

[0294] [Storage stabilizer (N)] The wavelength-converting photosensitive composition of this embodiment may contain a storage stabilizer (N).

[0295] The storage stabilizer (N) is not particularly limited, and known compounds can be used, such as 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.

[0296] The content of the storage stabilizer (N) is preferably 0.05 to 5.0% by mass relative to the total mass of the nonvolatile components of the wavelength conversion photosensitive composition.

[0297] [Organic solvent (O)] The wavelength-converting photosensitive composition of this embodiment can contain an organic solvent (O).

[0298] Examples of the organic solvent (O) include 1,2,3-trichloropropane, 1-methoxy-2-propanol, ethyl 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-methylbutanol. ethyl 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, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol 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, dipropylene glycol methyl ether acetate,Examples of the dipropylene glycol monoethyl ether include 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, and dibasic acid esters.

[0299] From an environmental perspective, the wavelength-converting photosensitive composition of this embodiment preferably does not substantially contain any organic solvents that are aromatic hydrocarbons (toluene, xylene, benzene, chlorobenzene, etc.) "Substantially not containing" means that the wavelength-converting photosensitive composition contains 50 ppm by mass or less, preferably 30 ppm by mass or less, and more preferably 10 ppm by mass or less.

[0300] The organic solvent (O) can be used alone or in combination of two or more kinds.

[0301] The content of the organic solvent (O) is preferably an amount such that the nonvolatile content of the wavelength-converting photosensitive composition is 5 to 70 mass %.

[0302] [Other ingredients (P)] The wavelength conversion photosensitive composition of this embodiment 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 (e.g., organic fluorescent dyes, inorganic fluorescent pigments, quantum dots, quantum dots, etc.), dye derivatives, curing catalysts, acid generators, and salt generators. The content of other components (P) can be appropriately set within a range that does not impair the effects of the present invention.

[0303] [Specific metal element content] The wavelength-converting photosensitive composition of this embodiment preferably contains Li, Na, K, Mg, Ca, Fe, and Cr (hereinafter also referred to as specific metal elements) in a total amount of 500 mass ppm or less.

[0304] A wavelength-converting photosensitive composition having a total amount of specific metal elements within the above range exhibits excellent stability and sensitivity even after storage. The content of specific metal elements can be measured by inductively coupled plasma atomic emission spectroscopy (ICP).

[0305] [Water content] The wavelength-converting photosensitive composition of this embodiment preferably contains water in an amount of 2.0 mass % or less.

[0306] A wavelength-converting photosensitive composition having a water content within the above range exhibits excellent stability and sensitivity even after storage. The water content can be measured by a known method such as the Karl Fischer method.

[0307] [Method for producing wavelength conversion photosensitive composition] The wavelength-converting photosensitive composition of this embodiment can be prepared by mixing the above-mentioned components. When preparing the composition, the components may be mixed together or may be dissolved or dispersed in the polymerizable compound (C) or the organic solvent (O) and then mixed sequentially. For example, a dispersion is produced by adding organic fluorescent particles (A), a resin (B1) having an aromatic carboxyl group, an organic solvent (O), and the like, and dispersing the mixture. The dispersion is then blended with a polymerizable compound (C), a polymerization initiator (D), and the like. The timing of blending each material is optional. The dispersion process can also be performed multiple times.

[0308] 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.

[0309] The wavelength-converting photosensitive composition of this embodiment is preferably used for pattern formation by photolithography, although the present invention is not limited thereto.

[0310] <Wavelength conversion layer> One embodiment of the present invention relates to a wavelength-converting layer formed using the wavelength-converting photosensitive composition of the above embodiment. In some embodiments, the wavelength-converting layer is preferably patterned. However, in other embodiments, the wavelength-converting layer may be used as a planar layer without being patterned.

[0311] [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.

[0312] [Coating process] The wavelength conversion photosensitive composition is applied onto a substrate. Examples of the substrate include substrates made of glass, resin, silicone, and other materials. 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 the upper layer, prevent diffusion of substances, and flatten the surface.

[0313] Any known coating method can be used, such as a dropping method, a slit coating method, a spray method, a roll coating method, a spin coating method, a casting coating method, an inkjet method, flexographic printing, screen printing, gravure printing, or offset printing.

[0314] The thickness of the wavelength conversion layer is preferably 1 to 50.0 μm, more preferably 3 to 20.0 μm. When a conventional resin composition is used to form a wavelength conversion layer, the curability of the resin composition decreases as the film thickness increases, and when a wavelength conversion layer with a thickness exceeding 10 μm is formed, it is difficult to obtain a desired pattern. In contrast, the wavelength conversion photosensitive composition of this embodiment provides excellent pattern formation properties, making it easy to thicken the wavelength conversion layer. According to some embodiments, forming a wavelength conversion layer with a thickness exceeding 10 μm makes it easy to realize a display device with a higher wavelength conversion rate and excellent light-emitting properties.

[0315] [Drying process] The method for drying the wavelength conversion photosensitive composition coated on the substrate is not particularly limited, and any known method can be used, such as reduced pressure drying using a vacuum dryer, heat drying using a hot plate, an IR oven, a convection oven, or the like, or a combination of these methods.

[0316] The drying temperature and time can be adjusted as appropriate. For example, the drying temperature is preferably about 50 to 130° C., and the drying time is preferably about 5 seconds to 5 minutes.

[0317] Next, a pattern is formed. Examples of methods for forming a pattern include photolithography and dry etching. Among these, photolithography is preferred. When the wavelength conversion layer is used as a flat layer, the step of forming a pattern is not necessary, and drying or exposure is performed after coating.

[0318] The method of forming a pattern by photolithography will be described in detail below. The photolithography method includes an exposure step in which the wavelength conversion photosensitive composition of this embodiment is applied to a substrate and dried, and then exposed to light in a pattern through a mask; a development step in which the unexposed portions are removed by development with an alkaline developer; and a post-bake step in which the pattern formed in the development step is heat-treated.

[0319] [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.

[0320] [Development process] Next, by treating with an alkaline developer, the unexposed portions are dissolved in the alkaline developer, leaving only the hardened portions, thereby obtaining a pattern. The alkaline developer may be an aqueous solution containing an alkaline compound, 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.

[0321] [Post-baking process] After development, a heat treatment (post-baking) is performed. Post-baking improves the resistance of the pattern (film). The temperature in the heat treatment is not particularly limited, but is preferably 80 to 260°C. The heating 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.

[0322] <Laminate> An embodiment of the present invention relates to a wavelength conversion member having the wavelength conversion layer of the above embodiment. The wavelength conversion member may be a laminate having the wavelength conversion layer of the above embodiment and a color filter layer. The color filter layer is not particularly limited, but preferably has at least one pixel selected from the group consisting of red pixels, green pixels, blue pixels, and yellow pixels. Known pixels can be used as these pixels.

[0323] <Display device> One embodiment of the present invention relates to a display device having the laminate of the above embodiment. In some embodiments, the display device preferably has an LED or an OLED as a light source. The form used in the display device is not particularly limited as long as it functions as a display device. Examples include a liquid crystal display, an organic EL display, etc.

[0324] Specifically, the configuration may be one 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), or "Display Devices" (by Ibuki Nobuaki, published by Sangyo Tosho Co., Ltd. in 1989).

[0325] FIG. 1 is a schematic cross-sectional view showing an example of the configuration of a display device according to this embodiment. For the sake of explanation, FIG. 1 shows only the characteristic components enlarged. Therefore, the components and their dimensional ratios are not the same as those in the actual display. As shown in FIG. 1, an example of a display device according to this embodiment may have RGBY pixels formed on a TFT (thin film transistor) substrate 10. A light source (blue LED) 11 is provided for each of the four color pixels, and wavelength conversion layers 12 are formed in the R (red), G (green), and Y (yellow) pixels. In the R (red), G (green), and Y (yellow) pixels, blue light from the light source is converted by the wavelength conversion layer, and red, green, and yellow light are generated through the color filter. On the other hand, in the B (blue) pixel, a transparent layer 13 is formed for the light source (blue LED) 11. Therefore, the light from the light source is not color-converted, and blue light is generated. In FIG. 1 , reference symbols 12RCC, 12GCC, and 12YCC denote wavelength conversion layers formed in R, G, and Y pixels, respectively, and reference symbol 14 denotes a partition wall. Reference symbols 15RCF, 15GCF, 15BCF, and 15YCF denote color filters for forming R, G, B, and Y pixels, respectively, and reference symbol 16 denotes a substrate (transparent substrate). According to the display device of this embodiment, light from a light source can be efficiently converted by the wavelength conversion layer, making it easy to realize a full-color display device with excellent luminous efficiency using an LED or the like as a light source. Furthermore, since the wavelength-converting photosensitive composition used to form the wavelength conversion layer has excellent developability and pattern formability, it is easy to realize a high-quality display device with excellent properties such as color reproducibility, contrast, and brightness. [Example]

[0326] 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." In addition, in the present invention, the nonvolatile content (solid content) or nonvolatile content concentration refers to the mass residue after leaving the product to stand in an oven at 110°C for 3 hours.

[0327] Before describing the examples, each measurement method will be explained.

[0328] The weight average molecular weight (Mw), number average molecular weight (Mn), acid value (mgKOH / g), and extinction coefficient (L / mol·cm) of the resin were measured as follows.

[0329] (Molecular weight of resin) The number-average molecular weight (Mn) and weight-average molecular weight (Mw) were measured by gel permeation chromatography (GPC) equipped with an RI detector. The instrument used was an HLC-8220GPC (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.

[0330] (acid number) 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.

[0331] (Extinction coefficient) 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.

[0332] <Production of Resin (B)> (Resin (B1-1) solution having aromatic carboxyl groups) 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 propylene glycol monomethyl ether acetate (PGMAc), and the atmosphere was purged with nitrogen. The reaction vessel was heated to 50°C, and 12 parts 3-mercapto-1,2-propanediol was added with stirring. The temperature was raised to 90°C, and a solution of 2,2'-azobisisobutyronitrile (a polymerization initiator) in PGMAc was added while the reaction was continued for 7 hours. Measurement of the nonvolatile content confirmed that 95% reaction had occurred. 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. The reaction was terminated after confirming that 98% or more of the acid anhydride had been half-esterified by measuring the acid value. After cooling, PGMAc was added to make the nonvolatile content 30% by mass, and a resin (B1-1) solution having aromatic carboxyl groups was prepared. The acid value of the resin was 70 mgKOH / g, and the weight-average molecular weight was 9,000.

[0333] (Resin (B1-2) solution having aromatic carboxyl groups) A reaction vessel equipped with a thermometer, reflux condenser, nitrogen gas inlet, and stirrer was charged with 12 parts of pyromellitic dianhydride, 8.0 parts of 3-mercapto-1,2-propanediol, 50.0 parts of PGMAc, and 0.01 parts of monobutyltin (IV) oxide as a catalyst. After purging with nitrogen gas, the reaction vessel was heated to 100°C and reacted for 7 hours. Acid value measurement confirmed that more than 95% of the acid anhydride had been half-esterified. Next, the reaction vessel was heated to 70°C and charged with 40.0 parts tert-butyl acrylate, 80.0 parts tert-butyl methacrylate, 50.0 parts (3-ethyloxetan-3-yl)methyl methacrylate (Ube Industries, Ltd., "ETERNACOLL® OXMA"), 5.0 parts methyl methacrylate, 5.0 parts methacrylic acid, 20.0 parts 2-hydroxyethyl methacrylate, and 10.0 parts PGMAc. While stirring, the polymerization initiator 2,2'-azobisisobutyronitrile was added in 15 portions every 30 minutes. One hour after the final addition, the nonvolatile content was measured, and the reaction was terminated after confirming that 95% or more of the reaction had occurred. After cooling, PGMAc was added to adjust the nonvolatile content to 30% by mass to prepare a resin (B1-2) solution having aromatic carboxyl groups. The resin had an acid value of 60 mgKOH / g and a weight-average molecular weight of 18,000.

[0334] (Resin (B1-3) solution having aromatic carboxyl groups) A reaction vessel equipped with a thermometer, reflux condenser, nitrogen gas inlet, and stirrer was charged with 108 parts of 3-mercapto-1,2-propanediol, 174 parts of pyromellitic dianhydride, 650 parts of PGMAc, and 0.2 parts of monobutyltin (IV) oxide as a catalyst. After purging with nitrogen gas, the reaction was carried out at 120°C for 5 hours (first step). Acid value measurement confirmed that 95% or more of the acid anhydride had been half-esterified. Next, 160 parts of the compound obtained in the first step (based on nonvolatile content), 200 parts of 2-hydroxypropyl methacrylate, 200 parts of ethyl acrylate, 150 parts of tert-butyl acrylate, 200 parts of 2-methoxyethyl acrylate, 200 parts of methyl acrylate, 50 parts of methacrylic acid, and 663 parts of PGMAc were charged into a reaction vessel, which was heated to 80°C. 2,2'-azobis(2,4-dimethylvaleronitrile) was added as a polymerization initiator, and the reaction proceeded for 12 hours (second step). Measurement of the nonvolatile content confirmed that 95% had reacted. Finally, 500 parts of a 50% PGMAc solution of the compound obtained in the second step, 27.0 parts of 2-methacryloyloxyethyl isocyanate, and 0.1 parts of hydroquinone were charged, and IR analysis revealed a 2,270 cm3 NMR spectrum based on the isocyanate group. -1 The reaction was continued until the disappearance of the peak was confirmed (third step). After cooling, PGMAc was added so that the nonvolatile content was 30% by mass, and a resin (B1-3) solution having aromatic carboxyl groups was prepared. The acid value of the resin was 68 mg KOH / g, and the weight-average molecular weight was 13,000.

[0335] (Resin (B1-4) solution having aromatic carboxyl groups) A reaction vessel equipped with a thermometer, reflux condenser, nitrogen gas inlet, and stirrer was charged with 20.0 parts tert-butyl acrylate, 45.0 parts methyl methacrylate, 30.0 parts ethyl acrylate, 5.0 parts methacrylic acid, and 25.0 parts PGMAc, and the atmosphere was purged with nitrogen gas. The reaction vessel was heated to 50°C, and 6.0 parts 3-mercapto-1,2-propanediol was added. The temperature was then raised to 90°C, and a solution of 2,2'-azobisisobutyronitrile (polymerization initiator) dissolved in PGMAc was added, followed by a 10-hour reaction. Measurement of the nonvolatile content confirmed that 95% of the mixture had reacted. Next, 14.5 parts pyromellitic dianhydride, 38.0 parts PGMAc, and 0.2 parts 1,8-diazabicyclo-[5.4.0]-7-undecene (catalyst) were added, and the reaction was continued at 120°C for 5 hours. Then, 12.1 parts of 3-methoxybutanol was added and the reaction was continued at 120°C for 3 hours. The reaction was terminated after confirming that 98% or more of the acid anhydride had been half-esterified by measuring the acid value. After cooling, PGMAc was added to the mixture to adjust the nonvolatile content to 30% by mass, thereby preparing a solution of a resin (B1-4) having aromatic carboxyl groups. The acid value of the resin was 105 mgKOH / g, and the weight-average molecular weight was 9,500.

[0336] (Resin (B1-5) solution having aromatic carboxyl groups) A reaction vessel equipped with a thermometer, reflux condenser, nitrogen gas inlet, and stirrer was charged with 62.6 parts of 1-dodecanol, 287.4 parts of ε-caprolactone, and 0.1 parts of monobutyltin(IV) oxide as a catalyst. The atmosphere was purged with nitrogen gas, and the mixture was heated and stirred at 120°C for 4 hours. After measuring the nonvolatile content to confirm that 98% of the mixture had reacted, 73.3 parts of pyromellitic dianhydride was added and the mixture was allowed to react at 120°C for 2 hours. The reaction was terminated when acid value measurement confirmed that at least 98% of the anhydride had been half-esterified. After cooling, PGMAc was added to obtain a solution of resin (B1-5) having aromatic carboxyl groups, with a nonvolatile content of 30% by weight. The resin had an acid value of 49 mgKOH / g and a weight-average molecular weight of 5,000.

[0337] (Resin (B2-1) solution without aromatic carboxyl groups) A reaction vessel equipped with a thermometer, reflux condenser, nitrogen gas inlet, and stirrer was charged with 200.0 parts of PGMAc. While injecting nitrogen gas into the vessel, the vessel was heated to 120°C. At the same temperature, a mixture of 16.7 parts of styrene, 76.8 parts of glycidyl methacrylate, 66.1 parts of dicyclopentanyl methacrylate, the polymerization initiator tert-butylperoxy-2-ethylhexanoate, and PGMAc was added dropwise over 2.5 hours via the dropping tube. After the dropwise addition was completed, the mixture was stirred at 120°C for an additional 2 hours to obtain a precursor. The flask was then purged with air, and 38.9 parts of acrylic acid as a modifying compound, 0.6 parts of triphenylphosphine as a catalyst, and 0.2 parts of methylhydroquinone were added. The mixture was then reacted at 110°C for 10 hours. This allowed the epoxy group of glycidyl methacrylate to react with the carboxyl group of acrylic acid, generating hydroxyl groups through cleavage of the epoxy groups while simultaneously introducing polymerizable unsaturated groups. Next, 40.0 parts of succinic anhydride was added as a modifying compound and reacted at 110°C for 4 hours. This allowed some of the hydroxyl groups to react with succinic anhydride, introducing acidic groups. PGMAc was then added to a non-volatile content of 40% by mass to obtain a resin (B2-1) solution without aromatic carboxyl groups. The resin had an acid value of 95 mgKOH / g and a weight-average molecular weight of 5,000.

[0338] (Resin (B2-2) solution without aromatic carboxyl groups) A reaction vessel equipped with a thermometer, reflux condenser, nitrogen gas inlet, and stirrer was charged with 200.0 parts of PGMAc. The vessel was heated to 120 °C while injecting nitrogen gas into it. At the same temperature, a mixture of 49.7 parts of 2-ethylhexyl acrylate, 99.4 parts of glycidyl methacrylate, 6.6 parts of dicyclopentanyl methacrylate, tert-butyl peroxy-2-ethylhexanoate (polymerization initiator), and PGMAc was added dropwise over 2.5 hours. After the addition was complete, the mixture was stirred at 120 °C for another 2 hours to obtain a precursor. The atmosphere in the flask was then replaced with air, and 50.4 parts of acrylic acid (modified compound), 0.6 parts of triphenylphosphine (catalyst), and 0.2 parts of methylhydroquinone (catalyst) were added. The mixture was then reacted at 110 °C for 10 hours. This allowed the epoxy groups of glycidyl methacrylate to react with the carboxyl groups of acrylic acid, generating hydroxyl groups through cleavage of the epoxy groups and simultaneously introducing polymerizable unsaturated groups. Next, 21.3 parts of tetrahydrophthalic anhydride was added as a modifying compound and allowed to react at 110°C for 4 hours. This allowed some of the hydroxyl groups to react with the tetrahydrophthalic anhydride, introducing acidic groups. PGMAc was then added to the solution to achieve a nonvolatile content of 40% by mass, preparing a resin (B2-2) solution lacking aromatic carboxyl groups. The resin had an acid value of 38 mgKOH / g and a weight-average molecular weight of 12,000.

[0339] (Resin (B2-3) solution without aromatic carboxyl groups) A reaction vessel equipped with a thermometer, reflux condenser, nitrogen gas inlet, and stirrer was charged with 182.0 parts of PGMAc. The mixture was stirred while purging with nitrogen and heated to 100°C. Next, a mixture of 70.5 parts of benzyl methacrylate, 43.0 parts of methacrylic acid, 22.0 parts of dicyclopentanyl methacrylate, azobisisobutyronitrile (a polymerization initiator), and PGMAc was added dropwise from the addition funnel to the flask over 2.5 hours. After the addition was completed, the mixture was stirred at 100°C for an additional 5 hours to allow the reaction to proceed. Next, the atmosphere in the flask was changed from nitrogen to air, and 35.5 parts of glycidyl methacrylate, 0.9 parts of tris(dimethylaminomethyl)phenol, and 0.145 parts of hydroquinone were added to the flask, and the reaction was continued at 110°C for 6 hours. This allowed the carboxyl groups of methacrylic acid to react with the epoxy groups of glycidyl methacrylate, generating hydroxyl groups through cleavage of the epoxy groups of glycidyl methacrylate and simultaneously introducing polymerizable unsaturated groups. PGMAc was then added to the solution to achieve a nonvolatile content of 40% by mass, resulting in a solution of resin (B2-3) lacking aromatic carboxyl groups. The resin had an acid value of 78 mg KOH / g and a weight-average molecular weight of 17,000.

[0340] (Resin (B2-4) solution without aromatic carboxyl groups) A reaction vessel equipped with a thermometer, reflux condenser, nitrogen gas inlet, and stirrer was charged with 100.0 parts of PGMAc. The mixture was stirred while purging with nitrogen and heated to 120°C. Next, a mixture of 109.3 parts of benzyl methacrylate, 24.1 parts of methacrylic acid, 22.1 parts of dicyclopentanyl methacrylate, azobisisobutyronitrile (a polymerization initiator), and PGMAc was added dropwise to the flask over 2.5 hours. After the addition was complete, the mixture was stirred at 120°C for an additional 2 hours to allow the reaction to proceed. PGMAc was then added to a nonvolatile content of 40% by weight to prepare a solution of resin (B2-4) lacking aromatic carboxyl groups. The resin had an acid value of 98 mgKOH / g and a weight-average molecular weight of 17,500.

[0341] (Resin (B2-5) solution without aromatic carboxyl groups) A reaction vessel equipped with a thermometer, reflux condenser, nitrogen gas inlet, and stirrer was charged with 100 parts of propylene glycol monomethyl ether, which was stirred while purging with nitrogen and heated to 78 ° C. Next, a mixture of 25.2 parts of Karenz MOI-DEM (2-methyl-1-oxo-2-propenyl)oxyethylaminocarbonyl 1,3-diethyl malonate, 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 polymerization initiator, 2,2'-azobis(2,4-dimethylvaleronitrile), dissolved in PGMAc, were added dropwise from the dropping funnel to the flask. After the dropwise addition, the mixture was stirred at 78 ° C for an additional 3 hours to react. PGMAc was then added to the resin so that the nonvolatile content was 40% by mass, to prepare a solution of a resin (B2-5) having no aromatic carboxyl groups. The resin had an acid value of 74 mgKOH / g and a weight-average molecular weight of 8,000.

[0342] (Resin (B2-6) solution without aromatic carboxyl groups) A flask equipped with a thermometer, reflux condenser, nitrogen gas inlet tube, dropping tube, and stirrer was charged with 150.0 parts of PGMAc and heated to 80°C. The flask was then purged with nitrogen. Then, 21.8 parts of 2-hydroxyethyl methacrylate, 38.9 parts of Aronix M-110 (manufactured by Toagosei Co., Ltd., paracumylphenol ethylene oxide-modified acrylate), 35.8 parts of n-butyl methacrylate, 39.0 parts of benzyl methacrylate, 20.2 parts of methacrylic acid, a polymerization initiator, 2,2'-azobisisobutyronitrile, and a mixture of PGMAc were added dropwise over 2 hours. After the addition was completed, the reaction was continued for another 3 hours. Cyclohexanone was then added until the nonvolatile content reached 40% by mass, yielding a solution of a resin (B2-6) lacking an aromatic carboxyl group. The acid value of the resin was 81 mgKOH / g and the weight average molecular weight was 28,000.

[0343] In the production of the resin (B), the amount of the polymerization initiator added was adjusted appropriately so as to achieve the weight average molecular weight of each resin.

[0344] <Production of polymerizable compound (C)> (Polymerizable compound (C-4)) A five-neck flask equipped with a stirrer, a reflux condenser, a nitrogen gas inlet tube, a thermometer, and a dropping tube was charged with 400 parts of dipentaerythritol pentaacrylate, 100 parts of PGMAc, and 0.5 parts of N,N-dimethylbenzylamine, and the temperature was raised to 70°C. A mixture of 66 parts of toluene diisocyanate and 66 parts of PGMAc was added dropwise from the dropping tube over 2 hours. After the dropwise addition, the mixture was reacted at a temperature of 50 to 70°C for 8 hours, and the IR reading was 2,180 cm. -1 The disappearance of the isocyanate absorption was confirmed. Next, 35 parts of mercaptoacetic acid and 0.6 parts of 4-methoxyphenol were charged and reacted at a temperature of 50 to 60°C for 6 hours to obtain an acrylate having a urethane bond. Thereafter, PGMAc was added so that the nonvolatile content became 50% by mass.

[0345] <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 size of 2.50 μm, producing an organic fluorescent particle dispersion (MA-1). The nonvolatile content was 39.0 mass%. Resin particles dyed with organic fluorescent dye (A1-1): 30.00 parts Aromatic carboxyl group-containing resin (B1-1) solution: 30.00 parts Organic solvent (O-1): 40.00 parts

[0346] (Organic fluorescent particle dispersions (MA-2) to (MA-18)) Organic fluorescent particle dispersions (MA-2) to (MA-18) were produced in the same manner as organic fluorescent particle dispersion (MA-1), except that the raw materials and blending amounts were changed to those shown in Table 1.

[0347] [Table 1]

[0348] The components listed in Table 1 are as follows:

[0349] [Organic fluorescent particles (A)] (Resin particles dyed with organic fluorescent dye (A1)) A1-1: SHNLOIHI COLOR FA-006 (manufactured by SHNLOIHI Co., Ltd.; resin particles dyed with an organic fluorescent dye with an emission wavelength of 574 nm, containing a melamine-based resin with a free formaldehyde content of 0.2% by mass or less) A1-2: SHNLOIHI COLOR FA-227LF (manufactured by SHNLOIHI, resin particles dyed with an organic fluorescent dye with an emission wavelength of 626 nm, containing melamine-based resin with a free formaldehyde content of 0.2% by mass or less) A1-3: SHNLOIHI COLOR FZ-277 (manufactured by SHNLOIHI, resin particles dyed with an organic fluorescent dye with an emission wavelength of 626 nm, containing a melamine-based resin with a free formaldehyde content of 0.2% by mass or less) A1-4: SHNLOIHI COLOR FA-005 (manufactured by SHNLOIHI Co., Ltd.; resin particles dyed with an organic fluorescent dye with an emission wavelength of 523 nm, containing a melamine-based resin with a free formaldehyde content of 0.2% by mass or less) A1-5: SHNLOIHI COLOR FA-5005 (manufactured by SHNLOIHI, resin particles dyed with an organic fluorescent dye with an emission wavelength of 517 nm, containing melamine-based resin with a free formaldehyde content of 0.2% by mass or less)

[0350] (Organic fluorescent particles other than resin particles (A1) dyed with organic fluorescent dye) A2-1: Compound of the following structure

[0351] [ka]

[0352] [Resin (B)] (Resin (B2) having no aromatic carboxyl group) B2-7: DISPERBYK-111 (BYK-Chemie, phosphate ester resin, acid value 129 mg KOH / g, non-volatile content 95% by mass)

[0353] [Organic solvent (O)] O-1:PGMAc

[0354] <Production of scattering particle dispersion (ME)> (Scattering particle dispersion (ME-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 (E1-1) had an average particle size of 0.25 μm, producing a scattering particle dispersion (ME-1). The nonvolatile content was 46.0 mass%. Inorganic particles (E1-1): 40.00 parts Aromatic carboxyl resin (B1-1) solution: 20.00 parts Organic solvent (O-1): 40.00 parts

[0355] (Scattering particle dispersion (ME-2)~(ME-10)) Organic fluorescent particle dispersions (ME-2) to (ME-10) were produced in the same manner as the scattering particle dispersion (ME-1), except that the raw materials and blending amounts were changed to those shown in Table 2.

[0356] [Table 2]

[0357] The components listed in Table 2 are as follows: [Scattered particles (E)] (Inorganic particles (E1)) E1-1: CR-50 (Ishihara Sangyo Kaisha, Ltd., alumina-treated rutile titanium dioxide, refractive index 2.72) E1-2: CR-90 (Ishihara Sangyo Kaisha, Ltd., alumina / silica-treated rutile titanium dioxide, refractive index 2.72) E1-3: R-980 (Ishihara Sangyo Kaisha, Ltd., alumina / organic treated rutile titanium dioxide, refractive index 2.72) E1-4: R-38L (Sakai Chemical Industry Co., Ltd., alumina / zirconia-treated rutile titanium dioxide, refractive index 2.72) E1-5: A-190 (Sakai Chemical Co., Ltd., alumina-treated anatase titanium dioxide, refractive index 2.52) E1-6: Advanced Alumina AA-04 (Sumitomo Chemical Co., Ltd., aluminum oxide, refractive index 1.76) E1-7: Seahoster KE-P50 (Nippon Shokubai Co., Ltd., silica, refractive index 1.43)

[0358] (Scattering particles (E2) other than inorganic particles (E1)) E2-1: Eposter S12 (Nippon Shokubai Co., Ltd., melamine-formaldehyde resin, refractive index 1.66)

[0359] [Resin (B)] (Resin (B2) having no aromatic carboxyl group) B2-7: DISPERBYK-111 (BYK-Chemie, phosphate ester resin, acid value 129 mg KOH / g, non-volatile content 95% by mass)

[0360] [Organic solvent (O)] O-1:PGMAc

[0361] <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 size of 1.00 μm, producing inorganic fluorescent particle dispersion (MP-1). The nonvolatile content was 39.0 mass%. Inorganic fluorescent particles (P-1): 30.00 parts Aromatic carboxyl resin (B1-1) solution: 30.00 parts Organic solvent (O-1): 40.00 parts

[0362] Inorganic fluorescent particles (P-1) were D3450 (YAlO 12 :Ce). The organic solvent (O-1) is PGMAc.

[0363] <Production of wavelength conversion photosensitive composition> [Example 1] (Wavelength conversion photosensitive composition 1) The following raw materials were mixed and stirred to produce wavelength conversion photosensitive composition 1. The nonvolatile content was 41.0 mass %. Organic fluorescent particle dispersion (MA-1): 61.50 parts Scattering particle dispersion (ME-1): 10.25 parts Resin (B2-1) solution not containing aromatic carboxyl groups: 13.50 parts Resin (B2-2) solution without aromatic carboxyl groups: 2.25 parts Resin (B2-3) solution without aromatic carboxyl groups: 1.50 parts Polymerizable compound (C-1): 4.50 parts Polymerizable compound (C-2): 0.50 part Polymerization initiator (D1-1): 0.25 parts Polymerization initiator (D1-2): 0.14 parts Leveling agent (M): 1.00 parts Organic solvent (O-2): 4.61 parts

[0364] [Examples 2 to 51 and Comparative Example 1] (Wavelength-converting photosensitive compositions 2 to 52) Wavelength-converting photosensitive compositions 2 to 52 were produced in the same manner as in Example 1, except that the raw materials and blending amounts were changed to those shown in Table 3.

[0365] [Table 3]

[0366] [Table 3-1]

[0367] [Table 3-2]

[0368] [Table 3-3]

[0369] In Table 3, the blending amount (*) of the resin (B1) solution having an aromatic carboxyl group corresponds to the value calculated from the blending amount of the resin (B1) solution blended during the preparation of the organic fluorescent particle dispersion (MA), the scattering particle dispersion (ME), and the inorganic fluorescent particle dispersion (MP). In other words, the resin (B1) solution was not additionally blended during the preparation of the wavelength conversion photosensitive composition. Therefore, in this embodiment, the ratio of the resin (B1) having an aromatic carboxyl group in the resin (B) is calculated based on the blending amount of the resin (B1) solution shown in Tables 1 and 2, from the blending amount in the organic fluorescent particle dispersion (MA) and the scattering particle dispersion (ME) shown in Table 3, and from the blending amount in the inorganic fluorescent particle dispersion (MP) described above. Meanwhile, for composition 41, 21 parts by mass of the resin (B1) solution was blended during the preparation of the wavelength conversion photosensitive composition. Therefore, in such an embodiment, the ratio of the resin (B1) having an aromatic carboxyl group in the resin (B) is a value calculated based on the total amount of the resin (B1) solution shown in Tables 1 and 2 and the amount of the newly added resin (B1) solution.

[0370] The raw materials listed in Table 3 are as follows: [Polymerizable compound (C)] C-1: Aronix M-402 (manufactured by Toagosei Co., Ltd., a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate) C-2: Aronix M-306 (manufactured by Toagosei Co., Ltd., a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate) C-3: KAYARAD DPCA-30 (Nippon Kayaku Co., Ltd., lactone-modified multifunctional acrylate) C-4: CN9906NS (Arkema, multifunctional acrylate with an amine structure)

[0371] [Polymerization initiator (D)] (Polymerization initiator (D1)): A polymer having an absorption coefficient of 5.0 x 10 for light having a wavelength of 365 nm in propylene glycol monomethyl ether acetate. 3 L / mol cm or more polymerization initiator D1-1: The above compound (D1-1) (absorption coefficient of light at a wavelength of 365 nm is 13,410 L / mol cm) D1-2: The above compound (D1-2) (absorption coefficient of light at a wavelength of 365 nm is 14,214 L / mol cm) D1-3: The above compound (D1-3) (absorption coefficient of light at a wavelength of 365 nm is 7,051 L / mol cm) D1-4: The above compound (D1-4) (absorption coefficient of light at a wavelength of 365 nm is 8,423 L / mol cm) D1-5: The above compound (D1-5) (absorption coefficient of light at a wavelength of 365 nm is 18,334 L / mol cm) D1-6: The above compound (D1-6) (absorption coefficient of light at a wavelength of 365 nm is 14,127 L / mol cm)

[0372] (Polymerization initiator (D2) other than polymerization initiator (D1)) D2-1: Irgacure OXE-01 (BASF)

[0373] D2-2: Compound of the following structure [ka]

[0374] [Thermal crosslinkable compound (G)] G-1: EHPE-3150 (Daicel Corporation, epoxy compound) G-2: Duranate MF-K60B (manufactured by Asahi Kasei Corporation, blocked isocyanate compound, non-volatile content 60% by mass)

[0375] [Silane coupling agent (I)] I-1: X-12-1048 (Shin-Etsu Silicone Co., Ltd.) I-2: KBE-403 (Shin-Etsu Silicone Co., Ltd.)

[0376] [Leveling agent (M)] A solution in which 2 parts of BYK-330 (manufactured by BYK-Chemie) was dissolved in 98 parts of PGMAc was used as a leveling agent (M).

[0377] [Organic solvent (O)] O-2: Ethyl 3-ethoxypropionate

[0378] <Evaluation of wavelength conversion photosensitive composition> The following evaluations were carried out on the obtained wavelength-converting photosensitive compositions 1 to 52. The evaluation results are shown in Table 4.

[0379] [Developability evaluation] The obtained wavelength-converting photosensitive composition was applied to a 100 mm x 100 mm x 0.7 mm thick glass substrate (Corning Eagle 2000) using a spin coater to a dry film thickness of 10.0 μm, and then dried on a hot plate at 90°C for 2 minutes. After cooling to room temperature, the substrate was irradiated with an ultra-high pressure mercury lamp at an illuminance of 30 mW / cm through a photomask with a 100 μm wide stripe pattern. 2 , 50 mJ / cm 2 After cooling the substrate to room temperature, it was spray-developed using an aqueous developer containing 0.12% by mass of a nonionic surfactant and 0.04% by mass of potassium hydroxide at 23°C, washed with ion-exchanged water, and air-dried. The substrate was observed under an optical microscope to confirm the presence or absence of residues in the unexposed areas. The evaluation criteria are as follows, with a rating of 3 or higher being considered practical. 5: No residue was left in the unexposed areas after the shortest development time possible for pattern formation. 4: No residue was left in the unexposed areas after development for 5 seconds longer than the shortest possible time for pattern formation. 3: No residue was left in the unexposed areas after development for 10 seconds longer than the shortest possible time for pattern formation. 2: No residue was left in the unexposed areas after development for 15 seconds longer than the shortest possible time for pattern formation. 1: Even after development for 20 seconds longer than the shortest possible time for pattern formation, residue was found in the unexposed areas.

[0380] [Evaluation of pattern formation: (1) Adhesion] The obtained wavelength-converting photosensitive composition was applied to a 100 mm x 100 mm x 0.7 mm thick glass substrate (Corning Eagle 2000) using a spin coater to a dry film thickness of 10.0 μm, and then dried on a hot plate at 90°C for 2 minutes. After cooling to room temperature, the substrate was illuminated with an ultra-high pressure mercury lamp at an illuminance of 30 mW / cm through a photomask with a stripe pattern of 5 μm, 10 μm, 15 μm, 20 μm, and 25 μm widths. 2 , 50 mJ / cm 2 The substrate was cooled to room temperature and then spray-developed using an aqueous developer containing 0.12% by mass of a nonionic surfactant and 0.04% by mass of potassium hydroxide at 23°C, then washed with ion-exchanged water, air-dried, and post-baked in a clean oven at 180°C for 30 minutes. Spray development was performed for each wavelength conversion photosensitive composition for the shortest time possible to form a pattern without residual development. The patterns having a width of 5 to 25 μm obtained as described above were observed under an optical microscope to confirm the remaining patterns. The evaluation criteria are as follows, with a rating of 3 or higher being considered practical. 5: Patterns of 10 μm or less remain. 4: Patterns of 15 μm or more remain. Patterns of 10 μm or less do not remain. 3: Patterns of 20 μm or more remain. Patterns of 15 μm or less do not remain. 2: 25 μm patterns remain. No patterns of 20 μm or less remain. 1: No pattern remains.

[0381] [Pattern Formation Evaluation (2): Linearity] The obtained wavelength-converting photosensitive composition was applied to a 100 mm x 100 mm x 0.7 mm thick glass substrate (Corning Eagle 2000) using a spin coater to a dry film thickness of 10.0 μm, and then dried on a hot plate at 90°C for 2 minutes. After cooling to room temperature, the substrate was irradiated with an ultra-high pressure mercury lamp at an illuminance of 30 mW / cm through a photomask with a 100 μm wide stripe pattern. 2 , 50 mJ / cm 2 The substrate was cooled to room temperature and then spray-developed using an aqueous developer containing 0.12% by mass of a nonionic surfactant and 0.04% by mass of potassium hydroxide at 23°C, then washed with ion-exchanged water, air-dried, and post-baked in a clean oven at 180°C for 30 minutes. Spray development was performed for each wavelength conversion photosensitive composition for the shortest time possible to form a pattern without residual development. The edge of the pattern obtained as described above (the boundary between the exposed and unexposed areas) was observed using a scanning electron microscope ("S-3000H" manufactured by Hitachi High-Tech Corporation) to confirm the shape. The evaluation criteria are as follows, with a rating of 3 or higher being practical. 5: The pattern edges are straight and smooth. 4: A slight amount of unevenness was observed on the pattern edge, but it was almost straight. 3: Slight irregularities were observed on the pattern edges, but they were generally straight. 2: Unevenness was observed on the pattern edge. 1: Significant unevenness was observed on the pattern edge.

[0382] [Evaluation of pattern formation: (3) Surface smoothness] The obtained wavelength-converting photosensitive composition was applied to a 100 mm x 100 mm x 0.7 mm thick glass substrate (Corning Eagle 2000) using a spin coater so that the dried film thickness would be 10.0 μm, and then dried on a hot plate at 90°C for 2 minutes. After cooling the substrate to room temperature, an ultra-high pressure mercury lamp was used to illuminate the substrate through a photomask with a 20 μm square pattern at an illumination intensity of 30 mW / cm. 2, 50 mJ / cm 2 The substrate was then spray-developed using an aqueous developer containing 0.12% by mass of a nonionic surfactant and 0.04% by mass of potassium hydroxide at 23°C, washed with ion-exchanged water, air-dried, and post-baked in a clean oven at 180°C for 30 minutes. The spray development was carried out for each wavelength conversion photosensitive composition for the shortest time possible to form a pattern without leaving any residual development residue. The film thickness was measured using an optical film thickness meter (F50) manufactured by Filmetrics, Inc. The evaluation was performed by calculating the difference in film thickness between the thinnest part and the thickest part (hereinafter referred to as film thickness difference). The evaluation criteria are as follows, with a rating of 3 or higher being practical. 5: Film thickness difference is 0.03 μm or less 4: The difference in film thickness is greater than 0.03 μm and less than 0.05 μm 3: The difference in film thickness is greater than 0.05 μm and less than 0.08 μm 2: The difference in film thickness is greater than 0.08 μm and less than 0.10 μm 1: The difference in film thickness is greater than 0.10 μm

[0383] [Color conversion efficiency evaluation] The obtained wavelength-converting photosensitive composition was applied to a 100 mm x 100 mm x 0.7 mm thick glass substrate (Corning Eagle 2000) using a spin coater to a dry film thickness of 10.0 μm, and then dried on a hot plate at 90°C for 2 minutes. After cooling to room temperature, the substrate was irradiated with an ultra-high pressure mercury lamp at an illuminance of 30 mW / cm. 2 , 50 mJ / cm 2 After cooling the substrate to room temperature, it was spray-developed using an aqueous developer containing 0.12% by mass of a nonionic surfactant and 0.04% by mass of potassium hydroxide at 23°C, then washed with ion-exchanged water and air-dried. It was then post-baked in a clean oven at 180°C for 30 minutes to obtain a substrate for evaluating color conversion efficiency. The color conversion efficiency evaluation substrate was placed on a planar light-emitting device equipped with a blue LED element with an emission peak wavelength of 460 nm, and the blue LED element was turned on. The emission spectrum was measured using a spectroradiometer (Konica Minolta "CS-1000") The color conversion efficiency was calculated using the following formula (2).

[0384] Equation (2): Color conversion efficiency (%) = I F / (I0-I B ) x 100 [In formula (2), I0 represents the number of photons at wavelengths of 400 nm or more and less than 500 nm when the substrate for evaluating color conversion efficiency is not placed, and I B represents the number of photons at wavelengths between 400 nm and 500 nm when the color conversion efficiency evaluation substrate is mounted, and I F represents the number of photons in the wavelength range of 500 nm to 780 nm when the substrate for evaluating color conversion efficiency is mounted.

[0385] The evaluation criteria are as follows, with a rating of 3 or higher being practical. 5: Color conversion efficiency (%) is 35% or more 4: Color conversion efficiency (%) is 33% or more and less than 35% 3: Color conversion efficiency (%) is 30% or more and less than 33% 2: Color conversion efficiency (%) is 27% or more and less than 30% 1: Color conversion efficiency (%) is less than 27%

[0386] [Table 4] [Explanation of symbols]

[0387] 10: TFT substrate 11: Light source (blue LED) 12: Wavelength conversion layer 12RCC: wavelength conversion layer in red pixel, 12GCC: wavelength conversion layer in green pixel, 12YCC: wavelength conversion layer in yellow pixel 13:Transparent layer 14: Bulkhead 15: color filter layer, 15RCF: color filter constituting red pixels, 15GCF: color filter constituting green pixels, 15BCF: color filter constituting blue pixels, 15YCF: color filter constituting yellow pixels 16: Circuit board

Claims

1. The composition comprises organic fluorescent particles (A), a resin (B), a polymerizable compound (C), and a polymerization initiator (D), The wavelength-converting photosensitive composition, wherein the resin (B) includes a resin (B1) having an aromatic carboxyl group.

2. 2. The wavelength-converting photosensitive composition according to claim 1, wherein the content of the organic fluorescent particles (A) is 20 to 60 mass % based on the total mass of the nonvolatile content of the wavelength-converting photosensitive composition.

3. 2. The wavelength-converting photosensitive composition according to claim 1, wherein the organic fluorescent particles (A) comprise resin particles (A1) dyed with an organic fluorescent dye.

4. 2. The wavelength conversion photosensitive composition according to claim 1, wherein the resin (B1) having an aromatic carboxyl group comprises a resin having a repeating unit represented by the following formula (1): 【Chemistry 1】 [In formula (1), Ar １ represents a group having an aromatic carboxyl group, L １ represents —COO— or —CONH—, L ２ represents a trivalent linking group, P １ represents a polymer chain.]

5. The polymerization initiator (D) has an absorption coefficient of 5.0×10 at a wavelength of 365 nm in propylene glycol monomethyl ether acetate. ３ The wavelength-converting photosensitive composition according to claim 1 , comprising a polymerization initiator (D1) having a viscosity of at least L / mol·cm.

6. The wavelength conversion photosensitive composition according to claim 1 , further comprising scattering particles (E).

7. A wavelength-converting layer formed from the wavelength-converting photosensitive composition according to any one of claims 1 to 6.

8. A laminate comprising the wavelength conversion layer according to claim 7 and a color filter layer.

9. A display device comprising the laminate according to claim 8 .

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