Non-polymer compound and composition for film formation

Abstract

Provided is a novel non-polymer compound having excellent ultraviolet absorption properties, visible light transmittance properties, and solubility properties in an organic solvent, and being represented by formula (1). (In the formula, n represents an integer of 3-6, A represents an n-valent organic group which may have a hetero atom selected from the group consisting of a nitrogen atom and an oxygen atom, k represents 0 or 1, and X represents an ultraviolet absorbing group.)

Description

Non-polymeric compounds and film-forming compositions

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

[0002] Transparent resins made from polymeric materials with excellent transparency in the visible light range are widely used in the field of optical components such as eyeglass lenses, Fresnel lenses, lenticular lenses, aspherical lenses, optical disks, optical fibers, and optical waveguides.

[0003] In recent years, transparent resins made from polymeric materials with excellent transmittance in the visible light range have been widely used for optical components such as protective films, planarizing films, insulating films, anti-reflection films, refractive index control films, microlenses, inner-layer lenses, optical waveguides, and film substrates 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.

[0004] In many cases, optical components require not only transparency but also excellent light resistance. However, optical components made primarily of transparent resins using the above-mentioned polymeric materials are known to be susceptible to deterioration due to the action of ultraviolet light, resulting in quality degradation such as discoloration, and therefore are unable to withstand long-term use.

[0005] In order to improve the light resistance of optical components, it is common to incorporate an ultraviolet absorber (see Patent Documents 1 to 4). Known examples of ultraviolet absorbers include benzophenone-based ultraviolet absorbers, benzotriazole-based ultraviolet absorbers, triazine-based ultraviolet absorbers, cyanoacrylate-based ultraviolet absorbers, salicylate-based ultraviolet absorbers, benzoate-based ultraviolet absorbers, oxanilide-based ultraviolet absorbers, and malonic acid ester-based ultraviolet absorbers.

[0006] The above-mentioned ultraviolet absorbers are used to form coating films (ultraviolet absorbing films) for protecting optical components, mainly from the viewpoint of improving light resistance (Patent Documents 5 to 6). In addition to the purpose of improving the light resistance of optical components, for example, ultraviolet absorbing films containing the above-mentioned ultraviolet absorbers are formed on optical components to impart ultraviolet shielding functions, antireflection functions, and the like (Patent Documents 7 to 10).

[0007] Such ultraviolet absorbing films need to be formed thicker to enhance ultraviolet absorption, but they also need to be formed thinner to minimize the impact on the optical properties of the optical component. To achieve both of these trade-off properties, an ultraviolet absorber that exhibits sufficient ultraviolet absorption for practical use even in a thin film is required.

[0008]

[0003] In addition, from the viewpoint of productivity of the film-forming composition, the UV absorber is required to be soluble in various organic solvents. In particular, when the UV absorber is mixed with an organic solvent other than the organic solvent in which the UV absorber is dissolved during the production process of the film-forming composition, the UV absorber may precipitate depending on the combination of organic solvents. In such cases, problems such as clogging of the piping in the production equipment may occur.

[0009] Furthermore, in optical components, another functional film (upper layer) may be formed on the ultraviolet absorbing film. In this case, a composition (varnish) for forming the upper layer is generally applied on the ultraviolet absorbing film. However, if the ultraviolet absorbing film does not have sufficient solvent resistance, a part of the film may be dissolved by the organic solvent used in the composition for forming the upper layer.

[0010] JP 2009-51992 A JP 2010-265170 A JP 2010-286644 A JP 2013-82233 A JP 2019-172846 A JP 2000-515141 A JP 9-265059 A JP 2003-107202 A JP 2006-243153 A JP 2007-99943 A

[0011] The present invention has been made in view of the above circumstances, and aims to provide a novel non-polymer compound that combines practical ultraviolet absorption and visible light transmittance with excellent solubility in organic solvents, and a film-forming composition containing the non-polymer compound that can form a coating film that combines practical ultraviolet absorption and visible light transmittance with excellent solvent resistance.

[0012] As a result of extensive research to achieve the above object, the present inventors have found that a specific non-polymer compound having 3 to 6 UV-absorbing groups in the molecule combines practical UV absorption and visible light transmittance with excellent solubility in organic solvents. They have also found that the use of this non-polymer compound as a UV absorber can provide a film-forming composition containing the non-polymer compound that can form a coating film that combines practical UV absorption and visible light transmittance with excellent solvent resistance, thereby completing the present invention.

[0013] That is, the present invention provides the following non-polymer compound and film-forming composition: 1. A non-polymer compound represented by the following formula (1): (wherein n represents an integer of 3 to 6, A represents an n-valent organic group which may have a heteroatom selected from the group consisting of nitrogen atoms and oxygen atoms, k represents 0 or 1, and X represents an ultraviolet absorbing group.) 2. The non-polymer compound of 1, wherein the ultraviolet absorbing groups are each independently a group having one selected from the group consisting of a benzotriazole skeleton, a triazine skeleton, a benzophenone skeleton, a cyanoacrylate skeleton, a salicylate skeleton, and an oxalic acid anilide skeleton. 3. The non-polymer compound of 2, wherein the ultraviolet absorbing groups are each independently a group having a triazine skeleton or a benzophenone skeleton. 4. The non-polymer compound of 3, wherein the ultraviolet absorbing groups are each independently a group represented by the following formula (x1) or formula (x2): (In formula (x1), R a each independently represents a hydrogen atom, a hydroxy group, a methyl group, or an ethyl group, and the R a At least one of R is a hydroxy group; 1 and R 2 each independently represents a methyl group or an ethyl group, each m1 independently represents an integer of 0 to 3, and m2 independently represents an integer of 0 to 2. In formula (x2), R b each independently represents a hydrogen atom or a hydroxy group, and bat least one of the n is a hydroxy group. * represents a bond.) 5. The non-polymer compound of 4, wherein the ultraviolet absorbing groups are each independently a group represented by the following formula (x1-1) or formula (x2-1), and at least one of the n ultraviolet absorbing groups is a group represented by the following formula (x1-1). (In the formula, R 1 each independently represent a methyl group or an ethyl group, each m3 independently represent an integer of 0 to 5, and * represents a bond. 6. Any of the non-polymer compounds of 1 to 5 having a molecular weight of 500 to 3,500. 7. Any of the non-polymer compounds of 1 to 6 which are the reaction product of a compound having 3 to 6 epoxy groups per molecule with the above compound having the ultraviolet absorbing group and a phenolic hydroxy group or carboxy group. 8. Any of the non-polymer compounds of 1 to 7 in which the organic group represented by A is a group represented by any of the following formulas (a1) to (a7): (wherein * represents a bond.) 9. A film-forming composition comprising a non-polymer compound represented by formula (1) of any one of 1 to 8, 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 non-polymer compound. 10. The film-forming composition of 9, wherein the curing agent is a polyfunctional blocked isocyanate compound. 11. The film-forming composition of 10, wherein the polyfunctional blocked isocyanate compound is a homopolymer of a (meth)acrylate having a blocked isocyanate group, or a copolymer containing a (meth)acrylate having a blocked isocyanate group. 12. The film-forming composition of any one of 9 to 11, further comprising a surfactant. 13. The film-forming composition of any one of 9 to 12, further comprising a light stabilizer. 14. A film obtained from the film-forming composition of 9 to 13.

[0014] The non-polymer compound of the present invention has practical UV absorption properties, visible light transmittance, and excellent solubility in organic solvents, and is therefore useful as an UV absorber. Furthermore, by using this non-polymer compound as a UV absorber, a film-forming composition can be obtained that can form a coating film that has practical UV absorption properties, visible light transmittance, and excellent solvent resistance. The coating film formed from the film-forming composition is suitable for optical components such as protective films, planarizing films, insulating films, anti-reflection films, refractive index control films, microlenses, intralayer lenses, optical waveguides, and film substrates.

[0015] The present invention will be described in more detail below. The non-polymer compound according to the present invention is characterized by being represented by the following formula (1): In the present invention, the term "non-polymer compound" refers to a compound having a molecular weight of 3,500 or less and which is not a polymer.

[0016] (In the formula, n represents an integer of 3 to 6, A represents an n-valent organic group which may have a heteroatom selected from the group consisting of nitrogen atoms and oxygen atoms, k represents 0 or 1, and X represents an ultraviolet-absorbing group.)

[0017] n represents an integer of 3 to 6, preferably 3 to 5.

[0018] Examples of the organic group represented by A include, but are not limited to, groups represented by any of the following formulae (a1) to (a7). (In the formula, * represents a bond.)

[0019] The X may be a group having any one selected from the group consisting of a benzotriazole skeleton, a triazine skeleton, a benzophenone skeleton, a cyanoacrylate skeleton, a salicylate skeleton, and an oxalic acid anilide skeleton. The multiple Xs may all be the same group or may be different groups.

[0020] Among the above Xs, from the viewpoints of solubility in organic solvents and ultraviolet absorption, groups having a triazine skeleton or a benzophenone skeleton are preferred, and it is also preferred to have both a group having a triazine skeleton and a group having a benzophenone skeleton.

[0021] Preferred embodiments of the ultraviolet absorbing group include groups represented by the following formulae (x1) and (x2).

[0022] (In formula (x1), R a each independently represents a hydrogen atom, a hydroxy group, a methyl group, or an ethyl group, and the R a At least one of R is a hydroxy group; 1 and R 2 each independently represents a methyl group or an ethyl group, each m1 independently represents an integer of 0 to 3, and m2 independently represents an integer of 0 to 2. In formula (x2), R b each independently represents a hydrogen atom or a hydroxy group, and b At least one of the groups is a hydroxy group. * represents a bond.

[0023] More preferred embodiments of the ultraviolet absorbing group include groups represented by the following formula (x1-1) and formula (x2-1): In addition, in consideration of ultraviolet absorbency, it is more preferable that at least one of the n ultraviolet absorbing groups is a group represented by formula (x1-1).

[0024] (In the formula, R 1 each independently represents a methyl group or an ethyl group, each m3 independently represents an integer of 0 to 5, and * represents a bond.

[0025] Specific examples of the ultraviolet absorbing group include groups represented by the following formulae (x1-1-1) and (x2-1-1), but are not limited to these.

[0026] (In the formula, * represents a bond.)

[0027] (In the formula, * represents a bond.)

[0028] Specific examples of the non-polymer compound include compounds represented by the following formulas (1-1) to (1-13), but are not limited to these.

[0029]

[0030]

[0031] In the formula, X 1 and X 2 represents a group represented by the following formula:

[0032] (In the formula, * represents a bond.)

[0033] From the viewpoint of solubility in organic solvents, the molecular weight of the non-polymer compound is, for example, 500 to 3,500, preferably 500 to 3,000, and more preferably 1,000 to 3,000.

[0034] The non-polymer compound can be obtained by reacting a compound having 3 to 6 epoxy groups in one molecule with the compound having the ultraviolet absorbing group and a phenolic hydroxy group or carboxy group.

[0035] Specific examples of the compound having 3 to 6 epoxy groups in one molecule include compounds represented by the following formulas (A1) to (A7), but are not limited thereto.

[0036]

[0037] Examples of compounds having an ultraviolet absorbing group and a phenolic hydroxy group or carboxy group include, but are not limited to, compounds represented by the following formulas (X1-1) and (X2-1).

[0038]

[0039]

[0040] The method for synthesizing the non-polymer compound is not particularly limited, but examples thereof include a method in which the above-mentioned compound having 3 to 6 epoxy groups per molecule and the above-mentioned compound having an ultraviolet absorbing group and a phenolic hydroxy group or carboxy group are dissolved in an organic solvent in an appropriate ratio (molar ratio) depending on the number of epoxy groups, and reacted in the presence of a catalyst at 60 to 150°C for 1 to 48 hours.

[0041] The organic solvent used in the reaction is not particularly limited as long as it dissolves the raw materials and catalyst used. Specific examples include the same organic solvents as those used in the film-forming composition described below. From the viewpoint of the 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 alone or in combination of two or more.

[0042] Furthermore, as the catalyst, any catalyst known to promote the reaction between an epoxy group and a phenolic hydroxy group or carboxy group can be used. In the present invention, however, quaternary phosphonium salts and quaternary ammonium salts can be suitably used, and quaternary phosphonium salts are more preferred.

[0043] 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 preferably used.

[0044] 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, methyltrioctylammonium chloride, etc. In the present invention, benzyltriethylammonium chloride can be preferably used.

[0045] The film-forming composition of the present invention is characterized by containing the non-polymer compound, a curing agent, and an organic solvent. In the following description, the solid content refers to the components other than the organic solvent that constitute the film-forming composition.

[0046] <Curing Agent> The curing agent is a component contained for the purpose of improving the chemical resistance (solvent resistance) of the coating film formed from the film-forming composition of the present invention.

[0047] Examples of the curing agent include polyfunctional (meth)acrylate compounds, hydroxymethyl- or alkoxymethyl-substituted phenol compounds, compounds having an alkoxyalkylated amino group, and polyfunctional blocked isocyanate compounds. In this specification, (meth)acrylate refers to methacrylate and acrylate. These curing agents may be used alone or in combination of two or more.

[0048] The content of the curing agent varies depending on the coating solvent used, the base substrate used, the required solution viscosity, the required film shape, etc., but is 15 parts by mass or more, 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, relative to 100 parts by mass of the non-polymer compound. These curing agents may undergo a curing reaction by self-condensation, but when crosslinkable substituents are present in the non-polymer compound of the present invention, they can undergo a crosslinking reaction with the crosslinkable substituents.

[0049] Examples of the polyfunctional (meth)acrylate compound 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, tricyclodecane dimethanol 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, phthalic acid di(meth)acrylate, 9,9 -bis[4-(2-(meth)acryloyloxyethoxy)phenyl]fluorene, glycerin di(meth)acrylate, glycerin tri(meth)achlorate, glycerin ethoxy tri(meth)acrylate, glycerin propoxy tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane ethoxy tri(meth)acrylate, trimethylolpropane propoxy tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, penta Examples of such an alkyl acrylate include erythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol ethoxy tetra(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.

[0050] Examples of the polyfunctional (meth)acrylate compound include (meth)acrylates having a hydroxy group, such as 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, glycerin di(meth)acrylate, pentaerythritol tri(meth)acrylate, and dipentaerythritol penta(meth)acrylate, or polyfunctional (meth)acrylates having a hydroxy group, and 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, 1,5-naphthalene diisocyanate, and m-phenylene diisocyanate. Also included are polyfunctional urethane (meth)acrylates obtained by reacting with diisocyanate compounds such as diisocyanate, p-phenylene diisocyanate, diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-dibenzyl 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.

[0051] Further examples of the polyfunctional (meth)acrylate compound include polyfunctional epoxy (meth)acrylates synthesized by reacting (meth)acrylic acid with a homopolymer or copolymer obtained by radical polymerization of a (meth)acrylate monomer having an epoxy group, such as glycidyl (meth)acrylate, glycidyloxybutyl (meth)acrylate, or 3,4-epoxycyclohexylmethyl (meth)acrylate. Here, "copolymer" refers to a polymer obtained by polymerizing two or more types of monomers. The copolymer may be a copolymer obtained by polymerizing two or more types of (meth)acrylates having an epoxy group, or a copolymer obtained by polymerizing a (meth)acrylate having an epoxy group and another (meth)acrylate.

[0052] The polyfunctional (meth)acrylate compounds are also commercially available. Examples of such commercially available products include the following: Aronix (registered trademark) 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, and M-9050 (all manufactured by Toagosei Co., Ltd.); KAYARAD (registered trademark) NPGDA, KAYARAD PEG400DA, KAYARAD FM-400, KAYARAD R-167, KAYARAD HX-220, KAYARAD HX-620, KAYARAD R-526, KAYARAD R-551, KAYARAD R-712, KAYARAD R-604, KAYARAD R-684, KAYARAD GPO-303, KAYARAD TMPTA, KAYARAD HDDA, KAYARAD TPGDA, KAYARAD 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, same as UXF-4001-M35, same as UXF-4002, same as DPHA-40H, same as UX-5000, same as UX-5102D-M20, same as UX-5103D, same as UX-5005 (all manufactured by Nippon Kayaku 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 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 Ekonoma A-PG5009E, same as A-PG5027E, same as A -PG5054E, NKORIGO 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, same as UA-200PA, same as UA-324A, same as UA-160TM, same as UA-290TM, same as UA-4200, same as UA-4400, same as UA-122P, same as UA-7100, same as UA-W2A (all manufactured by Shin-Nakamura Chemical Industry Co., Ltd.); Buscode #195, same as #230, same as #260, same as #310HP, same as #335HP, same as #700HV, same as #540, same as #802,#295, #300, #360, #230D, BAC-45, SPDBA-S30, and STAR-501 (all manufactured by Osaka Organic Chemical Industry Ltd.); Light Ester P-2M, EG, 2EG, 3EG, 4EG, 9EG, 14EG, 1.4BG, NP, 1.6HX, 1.9ND, G-101P, G-201P, BP-2EMK, TMP, Light Acrylate (registered trademark) 3EG-A, 4EG-A, 9EG-A, 14EG-A, PTMGA-250, NP-A, MPD-A, 1.6HX-A, 1.9ND-A, MOD-A, DCP-A, BP-4EAL, 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 (registered trademark) 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 (registered trademark) 243NS, 255, 261, 271, 502H, 504H, 505A-6, 550B, 575, 577, 700, 710, 730, 750, AQ-17, EM-90, EM-92, 371, and 381 (all manufactured by Arakawa Chemical Industries, Ltd.); Fancryl (registered trademark) 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, and FA-137M (all manufactured by Resonac Corporation); 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 Sartomer Corporation); 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 , 150, 11, 135, 40, 140, 1142, 180, 204, 205, 210, 215, 220, 230, 244, 245, 264, 265, 270, 280 / 151B, 284, 285, 294 / 25HD, 1259, 1290, 4820, 4858, 5129, 8210, 8254, 8301R, 8307, 8402, 8405, 8411,8465, 8800, 8804, 8807, 9260, 9270, 8311, 8701, 9227EA, 436, 438, 446, 450, 524, 525, 770, 800, 810, 811, 812, 1830, 846, 851, 852, 853, 1870, 884, 885, 600, 605, 645, 648, 860, 1606, 3500, 3603, 3608, 3700, 3701, 3702, 37 03, 3708, 6040, 8110, 271, 1258, 1291, 4100, 4200, 4500, 4680, 4220, 4265, 4491, 4513, 4587, 4666, 4683, 4738, 4740, 4250, 4510, KRM (registered trademark) 8200, 8200AE, 8296, 8452, 8904, 8667, 8912, 8981, 8762, 8713B, and 8528 (all manufactured by Daicel Allnex 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). ,

[0053] These polyfunctional (meth)acrylate compounds may be used alone or in combination of two or more.

[0054] 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 have been substituted with alkoxymethyl groups such as methoxymethyl groups or butoxymethyl groups. These hydroxymethyl group- or alkoxymethyl group-substituted phenol compounds may be used alone or in combination of two or more.

[0055] Examples of the compound having an alkoxyalkylated amino group include nitrogen-containing compounds having multiple active methylol groups in one molecule, such as (poly)methylolated melamine, (poly)methylolated glycoluril, (poly)methylolated benzoguanamine, and (poly)methylolated urea, in which at least one hydrogen atom of the hydroxy group in the methylol group is substituted with an alkyl group such as a methyl group or a butyl group.

[0056] The compound having the above-mentioned alkoxyalkylated amino group may be a mixture of a plurality of substituted compounds, and some of the mixtures may contain oligomer components formed by self-condensation of the compound, but any mixture can be used.

[0057] The compound having an alkoxyalkylated amino group can also be obtained as a commercially available product. Examples of such commercially available products include CYMEL series products such as hexamethoxymethylmelamine (manufactured by CYTEC Corporation, CYMEL (registered trademark) 303, 303LF), tetrabutoxymethylglycoluril (manufactured by CYTEC Corporation, CYMEL (registered trademark) 1170), and tetramethoxymethylbenzoguanamine (manufactured by CYTEC Corporation, CYMEL (registered trademark) 1123); tetramethoxymethylglycoluril (manufactured by CYTEC Corporation, and NIKALAC series products such as methylated melamine resins (manufactured by Sanwa Chemical Co., Ltd., Nikalac (registered trademark) MW-30HM, MW-390, MW-100LM, and MX-750LM) and methylated urea resins (manufactured by Sanwa Chemical Co., Ltd., Nikalac (registered trademark) MX-270, MX-280, and MX-290). These compounds having an alkoxyalkylated amino group may be used alone or in combination of two or more.

[0058] The polyfunctional blocked isocyanate compound has two or more isocyanate groups in one molecule, each isocyanate group being blocked with an appropriate protecting group, and when exposed to high temperatures during thermal curing, the protecting groups (blocking moieties) are thermally dissociated and removed, and the resulting isocyanate groups undergo a crosslinking reaction with the resin.

[0059] Such a polyfunctional blocked isocyanate compound can be obtained, for example, by reacting a polyfunctional isocyanate compound having two or more isocyanate groups in one molecule with an appropriate blocking agent.

[0060] Examples of the polyfunctional isocyanate compound 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, 1,3-bis(isocyanate), Bis(isocyanatemethyl)cyclohexane, 1,4-cyclohexyl diisocyanate, 2,6-bis(isocyanatemethyl)tetrahydrodicyclopentadiene, bis(isocyanatemethyl)dicyclopentadiene, bis(isocyanatemethyl)adamantane, 2,5-diisocyanatemethylnorbornene, 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(isocyanatemethyl)benzene, dianisidine diisocyanate, 3,3'-dimethyldiphenyl-4,4'-diisocyanate, diphenyl ether diisocyanate, 2,6-bis(isocyanate (trimethyl)decahydronaphthalene, bis(diisocyanatolyl)phenylmethane, 1,1'-methylenebis(3-methyl-4-isocyanatobenzene), 1,3-bis(1-isocyanato-1-methylethyl)benzene, 1,4-bis(1-isocyanato-1-methylethyl)benzene, 4,4'-biphenylene diisocyanate, 3,3'-dimethyl-4,4'-biphenylene diisocyanate, 3,3'-dimethoxy-4,Examples of such compounds include 4'-biphenylene diisocyanate, bis(isocyanatemethyl)thiophene, bis(isocyanatemethyl)tetrahydrothiophene, and modified compounds thereof (for example, isocyanurates, biurets, ethylene glycol adducts, propylene glycol adducts, trimethylolpropane adducts, ethanolamine adducts, polyester polyol adducts, polyether polyol adducts, polyamide adducts, and polyamine adducts).

[0061] Examples of the blocking agent 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, and 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; pyrazole, 3,5-dimethylpyrazole, 3-methylpyrazole, 4-benzylpyrazole, and the like; pyrazoles such as benzyl-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, acetoacetic acid esters, malonic acid dinitrile, acetylacetone, methylene disulfone, dibenzoylmethane, dipivaloylmethane, and acetone dicarboxylic acid diesters;Examples of the copolymer 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, maleic acid imide, and phthalic acid imide; and urea compounds such as urea, thiourea, and ethylene urea. The copolymer may also be an internally blocked copolymer formed by a uretdione bond (dimerization of an isocyanate group).

[0062] The polyfunctional blocked isocyanate compound can also be obtained as a commercially available product. Examples of such commercially available products include the following: Takenate (registered trademark) 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 (registered trademark) 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 (registered trademark) 2503, 2507, 2512, 2513, 2515, 2520, 2554, BI-301, AP-M, Millionate MS-50 (all manufactured by Tosoh Corporation); Burnock (registered trademark) D-500, D-550, DB-980K (all manufactured by DIC Corporation); Desmodur (registered trademark) BL-3175, BL-4165, BL-4265, BL-1100, BL-1265, TPLS-2957, TPLS-2062, TPLS-2078, TPLS-2117, BL-3475, Desmotherm (registered trademark) 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, and DP9C / 214 (all manufactured by Baxenden Chemicals); VESTANAT (registered trademark) B1358A, B1358 / 100, B1370, VESTAGON (registered trademark) B1065, B1400, B1530, BF1320, BF1540 (all manufactured by Evonik Industries).

[0063] Furthermore, examples of the polyfunctional blocked isocyanate compound include homopolymers or copolymers obtained by radical polymerization of a (meth)acrylate having a blocked isocyanate group. Here, copolymer refers to a polymer obtained by polymerizing two or more types of monomers. The copolymer may be a copolymer obtained by polymerizing two or more types of (meth)acrylates having a blocked isocyanate group, or a copolymer obtained by polymerizing a (meth)acrylate having a blocked isocyanate group and another (meth)acrylate. Such a (meth)acrylate having a blocked isocyanate group is also available as a commercially available product. Examples of such commercially available products include Karenz (registered trademark) MOI-BM, AOI-BM, MOI-BP, and AOI-BP, manufactured by Resonac Corporation.

[0064] These polyfunctional blocked isocyanate compounds may be used alone or in combination of two or more.

[0065] In the present invention, as a catalyst for accelerating the crosslinking reaction, acidic compounds such as p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium p-toluenesulfonate, salicylic acid, sulfosalicylic acid, citric acid, benzoic acid, hydroxybenzoic acid, and naphthalenecarboxylic acid; and thermal acid generators such as 2,4,4,6-tetrabromocyclohexadienone, benzoin tosylate, 2-nitrobenzyl tosylate, and other organic sulfonic acid alkyl esters can be blended, and the above-mentioned acidic compounds and thermal acid generators can also be blended in combination.

[0066] The amount of the catalyst to be added is preferably 0.0001 to 20 parts by mass, more preferably 0.0005 to 10 parts by mass, per 100 parts by mass of the non-polymer compound in the film-forming composition of the present invention.

[0067] <Organic Solvent> The organic solvent is not particularly limited as long as it dissolves the non-polymer compound. Specific examples thereof include methylcyclohexane, ethylcyclohexane, n-heptane, toluene, o-xylene, m-xylene, mesitylene, chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, anisole, phenetole, 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 propyl isobutyrate, n-butyl isobutyrate, isobutyl isobutyrate, tert-butyl isobutyrate, methyl lactate, ethyl lactate, n-propyl lactate, isopropyl lactate, n-butyl lactate, isobutyl lactate, tert-butyl lactate, methyl acetoacetate, ethyl acetoacetate, n-propyl acetoacetate, isopropyl acetoacetate, n-butyl acetoacetate, isobutyl acetoacetate, tert-butyl acetoacetate, dimethyl malonate, diethyl malonate, 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,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-dimethylisobutyramide, N-methyl-2-pyrrolidone, and N-ethyl-2-pyrrolidone. These organic solvents may be used alone or in combination of two or more.

[0068] Among the above organic solvents, from the viewpoint of improving the leveling properties of a coating film formed by applying the film-forming composition of the present invention onto a substrate, 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.

[0069] <Surfactant> The film-forming composition of the present invention may contain a surfactant for the purpose of improving the coating properties.Examples of the surfactant 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 tristearate; Nonionic surfactants such as isosorbitan fatty acid esters; Eftop (registered trademark) EF301, EF303, EF352 (all manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), Megafac (registered trademark) F171, F173, Megafac R-30, R-40, R-40-LM (all manufactured by DIC Corporation), Fluorad FC430, FC431 (all manufactured by 3M Japan Ltd.), Asahiguard (registered trademark) AG710, Surflon (registered trademark) S-382, Surflon SC101 Fluorine-based surfactants such as Ftergent series (manufactured by Neos Co., Ltd.), FTX-18, FTX-206D, FTX-212D, FTX-218, FTX-220D, FTX-230D, FTX-240D, FTX-212P, FTX-220P, FTX-228P, and FTX-240G (manufactured by AGC Co., Ltd.); 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, and No. 90, No. 90D-50, No. 95, No. 99C, No. PW-95 (all manufactured by Kyoeisha Chemical Co., Ltd.), and other non-fluorine-based surfactants.These surfactants may be used alone or in combination of two or more.

[0070] When the surfactant is contained, the content thereof 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, relative to 100 parts by mass of the non-polymer compound.

[0071] The film-forming composition of the present invention may contain additives such as antioxidants, light stabilizers (HALS: hindered amine light stabilizers), ultraviolet absorbers different from the non-polymer compound of the present invention, adhesion aids, plasticizers, and sensitizers, as needed, as long as the effects of the present invention are not impaired.

[0072] The method for preparing the film-forming composition of the present invention is not particularly limited, but for example, a method of dissolving the non-polymer compound and the curing agent in an organic solvent to form a uniform solution can be mentioned.Furthermore, at an appropriate stage of this preparation method, a method of further adding surfactants and other additives and mixing them can be mentioned.In addition, in order to obtain a thin film with a higher degree of flatness and good reproducibility, if necessary, the film-forming composition can be filtered using a submicrometer-order filter or the like during the preparation stage or after mixing all the components.

[0073] The solids concentration of the film-forming composition of the present invention is appropriately set taking into consideration the coatability of the composition and the properties of the object on which the film is to be formed, but is usually about 0.1 to 30 mass %, preferably about 1 to 25 mass %, and more preferably about 5 to 20 mass %.

[0074] The use of the film-forming composition of the present invention is described below. <Method for Producing a Coating Film> A method for producing a coating film using the film-forming composition of the present invention is described below. The film-forming composition of the present invention is applied to an organic film, film substrate (e.g., PET film, polyimide film), or member that is susceptible to deterioration by ultraviolet light using 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 coating film. 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 coating film may be performed in two or more steps. The thickness of the coating film formed is, for example, 0.001 to 1,000 μm, preferably 0.01 to 100 μm, and more preferably 0.1 to 10 μm.

[0075] A coating film prepared using the film-forming composition of the present invention can be used as a protective film for organic films, film substrates, or members that are susceptible to deterioration due to the action of ultraviolet light.

[0076] The present invention will be explained in more detail below with reference to Synthesis Examples, Examples and Comparative Examples, but the present invention is not limited to the following Examples.

[0077] The compounds used in the following synthesis examples, working examples, and comparative examples are as follows: [Solvents] PGME: propylene glycol monomethyl ether PGMEA: propylene glycol monomethyl ether acetate CHN: cyclohexanone EL: ethyl lactate MEK: methyl ethyl ketone THF: tetrahydrofuran

[0078] [Synthetic raw material] TGIC: Triglycidyl isocyanurate

[0079] TEPG: tetrakis(glycidyloxyphenyl)ethane (Asahi Organic Chemicals Co., Ltd., trade name: TEP-G)

[0080] EX512: Polyglycerol polyglycidyl ether (Nagase ChemteX Corporation, trade name: Denacol (registered trademark) EX-512)

[0081] EX614B: Sorbitol polyglycidyl ether (Nagase ChemteX Corporation, product name: Denacol (registered trademark) EX-614B)

[0082] EX521: Polyglycerol polyglycidyl ether (Nagase ChemteX Corporation, trade name: Denacol (registered trademark) EX-521)

[0083] EX810P: Ethylene glycol diglycidyl ether (Nagase ChemteX Corporation, product name: Denacol (registered trademark) EX-810P)

[0084] EX321L: Trimethylolpropane polyglycidyl ether (Nagase ChemteX Corporation, trade name: Denacol (registered trademark) EX-321L)

[0085] PETG: Epoxidation reaction product of pentaerythritol tetraallyl ether with hydrogen peroxide (Resonac Corporation, trade name: Showfree (registered trademark) PETG)

[0086] JER828: Bisphenol A type bifunctional epoxy resin (Mitsubishi Chemical Corporation, product name: jER (registered trademark) 828)

[0087] G01100: Epoxy group-containing acrylic polymer (NOF Corporation, product name: Marproof (registered trademark) G-01100), a polymer containing a repeating unit represented by the following formula and having more than six epoxy groups per molecule

[0088] 24DHBP: 2,4-dihydroxybenzophenone

[0089] DBDT: 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine

[0090] 244THBP: 2,4,4-trihydroxybenzophenone

[0091] UV416: 2-(4-benzoyl-3-hydroxyphenoxy)ethyl acrylate

[0092] MOIBP: 2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl methacrylate (Resonac Corporation, trade name: Karenz (registered trademark) MOI-BP)

[0093] The weight average molecular weight (Mw) and number average molecular weight (Mn) of the polymer were measured using a GPC apparatus manufactured by Shimadzu Corporation (column: Shodex (registered trademark) KF803L and KF804L (manufactured by Resonac Corporation); eluent: THF, flow rate: 1.0 mL / min, column temperature: 40°C, Mw and Mn: values ​​converted into standard polystyrene).

[0094] [1] Synthesis of Non-Polymer Compound [Example 1-1] 3.00 g (10.09 mmol) of TGIC, 6.49 g (30.28 mmol) of 24DHBP, and 0.15 g of ethyltriphenylphosphonium bromide as a catalyst were dissolved in 22.5 g of CHN, and the mixture was allowed to react at 120°C for 20 hours to obtain a solution (A-1) containing the non-polymer compound represented by the above formula (1-2) and having a solids concentration of 30 mass%.

[0095] Example 1-2 3.00 g (10.09 mmol) of TGIC, 2.16 g (10.09 mmol) of 24DHBP, 8.02 g (20.18 mmol) of DBDT, and 0.15 g of ethyltriphenylphosphonium bromide as a catalyst were dissolved in 53.3 g of CHN, and the mixture was allowed to react at 120° C. for 20 hours to obtain a solution (A-2) containing the non-polymer compound represented by the above formula (1-3) and having a solids concentration of 20 mass%.

[0096] Example 1-3 3.00 g (10.09 mmol) of TGIC, 12.03 g (30.28 mmol) of DBDT, and 0.15 g of ethyltriphenylphosphonium bromide as a catalyst were dissolved in 60.7 g of CHN, and the mixture was allowed to react at 120° C. for 20 hours to obtain a solution (A-3) containing the non-polymer compound represented by formula (1-1) and having a solids concentration of 20 mass%.

[0097] Example 1-4 3.00 g of TEPG (epoxy equivalent: 180), 3.57 g (16.67 mmol) of 24DHBP, and 0.12 g of ethyltriphenylphosphonium bromide as a catalyst were dissolved in 26.8 g of CHN, and the mixture was allowed to react at 120°C for 20 hours to obtain a solution (A-4) containing the non-polymer compound represented by the above formula (1-4) and having a solids concentration of 20 mass%.

[0098] Example 1-5 3.00 g of EX512 (epoxy equivalent: 168), 7.10 g (17.86 mmol) of DBDT, and 0.13 g of ethyltriphenylphosphonium bromide as a catalyst were dissolved in 40.9 g of CHN, and the mixture was allowed to react at 120°C for 20 hours to obtain a solution (A-5) containing the non-polymer compound represented by the above formula (1-6) and having a solids concentration of 20 mass%.

[0099] Example 1-6 3.00 g of EX614B (epoxy equivalent: 173), 6.89 g (17.34 mmol) of DBDT, and 0.13 g of ethyltriphenylphosphonium bromide as a catalyst were dissolved in 40.1 g of CHN, and the mixture was allowed to react at 120°C for 20 hours to obtain a solution (A-6) containing the non-polymer compound represented by formula (1-5) and having a solids concentration of 20 mass%.

[0100] Example 1-7 3.00 g of EX521 (epoxy equivalent: 183), 6.52 g (16.39 mmol) of DBDT, and 0.12 g of ethyltriphenylphosphonium bromide as a catalyst were dissolved in 38.6 g of CHN, and the mixture was allowed to react at 120°C for 20 hours to obtain a solution (A-7) containing the non-polymer compound represented by the above formula (1-7) and having a solids concentration of 20 mass%.

[0101] Example 1-8 3.00 g of TEPG (epoxy equivalent: 180), 6.62 g (16.67 mmol) of DBDT, and 0.06 g of ethyltriphenylphosphonium bromide as a catalyst were dissolved in 22.6 g of CHN, and the mixture was allowed to react at 120°C for 20 hours to obtain a solution (A-8) containing the non-polymer compound represented by the above formula (1-10) and having a solids concentration of 30 mass%.

[0102] Example 1-9 3.00 g of TEPG (epoxy equivalent: 180), 1.79 g of 24DHBP (8.33 mmol), 3.31 g of DBDT (8.33 mmol), and 0.06 g of ethyltriphenylphosphonium bromide as a catalyst were dissolved in 19.0 g of CHN, and the mixture was allowed to react at 120° C. for 20 hours to obtain a solution (A-9) containing the non-polymer compound represented by the above formula (1-11) and having a solids concentration of 30 mass%.

[0103] Example 1-10 3.00 g of EX321L (epoxy equivalent: 128), 9.31 g (23.44 mmol) of DBDT, and 0.12 g of ethyltriphenylphosphonium bromide as a catalyst were dissolved in 29.0 g of CHN, and the mixture was allowed to react at 120°C for 20 hours, thereby obtaining a solution (A-10) containing the non-polymer compound represented by the above formula (1-12) and having a solids concentration of 30 mass%.

[0104] [Example 1-11] 3.00 g of PETG (epoxy equivalent: 128), 12.86 g (32.36 mmol) of DBDT, and 0.12 g of ethyltriphenylphosphonium bromide as a catalyst were dissolved in 37.9 g of CHN, and the mixture was allowed to react at 120°C for 20 hours to obtain a solution (A-11) containing the non-polymer compound represented by the above formula (1-13) and having a solids concentration of 30% by mass.

[0105] Comparative Example 1-1 2.00 g of EX810P (epoxy equivalent: 95), 8.39 g (21.05 mmol) of DBDT, and 0.16 g of ethyltriphenylphosphonium bromide as a catalyst were dissolved in 42.1 g of CHN, and the mixture was allowed to react at 120°C for 20 hours, thereby obtaining a solution (A-12) having a solids concentration of 20 mass% containing non-polymer compounds that do not fall under the category of the non-polymer compounds represented by the above formula (1).

[0106] [Comparative Example 1-2] 3.00 g of JER828 (epoxy equivalent: 190), 2.73 g (11.84 mmol) of 244THBP, and 0.12 g of ethyltriphenylphosphonium bromide as a catalyst were dissolved in 23.4 g of CHN, and the mixture was allowed to react at 120°C for 20 hours to obtain a polymer solution (A-13) with a solids concentration of 20% by mass, which contained a polymer that did not fall under the category of the non-polymer compound represented by formula (1). The Mw of the resulting polymer was 5,300, and the Mn was 3,300.

[0107] [Comparative Example 1-3] 3.00 g of G01100 (epoxy equivalent: 170), 5.04 g (23.53 mmol) of 24DHBP, and 0.17 g of ethyltriphenylphosphonium bromide as a catalyst were dissolved in 36.9 g of CHN, and the mixture was allowed to react at 120°C for 20 hours to obtain a polymer solution (A-14) with a solids concentration of 20% by mass, which contained a polymer that did not fall under the category of non-polymer compounds represented by formula (1). The Mw of the resulting polymer was 21,300, and the Mn was 11,000.

[0108] [2] Synthesis of Curing Agent [Synthesis Example 1] 10.00 g (39.79 mmol) of MOIBP 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 a solid. The precipitated solid was filtered and dried under reduced pressure to obtain Polymer (B-1). The Mw of the obtained polymer was 32,000 and Mn was 14,000.

[0109] Synthesis Example 2 4.00 g (15.92 mmol) of MOIBP, 4.97 g (15.92 mmol) of UV416, and 0.52 g of azobisisobutyronitrile as a polymerization catalyst were dissolved in 38.0 g of CHN and reacted at 80°C for 20 hours to obtain a polymer solution with a solid content of 20% by mass. The obtained polymer solution was gradually added dropwise to 500 g of methanol to precipitate a solid. The precipitated solid was filtered and dried under reduced pressure to obtain Polymer (B-2). The Mw of the obtained polymer was 9,600 and Mn was 4,100.

[0110] [3] Preparation of film-forming composition [Example 2-1] 100 parts by mass, calculated as solid content, of A-1 obtained in Example 1-1, 40 parts by mass of curing agent B-1 obtained in Synthesis Example 1, and 0.02 parts by mass of DFX-18 (manufactured by Neos Corporation) as a surfactant were mixed, and CHN was added to this as an organic solvent to obtain a solution with a solid content concentration of 12.5 mass%. Thereafter, the obtained solution was filtered using a PTFE microfilter having a pore size of 0.2 μm to prepare a film-forming composition (C-1).

[0111] [Examples 2-1 to 2-8, Comparative Examples 2-1 to 2-3] Film-forming compositions (C-2) to (C-11) 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.

[0112]

[0113] [Example 3-1] A-4 obtained in Example 1-4 was purified by reprecipitation with a predetermined solvent, and then 100 parts by mass in terms of solid content, 20 parts by mass of the curing agent B-1 obtained in Synthesis Example 1, and 0.03 parts by mass of R-30 (manufactured by DIC Corporation) as a surfactant were mixed, and CHN was added to this as an organic solvent to obtain a solution with a solid content concentration of 31% by mass. Thereafter, the obtained solution was filtered using a PTFE microfilter with a pore size of 0.2 μm to prepare a film-forming composition (D-1).

[0114] [Examples 3-2 to 3-7, Comparative Examples 3-1 to 3-3] Film-forming compositions (D-2) to (D-7) and (D-10) to (D-12) were prepared in the same manner as in Example 3-1, except that the types and amounts of each component were changed as shown in Table 2.

[0115] [Examples 3-8] A-11 obtained in Example 1-11 was reprecipitated and purified in a predetermined solvent, and then 100 parts by mass in terms of solid content, 30 parts by mass of the curing agent B-1 obtained in Synthesis Example 1, 0.5 parts by mass of No. 90 (manufactured by Kyoeisha Chemical Co., Ltd.) as a surfactant, and 3 parts by mass of Tinuvin 144 (manufactured by BASF Japan Ltd.) as a light stabilizer were mixed, and CHN was added thereto as an organic solvent to obtain a solution with a solid content concentration of 31% by mass. Thereafter, the obtained solution was filtered using a PTFE microfilter having a pore size of 0.2 μm to prepare a film-forming composition (D-8).

[0116] Example 3-9 A film-forming composition (D-9) was prepared in the same manner as in Example 3-8, except that 5 parts by mass of Tinuvin 479 (manufactured by BASF Japan Ltd.) was added as an ultraviolet absorber different from the non-polymer compound of the present invention.

[0117]

[0118] [4] Film Preparation and Evaluation [Transmittance Measurement] Each of the film-forming compositions prepared in Examples 2-1 to 2-8 and Comparative Examples 2-1 to 2-3 was applied to a quartz substrate using a spin coater, and baked on a hot plate at 100°C for 1 minute and then at 150°C for 10 minutes to form a film with a thickness of 500 nm. The transmittance of these films was measured in the wavelength range of 200 to 800 nm using a UV-2600 ultraviolet-visible spectrophotometer (Shimadzu Corporation). Based on the measurement results, the ultraviolet absorption and visible light transmittance were evaluated according to the following criteria. The results are shown in Table 3.

[0119] The film-forming compositions prepared in Examples 3-1 to 3-9 and Comparative Examples 3-1 to 3-3 were each diluted with CHN to a predetermined concentration, then applied to a quartz substrate using a spin coater and baked on a hot plate at 100°C for 1 minute and then at 230°C for 10 minutes to form a film with a thickness of 1,000 nm. The transmittance of these films was measured in the wavelength range of 200 to 800 nm using a UV-2600 ultraviolet-visible spectrophotometer (manufactured by Shimadzu Corporation). Based on the measurement results, the ultraviolet absorbance and visible light transmittance were evaluated according to the following criteria. The results are shown in Table 4.

[0120] <Evaluation criteria for ultraviolet absorption> ○: The minimum transmittance measured in the wavelength range of 280 to 400 nm is less than 10%. ×: The minimum transmittance measured in the wavelength range of 280 to 400 nm is 10% or more. <Evaluation criteria for visible light transmittance> ○: The minimum transmittance measured in the wavelength range of 400 to 800 nm is 90% or more. ×: The minimum transmittance measured in the wavelength range of 400 to 800 nm is less than 90%.

[0121] [Solubility] 0.2 g of each of the film-forming compositions prepared in Examples 2-1 to 2-8 and Comparative Examples 2-1 to 2-3 was dropped into 1.8 g of each organic solvent (PGME, PGMEA, EL, MEK) shown in Table 3, and the occurrence of precipitation was visually observed. The solubility was evaluated according to the following criteria. The results are shown in Table 3.

[0122] To 1.8 g of each organic solvent (PGME, PGMEA, EL, MEK) shown in Table 4, 0.2 g of each of the film-forming compositions prepared in Examples 3-1 to 3-9 and Comparative Examples 3-1 to 3-3 was dropped, and the occurrence of precipitation was visually observed. The solubility was evaluated according to the following criteria. The results are shown in Table 4.

[0123] Evaluation criteria: ○: No deposition occurred ×: Deposition occurred

[0124] [Solvent Resistance] Each of the film-forming compositions prepared in Examples 2-1 to 2-8 and Comparative Examples 2-1 to 2-3 was applied to a silicon wafer using a spin coater, and baked on a hot plate at 100°C for 1 minute and then at 150°C for 10 minutes to form a film with a thickness of 500 nm. The resulting film was immersed in acetone for 10 minutes, dried on a hot plate at 100°C for 30 seconds, and then the film thickness was measured. The film thickness before and after immersion was used to calculate the film retention rate using the following formula. The film retention rate was then evaluated according to the following criteria. The results are shown in Table 3.

[0125] Each of the film-forming compositions prepared in Examples 3-1 to 3-9 and Comparative Examples 3-1 to 3-3 was applied to a silicon wafer using a spin coater, and baked on a hot plate at 100°C for 1 minute and then at 230°C for 10 minutes to form a film with a thickness of 3,000 nm. The resulting film was immersed in acetone for 10 minutes, dried on a hot plate at 100°C for 30 seconds, and then the film thickness was measured. The remaining film ratio was calculated using the following formula from the film thickness before and after immersion. The remaining film ratio was then evaluated according to the following criteria. The results are shown in Table 4.

[0126] Residual film rate (%) = [film thickness after immersion] / [film thickness before immersion] x 100 Evaluation criteria: ○: Residual film rate is 90% or more ×: Residual film rate is less than 90%

[0127]

[0128]

[0129] From the results in Tables 3 and 4, it can be seen that the films formed from the film-forming compositions of the Examples exhibited excellent ultraviolet absorption properties and excellent visible light transmittance, similar to the films formed from the film-forming compositions of the Comparative Examples.

[0130] The film-forming compositions of Examples did not precipitate when mixed with an organic solvent and exhibited excellent solubility in the organic solvent. On the other hand, the film-forming compositions of Comparative Examples 2-2, 2-3, 3-2, and 3-3 precipitated when mixed with a specific organic solvent, resulting in low solubility in the organic solvent.

[0131] The films formed from the film-forming compositions of the Examples exhibited high solvent resistance, whereas the films formed from the film-forming compositions of Comparative Examples 2-1 and 3-1 exhibited lower solvent resistance than the films formed from the film-forming compositions of the Examples.

Claims

1. A non-polymer compound represented by the following formula (1): (In the formula, n represents an integer of 3 to 6, A represents an n-valent organic group which may have a heteroatom selected from the group consisting of nitrogen atoms and oxygen atoms, k represents 0 or 1, and X represents an ultraviolet absorbing group.) 2. The non-polymer compound according to claim 1, wherein the ultraviolet absorbing groups are each independently a group having any one selected from the group consisting of a benzotriazole skeleton, a triazine skeleton, a benzophenone skeleton, a cyanoacrylate skeleton, a salicylate skeleton, and an oxalic acid anilide skeleton.

3. The non-polymer compound according to claim 2, wherein said ultraviolet absorbing groups are each independently a group having a triazine skeleton or a benzophenone skeleton.

4. The non-polymer compound according to claim 3, wherein the ultraviolet absorbing groups are each independently a group represented by the following formula (x1) or formula (x2): (In formula (x1), R a each independently represents a hydrogen atom, a hydroxyl group, a methyl group, or an ethyl group; a At least one of R is a hydroxy group; 1 and R 2 Each of m1 independently represents an integer of 0 to 3, and m2 independently represents an integer of 0 to 2. In formula (x2), R b each independently represents a hydrogen atom or a hydroxyl group; b At least one of the groups is a hydroxy group. * represents a bond.) 5. The non-polymer compound according to claim 4, wherein the ultraviolet absorbing groups are each independently a group represented by the following formula (x1-1) or formula (x2-1), and at least one of the n ultraviolet absorbing groups is a group represented by the following formula (x1-1). (In the formula, R 1 each independently represents a methyl group or an ethyl group, each m3 independently represents an integer of 0 to 5, and * represents a bond.

6. The non-polymeric compound of claim 1 having a molecular weight of 500 to 3,500.

7. The non-polymer compound according to claim 1, which is a reaction product of a compound having 3 to 6 epoxy groups in one molecule with a compound having the above ultraviolet absorbing group and a phenolic hydroxy group or carboxy group.

8. The non-polymer compound according to claim 1, wherein the organic group represented by A is a group represented by any one of the following formulas (a1) to (a7): (In the formula, * represents a bond.) 9. A film-forming composition comprising a non-polymer compound represented by formula (1) according to any one of claims 1 to 8, 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 non-polymer compound.

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

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

12. The film forming composition according to claim 9, further comprising a surfactant.

13. The film forming composition according to claim 9, further comprising a light stabilizer.

14. A film obtained from the film-forming composition according to claim 9.

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