Curable resin composition

Abstract

Provided is a curable resin composition that can be applied by an inkjet method, and also has excellent surface curability and low water absorption. The curable resin composition includes: a first (meth)acrylate compound including an aromatic ring group and two or more ethyleneoxy repeating units; a second (meth)acrylate compound including three or more ethyleneoxy repeating units but not including an aromatic ring group; a photoinitiator; and an amine compound. The curable resin composition has a viscosity of 150 mPa·s or less at 25°C.

Description

Curable resin composition

[0001] The present invention relates to a curable resin composition.

[0002] Compared to photolithography processes, inkjet coating methods require fewer steps and offer higher production efficiency, making them promising for applications in the electronics field, such as protecting circuits, shading specific areas, and forming spacers. For example, Japanese Patent Application Laid-Open No. 2010-155926 proposes a photocurable liquid resin composition for forming three-dimensional objects using the inkjet method. Japanese Patent Application Laid-Open No. 2012-241127 also proposes a photocurable resin composition containing a polymerizable (meth)acrylate having a polyethylene oxide structure and a benzophenone-based photoinitiator.

[0003] An object of one aspect of the present invention is to provide a curable resin composition that can be applied by an inkjet method, has excellent surface curing properties, and has low water absorption.

[0004] The present invention includes the following aspects: [1] A curable resin composition comprising a first (meth)acrylate compound containing two or more ethyleneoxy repeating units and an aromatic ring group, a second (meth)acrylate compound containing three or more ethyleneoxy repeating units and no aromatic ring group, a photopolymerization initiator, and an amine compound, and having a viscosity of 150 mPa s or less at 25°C.

[0005] [2] The curable resin composition according to [1], further comprising a third (meth)acrylate compound different from the first (meth)acrylate compound and the second (meth)acrylate compound, and having a viscosity of 30 mPa·s or less at 25°C.

[0006] [3] The curable resin composition according to [1] or [2], wherein the total content of the first (meth)acrylate compound and the second (meth)acrylate compound is 50 mass% or more, and the ratio of the content of the first (meth)acrylate compound to the total content of the first (meth)acrylate compound and the second (meth)acrylate compound is 0.01 or more and 0.35 or less.

[0007] [4] The curable resin composition according to any one of [1] to [3], wherein the photopolymerization initiator includes at least one selected from the group consisting of benzophenone derivatives and thioxanthone derivatives.

[0008] [5] The curable resin composition according to any one of [1] to [4], wherein the photopolymerization initiator includes at least one benzophenone derivative.

[0009] [6] The curable resin composition according to any one of [1] to [5], further comprising at least one selected from the group consisting of an acrylate compound having an epoxy group, an isocyanate compound, and a blocked isocyanate compound.

[0010] [7] The curable resin composition according to any one of [1] to [6], further comprising at least one selected from the group consisting of dyes and pigments.

[0011] According to one aspect of the present invention, it is possible to provide a curable resin composition that can be applied by an inkjet method, has excellent surface curing properties, and has low water absorption.

[0012] As used herein, the term "process" refers not only to an independent process, but also to processes that cannot be clearly distinguished from other processes, as long as the intended purpose of the process is achieved. When multiple substances corresponding to each component are present in the composition, the content of each component in the composition refers to the total amount of the multiple substances present in the composition, unless otherwise specified. Furthermore, the upper and lower limits of the numerical ranges described herein can be arbitrarily selected and combined from the numerical values ​​exemplified as numerical ranges. As used herein, "(meth)acrylate" is a general term referring to acrylate, methacrylate, and mixtures thereof, and the same applies to other similar expressions (e.g., (meth)acryloyl). As used herein, the solid content of a composition or its components refers to the residue remaining after removing volatile components (e.g., organic solvents) from the composition or its components. Hereinafter, embodiments of the present invention will be described in detail. However, the following embodiments are merely examples of photosensitive resin compositions intended to embody the technical concept of the present invention, and the present invention is not limited to the photosensitive resin compositions described below.

[0013] 1. Curable Resin Composition The curable resin composition includes a first (meth)acrylate compound containing two or more ethyleneoxy repeating units and an aromatic ring group, a second (meth)acrylate compound containing three or more ethyleneoxy repeating units and no aromatic ring group, a photopolymerization initiator, and an amine compound. The curable resin composition has a viscosity of 150 mPa s or less at 25°C.

[0014] The curable resin composition contains a first (meth)acrylate compound and a second (meth)acrylate compound having specific structures as polymerizable compounds, and thereby exhibits excellent surface curability, particularly in air, and low water absorption. Furthermore, it is possible to form a cured coating film with high strength and excellent dimensional stability. Furthermore, warping during curing is suppressed.

[0015] First (meth)acrylate compound The first (meth)acrylate compound contains two or more ethyleneoxy repeating units and an aromatic ring group in its structure. The first (meth)acrylate compound further contains at least one (meth)acryloyl group. The number of (meth)acryloyl groups contained in the first (meth)acrylate compound may be 1 or more and 10 or less, and preferably 1 or 2.

[0016] The ethyleneoxy repeating unit is —(CH ２ CH ２O)-, which is a structural unit capable of forming a polyethyleneoxy group consisting of a plurality of ethyleneoxy groups. The ethyleneoxy repeating unit in this specification does not include structural units containing an ethyleneoxy group as a partial structure, such as a propyleneoxy group. The ethyleneoxy repeating unit is formed, for example, by an addition reaction of ethylene oxide to a hydroxy group. The first (meth)acrylate compound may contain two or more consecutive ethyleneoxy repeating units in its molecular structure, and may contain 2 to 20, preferably 2 to 10, consecutive ethyleneoxy repeating units. The total number of ethyleneoxy repeating units contained in the first (meth)acrylate compound may be, for example, 2 or more and 50 or less, preferably 30 or less, and more preferably 20 or less. The first (meth)acrylate compound may have only one polyethyleneoxy group consisting of an ethyleneoxy repeating unit, or may have two or more.

[0017] The first (meth)acrylate compound contains an aromatic ring group in its structure. The total number of aromatic ring groups contained in the first (meth)acrylate compound may be, for example, 1 to 5, preferably 1 or 2, and more preferably 2. The number of carbon atoms in the aromatic ring group contained in the first (meth)acrylate compound may be, for example, 6 to 30. The aromatic ring group may be an aromatic hydrocarbon group or an aromatic heterocyclic group containing a heteroatom such as nitrogen, oxygen, or sulfur. The aromatic ring group may have a substituent. Examples of the substituent in the aromatic ring group include hydrocarbon groups having 1 to 20 carbon atoms, preferably 1 to 6 carbon atoms, hydroxyl groups, alkoxy groups, carboxy groups, halogen atoms, substituents containing phosphorus atoms, and substituents containing sulfur atoms. The aromatic ring group is formed by removing a hydrogen atom from an aromatic compound. Specific examples of aromatic compounds from which the aromatic ring group is derived include benzene, naphthalene, phenol, naphthol, dihydroxybiphenyl, dihydroxydiphenylmethane, and dihydroxydiphenylpropane.

[0018] The ethyleneoxy group in the first (meth)acrylate compound may be bonded to the aromatic ring group via a carbon atom or via an oxygen atom. Here, in an embodiment in which the ethyleneoxy group is bonded to the aromatic ring group via an oxygen atom, the terminal oxygen atom of the ethyleneoxy group may be bonded to the aromatic ring group, or the terminal carbon atom of the ethyleneoxy group may be bonded to the aromatic ring group via an oxygen atom. Furthermore, the (meth)acryloyl group may be bonded to the aromatic ring group via an oxygen atom or may be bonded to the ethyleneoxy group via an oxygen atom. In an embodiment in which the (meth)acryloyl group is bonded to the ethyleneoxy group via an oxygen atom, the terminal oxygen atom of the ethyleneoxy group may be bonded to the (meth)acryloyl group, or the terminal carbon atom of the ethyleneoxy group may be bonded to the (meth)acryloyl group via an oxygen atom.

[0019] In one embodiment, the first (meth)acrylate compound may be a compound having a (meth)acryloyl group, two or more ethyleneoxy repeating units, and an aromatic ring group derived from at least one aromatic compound selected from the group consisting of phenol, naphthol, dihydroxybiphenyl, dihydroxydiphenylmethane, and dihydroxydiphenylpropane.

[0020] Specific examples of the first (meth)acrylate compound include ethyleneoxy (EO) group-added bisphenol A di(meth)acrylate, ethyleneoxy (EO) group-added bisphenol F di(meth)acrylate, and phenoxydiethylene glycol (meth)acrylate. The curable resin composition may contain one type of first (meth)acrylate compound alone, or two or more types in combination. Commercially available first (meth)acrylate compounds include A-BP-4, ABE-300, A-BPE-4, A-BPE-10, and A-BPE-20 (all manufactured by Shin-Nakamura Chemical Co., Ltd.), P2H-A, and Light Acrylate P-200A (all manufactured by Kyoeisha Chemical Co., Ltd.), and M-208 and M-211B (all manufactured by Toagosei Co., Ltd.).

[0021] Second (meth)acrylate compound The second (meth)acrylate compound contains three or more ethyleneoxy repeating units in its structure and does not contain an aromatic ring group. The second (meth)acrylate compound further contains at least one (meth)acryloyl group. The number of (meth)acryloyl groups contained in the second (meth)acrylate compound may be 1 or more and 20 or less, preferably 2 or 3.

[0022] The second (meth)acrylate compound may contain two or more consecutive ethyleneoxy repeating units in its structure, and may contain 2 to 50 consecutive ethyleneoxy repeating units. The total number of ethyleneoxy repeating units contained in the second (meth)acrylate compound may be, for example, 3 to 50, preferably 3 to 30, and more preferably 3 to 20. The second (meth)acrylate compound may have only one polyethyleneoxy group composed of ethyleneoxy repeating units, or may have two or more. When the total number of ethyleneoxy repeating units is 3 or more, peroxide radicals can be more effectively captured, and surface curability can be further improved. When the total number of ethyleneoxy repeating units is 50 or less, preferably 30 or less, and more preferably 20 or less, water solubility is not too high, and water absorption can be more effectively suppressed.

[0023] By including a second (meth)acrylate having a specific structure in the curable composition, excellent surface curing properties and low water absorption can be achieved. This can be explained, for example, as follows: It is believed that the ethyleneoxy repeating units contained in the structure of the second (meth)acrylate compound capture the generated peroxide radicals and generate radicals that can be polymerized again, thereby improving the photocuring properties of the coating film. Furthermore, it is believed that the combined use of a first (meth)acrylate and a second (meth)acrylate makes it easier for the first (meth)acrylate to be incorporated into the polymer chain, and the hydrophobic effect of the aromatic ring derived from the first (meth)acrylate is more strongly expressed, thereby reducing water absorption.

[0024] In addition to the ethyleneoxy repeating unit and the (meth)acryloyl group, the second (meth)acrylate compound may further contain a group derived from a hydrocarbon compound having 1 to 30 carbon atoms, a group derived from a polyalcohol compound having 3 to 30 carbon atoms, or the like. The hydrocarbon compound having 1 to 30 carbon atoms does not have to be an aromatic compound, and may be a saturated or unsaturated hydrocarbon compound. The hydrocarbon compound may be linear, branched, cyclic, or a combination thereof. The hydrocarbon compound may preferably have 1 to 10 carbon atoms. Examples of polyalcohol compounds having 3 to 30 carbon atoms include glycerin and trimethylolpropane. The polyalcohol compound may preferably have 3 to 10 carbon atoms. In the second (meth)acrylate compound, the (meth)acryloyl group may be bonded to the ethyleneoxy group via an oxygen atom.

[0025] In one embodiment, the second (meth)acrylate compound may be a compound that includes a (meth)acryloyl group and three or more ethyleneoxy repeating units, and may further include a group derived from a polyalcohol compound having 3 to 30 carbon atoms.

[0026] Specific examples of the second (meth)acrylate compound include polyethylene glycol #200 di(meth)acrylate, polyethylene glycol #400 di(meth)acrylate, ethylene oxide-modified trimethylolpropane tri(meth)acrylate, etc. The curable resin composition may contain one type of second (meth)acrylate compound alone, or may contain two or more types in combination. Commercially available products of the second (meth)acrylate compound include Light Acrylate 3EG-A, Light Acrylate 4EG-A, Light Acrylate 9EG-A, Light Acrylate 14EG-A, Light Acrylate MTG-A, Light Acrylate 130A, Light Ester 3EG, Light Ester 4EG, Light Ester 9EG, and Light Ester 14EG (all manufactured by Kyoeisha Chemical Co., Ltd.), PEG200DA, PEG400DA, EBECRYL11, EBECRYL160S, EBECRYL50, and EBECRYLPEG200DMA (all manufactured by Daicel-Allnex Corporation), and LR8863 (manufactured by BASF Japan Ltd.).

[0027] The total content of the first (meth)acrylate compound and the second (meth)acrylate compound in the curable resin composition may be, for example, 50% by mass or more, preferably 55% by mass or more, more preferably 60% by mass or more, 70% by mass or more, or 75% by mass or more, relative to the total amount of the curable resin composition. The total content of the first (meth)acrylate compound and the second (meth)acrylate compound may be, for example, 95% by mass or less, preferably 90% by mass or less, more preferably 80% by mass or less, relative to the total amount of the curable resin composition. If the total content of the first (meth)acrylate compound and the second (meth)acrylate compound is within the above range, the effect of oxygen inhibition during curing of the curable resin composition is further suppressed, and the surface curability tends to be further improved.

[0028] In addition, the mass ratio of the content of the first (meth)acrylate compound to the total content of the first (meth)acrylate compound and the second (meth)acrylate compound in the curable resin composition may be, for example, 0.01 or more and 0.35 or less, preferably 0.05 or more, more preferably 0.1 or more, or 0.15 or more, and preferably 0.5 or less, more preferably 0.4 or less. In one aspect, the mass ratio of the content of the first (meth)acrylate compound to the total content of the first (meth)acrylate compound and the second (meth)acrylate compound may be 0.25 or less, or 0.2 or less. When the content ratio of the first (meth)acrylate compound is within the above range, water absorption tends to be further improved.

[0029] Third (meth)acrylate compound In addition to the first (meth)acrylate compound and the second (meth)acrylate compound, the curable resin composition may further contain, as the polymerizable compound, a third (meth)acrylate compound that is a (meth)acrylate compound different from the first (meth)acrylate compound and the second (meth)acrylate compound and has a viscosity of 30 mPa s or less at 25° C. By including the third (meth)acrylate compound, the viscosity of the curable resin composition tends to be further reduced, making it possible to form a cured coating film with further reduced water absorption.

[0030] The third (meth)acrylate compound may be a compound containing at least one (meth)acryloyl group and no ethyleneoxy repeating unit. The number of (meth)acryloyl groups contained in the third (meth)acrylate compound may be 1 or more and 10 or less, preferably 1 or 2.

[0031] The viscosity of the third (meth)acrylate compound at 25° C. may be 30 mPa·s or less, preferably 25 mPa·s or less, or 20 mPa·s or less. The viscosity of the third (meth)acrylate compound at 25° C. may be, for example, 1 mPa·s or more. The viscosity of the third (meth)acrylate compound is measured in the same manner as the viscosity measurement method described below.

[0032] Specific examples of the tertiary (meth)acrylate compound include acrylates having a linear structure such as 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 2-(allyloxymethyl)acrylic acid alkyl ester, and polypropylene di(meth)acrylate. Furthermore, examples of acrylate compounds having a cyclic structure include isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, tetrahydrofuryl (meth)acrylate, benzyl (meth)acrylate, (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl acrylate, cyclic trimethylolpropane formal acrylate, 3,3,5-trimethylcyclohexyl acrylate, and dimethylol-tricyclodecane diacrylate. The curable resin composition may contain one type of tertiary (meth)acrylate compound alone, or may contain two or more types in combination. Commercially available tertiary (meth)acrylate compounds include Light Acrylate 1.6HX-A, Light Acrylate 1.9-ND-A, Light Acrylate PTMGA-250, Light Acrylate NP-A, Light Acrylate MPD-A, Light Ester CH, Light Ester THF (1000), Light Ester BZ, Light Ester HO-250 (N), Light Ester HOP (N), Light Ester HOA (N), Light Ester HOP-A (N), Light Ester HOB (N), Light Ester 1.4BG, and Light Ester Light Ester NP, Light Ester 1.6HX, Light Ester 1.9ND (all manufactured by Kyoeisha Chemical Co., Ltd.), IBOA-B, DPGDA, TPGDA, EBECRYLIBOMA (all manufactured by Daicel Allnex Corporation), Viscoat #150, Viscoat #155, Viscoat #160, Viscoat #190, Viscoat #195, Viscoat #196, Viscoat #200, MEDOL-10 (all manufactured by Osaka Organic Chemical Industry Ltd.), VEEA, VEEM, AOMA (all manufactured by Nippon Shokubai Co., Ltd.), and the like.

[0033] Regarding the contents of the first (meth)acrylate compound, the second (meth)acrylate compound, and the third (meth)acrylate compound (hereinafter sometimes collectively referred to as (meth)acrylate compounds) in the curable resin composition, when the total amount of the (meth)acrylate compounds is 100 parts by mass, converted into solid content, the content of the first (meth)acrylate compound may be, for example, 3 parts by mass or more and 50 parts by mass or less, preferably 5 parts by mass or more, more preferably 8 parts by mass or more, 10 parts by mass or more, or 12 parts by mass or more, and also preferably 45 parts by mass or less, more preferably 40 parts by mass or less, 30 parts by mass or less, 20 parts by mass or less, or 18 parts by mass or less. When the total amount of (meth)acrylate compounds is 100 parts by mass, the content of the second (meth)acrylate compound may be, for example, 5 parts by mass or more and 95 parts by mass or less, preferably 10 parts by mass or more, more preferably 15 parts by mass or more, 20 parts by mass or more, 30 parts by mass or more, 40 parts by mass or more, 50 parts by mass or more, or 58 parts by mass or more, and preferably 90 parts by mass or less, more preferably 85 parts by mass or less, 75 parts by mass or less, or 70 parts by mass or less. When the total amount of (meth)acrylate compounds is 100 parts by mass, the content of the third (meth)acrylate compound may be, for example, 0.1 parts by mass or more and 80 parts by mass or less, preferably 5 parts by mass or more, more preferably 10 parts by mass or more, or 18 parts by mass or more, and preferably 70 parts by mass or less, more preferably 60 parts by mass or less, 40 parts by mass or less, 30 parts by mass or less, or 25 parts by mass or less.

[0034] The mass ratio of the content of the third (meth)acrylate compound to the total content of the first (meth)acrylate compound and the second (meth)acrylate compound in the curable resin composition, calculated as solid content, may be, for example, 0.1 to 2, preferably 0.15 to 0.2, and preferably 1.2 to 0.8, 0.6 to 0.3. When the total content of the first (meth)acrylate compound and the second (meth)acrylate compound in the curable resin composition is 100 parts by mass, the content of the third (meth)acrylate compound, calculated as solid content, may be, for example, 0.1 to 50 parts by mass, preferably 5 parts by mass or more, or 10 parts by mass or more, and preferably 45 parts by mass or less, or 40 parts by mass or less. When the content ratio of the third (meth)acrylate compound is within the above range, there is a tendency that the viscosity of inkjet ejection can be controlled to a good value while maintaining high coating film strength.

[0035] In addition to the first (meth)acrylate compound, the second (meth)acrylate compound, and the third (meth)acrylate compound, the curable resin composition may further contain, as necessary, another compound having an ethylenically unsaturated bond. Examples of the compound having an ethylenically unsaturated bond include vinyl compounds, allyl compounds, and substituted allyl compounds. The curable resin composition may contain one or more of the compounds having an ethylenically unsaturated bond, either singly or in combination. Commercially available examples of the compound having an ethylenically unsaturated bond include NPVE, IPVE, NBVE, IBVE, EHVE, CHVE, HEVE, HBVE, CHMVE, BDVE, DEGDVE, CHDVE, and TEGDVE (all manufactured by Nippon Carbide Industries Co., Ltd.), DEGV (manufactured by Maruzen Petrochemical Co., Ltd.), N-vinylpyrrolidone, and N-vinyl-2-caprolactam (all manufactured by Mitsui Pharma Food & Chemical Co., Ltd.).

[0036] When the curable resin composition further contains another compound having an ethylenically unsaturated bond, the content of the compound having an ethylenically unsaturated bond may be, for example, 0.1 parts by mass or more and 30 parts by mass or less, preferably 20 parts by mass or less, more preferably 10 parts by mass or less, 2 parts by mass or less, or 1 part by mass or less, in terms of solid content, as a mass ratio relative to the total amount of the (meth)acrylate compound.

[0037] Photopolymerization Initiator The curable resin composition contains at least one photopolymerization initiator. Examples of photopolymerization initiators in the curable resin composition include benzophenone derivatives, thioxanthone derivatives, oxime ester compounds, benzoin derivatives, acetophenone derivatives, α-aminoacetophenone derivatives, hydroxyacetophenone derivatives, anthraquinone derivatives, and acylphosphine oxide compounds. The photopolymerization initiator may contain at least one selected from the group consisting of these, preferably at least one selected from the group consisting of benzophenone derivatives, thioxanthone derivatives, and oxime ester compounds, or at least one selected from the group consisting of benzophenone derivatives and thioxanthone derivatives, or may contain at least a benzophenone derivative. When the photopolymerization initiator contains a compound having the specific structure described above, the surface curability of the curable resin composition tends to be further improved. The curable resin composition may contain one photopolymerization initiator alone, or two or more photopolymerization initiators in combination.

[0038] Examples of the benzophenone derivatives include benzophenone, 4-phenylbenzophenone, 4,4'-bisdiethylaminobenzophenone, methyl-o-benzoylbenzoate, 4-(4-methylphenylthio)benzophenone, 1-[4-(4-benzoylphenylsulfanyl)phenyl]-2-methyl-2-(4-methylphenylsulfonyl)propan-1-one, 4,4'-dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone, and 3,3'-dimethyl-4-methoxybenzophenone. As the benzophenone derivative, commercially available products such as OMNIPOL BP, OMNIPOL 4PBZ, OMNIRAD EMK, OMNIRAD OMBB, OMNIRAD BMS, and Esacure 1001M (all manufactured by IGM Japan LLC), Speedcure PBZ, and Speedcure BMS (all manufactured by Arkema K.K.) may be used.

[0039] Examples of thioxanthone derivatives include 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone, 4-isopropylthioxanthone, etc. Commercially available thioxanthone derivatives such as DETX and ITX (both manufactured by Arkema Inc.) may also be used.

[0040] Examples of the oxime ester compounds include 2-(O-benzoyloxime)-1-[4-(phenylthio)phenyl]-1,2-butanedione, 2-(O-benzoyloxime)-1-[4-(phenylthio)phenyl]-1,2-pentanedione, 2-(O-benzoyloxime)-1-[4-(phenylthio)phenyl]-1,2-hexanedione, 2-(O-benzoyloxime)-1-[4-(phenylthio)phenyl]-1,2-heptanedione, and 2-(O-benzoyloxime)-1-[4-(phenylthio)phenyl]- 1,2-Octanedione, 2-(O-benzoyloxime)-1-[4-(methylphenylthio)phenyl]-1,2-butanedione, 2-(O-benzoyloxime)-1-[4-(ethylphenylthio)phenyl]-1,2-butanedione, 2-(O-benzoyloxime)-1-[4-(butylphenylthio)phenyl]-1,2-butanedione, 1-(O-acetyloxime)-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone, 1-(O-acetyloxime)-1-[9-methyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone, 1-(O-acetyloxime )-1-[9-propyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone, 1-(O-acetyloxime)-1-[9-ethyl-6-(2-ethylbenzoyl)-9H-carbazol-3-yl]ethanone, 1-(O-acetyloxime)-1-[9-ethyl-6-(2-butylbenzoyl)-9H-carbazol-3-yl]ethanone, 2-(benzoyloxyimino)-1-[4-(phenylthio)phenyl]-1-octanone, 2-(acetoxyimino)-4-(4-chlorophenylthio)-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-butanone, and the like. As the oxime ester compound, commercially available products such as Irgacure OXE-01, Irgacure OXE-02, Irgacure OXE-03, and Irgacure OXE-04 (all manufactured by BASF Japan Ltd.), and N-1919, NCI-730, NCI-831, and NCI-930 (all manufactured by ADEKA Corporation) may be used.

[0041] Examples of the benzoin derivatives include benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether.

[0042] Examples of the acetophenone derivatives include acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, and 1,1-dichloroacetophenone.

[0043] Examples of α-aminoacetophenone derivatives include 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, and N,N-dimethylaminoacetophenone.

[0044] Examples of the hydroxyacetophenone derivatives include 2-hydroxy-1-(4-(4-(2-hydroxy-2-methylpropionyl)benzyl)phenyl)-2-methylpropan-1-one.

[0045] Examples of anthraquinone derivatives include 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone, etc. Examples of acylphosphine oxide compounds include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphine oxide, etc.

[0046] The content of the photopolymerization initiator in the curable resin composition may be, for example, 1 part by mass or more and 20 parts by mass or less, preferably 1.5 parts by mass or more, or 2 parts by mass or more, and also preferably 15 parts by mass or less, 10 parts by mass or less, or 6 parts by mass or less, when the total amount of the (meth)acrylate compound is 100 parts by mass, converted into solid content.

[0047] Amine Compound The curable resin composition may contain at least one amine compound. By including an amine compound in addition to a photopolymerization initiator, the hydrogen abstraction reaction by the photopolymerization initiator proceeds more efficiently, and surface curing resistance to oxygen inhibition can be further enhanced. The amine compound in the curable resin composition may be an aromatic amine compound or an aliphatic amine compound. The amine compound may also be a compound having a tertiary amino group. Specific examples of the amine compound include aromatic amine compounds such as N,N-dimethylaminobenzoic acid ethyl ester, N,N-dimethylaminobenzoic acid isoamyl ester, N,N-dimethylaminobenzoic acid pentyl ester, and polyethylene glycol bis(N,N-dimethylaminobenzoic acid ester), and aliphatic amine compounds such as triethylamine and triethanolamine. Furthermore, examples of commercially available amine compounds include Omnipol ASA (weight average molecular weight Mw 480; manufactured by IGM Japan LLC), GENOPOL-AB-1 (weight average molecular weight Mw 860; manufactured by Rahn AG), CN371NS, CN373, CN383, CN386 (all manufactured by Arkema K.K.), EBECRYL80 (weight average molecular weight Mw 1000), EBECRYL7100 (all manufactured by Daicel-Allnex Co., Ltd.), etc. The amine compounds may be used alone or in combination of two or more.

[0048] The molecular weight of the amine compound may be, for example, 300 or more, preferably 350 or more, or 5000 or less. When the amine compound contains a polymer moiety, the molecular weight of the amine compound may be a weight-average molecular weight. When the molecular weight of the amine compound is within the above range, warpage and water absorbency tend to be further improved.

[0049] The content of the amine compound in the curable resin composition may be, for example, 0.1 parts by mass or more and 30 parts by mass or less, preferably 0.5 parts by mass or more, 1 part by mass or more, or 2 parts by mass or more, and preferably 25 parts by mass or less, 20 parts by mass or less, 10 parts by mass or less, or 5 parts by mass or less, when the total amount of the (meth)acrylate compounds is taken as 100 parts by mass in terms of solid content. Furthermore, the content of the amine compound in the curable resin composition may be, for example, 10% by mass or more and 95% by mass or less, preferably 20% by mass or more, 60% by mass or more, or 70% by mass or more, and preferably 90% by mass or less, or 80% by mass or less, as the total amount relative to the content of the photopolymerization initiator.

[0050] Thermosetting Component The curable resin composition may further contain a thermosetting component. Examples of the thermosetting component include amino resins such as melamine resins, benzoguanamine resins, melamine derivatives, and benzoguanamine derivatives; isocyanate compounds, blocked isocyanate compounds; cyclocarbonate compounds; compounds having a cyclic (thio)ether group such as epoxy compounds and oxetane compounds; bismaleimide resins, carbodiimide resins; and thermosetting resins such as epoxy resins. Among these, the thermosetting component may contain at least one selected from the group consisting of acrylate compounds containing an epoxy group, isocyanate compounds, and blocked isocyanate compounds. The thermosetting component may be used alone or in combination of two or more.

[0051] Examples of acrylate compounds containing an epoxy group include glycidyl ether-containing bisphenol A acrylate (for example, EA1010 manufactured by Shin-Nakamura Chemical Co., Ltd.).

[0052] The isocyanate compound may be a polyisocyanate compound having multiple isocyanate groups in one molecule. Examples of the polyisocyanate compound include aromatic polyisocyanates, aliphatic polyisocyanates, and alicyclic polyisocyanates. The aliphatic group contained in the aliphatic polyisocyanate may be linear or branched.

[0053] Specific examples of aromatic polyisocyanates include diphenylmethane diisocyanate (e.g., 4,4'-diphenylmethane diisocyanate), tolylene diisocyanate (e.g., 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate), naphthalene diisocyanate (e.g., naphthalene-1,5-diisocyanate), xylylene diisocyanate (e.g., o-xylylene diisocyanate, m-xylylene diisocyanate), and the like.

[0054] Specific examples of the aliphatic polyisocyanate include tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, and trimethylhexamethylene diisocyanate.

[0055] Specific examples of alicyclic polyisocyanates include bicycloheptane triisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylylene diisocyanate, 4,4-methylenebis(cyclohexyl isocyanate), and isophorone diisocyanate.

[0056] The polyisocyanate compound may be an adduct, biuret, isocyanurate, or the like of the polyisocyanate compound described above. The adduct of the polyisocyanate compound is, for example, an adduct-type isocyanate compound obtained by reacting the various isocyanate compounds described above with a trifunctional or higher polyhydric alcohol such as glycerin, trimethylolpropane, trimethylolethane, 1,2,6-hexanetriol, 1,2,4-butanetriol, erythritol, sorbitol, pentaerythritol, or dipentaerythritol. The biuret of the polyisocyanate compound is, for example, a biuret-type isocyanate compound obtained by reacting a polyisocyanate compound with water. The isocyanurate of the polyisocyanate compound is, for example, an isocyanurate-type isocyanate compound obtained by isocyanating the isocyanate group of the polyisocyanate compound.

[0057] A blocked isocyanate compound is a compound having multiple blocked isocyanate groups in one molecule. A blocked isocyanate group is a group in which an isocyanate group is protected and temporarily inactivated by reaction with a blocking agent, and when heated to a predetermined temperature, the blocking agent dissociates to generate an isocyanate group. The blocked isocyanate compound may be a compound obtained by blocking the isocyanate groups of the above-mentioned polyisocyanate compound.

[0058] Examples of blocking agents include phenol-based blocking agents such as phenol, cresol, xylenol, chlorophenol, and ethylphenol; lactam-based blocking agents such as ε-caprolactam, δ-valerolactam, γ-butyrolactam, and β-propiolactam; active methylene-based blocking agents such as ethyl acetoacetate and acetylacetone; and alcohol-based blocking agents such as methanol, ethanol, propanol, butanol, amyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, benzyl ether, methyl glycolate, butyl glycolate, diacetone alcohol, methyl lactate, and ethyl lactate. Blocking agents include oxime-based blocking agents such as formaldehyde oxime, acetaldoxime, acetoxime, methyl ethyl ketoxime, diacetyl monooxime, and cyclohexane oxime; mercaptan-based blocking agents such as butyl mercaptan, hexyl mercaptan, t-butyl mercaptan, thiophenol, methylthiophenol, and ethylthiophenol; acid amide-based blocking agents such as acetic acid amide and benzamide; imide-based blocking agents such as succinimide and maleic acid imide; amine-based blocking agents such as xylidine, aniline, butylamine, and dibutylamine; imidazole-based blocking agents such as imidazole and 2-ethylimidazole; imine-based blocking agents such as methyleneimine and propyleneimine; and pyrazole-based blocking agents such as dimethylpyrazole.

[0059] When the curable resin composition contains a thermosetting component, the content of the thermosetting component in the curable resin composition, in terms of solid content, relative to 100 parts by mass of the total amount of the (meth)acrylate compound, may be, for example, 1 part by mass or more and 50 parts by mass or less, preferably 2 parts by mass or more, more preferably 3 parts by mass or more, 6 parts by mass or more, or 9 parts by mass or more, and may also be preferably 40 parts by mass or less, more preferably 30 parts by mass or less, 20 parts by mass or less, or 15 parts by mass or less.

[0060] When the curable resin composition contains a thermosetting component, it may further contain at least one thermosetting catalyst, if necessary. Examples of the thermosetting catalyst include melamine and melamine derivatives, imidazole derivatives, and phosphorus compounds. The thermosetting catalyst may be used alone or in combination of two or more.

[0061] The content of the thermosetting catalyst in the curable resin composition may be, for example, 0.001 parts by mass or more and 5 parts by mass or less, and preferably 0.002 parts by mass or more and 3 parts by mass or less, relative to 100 parts by mass of the total amount of the curable resin composition, in terms of solid content.

[0062] The curable resin composition may further contain at least one colorant selected from the group consisting of dyes and pigments. The colorant may have a color tone selected depending on the purpose, and may be a colorant of white, black, or other color tone.

[0063] Examples of white colorants include white pigments. Known white pigments such as titanium oxide, zinc oxide, magnesium oxide, zirconium oxide, aluminum oxide, barium sulfate, silica, talc, mica, aluminum hydroxide, calcium silicate, aluminum silicate, hollow resin particles, and zinc sulfide can be used. Among these, titanium oxide is preferred due to its high coloring properties and reflectance. These white pigments may be used alone or in combination of two or more.

[0064] The titanium oxide may be of any of rutile, anatase, and ramsdellite structures, and may be used alone or in combination of two or more. Of these, rutile titanium oxide is preferred.

[0065] Examples of black colorants include carbon black and iron oxide (Fe ３ O ４ Examples of suitable black pigments include inorganic pigments such as black titanium oxide, zirconium nitride, copper manganese black, copper chromium black, and cobalt black, as well as organic pigments such as perylene black, lactone black, cyanine black, and aniline black. Furthermore, black pigments and dyes or pigments such as red, blue, green, and yellow, which will be described later, can be mixed with the black pigment to produce black or a black-like color. These black colorants may be used alone or in combination of two or more.

[0066] Colorants of other colors include red, blue, green and yellow pigments and dyes, and known ones represented by the Color Index can be used.For example, PigmentBlue15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 60, SolventBlue35, 63, 68, 70, 83, 87, 94, 97, 122, 136, 67, 70, PigmentGreen7, 36, 3, 5 , 20, 28, SolventYellow163, PigmentYellow24, 108, 193, 147, 199, 202 , 110, 109, 13917918593, 94, 95, 128, 155, 166, 180, 120, 151, 154, 156, 175, 181, 1, 2, 3, 4, 5, 6, 9, 10, 12, 61, 62, 62:1, 65, 73, 74, 75, 97, 100, 1 04, 105, 111, 116, 167, 168, 169, 182, 183, 12, 13, 14, 16, 17, 55, 63, 81, 83, 87, 126, 127, 152, 170, 172, 174, 176, 188, 198, PigmentOrange1, 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 61, 63, 64, 71, 73, Pigmen tRed1, 2, 3, 4, 5, 6, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 112, 114, 1 46, 147, 151, 170, 184, 187, 188, 193, 210, 245, 253, 258, 266, 267, 268, 269, 37, 38, 41, 48:1, 48:2, 48:3, 48:4, 49:1, 49:2, 50:1, 52:1, 52:2, 5 3:1, 53:2, 57:1, 58:4, 63:1, 63:2, 64:1, 68, 171, 175, 176, 185, 208, 12 3, 149, 166, 178, 179, 190, 194, 224, 254, 255, 264, 270, 272, 220, 144, 166, 214, 220, 221, 242, 168, 177, 216, 122, 202, 206, 207, 209, Solvent Red 135, 179, 149, 150, 52, 207, Pigment Violet 19, 23, 29, 32, 36, 38, 42, Solvent Violet 13, 36, Pigment Brown 23, 25, Pigment Black 1, 7, etc.

[0067] When the curable resin composition contains a colorant, the content thereof in terms of solid content may be 1 part by mass or more and 50 parts by mass or less, and preferably 20 parts by mass or less, per 100 parts by mass of the curable resin composition.

[0068] The curable resin composition may further contain additives, as necessary, such as polymerization inhibitors such as hydroquinone, hydroquinone monomethyl ether, t-butylcatechol, pyrogallol, and phenothiazine; inorganic fillers such as zirconium oxide, barium titanate, clay, magnesium carbonate, calcium carbonate, aluminum hydroxide, and mica powder; thickeners such as finely divided silica, organic bentonite, and montmorillonite; at least one of silicone-based, fluorine-based, and polymer-based defoamers and leveling agents, antioxidants, photopolymerization sensitizers, light stabilizers, dispersants, curing accelerators, flame retardants, flame retardant assistants, and silane coupling agents.

[0069] The viscosity of the curable resin composition at 25°C may be 150 mPa·s or less. The viscosity of the curable resin composition at 25°C may preferably be 100 mPa·s or less, or 50 mPa·s or less. The viscosity of the curable resin composition at 25°C may be 5 mPa·s or more. When the viscosity is within the above range, the composition is suitable for use in inkjet printers. Therefore, the curable resin composition can be used as an ink to directly draw a pattern on a substrate for a printed wiring board or the like by an inkjet method.

[0070] Here, the viscosity of the curable resin composition is measured in accordance with "Method of measuring viscosity using a cone-plate rotational viscometer" in JIS Z8803:2011(10) at 25°C, 50 rpm, and 30 seconds using a cone-plate viscometer (TVE-33H, manufactured by Toki Sangyo Co., Ltd.) using a 1°34' x R24 cone rotor.

[0071] The present invention may include a cured product as one embodiment. The cured product can be obtained by irradiating a curable resin composition layer containing a curable resin composition with light to photocure the curable resin composition layer. The light irradiation may be performed by irradiation with active energy rays such as ultraviolet rays, electron beams, or actinic rays, and is preferably performed by ultraviolet irradiation. In an inkjet printer, ultraviolet irradiation can be performed, for example, by attaching a light source such as a high-pressure mercury lamp, a metal halide lamp, or an ultraviolet LED to the side of the print head and scanning by moving the print head or the substrate. In this case, printing and ultraviolet irradiation can be performed almost simultaneously.

[0072] Furthermore, when the curable resin composition contains a thermosetting component, it can be thermally cured by using an appropriately selected heating means, for example, a heating furnace such as a hot air furnace, an electric furnace, an infrared induction heating furnace, etc. The thermal curing conditions may be, for example, a heat treatment at a temperature of 120°C or higher and 170°C or lower for 5 minutes or longer and 60 minutes or shorter.

[0073] The cured product obtained from the curable resin composition has excellent flexibility and is therefore particularly suitable as a solder resist for flexible printed wiring boards. Examples of substrates for flexible printed wiring boards include films made of glass polyimide, polyimide, polyethylene terephthalate, liquid crystal polymer, polycarbonate, etc.

[0074] The present invention may also include, as one embodiment, an electronic component having a cured product. Here, the term "electronic component" refers to a component used in an electronic circuit, and includes active components such as printed wiring boards, particularly flexible printed wiring boards, transistors, light-emitting diodes, and laser diodes, as well as passive components such as resistors, capacitors, inductors, and connectors. The cured product of the curable resin composition is suitable as an insulating cured coating film for these components.

[0075] Other aspects of the present invention include use of the curable resin composition in the production of a cured product or an electronic component, and the curable resin composition used in the production of a cured product or an electronic component.

[0076] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, "parts" and "%" are based on mass.

[0077] The following materials were prepared as materials for preparing a curable resin composition: First (meth)acrylate compound A-BPE-4: ethoxylated bisphenol A diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.)

[0078] P2H-A: Phenoxydiethylene glycol acrylate (manufactured by Kyoeisha Chemical Co., Ltd.)

[0079]

[0080] Secondary (meth)acrylate compound 4EG-A: PEG #200 diacrylate (manufactured by Kyoeisha Chemical Co., Ltd.)

[0081] 9EG-A: PEG #400 diacrylate (manufactured by Kyoeisha Chemical Co., Ltd.)

[0082] LR8863: EO-modified trimethylpropane triacrylate (manufactured by BASF Japan Ltd.)

[0083]

[0084] Tertiary (meth)acrylate compound: 1,9-NDDA: 1,9-nonanediol diacrylate (manufactured by Kyoeisha Chemical Co., Ltd.)

[0085] AOMA: 2-(allyloxymethyl)methyl acrylate (manufactured by Nippon Shokubai Co., Ltd.)

[0086] DPGDA: Dipropylene glycol diacrylate (manufactured by Daicel Allnex Co., Ltd.)

[0087]

[0088] Photopolymerization initiator: Esacure 1001M: 1-[4-(4-benzoylphenylsulfanyl)phenyl]-2-methyl-2-(4-methylphenylsulfonyl)propan-1-one (manufactured by IGM Japan LLC)

[0089] Omnirad OMBB: methyl o-benzoyl benzoate (manufactured by IGM Japan LLC)

[0090] 2-ITX: 2-isopropylthioxanthone (manufactured by Nippon Kayaku Co., Ltd.)

[0091] Irugacure OXE04: Oxime initiator (manufactured by BASF Japan Ltd.)

[0092] Amine compound: Omnipol ASA (manufactured by IGM Japan LLC; Mw 480)

[0093] GENOPOL-AB-1 (Rahn AG; Mw860)

[0094] Thermosetting component EA1010: glycidyl ether-blended bis-A acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.)

[0095] Coloring agent CR-97: Titanium oxide (manufactured by Ishihara Sangyo Kaisha) MA-100: Carbon black (manufactured by Mitsubishi Chemical Corporation)

[0096] Others: BYK-315N: Surface conditioner (manufactured by BYK Japan Co., Ltd.) Melamine (manufactured by Nissan Chemical Co., Ltd.)

[0097] Preparation of Curable Resin Compositions The components were blended in the proportions (unit: parts by mass) shown in Tables 1 and 2 below, and the mixture was stirred with a dissolver (room temperature, rotation speed: 500 rpm, 5 minutes). Subsequently, a dispersion treatment was carried out for 2 hours with zirconia beads using a bead mill (conical type K-8 (manufactured by Buhler Co., Ltd.)) (under the conditions of rotation speed: 1200 rpm, discharge rate: 20%, bead particle size: 0.65 mm, and filling rate: 88%) to obtain curable resin compositions (Examples 1 to 15) and comparative curable resin compositions (Comparative Examples 1 to 6). Note that "-" in the tables indicates that no component was added.

[0098] Viscosity The viscosity of the curable resin composition was measured to evaluate whether it could be inkjet coated. The viscosity of the curable resin composition was measured at 25°C, 50 rpm, and 30 seconds using a cone-plate viscometer (TVE-33H, manufactured by Toki Sangyo Co., Ltd.) with a 1°34' x R24 cone rotor. The measured values ​​were evaluated according to the following evaluation criteria, and the results are shown in Tables 1 and 2.

[0099] Evaluation criteria A: Less than 30 mPa·s, inkjet coating possible. B: 30 mPa·s or more and less than 50 mPa·s, inkjet coating possible. C: 50 mPa·s or more and less than 80 mPa·s, inkjet coating not possible. D: 80 mPa·s or more, inkjet coating not possible.

[0100] Surface curability Using an inkjet printing device (CPS6151, manufactured by Microcraft Co., Ltd.), a coating film was applied to an F1 glass substrate (160 × 110 mm × 1 mm) so that the thickness after photocuring would be 30 μm. ２ ) was used, and UV irradiation was carried out at various cumulative doses to form substrates for evaluating surface curability. The surface of the cured coating film on the obtained substrate for evaluating surface curability was tested for the absence of marks by rubbing a cotton swab in a straight line for 3 cm at a pressure of 3 N. The minimum cumulative dose that did not leave a mark was evaluated according to the following evaluation criteria, and the results are shown in Tables 1 and 2.

[0101] Evaluation criteria A: 200 mJ / cm ２ B: 200 mJ / cm or less. ２ exceeding 400 mJ / cm ２ C: 400 mJ / cm or less. ２ exceeding 600 mJ / cm ２ D: 600 mJ / cm or less. ２ exceeded.

[0102] Water absorption: Using an inkjet printing device (CPS6151, manufactured by Microcraft Co., Ltd.), a 5 cm x 5 cm coating film was formed on an F1 glass substrate (160 x 110 mm x 1 mm) so that the thickness after photocuring would be 30 μm. An LED with an emission wavelength of 365 nm was used to apply the coating at an accumulated irradiation dose of 600 mJ / cm. ２ The resulting substrate for evaluating water absorbency was left in water at room temperature of 23° C. for 24 hours, and the mass was measured before and after the time, and the mass change rate was calculated using the following formula.

[0103] The measured values ​​were evaluated according to the following evaluation criteria, and the results are shown in Tables 1 and 2.

[0104] Evaluation criteria A: Less than 0.5% B: 0.5% to less than 1.0% C: 1.0% to less than 1.5% D: 1.5% or more

[0105] Warpage: Using an inkjet printing device (CPS6151, manufactured by Microcraft Co., Ltd.), a coating film with a thickness of 30 μm after photocuring was formed on copper foil (18 μm), and an LED with an emission wavelength of 365 nm was used to apply an accumulated irradiation dose of 600 mJ / cm ２ After photo-curing by UV irradiation, the copper foil was cut into a 5 cm x 5 cm piece to prepare a sample for warpage evaluation. The sample for warpage evaluation was placed on a horizontal wooden board, and the average amount of lift at the four corners was measured. The measured values ​​were evaluated according to the following evaluation criteria, and the results are shown in Tables 1 and 2.

[0106] Evaluation criteria: A: 2 mm or less. B: More than 2 mm and 3 mm or less. C: More than 3 mm and 4 mm or less. D: More than 4 mm.

[0107] Coating strength: Using an inkjet printing device (CPS6151, manufactured by Microcraft Co., Ltd.), a coating film having a thickness of 30 μm after photocuring and measuring 5 cm × 5 cm was formed on an F1 glass substrate (160 mm × 110 mm × 1 mm), and an LED with an emission wavelength of 365 nm was used to apply an accumulated irradiation dose of 600 mJ / cm ２The coating was photocured by irradiating the coating with UV light of 1000 W at ...

[0108] Evaluation criteria: A: 3H or more. B: 2H. C: H. D: F or less.

[0109]

[0110]

[0111] The thermosetting resin composition obtained in Example 8 was photocured and then heat-treated at 150°C for 60 minutes to be heat-cured, thereby preparing a heat-cured sample. The obtained heat-cured sample was evaluated for water absorption, warpage, and coating strength in the same manner as above, and the results were water absorption: A, warpage: A, and coating strength: A.

[0112] The disclosure of Japanese Patent Application No. 2023-052282 (filing date: March 28, 2023) is incorporated herein by reference in its entirety. All documents, patent applications, and technical standards mentioned herein are incorporated herein by reference to the same extent as if each individual document, patent application, and technical standard was specifically and individually indicated to be incorporated by reference.

Claims

1. a first (meth)acrylate compound containing two or more ethyleneoxy repeating units and an aromatic ring group; a second (meth)acrylate compound containing three or more ethyleneoxy repeating units and two or three (meth)acryloyl groups, but not containing an aromatic ring group; a photopolymerization initiator; and an amine compound; the total content of the first (meth)acrylate compound and the second (meth)acrylate compound is 50% by mass or more, A curable resin composition having a viscosity at 25°C of 150 mPa·s or less.

2. 2. The curable resin composition according to claim 1, further comprising a third (meth)acrylate compound different from the first (meth)acrylate compound and the second (meth)acrylate compound, the third (meth)acrylate compound having a viscosity of 30 mPa·s or less at 25°C.

3. a total content of the first (meth)acrylate compound and the second (meth)acrylate compound is 50% by mass or more in terms of solid content, 3. The curable resin composition according to claim 1, wherein a ratio of a content of the first (meth)acrylate compound to a total content of the first (meth)acrylate compound and the second (meth)acrylate compound is 0.01 or more and 0.35 or less in terms of solid content.

4. The curable resin composition according to claim 1 or 2, wherein the photopolymerization initiator comprises at least one selected from the group consisting of benzophenone derivatives and thioxanthone derivatives.

5. The curable resin composition according to claim 1 or 2, wherein the photopolymerization initiator comprises at least one benzophenone derivative.

6. The curable resin composition according to claim 1 or 2, further comprising at least one selected from the group consisting of an epoxy group-containing acrylate compound, an isocyanate compound, and a blocked isocyanate compound.

7. The curable resin composition according to claim 1 or 2, further comprising at least one selected from the group consisting of dyes and pigments.