Non-polymer compound and composition for film formation

Abstract

The purpose of the present invention is to provide: a non-polymer compound represented by formula (1) as a novel non-polymer compound having exceptional solubility in organic solvents; and a composition for film formation containing the non-polymer compound, the composition making it possible to form a cured film having both a high refractive index and light resistance. (In the formula, X represents a n-valent functional group having a triazine skeleton and a phenolic hydroxy group; k represents 0 or 1; each Ar independently represents a C6-14 aromatic hydrocarbon group or a C3-14 aromatic heterocyclic group optionally having a C1-4 alkyl group as a substituent; and n represents 2 or 3.)

Description

Non-polymer compound and film-forming composition

[0001] The present invention relates to a non-polymer compound and a film-forming composition containing the same.

[0002] In the field of optical members such as spectacle lenses, Fresnel lenses, lenticular lenses, aspherical lenses, optical discs, optical fibers, and optical waveguides, transparent resins employing polymer materials excellent in transparency in the visible light region are widely used.

[0003] In recent years, also in the field of electronic devices such as liquid crystal displays, organic electroluminescence (EL) displays, light-emitting diodes, solar cells, and CCD / CMOS image sensors, for optical members such as protective films, planarization films, insulating films, antireflection films, refractive index control films, microlenses, intra-layer lenses, optical waveguides, and film substrates, transparent resins employing polymer materials excellent in light transmittance in the visible light region are widely used.

[0004] In such applications of optical members, not only transparency but also a high refractive index is often required. Further, from the viewpoint of the productivity of the film-forming composition, its raw material is required to be soluble in various organic solvents. In particular, in the manufacturing process of the film-forming composition, when the raw material is mixed with an organic solvent other than the organic solvent in which the raw material is dissolved, it may precipitate depending on the combination of the organic solvents. In such a case, problems such as clogging of the piping of the production equipment will occur.

[0005] Patent Document 1 discloses an addition polymer synthesized from a specific benzophenone derivative and a diepoxy compound as a novel polymer having excellent ultraviolet absorption, visible light transparency, heat resistance, and light resistance for use in applications of optical members, but further improvement is required in solubility in organic solvents and the refractive index of the cured product.

[0006] Japanese Patent Application Laid-Open No. 2019-172846

[0007] The present invention has been made in view of the above circumstances, and aims to provide a novel nonpolymer compound having excellent solubility in organic solvents. It also aims to provide a film-forming composition containing the above nonpolymer compound that can form a cured film possessing both high refractive index and light resistance.

[0008] The inventors, through diligent research to achieve the above objective, discovered that certain nonpolymer compounds having a triazine skeleton and a phenolic hydroxyl group in their molecule exhibit excellent solubility in organic solvents. They then discovered that by using this nonpolymer compound as a raw material, a film-forming composition containing the nonpolymer compound can be obtained that can form a cured film possessing both high refractive index and light resistance, thus completing the present invention.

[0009] In other words, the present invention provides the following nonpolymer compounds and film-forming compositions: 1. A nonpolymer compound represented by the following formula (1). (In the formula, X represents an n-valent functional group having a triazine skeleton and a phenolic hydroxyl group, k represents 0 or 1, Ar each independently represents an aromatic hydrocarbon group having 6 to 14 carbon atoms or an aromatic heterocyclic group having 3 to 14 carbon atoms, which may have an alkyl group having 1 to 4 carbon atoms as a substituent, and n represents 2 or 3.) 2. One nonpolymer compound represented by the following formula (x1) or formula (x2) above, wherein X is... (In the formula, Z represents a C6-20 aromatic hydrocarbon group or a C3-10 non-aromatic heterocyclic group which may have substituents selected from the group consisting of a C1-C8 alkyl group, a C1-C8 alkoxy group, or a C1-C8 alkyl group and a C1-C8 alkoxy group, and * represents a bond.) 3. The nonpolymer compound of 1 or 2, wherein each of the above aromatic hydrocarbon groups is independently a group having a benzene ring or a naphthalene ring, and each of the above aromatic heterocyclic groups is independently a group having a furan ring, a thiophene ring, a pyridine ring, a thiazole ring, a benzothiazole ring, a quinoline ring, an isoquinoline ring, a benzofuran ring, an isobenzofuran ring, or a carbazole ring. 4. 2 or 3 nonpolymer compounds in which Z is a C6-C14 aromatic hydrocarbon group or a C3-C6 non-aromatic heterocyclic group, and Z may have substituents selected from the group consisting of a C1-C4 alkyl group, a C1-C4 alkoxy group, or a C1-C4 alkyl group and a C1-C4 alkoxy group. 5. Any of 2-4 nonpolymer compounds represented by the following formula (1-1) or formula (1-2). (In the formulas, Ar and k are the same as defined in formula (1) above, and Z is the same as defined in formula (x1).) 6. Any of 1 to 5 nonpolymer compounds having a molecular weight of 500 to 3,500. 7. Any of 1 to 6 nonpolymer compounds that are reaction products of a compound represented by the following formula (1a) and a compound represented by the following formula (1b). (In the formula, X, k, n and Ar are the same as the definitions in formula (1) above.) 8. A film-forming composition comprising a nonpolymer compound represented by any of formula (1) from 1 to 7, a curing agent, and an organic solvent, wherein the content of the curing agent is 15 parts by mass or more per 100 parts by mass of the nonpolymer compound. 9. The film-forming composition of 8, wherein the curing agent is a polyfunctional blocked isocyanate compound. 10. The film-forming composition of 9, wherein the polyfunctional blocked isocyanate compound is a homopolymer of (meth)acrylate having a blocked isocyanate group, or a copolymer containing (meth)acrylate having a blocked isocyanate group. 11. The film-forming composition of any of 8 to 10 further comprising a hindered amine-based light stabilizer. 12. The film-forming composition of any of 8 to 11 further comprising a surfactant. 13. A microlens made from a cured product of any of the film-forming compositions of 8 to 12. 14. An electronic device equipped with the microlens of 13.

[0010] The nonpolymer compound of the present invention has excellent solubility in organic solvents. By using this nonpolymer compound as a raw material, a film-forming composition can be obtained that can form a cured film possessing both high refractive index and light resistance. The cured film formed from the above film-forming composition is suitable as an optical component such as a protective film, planarization film, insulating film, anti-reflective film, refractive index control film, microlens, intralayer lens, optical waveguide, and film substrate.

[0011] The present invention will be described in more detail below. The nonpolymer compound according to the present invention is characterized by being represented by the following formula (1). In this invention, "nonpolymer compound" means a compound that has a molecular weight of 3,500 or less and is not a polymer.

[0012]

[0013] In the formula, X represents an n-valent functional group having a triazine skeleton and a phenolic hydroxyl group, k represents 0 or 1, Ar independently represents a C6-C14 aromatic hydrocarbon group or a C3-C14 aromatic heterocyclic group which may have a C1-C4 alkyl group as a substituent, and n represents 2 or 3.

[0014] Examples of the functional group represented by X above include, but are not limited to, the group represented by the following formula (x1) or formula (x2).

[0015]

[0016] In the formula, Z represents a C6-C20 aromatic hydrocarbon group or a C3-C10 non-aromatic heterocyclic group, which may have substituents selected from the group consisting of a C1-C8 alkyl group, a C1-C8 alkoxy group, or a C1-C8 alkyl group and a C1-C8 alkoxy group, and * represents a bond.

[0017] Examples of aromatic hydrocarbon groups having 6 to 20 carbon atoms include phenyl, biphenyl, terphenyl, naphthyl, fluorenyl, benzofluorenyl, dibenzofluorenyl, phenanthryl, fluoranthenyl, anthryl, chrysenyl, pyrenyl, triphenylene, or perilenyl groups. In the present invention, aromatic hydrocarbon groups having 6 to 14 carbon atoms are preferred, groups having a benzene ring or a naphthalene ring are preferred, and phenyl, naphthyl, and biphenyl groups are more preferred.

[0018] Examples of non-aromatic heterocyclic groups having 3 to 10 carbon atoms include monovalent groups having a tetrahydrofuran ring, pyrrolidine ring, piperidine ring, imidazolidine ring, imidazoline ring, pyrazolidine ring, pyrazoline ring, oxazolidine ring, oxazoline ring, thiazolidine ring, thiazoline ring, morpholine ring, etc. More specifically, examples include non-aromatic heterocyclic groups containing at least one heteroatom such as a nitrogen atom, oxygen atom, or sulfur atom, such as a tetrahydrofuranyl group, pyrrolidyl group, piperidyl group, imidazolidyl group, imidazolyl group, pyrazolidine group, pyrazolyl group, oxazolidine group, oxazolyl group, thiazolidyl group, thiazolyl group, or morpholino group. In the present invention, among these, non-aromatic heterocyclic groups having 3 to 6 carbon atoms are preferred, oxazolidine groups and morpholino groups are preferred, and morpholino groups are more preferred.

[0019] Examples of alkyl groups having 1 to 8 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, and n-octyl group. In the present invention, alkyl groups having 1 to 4 carbon atoms are preferred among these, with methyl group and ethyl group being preferred, and methyl group being more preferred.

[0020] Examples of alkoxy groups having 1 to 8 carbon atoms include methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy, n-pentoxy, n-hexyloxy, n-heptyloxy, and n-octyloxy groups. In the present invention, among these, alkoxy groups having 1 to 4 carbon atoms are preferred, methoxy and ethoxy groups are preferred, and methoxy groups are more preferred.

[0021] Suitable specific examples of Z include, but are not limited to, the groups represented by the following formulas (z1) to (z4).

[0022] (In the formula, * represents a bond.)

[0023] Preferred embodiments of the functional group represented by X above include the groups represented by the following formulas (x1-1) and (x2-1).

[0024] (In the equation, Z is equivalent to the definition in equation (x1). * represents a bond.)

[0025] Examples of aromatic hydrocarbon groups having 6 to 14 carbon atoms represented by Ar include phenyl, naphthyl, anthracenyl, phenantrenyl, fluorenyl, and biphenylyl groups. In the present invention, among these, phenylene, naphthylene, and biphenylylene groups are preferred.

[0026] Examples of aromatic heterocyclic groups having 3 to 14 carbon atoms and represented by Ar include monovalent groups having a furan ring, thiophene ring, pyridine ring, thiazole ring, benzothiazole ring, quinoline ring, isoquinoline ring, benzofuran ring, isobenzofuran ring, or carbazole ring. More specifically, examples include aromatic heterocyclic groups containing at least one heteroatom such as a nitrogen atom, oxygen atom, or sulfur atom, such as a furyl group, thienyl group, pyridinyl group, thiazolyl group, benzothiazolyl group, quinolyl group, isoquinolinyl group, benzofuryl group, isobenzofuryl group, or carbazolyl group. In the present invention, among these, the carbazolyl group is preferred.

[0027] The above-mentioned aromatic hydrocarbon group and aromatic heterocyclic group may have a C1-C4 alkyl group as a substituent. Examples of C1-C4 alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, i-butyl, s-butyl, and t-butyl groups. When these groups have substituents, the number is not particularly limited and may be one or two or more.

[0028] Preferred embodiments of the above nonpolymer compound include, but are not limited to, those represented by the following formulas (1-1) or (1-2).

[0029] (In the formula, Ar and k are the same as defined in formula (1) above, and Z is the same as defined in formula (x1).)

[0030] Specific examples of the above non-polymer compound include, but are not limited to, compounds represented by the following formulas (1-1-1) to (1-2-3).

[0031]

[0032]

[0033]

[0034] From the perspective of solubility in an organic solvent, the molecular weight of the above non-polymer compound is, for example, 500 to 3,500, preferably 500 to 3,000, more preferably 1,000 to 3,000.

[0035] The above non-polymer compound can be obtained by reacting a compound represented by the following formula (1a) with a compound represented by the following formula (1b).

[0036] (In the formula, X, k, n, and Ar are synonymous with the definitions in the above formula (1).)

[0037] Specific examples of the compound represented by the above formula (1a) include, but are not limited to, compounds represented by the following formulas (1a-1) to (1a-2). <000009​​​​​​​​​​​​The organic solvent used in the above reaction is not particularly limited as long as it dissolves the raw materials and catalyst used. Specific examples include those similar to the organic solvents used in the film-forming compositions described later, but from the viewpoint of solubility of the raw material compounds, tetrahydropyran, 1,4-dioxane, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclopentanone, cyclohexanone, N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, and N-ethyl-2-pyrrolidone are preferred. These organic solvents may be used individually or in combination of two or more.

[0043] Furthermore, while catalysts known to promote the reaction between epoxy groups and phenolic hydroxyl groups or carboxyl groups can be used as the catalyst, in the present invention, quaternary phosphonium salts and quaternary ammonium salts can be suitably used, with quaternary phosphonium salts being more preferred.

[0044] Examples of quaternary phosphonium salts include methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, butyltriphenylphosphonium bromide, hexyltriphenylphosphonium bromide, tetrabutylphosphonium bromide, benzyltriphenylphosphonium bromide, methyltriphenylphosphonium chloride, ethyltriphenylphosphonium chloride, butyltriphenylphosphonium chloride, hexyltriphenylphosphonium chloride, tetrabutylphosphonium chloride, benzyltriphenylphosphonium chloride, methyltriphenylphosphonium iodide, ethyltriphenylphosphonium iodide, butyltriphenylphosphonium iodide, hexyltriphenylphosphonium iodide, tetrabutylphosphonium iodide, and benzyltriphenylphosphonium iodide. In the present invention, ethyltriphenylphosphonium bromide and tetrabutylphosphonium bromide can be suitably used.

[0045] Examples of quaternary ammonium salts include tetramethylammonium fluoride, tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium nitrate, tetramethylammonium sulfate, tetramethylammonium acetate, tetraethylammonium chloride, tetraethylammonium bromide, tetrapropylammonium chloride, tetrapropylammonium bromide, tetrabutylammonium fluoride, tetrabutylammonium chloride, tetrabutylammonium bromide, benzyltrimethylammonium chloride, phenyltrimethylammonium chloride, benzyltriethylammonium chloride, methyltributylammonium chloride, benzyltributylammonium chloride, and methyltrioctylammonium chloride. In the present invention, benzyltriethylammonium chloride can be preferably used.

[0046] The film-forming composition of the present invention is characterized by containing the above-mentioned nonpolymer compound, a curing agent, and an organic solvent. In the following description, "solid content" refers to components other than the organic solvent that constitute the film-forming composition.

[0047] <Curing Agent> The curing agent is a component included for the purpose of improving the chemical resistance (solvent resistance) of the cured film formed from the film-forming composition of the present invention.

[0048] Examples of the curing agents mentioned above include polyfunctional (meth)acrylate compounds, hydroxymethyl or alkoxymethyl group-substituted phenol compounds, compounds having alkoxyalkylated amino groups, and polyfunctional blocked isocyanate compounds. In this specification, (meth)acrylate means methacrylate and acrylate. These curing agents may be used individually or in combination of two or more.

[0049] The curing agent content varies depending on the coating solvent used, the substrate used, the required solution viscosity, the required film shape, etc., but is 15 parts by mass or more per 100 parts by mass of the nonpolymer compound, preferably 15 to 80 parts by mass, more preferably 15 to 70 parts by mass, and even more preferably 20 to 60 parts by mass. These curing agents may undergo a curing reaction by self-condensation, but if crosslinkable substituents are present in the nonpolymer compound of the present invention, they can undergo a crosslinking reaction with those crosslinkable substituents.

[0050] Examples of the above polyfunctional (meth)acrylate compounds include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, and polypropylene glycol di(meth)acrylate. , 1,4-butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, tricyclodecanedimethanol di(meth)acrylate, dicyclopentanyl di(meth)acrylate, bisphenol A di(meth)acrylate, ethoxylated bisphenol A di(meth)acrylate, propoxylated bisphenol A di(meth)acrylate, bisphenol S di(meth)acrylate, phthalate di(meth)acrylate, 9,9 - Bis[4-(2-(meth)acryloyloxyethoxy)phenyl]fluorene, glycerin di(meth)acrylate, glycerin tri(meth)acrolate, glycerin ethoxytri(meth)acrylate, glycerin propoxytri(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane ethoxytri(meth)acrylate, trimethylolpropane propoxytri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, penta Examples include erythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol ethoxytetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, sorbitol hexa(meth)acrylate, tris(2-(meth)acryloyloxyethyl) isocyanurate, and ε-caprolactone-modified tris-(2-(meth)acryloyloxyethyl) isocyanurate.

[0051] Furthermore, the above-mentioned polyfunctional (meth)acrylate compounds include hydroxyl group-containing (meth)acrylates or polyfunctional (meth)acrylates containing hydroxyl groups, such as 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, glycerin di(meth)acrylate, pentaerythritol tri(meth)acrylate, and dipentaerythritol penta(meth)acrylate, as well as 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylene diisocyanate, 1,4-xylene diisocyanate, xylylene diisocyanate, 1,5-naphthalene diisocyanate, and m-phenylene Examples include polyfunctional urethane (meth)acrylates obtained by reacting diisocyanate compounds such as diisocyanate, p-phenylenediisocyanate, diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-dibenzyle diisocyanate, isophorone diisocyanate, 1,6-hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,3-bis(isocyanatomethyl)benzene, and 1,3-bis(isocyanatomethyl)cyclohexane.

[0052] Furthermore, as the above-mentioned polyfunctional (meth)acrylate compounds, polyfunctional epoxy (meth)acrylates can also be mentioned, which are synthesized by reacting (meth)acrylic acid with homopolymers or copolymers obtained by radical polymerization of epoxy group-containing (meth)acrylate monomers such as glycidyl (meth)acrylate, glycidyloxybutyl (meth)acrylate, and 3,4-epoxycyclohexylmethyl (meth)acrylate. Here, copolymer means a polymer obtained by polymerizing two or more monomers. The copolymer may be a copolymer obtained by polymerizing two or more epoxy group-containing (meth)acrylates, or it may be a copolymer obtained by polymerizing epoxy group-containing (meth)acrylate and other (meth)acrylates.

[0053] The above-mentioned polyfunctional (meth)acrylate compounds are also available commercially. Examples of such commercially available products include the following: Arronix® M-208, M-210, M-211B, M-215, M-220, M-225, M-233, M-240, M-245, M-260, M-270, M-303, M-305, M-306, M-309, M-310, M-313, M-315, M-321, M-350, M-360, M-400, M-402, M-403, M-404, M-405, and M-406. , M-408, M-450, M-452, M-460, M-510, M-520, M-1100, M-1200, M-1210, M-1310, M-1600, M-1960, M-6100, M-6200, M-6250, M-6500, M-7100, M-7300K, M-8030, M-8060, M-8100, M-8530, M-8560, M-9050 (all manufactured by Toagosei Co., Ltd.); KAYARAD® NPGDA, PEG400DA, FM-400, R-167, HX-220, HX-620, R-526, R-551, R-712, R-604, R-684, GPO-303, TMPTA, HDDA, TPGDA, KS-HDD A, KS-TPGDA, MANDA, THE-330, TPA-320, TPA-330, PET-30, T-1420, T-1 420(T), RP-1040, DPHA, DPEA-12, D-310, D-330, DPCA-20, DPCA-30, DP CA-60, DPCA-120, FM-700, DN-0075, DN-2475, TC-120S, R-115, R-130, R-381, EAM-2160, CCR-1291H, CCR-1235, ZAR-1035, ZAR-2000, ZFR-1401 H, ZFA-1491H, ZCR-1569H, ZCR-1601H, ZCR-1797H, ZCR-1798H, UXE-3000 , UXE-3024, UX-3204, UX-4101, UXT-6100, UX-6101, UX-7101, UX-8101,Same as UX-0937, UXF-4001-M35, UXF-4002, DPHA-40H, UX-5000, UX-5102D-M20, UX-5103D, UX-5005 (all manufactured by Nippon Pharmaceutical Co., Ltd.); NKエステルA200, same as A-400, same as A-600, same as A-1000, same as A-1500, same as A-2000, same as A BE-300, same as A-BPE-4, same as A-BPE-6, same as A-BPE-10, same as A-BPE-20, same as A-BPE- 30. The same as A-BPEF, the same as A-BPP-3, the same as A-DCP, the same as A-DOD-N, the same as A-HD-N, the same as A-NOD, the same as A-GLY-3E, same as A-GLY-9E, same as A-GLY-20E, same as A-TMPT, same as A-TMPT-3EO, same as A- TMPT-9EO, same as ATM-4E, same as ATM-35E, same as APG-100, same as APG-200, same as APG-400, same as APG-700, same as A-PTMG-65, same as A-1000PER, same as A-B1206PE, same as 701A, same as A-9300, same as A-9300-1CL, same as A-9300-6CL, same as A-9530, same as ADP-51EH, same as ATM-31EH, same as A-TMM-3, same as A-TMM-3L, same as A-TMM-3LM-N, same as AD-TMP, same as A-TMMT, same as A-9550, same as A-DPH, same as A-DPH-12E, same as 1G, same as 2G, same as 3G, same as 4G, same as 9G, same as 14G, same as 23G, same as BPE-80N, same as BPE-100, same as BPE-100N, same as BPE-200, same as BPE-500, same as BPE-900, same as BPE-1300N, same as DCP, same as DOD-N, same as HD-N, same as NOD-N, same as NPG, same as 1206PE, same as 701, same as 3PG, same as 9PG, same as TMPT, NK Economizer A-PG5009E, same as A-PG5027E, same as A -PG5054E, NK Origo U-2PPA, same as U-6LPA, same as U-10HA, same as U-10PA, same as UA-1100H, same as U-4H, same as U-6H, same as U-4HA, same as U-6HA, same as U-15HA, same as UA-32P, same as UA-33H, Same as UA-53H, U-200PA, U-324A, UA-160TM, UA-290TM, UA-4200, UA-4400, UA-122P, UA-7100, UA-W2A (all manufactured by Shin-Nakamura Chemical Industry Co., Ltd.); Viscort #195, same as #230, same as #260, same as #310HP, same as #335HP, same as #700HV, same as #540, same as #802.Same as #295, same as #300, same as #360, same as #230D, BAC-45, SPDBA-S30, STAR-501 (all manufactured by Osaka Organic Chemical Industry Co., Ltd.); Light Ester P-2M, P-2M, P-2M, P-2M, P-3M, P-4M, P-9M, P-14M, P-14M, P-14M, P-4M, P-5M, P-6M, P-101P, P-2M, P-2EMK, P-4M, P-5M, P-6M, P-4M, P-6M, P-9M, P-14M, P-6M, P-4M, P-6M, P-6M, P-7M, P-8M, P-9M, P-4M, P-6 BP-4PA, HPP-A, G-201P, TMP-A, PE-3A, PE-4A, DPE-6A, epoxy ester 40EM, 70PA, 200PA, 80MFA, 3002M(N), 3002A(N), 3000MK, 3000A, EX-0205, AH-600, AT-600, UA-306H, UA-306T, UA-306I, UA-510H, UF-8001G, DAUA-167 (all manufactured by Kyoeisha Chemical Co., Ltd.); Art Resin® UN-333, UN-350, UN-1255, UN-2600, UN-2700, UN-5200, UN-5500, UN-5590, UN-5507, UN-6060PTM, UN-6200, UN-6202, UN-6300, UN-6301, UN-7600, UN-7700, UN-90 00H, UN-9000PEP, UN-9200A, UN-3320HA, UN-3200HB, UN-3320HC, UN-3320HS, UN-904, UN -906S, UN-901T, UN-905, UN-906, UN-952, HDP-4T, HMP-2, H-61, HDP-M20 (manufactured by Negami Kogyo Co., Ltd.); Shiko [registered trademark] UV-1400B, UV-1700B, UV-2000B, UV-2010B, UV-2750B, UV-3000B, UV-3200B, UV-3210EA, UV-3 300B, UV-3310B, UV-3500BA, UV-3520TL, UV-3610D80, UV-3630D80, UV-3640PE80, UV-3700B, UV-6100B,UV-6300B, UV-6640B, UV-7000, UV-7000B, UV-7461TE, UV-7510B, UV-7550B, UV-7600B, UV-7605B, UV-7610B, UV- 7620EA, UV-7630B, UV-7640B, UV-7650B, UV-NS001, UV-NS034, UV-NS054, UV-NS063, UV-NS077 (manufactured by Nippon Gosei Kagaku Kogyo Co., Ltd.); Beamset® 243NS, 255, 261, 271, 502H, 504H, 505A-6, 550B, 575, 577, 700, 710, 730, 750, AQ-17, EM-90, EM-92, 371, 381 (all manufactured by Arakawa Chemical Industries, Ltd.); Funcryl® FA-124AS, FA-129AS, FA-222A, FA-240A, FA-P240A, FA-P270A, FA-321A, FA-324A, FA-PTG9A, FA-731A, FA-121M, FA-124M, FA-125M, FA-220M, FA-240M, FA-320M, FA-321M, FA-3218M, FA-PTG9M, FA-137M (all manufactured by Resonac Co., Ltd.); SR212, SR213, SR230, SR238F, SR259, SR268, SR272, SR306H, SR344, SR349, SR508, CD560, CD561, CD564, SR601, SR602, SR610, SR833S , SR9003, CD9043, SR9045, SR9209, SR205, SR206, SR209, SR210, SR214, SR231, SR239, SR248, SR252, SR297, SR348, SR480, CD540, CD5 41, CD542, SR603, SR644, SR9036, SR351S, SR368, SR415, SR444, SR454, SR492, SR499, CD501, SR502, SR9020, CD9021, SR9035, SR350, SR295, SR355, SR399, SR494, SR9041, SR9041, CN929, CN961E75, CN961H81, CN962, CN963, CN963A80, CN963B80, CN963E75, CN963E80,CN963J85, CN964, CN964E75, CN964A85, CN965, CN965A80, CN966A80, CN966H90, CN966J75, C N966R60, CN968, CN980, CN981, CN981A75, CN981B88, CN982, CN982A75, CN982B88, CN982E75, CN983, CN985B88, CN996, CN9001, CN9002, CN9788, CN9893, CN970A60, CN970E60, CN971, CN97 1A80, CN972, CN973A80, CN973H85, CN973J75, CN975, CN977C70, CN978, CN9782, CN9783, CN10 4, CN104A80, CN104B80, CN111, CN112C60, CN115, CN116, CN118, CN120, CN120A60, CN120A75 , CN120B60, CN120B80, CN120C60, CN120C80, CN120D80, CN102E50, CN120M50, CN124, CNUVE15 1. CNUVE151 / 80, CN151, CN2203, CN2270, CN2271, CN2273, CN2274, CN307, CN371, CN550, CN551, SB401, SB402, SB404, SB500E50, SB500K60, SB510E35, SB520E35, SB520M35 (all manufactured by Sartmar); DPGDA, HODA, TPGDA, PEG400DA-D, HPNDA, PETIA, PETRA, TMPTA, TMPEOTA, OTA480, DPHA, IRR214-K, IRR679, IRR742, IRR793, (ACA) Z200M, (ACA) Z230AA, (ACA) Z250, (ACA) Z251, (ACA) Z300, (ACA) Z320, (ACA) Z254F, EBECRYL® 145 , same 150, same 11, same 135, same 40, same 140, same 1142, same 180, same 204, same 205, same 210, same 215, same 220, same 230, same 244, same 245, same 264, same 265, same 270, same 280 / 151B, same 284, same 285, same 294 / 25HD, same 1259, same 1290, same 4820, same 4858, same 5129, same 8210, same 8254, same 8301R, same 8307, same 8402, same 8405, same 8411,Same 8465, same 8800, same 8804, same 8807, same 9260, same 9270, same 8311, same 8701, same 9227EA, same 436, same 438, same 446, same 450, same 524, same 525, same 770, same 800, same 810, same 811, same 812, same 1830, same 846, same 851, same 852, same 853, same 1870, same 884, same 885, same 600, same 605, same 645, same 648, same 860, same 1606, same 3500, same 3603, same 3608, same 3700, same 3701, same 3702, same 37 03, 3708, 6040, 8110, 271, 1258, 1291, 4100, 4200, 4500, 4680, 4220, 4265, 4491, 4513, 4587, 4666, 4683, 4738, 4740, 4250, 4510, KRM® 8200, 8200AE, 8296, 8452, 8904, 8667, 8912, 8981, 8762, 8713B, 8528 (all manufactured by Daicel Ornex Co., Ltd.); BAEA-100, BAEM-100, BAEM-50, BEEM-50, BFEA-50, HPEA-100, CNEA-100, PNEM-50, RNEA-100, TEA-100, KUA-4I, KUA-6I, KUA-9N, KUA-10H, KUA-15N, KUA-C2I, KUA-PC2I, KUA-PEA2I, KUA-PEB2I, KUA-PEC2I, RP-274S, RP-310 (all manufactured by KSM Corporation). ,

[0054] These polyfunctional (meth)acrylate compounds may be used individually or in combination of two or more.

[0055] Examples of the hydroxymethyl group or alkoxymethyl group-substituted phenol compounds include 1,3,5-trihydroxymethylbenzene, 2,6-dihydroxymethyl-4-methylphenol, 2,4-dihydroxymethyl-6-methylphenol, bis(2-hydroxy-3-hydroxymethyl-5-methylphenyl)methane, bis(4-hydroxy-3-hydroxymethyl-5-methylphenyl)methane, 2,2-bis(4-hydroxy-3,5-dihydroxymethylphenyl)propane, 3,3',5,5'-tetrahydroxymethyl-4,4'-bisphenol, and compounds in which some or all of the hydroxymethyl groups in these compounds are substituted with alkoxymethyl groups such as methoxymethyl groups and butoxymethyl groups. These hydroxymethyl group or alkoxymethyl group-substituted phenol compounds may be used individually or in combination of two or more.

[0056] Examples of compounds having the above-mentioned alkoxyalkylated amino group include nitrogen-containing compounds having multiple active methylol groups in a single molecule, such as (poly)methylolated melamine, (poly)methylolated glycoluryl, (poly)methylolated benzoguanamine, and (poly)methylolated urea, in which at least one hydrogen atom of the hydroxyl group in the methylol group is substituted with an alkyl group such as a methyl group or a butyl group.

[0057] The above-mentioned compound having an alkoxyalkylated amino group may be a mixture of multiple substituted compounds, and some mixtures may contain oligomeric components formed by the self-condensation of the compound, but any of these mixtures can be used.

[0058] The above-mentioned compounds having alkoxyalkylated amino groups can also be obtained as commercial products. Such commercial products include, for example, hexamethoxymethylmelamine (manufactured by CYTEC, CYMEL® 303, 303LF), tetrabutoxymethylglycoluryl (manufactured by CYTEC, CYMEL® 1170), tetramethoxymethylbenzoguanamine (manufactured by CYTEC, CYMEL® 1123), and other products in the CYMEL series; tetramethoxymethylglycoluryl (manufactured by CYTEC, Examples include products in the POWDERLINK series such as POWDERLINK® 1174), and products in the Nikalac series such as methylated melamine resin (manufactured by Sanwa Chemical Co., Ltd., Nikalac® MW-30HM, MW-390, MW-100LM, MX-750LM) and methylated urea resin (manufactured by Sanwa Chemical Co., Ltd., Nikalac® MX-270, MX-280, MX-290). These compounds having alkoxyalkylated amino groups may be used individually or in combination of two or more.

[0059] The above-mentioned polyfunctional blocked isocyanate compound has two or more isocyanate groups in one molecule, each isocyanate group blocked by an appropriate protecting group, and when exposed to the high temperature during thermal curing, the protecting group (blocking portion) thermally dissociates and detaches, and the resulting isocyanate group undergoes a crosslinking reaction with the resin.

[0060] Such polyfunctional blocked isocyanate compounds can be obtained, for example, by reacting a suitable blocking agent with a polyfunctional isocyanate compound having two or more isocyanate groups in one molecule.

[0061] The above polyfunctional isocyanate compounds include 1,4-tetramethylene diisocyanate, 1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate, 2,2,4-trimethyl-1,6-hexamethylene diisocyanate, 1,3,6-hexamethylene triisocyanate, lysine diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, and 1,3-bis(isocyanate). Anate-methyl)cyclohexane, 1,4-cyclohexyl diisocyanate, 2,6-bis(isocyanate-methyl)tetrahydrodicyclopentadiene, bis(isocyanate-methyl)dicyclopentadiene, bis(isocyanate-methyl)adamantane, 2,5-diisocyanate-methylnorbornene, norbornane diisocyanate, dicycloheptane triisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4 -Tolylene diisocyanate, 2,6-tolylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, 1,5-naphthalene diisocyanate, p-phenylene diisocyanate, 1,3-bis(isocyanate methyl)benzene, dianisidine diisocyanate, 3,3'-dimethyldiphenyl-4,4'-diisocyanate, diphenyl ether diisocyanate, 2,6-bis(isocyanate Tomethyl)decahydronaphthalene, bis(diisocyanate tolyl)phenylmethane, 1,1'-methylenebis(3-methyl-4-isocyanate-benzene), 1,3-bis(1-isocyanate-1-methylethyl)benzene, 1,4-bis(1-isocyanate-1-methylethyl)benzene, 4,4'-biphenylenediisocyanate, 3,3'-dimethyl-4,4'-biphenylenediisocyanate, 3,3'-dimethoxy-4,Examples include 4'-biphenylenediisocyanate, bis(isocyanate-methyl)thiophene, bis(isocyanate-methyl)tetrahydrothiophene, and modified compounds thereof (e.g., isocyanurate, biuret, ethylene glycol adduct, propylene glycol adduct, trimethylolpropane adduct, ethanolamine adduct, polyester polyol adduct, polyether polyol adduct, polyamide adduct, polyamine adduct).

[0062] Examples of the above blocking agents include alcohols such as methanol, ethanol, isopropanol, n-butanol, heptanol, hexanol, 2-ethoxyhexanol, cyclohexanol, octanol, isononyl alcohol, stearyl alcohol, benzyl alcohol, 2-ethoxyethanol, methyl lactate, ethyl lactate, amyl lactate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether), triethylene glycol monoethyl ether, N,N-dimethylaminoethanol, N,N-diethylaminoethanol, N,N-dibutylaminoethanol, phenol, ethylphenol, propylphenol, butylphenol, octylphenol, nonylphenol, nitrophenol, chlorophenol, o- Phenols such as cresol, m-cresol, p-cresol, and xylenol; lactams such as α-pyrrolidone, β-butyrolactam, β-propiolactam, γ-butyrolactam, δ-valerolactam, and ε-caprolactam; oximes such as acetone oxime, methyl ethyl ketone oxime, methyl isobutyl ketone oxime, diethyl ketone oxime, cyclohexanone oxime, acetophenone oxime, and benzophenone oxime; pyrazoles, 3,5-dimethylpyrazole, 3-methylpyrazole, and 4-methylpyrazole. Pyrazoles such as 3,5-dimethylpyrazole, 4-nitro-3,5-dimethylpyrazole, 4-bromo-3,5-dimethylpyrazole, and 3-methyl-5-phenylpyrazole; mercaptans such as butyl mercaptan, hexyl mercaptan, dodecyl mercaptan, and benzenethiol; active methylene compounds such as malonic acid diesters, acetoacetate esters, malonic acid dinitrile, acetylacetone, methylenedisulfone, dibenzoylmethane, dipivaloylmethane, and acetone dicarboxylic acid diesters;Examples include amines such as dibutylamine, diisopropylamine, di-tert-butylamine, di(2-ethylhexyl)amine, dicyclohexylamine, benzylamine, diphenylamine, aniline, and carbazole; imidazoles such as imidazole and 2-ethylimidazole; imines such as methyleneimine, ethyleneimine, polyethyleneimine, and propyleneimine; acid amides such as acetanilide, acrylamide, acetic acid amide, and dimer acid amide; acid imides such as succinimide, maleimide, and phthalimide; and urea compounds such as urea, thiourea, and ethyleneurea. Furthermore, internal block types due to uretdione bonding (dimerization of isocyanate groups) may also be present.

[0063] The above-mentioned polyfunctional blocked isocyanate compounds are also available commercially. Examples of such commercially available products include the following: Takenate® B-815N, B-830, B-842N, B-846N, B-870, B-870N, B-874, B-874N, B-882, B-882N, B-5010, B-7005, B-7030, and B-7075 (all manufactured by Mitsui Chemicals, Inc.); Duranate® ME20-B80S, MF-B60B, MF-B60X, MF-B90B, MF-K60B, MF-K60X, SBN-70D, 17B-60P, 17B-60PX, TPA-B80E, TPA-B80X, E402-B80B, E402-B80T, K6000 (all manufactured by Asahi Kasei Corporation); Coronate® 2503, 2507, 2512, 2513, 2515, 2520, 2554, BI-301, AP-M, Millionate MS-50 (all manufactured by Tosoh Corporation); Barnock® D-500, D-550, DB-980K (all manufactured by DIC Corporation); Desmodule® BL-3175, BL-4165, BL-4265, BL-1100, BL-1265, TPLS-2957, TPLS-2062, TPLS-2078, TPLS-2117, BL-3475, Desmosarm® 2170, 2265 (all manufactured by Sumika Covestro Urethane Co., Ltd.); TRIXENE BI-7641, BI-7642, BI-7986, BI-7987, BI-7950, BI-7951, BI-7960, BI-7961, BI-7963, BI-7981, BI-7982, BI-7984, BI-7986, BI-7990, BI-7991, BI-7992, BI-7770, BI-7772, BI-7779, DP9C / 214 (all manufactured by Bakusenden Chemicals Co., Ltd.); VESTANAT® B1358A, B1358 / 100, B1370, VESTAGON® B1065, B1400, B1530, BF1320, BF1540 (all manufactured by Evonik Industries).

[0064] Furthermore, examples of the polyfunctional blocked isocyanate compounds include homopolymers or copolymers obtained by radical polymerization of (meth)acrylates having blocked isocyanate groups. Here, copolymer means a polymer obtained by polymerizing two or more monomers. The copolymer may be a copolymer obtained by polymerizing two or more (meth)acrylates having blocked isocyanate groups, or a copolymer obtained by polymerizing a (meth)acrylate having blocked isocyanate groups and other (meth)acrylates. Such (meth)acrylates having blocked isocyanate groups can also be obtained as commercial products. Examples of such commercial products include Karens® MOI-BM, AOI-BM, MOI-BP, and AOI-BP manufactured by Resonaq Corporation.

[0065] Specific examples of homopolymers or copolymers obtained by radical polymerization of (meth)acrylates having blocked isocyanate groups include those represented by the following formulas (B-1) to (B-5).

[0066]

[0067] These polyfunctional block isocyanate compounds may be used individually or in combination of two or more.

[0068] In the present invention, as a catalyst to promote the above crosslinking reaction, acidic compounds such as p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium-p-toluenesulfonic acid, salicylic acid, sulfosalicylic acid, citric acid, benzoic acid, hydroxybenzoic acid, and naphthalenecarboxylic acid can be incorporated; and thermoacid generators such as 2,4,4,6-tetrabromocyclohexadienone, benzoin tosylate, 2-nitrobenzyl tosylate, and other organic alkyl sulfonates can be incorporated. The above acidic compounds and thermoacid generators can also be incorporated in combination.

[0069] The amount of catalyst added is preferably 0.0001 to 20 parts by mass, and more preferably 0.0005 to 10 parts by mass, per 100 parts by mass of the nonpolymer compound in the film-forming composition of the present invention.

[0070] <Organic Solvents> The organic solvent is not particularly limited as long as it dissolves the above-mentioned nonpolymer compounds. Specific examples include methylcyclohexane, ethylcyclohexane, n-heptane, toluene, o-xylene, m-xylene, mesitylene, chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, anisole, phenethole, di-n-propyl ether, di-n-butyl ether, diisobutyl ether, di-n-pentyl ether, diisopentyl ether, di-n-hexyl ether, n-butyl ethyl ether, methyl-n-pentyl ether, cyclopentyl methyl ether, tetrahydropyran, 1,3-dioxane, 1,4-dioxane, 1-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 1-pentanol, 2-pentanol, 3-pentanol, cyclopentanol, benzyl alcohol, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol Diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, triethylene glycol monomethyl ether, triethylene glycol dimethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol dimethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, n-butyl formate, isobutyl formate, n-pentyl formate, isopentyl formate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, tert-butyl acetate, n-pentyl acetate, isopentyl acetate, n-hexyl acetate, isohexyl acetate, n-heptyl acetate, isoheptyl acetate, n-octyl acetate,Isooctyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol diacetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate , propylene glycol diacetate, triacetin, ethyl propionate, n-propyl propionate, isopropyl propionate, n-butyl propionate, isobutyl propionate, tert-butyl propionate, propylene glycol monomethyl ether propionate, methyl butyrate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, isobutyl butyrate, tert-butyl butyrate, methyl isobutyrate, ethyl isobutyrate, n-propyl isobutyrate, isopropyl Ropyluisobutyrate, n-butylisobutyrate, isobutylisobutyrate, tert-butylisobutyrate, methyl lactate, ethyl lactate, n-propyl lactate, isopropyl lactate, n-butyl lactate, isobutyl lactate, tert-butyl lactate, methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, tert-butyl acetate, dimethylmalonate, diethylmalonate, Methyl glycolate, ethyl glycolate, methyl pyruvate, ethyl pyruvate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, dimethyl carbonate, diethyl carbonate, 2-pentanone, 3-pentanone, cyclopentanone, 2,4-pentanedione, 4-methyl-2-pentanone, 4-hydroxy-4-methyl-2-pentanone, 2-hexanone, 3-hexanone, 3-methyl-2-hexanone, 5-methyl-2-hexanone,Examples include 2-methyl-3-hexanone, 5-methyl-3-hexanone, cyclohexanone, 2-methylcyclohexanone, 3-methylcyclohexanone, 4-methylcyclohexanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-methyl-3-heptanone, 5-methyl-3-heptanone, 2,6-dimethyl-4-heptanone, cycloheptanone, γ-butyrolactone, γ-valerolactone, γ-caprolactone, δ-valerolactone, δ-caprolactone, ε-caprolactone, N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, N,N-diethylacetamide, N,N-dimethylisobutylamide, N-methyl-2-pyrrolidone, and N-ethyl-2-pyrrolidone. These organic solvents may be used individually or in combination of two or more.

[0071] Among the above organic solvents, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, ethyl lactate, n-butyl lactate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, 2-heptanone, cyclopentanone, cyclohexanone, γ-butyrolactone, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, and N-ethyl-2-pyrrolidone are preferred from the viewpoint of improving the leveling properties of the coating film formed by applying the film-forming composition of the present invention to a substrate.

[0072] <Surfactants> The film-forming composition of the present invention may also contain surfactants for the purpose of improving its applicability. Examples of such surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether; polyoxyethylene alkylaryl ethers such as polyoxyethylene octylphenyl ether and polyoxyethylene nonylphenyl ether; polyoxyethylene / polyoxypropylene block copolymers; sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, and sorbitan tristearate; polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan. Nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters including ristearate; F-Top® EF301, EF303, EF352 (all manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), Megafac® F171, F173, R-30, R-40, R-40-LM (all manufactured by DIC Corporation), Florard FC430, FC431 (both manufactured by 3M Japan Ltd.), Asahi Guard® AG71 0. Fluorine-based surfactants such as Surflon® S-382, SC101, SC102, SC103, SC104, SC105, SC106 (all manufactured by AGC Inc.), DFX-18, FTX-206D, FTX-212D, FTX-218, FTX-220D, FTX-230D, FTX-240D, FTX-212P, FTX-220P, FTX-228P, FTX-240G, and other Futergent series (all manufactured by Neos Co., Ltd.);Examples include non-fluorinated surfactants such as organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow No. 7, No. 36, No. 50E, No. 75, No. 77, No. 85, No. 85HF, No. 90, No. 90D-50, No. 95, No. 99C, and PW-95 (all manufactured by Kyoeisha Chemical Co., Ltd.), and BYK-302, BYK-307, BYK-322, BYK-323, BYK-330, BYK-333, BYK-370, BYK-375, BYK-378, and BYK-399 (all manufactured by BYK Japan Co., Ltd.). These surfactants may be used individually or in combination of two or more.

[0073] If the above surfactant is included, its content is preferably 0.0001 to 3 parts by mass, more preferably 0.001 to 1 part by mass, and even more preferably 0.01 to 0.5 parts by mass, per 100 parts by mass of the above nonpolymer compound.

[0074] <Other Additives> The film-forming composition of the present invention may optionally contain additives such as antioxidants, light stabilizers (HALS: hindered amine-based light stabilizers), thermobase generators, ultraviolet absorbers different from the nonpolymer compounds of the present invention (hereinafter sometimes referred to as "other ultraviolet absorbers"), adhesion aids, plasticizers, and sensitizers, as long as they do not impair the effects of the present invention.

[0075] As the light stabilizer (HALS), a hindered amine-based light stabilizer is preferred.Known hindered amine-based light stabilizers can be used, specifically bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis(1-methoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(1-ethoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(1-propoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(1-butoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate Sebacate, Bis(1-pentyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, Bis(1-hexyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, Bis(1-heptyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, Bis(1-octoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, Bis(1-nonyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, Bis(1-decanyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, Bis (1-dodecyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)-2-(4-methoxybenzylidene) malonate, bis(1,2,2,6,6-pentamethyl-4-piperidinyl)-[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]butyl malonate, tetrakis(2,2,6,6-pentamethyl-4-piperidyl)1,2,3,4-butanetetracarboxylate, tetrakis(1,2,2,6,6-pentamethyl-4-piperi Examples include 1,2,3,4-butanetetracarboxylate, a condensate of 1,2,3,4-butanetetracarboxylic acid, 1,2,2,6,6-pentamethyl-4-piperidinol, and β,β,β,β-tetramethyl-3,9-(2,4,8,10-tetraoxaspiro[5,5])undecane)diethanol, and a condensate of 1,2,3,4-butanetetracarboxylic acid, 2,2,6,6-pentamethyl-4-piperidinol, and β,β,β,β-tetramethyl-3,9-(2,4,8,10-tetraoxaspiro[5,5])undecane)diethanol.The UV absorbers listed above may be used individually or in combination of two or more types.

[0076] Commercially available hindered amine light stabilizers can also be used. Examples of commercially available products include TINUVIN® 123, TINUVIN® 292, TINUVIN® 152, TINUVIN® 144, TINUVIN® 622SF, TINUVIN® 111FDL, TINUVIN® 249 (all manufactured by BASF); ADEKA STAB® LA-52, ADEKA STAB® LA-57, ADEKA STAB® LA-63P, ADEKA STAB® LA-68, ADEKA STAB® LA-72, ADEKA STAB® LA-81, ADEKA STAB® LA-82, ADEKA STAB® LA-87 (all manufactured by ADEKA Corporation).

[0077] If the above-mentioned light stabilizer is included, its content is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 7 parts by mass, and even more preferably 0.5 to 5 parts by mass, per 100 parts by mass of the above-mentioned nonpolymer compound.

[0078] A thermal base generator is a compound that generates a base by undergoing bond cleavage upon heating. Specific examples of thermal base generators include 1,8-diazabicyclo[5.4.0]undecene-7 2-ethylhexanoate, 1,8-diazabicyclo[5.4.0]undecene-7 phenol salt, 1,8-diazabicyclo[5.4.0]undecene-7 formate, 1,8-diazabicyclo[5.4.0]undecene-7 o-phthalate, 1,8-diazabicyclo[5.4.0]undecene-7 p-toluenesulfonate, 1,5-diazabicyclo[4.3.0]nonene-5 2-ethylhexanoate, benzyltriphenylphosphonium bromide, bis(2-morpholinoethyl) ether, and 1,1'-[[3-(dimethylamino)propyl]imino]bis(2-propanol). These compounds may be used individually or in combination of two or more.

[0079] The above-mentioned thermal base generators can also be commercially available. Commercially available products include U-CAT(registered trademark) SA1, U-CAT(registered trademark) SA102, U-CAT(registered trademark) SA102-50, U-CAT(registered trademark) SA106, U-CAT(registered trademark) SA112, U-CAT(registered trademark) SA506, U-CAT(registered trademark) SA603, U-CAT(registered trademark) 1000, U-CAT(registered trademark) 1102, U-CAT(registered trademark) 2000, U-CAT(registered trademark) 2024, U-CAT(registered trademark) 2026, U-CAT(registered trademark) 2030, U-CAT(registered trademark) Examples include 2110, U-CAT® 2313, U-CAT® 651M, U-CAT® 660M, U-CAT® 18X, U-CAT® 201G, U-CAT® 202, U-CAT® 420A, U-CAT® 130 (all manufactured by Sunapro Co., Ltd.), POLYCAT® 8, POLYCAT® 9, POLYCAT® 12, POLYCAT® 41 (all manufactured by Evonik Industries, Ltd.).

[0080] When the above-mentioned thermobase generating agent is included, its content is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 7 parts by mass, and even more preferably 0.5 to 5 parts by mass, per 100 parts by mass of the above-mentioned nonpolymer compound.

[0081] Specific examples of the above-mentioned other UV absorbers include 2-[4-(4,6-bis[1,1'-biphenyl]-4-yl)-1,3,5-triazine-2-yl]-3-hydroxyphenoxy-isooctylpropionate, 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxy-phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, and 2-[4-[(2-hydroxy-3-tridecyloxypropyl [2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[4-[(2-hydroxy-3-(2-ethyl-hexyloxy)propyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis(2-hydroxy-4-butyroxyphenyl)-6-(2,4-bis-butyroxyphenyl)-1,3,5-triazine, 2-(2- Examples include benzotriazine-based UV absorbers such as hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)-4,6-bis(4-phenylphenyl)-1,3,5-triazine; benzotriazole-based UV absorbers such as 2-(2H-benzotriazole-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, 2-(2-hydroxy-5-tert-butylphenyl)-2H-benzotriazole, and 2-[2-hydroxy-5-(2-(meth)acryloyloxyethyl)phenyl]-2H-benzotriazole; benzophenone-based UV absorbers such as 2,4-dihydroxybenzophenone and 2-hydroxy-4-methoxybenzophenone; cyanoacrylate-based UV absorbers such as ethyl-2-cyano-3,3-diphenylacrylate and octyl-2-cyano-3,3-diphenylacrylate; and inorganic microparticles that absorb ultraviolet light such as titanium dioxide microparticles, zinc oxide microparticles, and tin oxide microparticles. The UV absorbers listed above may be used individually or in combination of two or more types.

[0082] Commercially available UV absorbers can also be used. Examples of commercially available products include TINUVIN® PS, TINUVIN® 99-2, TINUVIN® 234, TINUVIN® 326, TINUVIN® 329, TINUVIN® 900, TINUVIN® 928, TINUVIN® 360, TINUVIN® 384-2, TINUVIN® 400, TINUVIN® 405, and TINUVIN® Examples include [Registered Trademark] 460, TINUVIN [Registered Trademark] 477, TINUVIN [Registered Trademark] 479 (all manufactured by BASF); Adeka Stab [Registered Trademark] LA-46, Adeka Stab [Registered Trademark] LA-F70, Adeka Stab [Registered Trademark] LA-29, Adeka Stab [Registered Trademark] LA-31G, Adeka Stab [Registered Trademark] LA-32, Adeka Stab [Registered Trademark] LA-36 (all manufactured by ADEKA Corporation); RUVA-93 (manufactured by Otsuka Chemical Co., Ltd.), etc.

[0083] If the above-mentioned other ultraviolet absorbers are included, their content is preferably 0.1 to 15 parts by mass, more preferably 0.5 to 10 parts by mass, and even more preferably 1 to 7 parts by mass, per 100 parts by mass of the above-mentioned nonpolymer compound.

[0084] The method for preparing the film-forming composition of the present invention is not particularly limited, but for example, one method is to dissolve the above-mentioned nonpolymer compound and curing agent in an organic solvent to obtain a homogeneous solution. Furthermore, at an appropriate stage of this preparation method, a surfactant and other additives may be added and mixed as needed. In order to obtain a thin film with higher flatness with good reproducibility, the film-forming composition may be filtered using a sub-micrometer-order filter or the like at an intermediate stage in preparation or after all components have been mixed, as needed.

[0085] The solid content concentration of the film-forming composition of the present invention is set appropriately considering the coating properties of the composition and the characteristics of the object to which the film is to be formed, but is usually about 0.1 to 30% by mass, preferably about 1 to 25% by mass, and more preferably about 5 to 25% by mass.

[0086] The use of the film-forming composition of the present invention will be described below. <Method for producing a cured film> A method for producing a cured film using the film-forming composition of the present invention will be described below. The film-forming composition of the present invention is applied to an organic film, a film substrate (e.g., PET film, polyimide film), or a component by an appropriate coating method such as a spinner or coater, and then baked using a heating means such as a hot plate or oven to produce a cured film. The baking conditions are appropriately selected from a baking temperature of 50 to 300°C and a baking time of 0.1 to 360 minutes. The baking process for producing the cured film may be carried out in two or more steps. The thickness of the formed cured film is, for example, 0.001 to 1,000 μm, preferably 0.01 to 100 μm, and more preferably 0.1 to 10 μm.

[0087] The cured film produced using the film-forming composition of the present invention can be used as an optical component such as a protective film, planarization film, insulating film, anti-reflective film, refractive index control film, microlens, intralayer lens, optical waveguide, or film substrate.

[0088] The present invention will be described in more detail below with reference to synthesis examples, examples, and comparative examples, but the present invention is not limited to the following examples.

[0089] The compounds used in the following synthesis examples, examples, and comparative examples are as follows: [Solvents] PGME: Propylene glycol monomethyl ether PGMEA: Propylene glycol monomethyl ether acetate CHN: Cyclohexanone MEK: Methyl ethyl ketone EL: Ethyl lactate THF: Tetrahydrofuran

[0090] [Ingredients] BDMT: 2,4-bis(2,4-dihydroxyphenyl)-6-(methoxyphenyl)-1,3,5-triazine

[0091] TDPT: 2,4,6-Tris(2,4-dihydroxyphenyl)-1,3,5-triazine

[0092] EX-142-IM: 2-phenylphenol glycidyl ether (Nagase ChemteX Corporation, product name: Denacol® EX-142-IM)

[0093] EX-141: Phenylglycidyl ether (Nagase ChemteX Corporation, product name: Denacol® EX-141)

[0094] EX-146P: p-tert-butylphenyl glycidyl ether (Nagase ChemteX Corporation, product name: Denacol® EX-146P)

[0095] 4GCz: 4-Glycidyloxycarbazole

[0096] EX810P: Ethylene glycol diglycidyl ether (Nagase ChemteX Corporation, product name: Denacol® EX-810P)

[0097] JER828: Bisphenol A type bifunctional epoxy resin (Mitsubishi Chemical Corporation, product name: jER® 828)

[0098] DBDT: 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine

[0099] MOI-BP: 2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl methacrylate (Resonac Co., Ltd., product name: Karenz (registered trademark) MOI-BP)

[0100] MOI-BM: 2-[O-(1'-methylpropyleneneamino)carboxyamino]ethyl methacrylate (Resonac Co., Ltd., product name: Karenz (registered trademark) MOI-BM)

[0101] AOI-BP: 2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl acrylate (Resonac Co., Ltd., product name: Karenz® AOI-BP)

[0102] RUVA-93: 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole (Otsuka Chemical Co., Ltd., product name: RUVA-93)

[0103] Light stabilizer (HALS1): Bis(1,2,2,6,6-pentamethyl-4-piperidinyl)-[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]butylmalonate

[0104] Thermobase generator (SA102): 2-ethylhexanoate of 1,8-diazabicyclo[5.4.0]undecene-7

[0105] UV absorber (UVA1): 2-[4-(4,6-bis[1,1'-biphenyl]-4-yl)-1,3,5-triazine-2-yl]-3-hydroxyphenoxyisooctylpropionate

[0106] Furthermore, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) of the polymers were measured using a GPC instrument manufactured by Shimadzu Corporation (columns: Shodex® KF803L and KF804L (manufactured by Resonac Corporation); eluent: THF, flow rate: 1.0 mL / min, column temperature: 40°C, Mw and Mn: values ​​equivalent to standard polystyrene).

[0107] [Synthesis of raw materials for nonpolymer compounds] [Synthesis Example 1] 3.00 g (13.27 mmol) of 2,4-dichloro-6-phenyl-1,3,5-triazine and 3.89 g (29.20 mmol) of anhydrous aluminum trichloride were mixed with 90.1 g of o-dichlorobenzene as a solvent and heated to 70°C. 3.21 g (29.20 mmol) of resorcinol was added to the resulting solution and the mixture was reacted at 100°C for 6 hours. The reaction solution was added dropwise to a mixture of 32 g of 1 M aqueous hydrochloric acid and 90 g of water, and the precipitated solid was filtered and dried to obtain 4.07 g of 2,4-bis(2,4-dihydroxyphenyl)-6-phenyl-1,3,5-triazine:triazine compound T1 (yield 82%).

[0108]

[0109] [Synthesis Example 2] 3.00 g (16.67 mmol) of 2,4-dichloro-6-methoxy-1,3,5-triazine and 4.89 g (36.67 mmol) of anhydrous aluminum trichloride were mixed with 100.7 g of o-dichlorobenzene as a solvent and heated to 70°C. 4.03 g (36.67 mmol) of resorcinol was added to the resulting solution and the mixture was reacted at 100°C for 6 hours. The reaction mixture was added dropwise to a solution of 40 g of 1 M aqueous hydrochloric acid and 107 g of water, and the precipitated solid was filtered and dried to obtain 4.42 g of 2,4-bis(2,4-dihydroxyphenyl)-6-methoxy-1,3,5-triazine:triazine compound T2 (yield 81%).

[0110]

[0111] [Synthesis Example 3] 3.00 g (12.76 mmol) of 2,4-dichloro-6-morpholino-1,3,5-triazine and 3.74 g (28.01 mmol) of anhydrous aluminum trichloride were mixed with 100.7 g of o-dichlorobenzene as a solvent and heated to 70°C. 3.09 g (28.01 mmol) of resorcinol was added to the resulting solution and the mixture was reacted at 100°C for 6 hours. The reaction mixture was added dropwise to a solution of 40 g of 1 M aqueous hydrochloric acid and 107 g of water. The precipitated solid was filtered and dried to obtain 3.67 g of 2,4-bis(2,4-dihydroxyphenyl)-6-morpholino-1,3,5-triazine:triazine compound T3 (yield 75%).

[0112]

[0113] [1] Synthesis of Nonpolymer Compounds [Example 1-1] 3.93 g of EX-142-IM (240 g epoxy equivalent), 3.00 g of BDMT (7.44 mmol), and 0.17 g of ethyltriphenylphosphonium bromide as a catalyst were dissolved in 28.9 g of CHN and reacted at 120°C for 18 hours. The reaction solution was added dropwise to 289 g of methanol, and the precipitated solid was filtered and dried to obtain 5.67 g of powder of the nonpolymer compound (A-1) represented by the following formula, which corresponds to the nonpolymer compound represented by formula (1) above (yield 88%).

[0114]

[0115] [Example 1-2] 2.47 g of EX-141 (epoxy equivalent 151 g / equivalent), 3.00 g of BDMT (7.44 mmol), and 0.17 g of ethyltriphenylphosphonium bromide as a catalyst were dissolved in 22.5 g of CHN and reacted at 120°C for 18 hours. The reaction solution was added dropwise to 225 g of methanol, and the precipitated solid was filtered and dried to obtain 4.95 g of powder of a nonpolymer compound (A-2) represented by the following formula, which corresponds to the nonpolymer compound represented by formula (1) above (yield 95%).

[0116]

[0117] [Examples 1-3] 3.44 g of EX-146P (210 g epoxy equivalent), 3.00 g of BDMT (7.44 mmol), and 0.17 g of ethyltriphenylphosphonium bromide as a catalyst were dissolved in 26.4 g of CHN and reacted at 120°C for 18 hours. The reaction solution was added dropwise to 264 g of methanol, and the precipitated solid was filtered and dried to obtain 5.72 g of powder of the nonpolymer compound (A-3) represented by the following formula, which corresponds to the nonpolymer compound represented by formula (1) above (yield 95%).

[0118]

[0119] [Example 1-4] 4.05 g of EX-142-IM (260 g epoxy equivalent), 3.00 g (8.03 mmol) of triazine compound T1, and 0.12 g of ethyltriphenylphosphonium bromide as a catalyst were dissolved in 28.4 g of CHN and reacted at 120°C for 18 hours. The reaction solution was added dropwise to 284 g of methanol, and the precipitated solid was filtered and dried to obtain 5.88 g of powder of the nonpolymer compound (A-3) represented by the following formula, which corresponds to the nonpolymer compound represented by formula (1) above (yield 89%).

[0120]

[0121] [Examples 1-5] 4.61 g of EX-142-IM (260 g epoxy equivalent), 3.00 g (9,17 mmol) of triazine compound T2, and 0.14 g of ethyltriphenylphosphonium bromide as a catalyst were dissolved in 31.0 g of CHN and reacted at 120°C for 18 hours. The reaction solution was added dropwise to 310 g of methanol, and the precipitated solid was filtered and dried to obtain 6.08 g of powder of the nonpolymer compound (A-5) represented by the following formula, which corresponds to the nonpolymer compound represented by formula (1) above (yield 85%).

[0122]

[0123] [Example 1-6] 3.96 g of EX-142-IM (260 g epoxy equivalent), 3.00 g (7.85 mmol) of triazine compound T3, and 0.12 g of ethyltriphenylphosphonium bromide as a catalyst were dissolved in 28.3 g of CHN and reacted at 120°C for 18 hours. The reaction solution was added dropwise to 283 g of methanol, and the precipitated solid was filtered and dried to obtain 5.51 g of powder of the nonpolymer compound (A-6) represented by the following formula, which corresponds to the nonpolymer compound represented by formula (1) above (yield 83%).

[0124]

[0125] [Example 1-7] 3.00 g of EX-142-IM (260 g epoxy equivalent), 1.69 g of TDPT (4.17 mmol), and 0.07 g of ethyltriphenylphosphonium bromide as a catalyst were dissolved in 45.0 g of CHN and reacted at 120°C for 18 hours. The reaction solution was added dropwise to 300 g of methanol, and the precipitated solid was filtered and dried to obtain 4.02 g of powder of a nonpolymer compound (A-7) represented by the following formula, which corresponds to the nonpolymer compound represented by formula (1) above (yield 88%).

[0126]

[0127] [Example 1-8] 3.00 g of EX-141 (epoxy equivalent 151 g / equivalent), 2.68 g of TDPT (6.62 mmol), and 0.10 g of ethyltriphenylphosphonium bromide as a catalyst were dissolved in 52.0 g of CHN and reacted at 120°C for 18 hours. The reaction solution was added dropwise to 520 g of methanol, and the precipitated solid was filtered and dried to obtain 5.03 g of powder of a nonpolymer compound (A-8) represented by the following formula, which corresponds to the nonpolymer compound represented by formula (1) above (yield 92%).

[0128]

[0129] [Examples 1-9] 3.00 g of 4GCz (293 g epoxy equivalent), 1.69 g of TDPT (4.18 mmol), and 0.06 g of ethyltriphenylphosphonium bromide as a catalyst were dissolved in 40.0 g of CHN and reacted at 120°C for 18 hours. The reaction solution was added dropwise to 400 g of methanol, and the precipitated solid was filtered and dried to obtain 4.22 g of powder of the nonpolymer compound (A-9) represented by the following formula, which corresponds to the nonpolymer compound represented by formula (1) above (yield 90%).

[0130]

[0131] [Comparative Example 1-1] 2.00 g of EX810P (epoxy equivalent 95), 8.39 g of DBDT (21.05 mmol), and 0.16 g of ethyltriphenylphosphonium bromide as a catalyst were dissolved in 42.1 g of CHN and reacted at 120°C for 20 hours to obtain a solution with a solid content of 20% by mass containing a nonpolymer compound (A-10) represented by the following formula, which does not fall under the nonpolymer compound represented by formula (1) above.

[0132]

[0133] [Comparative Example 1-2] 4.41 g of EX-142-IM (260 g epoxy equivalent), 2.00 g (8.76 mmol) of 2,2-bis(4-hydroxyphenyl)propane, and 0.13 g of ethyltriphenylphosphonium bromide as a catalyst were dissolved in 26.1 g of CHN and reacted at 120°C for 18 hours. The reaction solution was added dropwise to 261 g of methanol, and the precipitated solid was filtered and dried to obtain 5.36 g of powder of a nonpolymer compound (A-11) represented by the following formula, which corresponds to the nonpolymer compound represented by formula (1) above (yield 90%).

[0134]

[0135] [Comparative Example 1-3] 4.37 g of EX-142-IM (260 g epoxy equivalent), 2.00 g (8.69 mmol) of 2,4,4'-trihydroxybenzophenone, and 0.13 g of ethyltriphenylphosphonium bromide as a catalyst were dissolved in 26.0 g of CHN and reacted at 120°C for 18 hours. The reaction solution was added dropwise to 260 g of methanol, and the precipitated solid was filtered and dried to obtain 5.22 g of powder of a nonpolymer compound (A-12) represented by the following formula, which corresponds to the nonpolymer compound represented by formula (1) above (yield 88%).

[0136]

[0137] [Comparative Example 1-4] 1.41 g of JER828 (epoxy equivalent 190 g / equal), 4.00 g of BDMT (9.92 mmol), and 0.08 g of ethyltriphenylphosphonium bromide as a catalyst were dissolved in 21.9 g of CHN and reacted at 120°C for 20 hours to obtain a polymer solution with a solid content of 20% by mass containing a polymer (A-15) having repeating units represented by the following formula, which does not fall under the nonpolymer compound represented by formula (1) above. The obtained polymer had a Mw of 6,300 and a Mn of 3,400.

[0138]

[0139] [Comparative Example 1-5] 2.15 g of G01100 (epoxy equivalent 170), 5.00 g of DBDT (12.58 mmol), and 0.17 g of ethyltriphenylphosphonium bromide as a catalyst were dissolved in 29.3 g of CHN and reacted at 120°C for 20 hours to obtain a polymer solution with a solid content of 20% by mass containing a polymer (A-16) having repeating units represented by the following formula, which does not fall under the nonpolymer compound represented by formula (1) above. The obtained polymer had a Mw of 23,000 and a Mn of 12,000.

[0140]

[0141] [2] Synthesis of curing agent [Synthesis example 4] 10.00 g (39.79 mmol) of MOI-BP and 0.78 g of azobisisobutyronitrile as a polymerization catalyst were dissolved in 25.1 g of PGMEA and reacted at 70°C for 20 hours to obtain a polymer solution with a solid content of 30% by mass. The obtained polymer solution was gradually added dropwise to 400 g of methanol to precipitate the solid. The precipitated solid was filtered off and dried under reduced pressure to obtain a polymer (B-1) having repeating units represented by the following formula. The obtained polymer had an Mw of 32,000 and an Mn of 14,000.

[0142]

[0143] [Synthesis Example 5] 10.00 g (41.27 mmol) of MOI-BM and 0.40 g of azobisisobutyronitrile as a polymerization catalyst were dissolved in 31.2 g of PGMEA and reacted at 80°C for 20 hours to obtain a polymer solution with a solid content of 25% by mass. The obtained polymer solution was gradually added dropwise to 500 g of methanol to precipitate the solid. The precipitated solid was filtered off and dried under reduced pressure to obtain a polymer (B-2) having repeating units represented by the following formula. The obtained polymer had a Mw of 7,800 and a Mn of 4,100.

[0144]

[0145] [Synthesis Example 6] 10.00 g (42.15 mmol) of AOI-BP and 0.42 g of azobisisobutyronitrile as a polymerization catalyst were dissolved in 32.0 g of PGMEA and reacted at 80°C for 20 hours to obtain a polymer solution with a solid content of 25% by mass. The obtained polymer solution was gradually added dropwise to 500 g of methanol to precipitate the solid. The precipitated solid was filtered off and dried under reduced pressure to obtain a polymer (B-3) having repeating units represented by the following formula. The obtained polymer had a Mw of 30,000 and a Mn of 13,000.

[0146]

[0147] [Synthesis Example 7] 5.00 g (19.90 mmol) of MOI-BP, 2.75 g (8.53 mmol) of RUVA-93, and 0.42 g of azobisisobutyronitrile as a polymerization catalyst were dissolved in 46.3 g of PGMEA and reacted at 70°C for 20 hours to obtain a polymer solution with a solid content of 15% by mass. The obtained polymer solution was gradually added dropwise to 500 g of methanol to precipitate the solid. The precipitated solid was filtered off and dried under reduced pressure to obtain a polymer (B-4) having repeating units represented by the following formula. The obtained polymer had a Mw of 21,000 and a Mn of 9,300.

[0148]

[0149] [Synthesis Example 8] 5.00 g (19.90 mmol) of MOI-BP, 1.63 g (8.53 mmol) of vinyl biphenyl, and 0.42 g of azobisisobutyronitrile as a polymerization catalyst were dissolved in 35.6 g of PGMEA and reacted at 70°C for 20 hours to obtain a polymer solution with a solid content of 15% by mass. The obtained polymer solution was gradually added dropwise to 500 g of methanol to precipitate the solid. The precipitated solid was filtered off and dried under reduced pressure to obtain a polymer (B-5) having repeating units represented by the following formula. The obtained polymer had a Mw of 31,000 and a Mn of 13,000.

[0150]

[0151] [3] Preparation of film-forming composition [Example 2-1] 100 parts by mass of the nonpolymer compound (A-1) obtained in Example 1-1 was mixed with 30 parts by mass of the polymer (B-1) obtained in Synthesis Example 4 as a curing agent, and 0.5 parts by mass of Polyflow No. 90 (manufactured by Kyoeisha Chemical Co., Ltd.) as a surfactant. CHN was added as an organic solvent to obtain a solution with a solid content of 21.0% by mass. The obtained solution was then filtered using a PTFE microfilter with a pore size of 0.2 μm to prepare the film-forming composition (C-1).

[0152] [Examples 2-2 to 2-16, Comparative Examples 2-1 to 2-5] Film-forming compositions (C-2) to (C-21) were prepared in the same manner as in Example 2-1, except that the types and amounts of each component were changed as shown in Table 1.

[0153]

[0154] [4] Evaluation of film-forming composition and cured film The solubility of the film-forming composition, as well as the refractive index and light resistance of the cured film formed using the composition, were evaluated according to the following procedure.

[0155] [Solubility] To 1.8 g of each organic solvent (PGME, PGMEA, MEK, EL) shown in Table 2, 0.2 g of the film-forming composition prepared in Examples 2-1 to 2-16 and Comparative Examples 2-1 to 2-5 was added, and the mixture was shaken and then allowed to stand for 24 hours. The mixture was visually inspected immediately after shaking and after 24 hours to check for precipitation or turbidity. Solubility was evaluated according to the following criteria. The results are shown in Table 2.

[0156] 《Evaluation Criteria》 ○: No precipitation or turbidity occurred immediately after shaking or after 24 hours of standing. ×: Precipitation or turbidity occurred either immediately after shaking or after 24 hours of standing.

[0157] [Refractive Index] The film-forming compositions prepared in Examples 2-1 to 2-16 and Comparative Examples 2-1 to 2-5 were each coated onto a silicon wafer using a spin coater, and baked on a hot plate at 100°C for 1 minute, followed by baking at 230°C for 10 minutes to form a cured film with a thickness of 1,000 nm. The refractive index at a wavelength of 550 nm was measured on the obtained cured film using a spectroscopic ellipsometer M-2000 (J.A. Woolam Japan Co., Ltd.). The results are shown in Table 2.

[0158] [Lightfastness Test] The film-forming compositions prepared in Examples 2-1 to 2-16 and Comparative Examples 2-1 to 2-5 were coated onto silicon wafers and quartz substrates, respectively, using a spin coater. The films were then baked on a hot plate at 100°C for 1 minute, followed by baking at 230°C for 10 minutes, to form films with a thickness of 1,000 μm. The transmittance of these films was measured in the wavelength range of 400 nm to 800 nm using a UV-2600 ultraviolet-visible spectrophotometer (manufactured by Shimadzu Corporation). Furthermore, the following lightfastness tests were performed on these films, and the film thickness and transmittance in the wavelength range of 400 nm to 800 nm were measured again. The lightfastness was evaluated based on the measurement results according to the following criteria. The results are shown in Table 2.

[0159] [Lightfastness Test Details] Equipment: Xenon accelerated weathering tester Q-Sun Xe-1-B (manufactured by Q-Lab Corporation) Light source: Xenon arc lamp Optical filter: Window-B / SL Illuminance: 60 W / m 2 (Wavelength 300nm to 400nm) Black panel temperature: 63°C Test time: 50 hours

[0160] 《Lightfastness (Transmittance Change) Evaluation Criteria》 ○: Minimum transmittance change measured in the wavelength range of 400-800 nm before and after the lightfastness test is less than 5%. ×: Minimum transmittance change measured in the wavelength range of 400-800 nm before and after the lightfastness test is 5% or more.

[0161] 《Lightfastness (Film Thickness Change) Evaluation Criteria》 ○: Film thickness change rate before and after the lightfastness test is less than 5%. ×: Film thickness change rate before and after the lightfastness test is 5% or more.

[0162]

[0163] The film-forming compositions of the examples did not precipitate or become cloudy when mixed with organic solvents, demonstrating excellent solubility in those organic solvents. On the other hand, the film-forming compositions of Comparative Examples 2-1 and 2-4 to 2-5 precipitated when mixed with specific organic solvents, resulting in low solubility in those organic solvents. Therefore, the film-forming compositions of the present invention have high solubility in organic solvents and can prevent problems such as clogging of equipment piping, thus being superior from a production standpoint.

[0164] The cured film formed from the film-forming composition of the example showed a high refractive index (1.67 or higher). Therefore, the cured film obtained from the film-forming composition of the present invention can improve light-gathering efficiency and enhance the properties of microlens materials and electronic devices.

[0165] The cured films formed from the film-forming compositions of the examples showed minimal changes in transmittance and film thickness even after light resistance testing. Therefore, the cured films formed from the film-forming compositions of the above examples exhibited high stability against ultraviolet light, which can improve the reliability of microlens materials and electronic devices.

Claims

1. A nonpolymer compound represented by the following formula (1). (In the formula, X represents an n-valent functional group having a triazine skeleton and a phenolic hydroxyl group, k represents 0 or 1, Ar independently represents a C6-C14 aromatic hydrocarbon group or a C3-C14 aromatic heterocyclic group which may have a C1-C4 alkyl group as a substituent, and n represents 2 or 3.) 2. The nonpolymer compound according to claim 1, wherein the above X is represented by the following formula (x1) or formula (x2). (In the formula, Z represents a C6-20 aromatic hydrocarbon group or a C3-10 non-aromatic heterocyclic group, which may have substituents selected from the group consisting of a C1-C8 alkyl group, a C1-C8 alkoxy group, or a C1-C8 alkyl group and a C1-C8 alkoxy group; and * represents a bond.) 3. The nonpolymer compound according to claim 1, wherein each of the aromatic hydrocarbon groups is independently a group having a benzene ring or a naphthalene ring, and each of the aromatic heterocyclic groups is independently a group having a furan ring, a thiophene ring, a pyridine ring, a thiazole ring, a benzothiazole ring, a quinoline ring, an isoquinoline ring, a benzofuran ring, an isobenzofuran ring, or a carbazole ring.

4. The nonpolymer compound according to claim 2, wherein Z may have substituents selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or an aromatic hydrocarbon group having 6 to 14 carbon atoms or a non-aromatic heterocyclic group having 3 to 6 carbon atoms.

5. The non-polymer compound according to claim 2, which is represented by the following formula (1-1) or formula (1-2). (In the formula, Ar and k have the same meanings as defined in the above formula (1), and Z has the same meaning as defined in the formula (x1).) 6. The nonpolymer compound according to claim 1, wherein the molecular weight is 500 to 3,500.

7. The nonpolymer compound according to claim 1, which is a reaction product of a compound represented by the following formula (1a) and a compound represented by the following formula (1b). (In the formula, X, k, n, and Ar are the same as those defined in formula (1) above.) 8. A film-forming composition comprising a nonpolymer compound represented by formula (1) according to any one of claims 1 to 7, a curing agent, and an organic solvent, wherein the content of the curing agent is 15 parts by mass or more per 100 parts by mass of the nonpolymer compound.

9. The film-forming composition according to claim 8, wherein the curing agent is a polyfunctional blocked isocyanate compound.

10. The film-forming composition according to claim 9, wherein the polyfunctional blocked isocyanate compound is a homopolymer of (meth)acrylate having a blocked isocyanate group, or a copolymer containing a (meth)acrylate having a blocked isocyanate group.

11. The film-forming composition according to claim 8, further comprising a hindered amine-based light stabilizer.

12. The film-forming composition according to claim 8, further comprising a surfactant.

13. A microlens comprising a cured product of the film-forming composition described in claim 8.

14. An electronic device comprising a microlens according to claim 13.

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