Photocurable composition, inkjet ink composition, active energy ray-curable ink composition, hardened product, and electronic component

Abstract

The present invention provides a photocurable composition capable of forming a reliable hardened product in a high-temperature constant-humidity environment, particularly having good ion migration resistance in a temperature region of 100°C or higher. The photocurable composition (Z) is obtained by adding an ion-trapping agent (Y) to a composition (X) containing a monofunctional acrylic monomer (A) and a multifunctional acrylic monomer (B), wherein the content of the monofunctional acrylic monomer (A) is 40 to 80% by weight relative to 100% by weight of the composition (X), and the content of the multifunctional acrylic monomer (B) is 10 to 50% by weight relative to 100% by weight of the composition (X). The present invention also provides an inkjet ink composition, an active energy ray-curable ink composition, a hardened product, and an electronic component each containing the photocurable composition (Z).

Description

Technical Field

[0001] The present invention relates to a photocurable composition that can be suitably used in the production of electronic circuit substrates such as display devices, printed wiring boards, flexible wiring boards, semiconductor package substrates, and solar cell substrates. The present invention particularly relates to a photocurable composition, an inkjet ink composition, an active energy ray-curable ink composition, a cured product, and an electronic component. Background Art

[0002] In the past, various studies have been conducted on coating agents for the purpose of forming a film on the surface of various substrates such as resin plates, glass plates, and metal plates used in building materials and electrical / electronic fields to protect the substrates from damage and contamination. As coating agents, thermosetting resins or photocuring resins are used. However, when photocuring resins are used, a hardened material with high surface hardness is often obtained. In addition, it hardens instantly by light irradiation and has high productivity. Therefore, photocuring resins are often used for surface protection of organic substrates. However, in general, the adhesion of hardened materials using photocuring resins to inorganic substrates is mostly insufficient. Therefore, various studies have been conducted to improve the adhesion to inorganic substrates.

[0003] For example, Patent Document 1 describes a photocurable inkjet ink comprising a specific monofunctional polymerizable monomer component (A), a polyfunctional polymerizable monomer (B), and a polymerization initiator (C) in predetermined amounts. This photocurable inkjet ink can form a cured product with excellent adhesion to an inorganic substrate.

[0004] Prior art literature

[0005] Patent Literature

[0006] Patent Document 1: International Patent Publication No. WO2013 / 015125 Summary of the Invention

[0007] Problems to be solved by the invention

[0008] However, as electronic components become thinner and smaller, the cured films using the photocurable inkjet ink described in Patent Document 1 have encountered some drawbacks. For example, in automotive components, where reliability is required in temperatures above 100°C, problems can arise due to ion migration. Ion migration, as it is known, refers to the phenomenon in which metals used as wiring or electrodes ionize, migrate, and grow, which can cause short circuits in electronic components. Therefore, from the perspective of electronic component reliability, preventing ion migration is crucial.

[0009] An object of the present invention is to provide a photocurable composition capable of forming a cured product having excellent reliability in a high-temperature and constant-humidity environment, particularly excellent ion migration resistance in a temperature range of 100° C. or higher.

[0010] Technical means to solve the problem

[0011] The present inventors conducted research to address this issue and discovered that a specific combination of components can produce a composition capable of forming a cured product with excellent adhesion to inorganic substrates and good ion migration resistance. The present invention is based on this finding and includes the following structure.

[0012] [1] A photocurable composition (Z) comprising a composition (X) containing a monofunctional acrylic monomer (A) and a polyfunctional acrylic monomer (B) and an ion scavenger (Y) added thereto, wherein

[0013] The content of the monofunctional acrylic monomer (A) is 40 to 80 wt % relative to 100 wt % of the composition (X).

[0014] The content of the polyfunctional acrylic monomer (B) is 10% by weight to 50% by weight relative to 100% by weight of the composition (X).

[0015] [2] The photocurable composition (Z) according to [1], wherein the amount of the ion scavenger (Y) added is 0.1 to 10 parts by weight relative to 100 parts by weight of the composition (X).

[0016] [3] The photocurable composition (Z) according to [1] or [2], wherein the ion scavenger (Y) is an inorganic particle.

[0017] [4] The photocurable composition (Z) according to any one of [1] to [3], wherein the ion scavenger (Y) is an inorganic particle containing any one of a zirconium compound, a magnesium compound, and an aluminum compound.

[0018] [5] The photocurable composition (Z) according to any one of [1] to [4], wherein the ion scavenger (Y) is a mixture of a zirconium compound, a magnesium compound, and an aluminum compound.

[0019] [6] The photocurable composition (Z) according to [1] or [2], wherein the hydroxyl value of the composition (X) is 1 mgKOH / g to 100 mgKOH / g.

[0020] [7] The photocurable composition (Z) according to any one of [1] to [6], wherein the composition (X) further contains a radically polymerizable compound (C) having a hydroxyl value of 100 to 300 mgKOH / g.

[0021] [8] The photocurable composition (Z) according to [7], wherein the weight average molecular weight of the radical polymerizable compound (C) is 100 to 5,000.

[0022] [9] The photocurable composition (Z) according to [7] or [8], wherein the content of the radically polymerizable compound (C) is 0.1% by weight to 30% by weight relative to 100% by weight of the composition (X).

[0023]

[10] The photocurable composition (Z) according to any one of [7] to [9], wherein the radical polymerizable compound (C) has a hydroxyl value of 150 mgKOH / g to 200 mgKOH / g.

[0024]

[11] The photocurable composition (Z) according to any one of [7] to

[10] , wherein the radically polymerizable compound (C) contains an acrylic oligomer.

[0025]

[12] The photocurable composition (Z) according to any one of [1] to

[11] , wherein the monofunctional acrylic monomer (A) contains a (meth)acrylate having one or more of the group consisting of a condensed cyclic hydrocarbon group, a polycyclic hydrocarbon group, and a monocyclic hydrocarbon group.

[0026]

[13] The photocurable composition (Z) according to

[12] , wherein the monofunctional acrylic monomer (A) is a monofunctional acrylic monomer represented by the following formula (1).

[0027] [Chemistry 1]

[0028]

[0029] In formula (1), R 1 is hydrogen or methyl, R 2 is a monovalent organic group having 4 to 30 carbon atoms and having a condensed cyclic hydrocarbon group, a polycyclic hydrocarbon group or a monocyclic hydrocarbon group, n A An integer from 0 to 10.

[0030]

[14] The photocurable composition (Z) according to

[13] , wherein R in the formula (1) 2 It is a group represented by any one of the following formulae (2) to (5).

[0031] [Chemistry 2]

[0032]

[0033] In formulas (2) to (5), R 3Each independently represents hydrogen or an alkyl group having 1 to 6 carbon atoms, and * represents a bonding bond.

[0034]

[15] The photocurable composition (Z) according to any one of [1] to

[14] , wherein the multifunctional acrylic monomer (B) is a difunctional acrylic monomer represented by the following formula (6).

[0035] [Chemistry 3]

[0036]

[0037] In formula (6), R 4 are independently hydrogen or methyl, R 5 is a divalent organic group having 4 to 30 carbon atoms and having a condensed cyclic hydrocarbon group, a polycyclic hydrocarbon group or a monocyclic hydrocarbon group, n B Each independently represents an integer from 0 to 10.

[0038]

[16] The photocurable composition (Z) according to

[15] , wherein R in the formula (6) 5 It is a group represented by any one of the following formulae (7) to (10).

[0039] [Chemistry 4]

[0040]

[0041] In formulas (7) to (10), * represents a bonding bond.

[0042]

[17] The photocurable composition (Z) according to any one of [1] to

[16] , further comprising 5 to 15 wt% of a photopolymerization initiator (D) in 100 wt% of the composition (X).

[0043]

[18] The photocurable composition (Z) according to any one of [1] to

[17] , which has a viscosity at 25° C. of 1 mPa·s to 100 mPa·s.

[0044]

[19] The photocurable composition (Z) according to any one of [1] to

[18] , wherein the hydroxyl value of the composition (X) is 5 mgKOH / g to 40 mgKOH / g.

[0045]

[20] An inkjet ink composition containing the photocurable composition (Z) according to any one of [1] to

[19] .

[0046]

[21] An active energy ray-curable ink composition comprising the inkjet ink composition according to

[20] .

[0047]

[22] A cured product obtained by photocuring the photocurable composition (Z) according to any one of [1] to

[19] , the inkjet ink composition according to

[20] , or the active energy ray-curable ink composition according to

[21] .

[0048]

[23] A cured product obtained by photocuring the photocurable composition (Z) according to any one of [1] to

[19] , the inkjet ink composition according to

[20] , or the active energy ray-curable ink composition according to

[21] and then thermally curing it.

[0049]

[24] An electronic component comprising the hardened material according to

[22] or

[23] .

[0050] Effects of the Invention

[0051] The photocurable composition (Z) of the present invention comprises a composition (X) containing a monofunctional acrylic monomer (A) and a polyfunctional acrylic monomer (B) to which an ion scavenger (Y) is added. The addition of the ion scavenger (Y) suppresses the generation of cations and anions that cause ion migration, fundamentally resolving the problem of ion migration. Furthermore, by adjusting the hydroxyl value of the composition (X), the resulting cured product can improve its ion migration resistance and adhesion to various substrates. DETAILED DESCRIPTION

[0052] First, the photocurable composition (X) (hereinafter also referred to as "composition (X)") is described. Composition (X) is a composition containing a monofunctional acrylic monomer (A) (hereinafter also referred to as "component (A)" or simply "(A)") and a polyfunctional acrylic monomer (B) (hereinafter also referred to as "component (B)" or simply "(B)"). Components (A) and (B) are compounds having a hydroxyl value of less than 100 mgKOH / g.

[0053] The content of component (A) in composition (X) is 40 to 80% by weight relative to 100% by weight of composition (X), and the content of component (B) is 10 to 50% by weight relative to 100% by weight of composition (X).

[0054] Components (A) and (B) in composition (X) contribute to improved ejection properties and photocurability when used as an inkjet ink, and also contribute to improved heat resistance and adhesion to substrates, particularly silicon substrates, glass substrates, or substrates on which conductors such as metal wiring and electrodes are formed.

[0055] The composition (X) itself preferably has a hydroxyl value adjusted to 1 to 100 mgKOH / g. This improves the ion migration resistance and adhesion to various substrates of the cured product obtained by curing the composition (X). From the perspective of producing a cured product with excellent ion migration resistance, the hydroxyl value of the composition (X) itself is more preferably 2 to 40 mgKOH / g, and even more preferably 5 to 40 mgKOH / g.

[0056] In order to adjust the hydroxyl value of composition (X) to a range of 1 to 100 mgKOH / g, for example, a component having a hydroxyl value of 1 mgKOH / g or more may be used as either component (A) or component (B), or both. Alternatively, a radically polymerizable compound (C) having a hydroxyl value of 100 to 300 mgKOH / g (hereinafter also referred to as "component (C)" or simply "(C)") may be used as a hydroxyl value adjuster.

[0057] When component (C) is used in composition (X), a part or all of component (A) may be component (C), a part or all of component (B) may be component (C), and component (C) may be contained as a radically polymerizable compound other than component (A) and component (B).

[0058] [Monofunctional acrylic monomer (A)]

[0059] The composition (X) contains a monofunctional acrylic monomer (A). Component (A) improves the ejectability of the photocurable composition (Z) when used as an ink. Furthermore, component (A) is a component with excellent photocurability and is suitable for forming a cured product with an excellent balance between heat resistance and adhesion to the substrate. From these viewpoints, the content of component (A) is preferably 40% to 80% by weight, and more preferably 50% to 75% by weight, relative to 100% by weight of the composition (X).

[0060] From the perspective of achieving good heat resistance and adhesion to substrates, particularly glass and silicon substrates, or substrates on which conductors such as metal wiring and electrodes are formed, component (A) preferably contains a (meth)acrylate having one or more of the group consisting of a condensed cyclic hydrocarbon group, a polycyclic hydrocarbon group, and a monocyclic hydrocarbon group. Examples of the monofunctional acrylic monomer having a condensed cyclic hydrocarbon group or a polycyclic hydrocarbon group include (a-1) and (a-2) a monofunctional polymerizable monomer having a monocyclic hydrocarbon group.

[0061] In this specification, “(meth)acrylate” refers to both or either acrylate and methacrylate, and “(meth)acryloyl” refers to both or either acryloyl and methacryloyl.

[0062] [Monofunctional acrylic monomer (a-1) having a condensed cyclic hydrocarbon group or a polycyclic hydrocarbon group]

[0063] The monofunctional acrylic monomer (a-1) having a condensed cyclic hydrocarbon group or a polycyclic hydrocarbon group is not particularly limited, but is preferably a monofunctional acrylic monomer containing an organic group having 7 to 50 carbon atoms and having a condensed cyclic hydrocarbon group or a polycyclic hydrocarbon group, and more preferably a monofunctional acrylic monomer containing an organic group having 7 to 30 carbon atoms and having a condensed cyclic hydrocarbon group or a polycyclic hydrocarbon group.

[0064] In addition, the "monofunctional acrylic monomer" refers to a monomer having one (meth)acryloyl group in one molecule.

[0065] In addition, the so-called "condensed cyclic hydrocarbon group" is a hydrocarbon (comprising carbon atoms and hydrogen atoms) group having two or more rings, and refers to a hydrocarbon group having at least one carbon atom constituting a certain ring and also constituting other rings. The so-called "polycyclic hydrocarbon group" is a hydrocarbon group having two or more rings, and refers to a hydrocarbon group in which one ring is bonded to other rings by a single bond or an alkylene group having 1 to 10 carbon atoms.

[0066] Furthermore, the "organic group having 7 to 50 carbon atoms and having a condensed cyclic hydrocarbon group or a polycyclic hydrocarbon group" refers to, for example, the organic group containing n-(meth)acryloyl groups other than the (meth)acryloyl group in the compound represented by the formula (1). A Repeating units and R 2 The base.

[0067] As the monomer (a-1), it is preferable to use a compound represented by the formula (1) in terms of obtaining a cured product having excellent heat resistance and adhesion to a substrate.

[0068] In the formula (1), R 2 It is a monovalent organic group having 4 to 30 carbon atoms and having a condensed cyclic hydrocarbon group or a polycyclic hydrocarbon group, preferably a non-polar monovalent organic group having 4 to 30 carbon atoms and having a condensed cyclic hydrocarbon group or a polycyclic hydrocarbon group, and more preferably a group represented by any one of the formulae (2) to (5). A , preferably 0 or 1.

[0069] In the above formulas (2) to (5), R 3 , preferably hydrogen. Furthermore, * is a bonding bond, and is bonded to the O- at the right end of the formula (1).

[0070] The monomer (a-1) is preferably at least one compound selected from the following compound group (I).

[0071] [Chemistry 5]

[0072]

[0073] Among these, considering the adhesion between the obtained cured product and the substrate and the heat resistance, the following compounds (11) to (20) are more preferred, and compound (11) and compound (17) are even more preferred.

[0074] [Chemistry 6]

[0075]

[0076]

[0077] The monomer (a-1) may be one compound selected from the above compounds, or a mixture of two or more thereof. Preferably, it is a mixture of compound (11) and compound (17). When the two are used in combination, the weight ratio of compound (11):compound (17) is preferably 5:10 to 10:5, more preferably 7:10 to 10:7, and even more preferably 9:10 to 10:9.

[0078] As the monomer (a-1), a compound produced by a known method can be used. In addition, the following commercially available products can also be used: dicyclopentanyl acrylate (trade name: FANCRYL FA-513AS: Hitachi Chemical Industries, Ltd.), dicyclopentanyl methacrylate (trade name: FANCRYL FA-513M: Hitachi Chemical Industries, Ltd.), dicyclopentenyl acrylate (trade name: FANCRYL FA-511AS: Hitachi Chemical Industries, Ltd.), dicyclopentenyl methacrylate (trade name: FANCRYL FA-511M: Hitachi Chemical Industries, Ltd.), Chemical Industries, Ltd.), dicyclopentenyloxyethyl acrylate (trade name; FANCRYL FA-512AS: Hitachi Chemical Industries, Ltd.), dicyclopentenyloxyethyl methacrylate (trade name; FANCRYL FA-512M: Hitachi Chemical Industries, Ltd.), isobornyl acrylate (trade name; IB-XA: Kyoeisha Chemical Co., Ltd.), isobornyl methacrylate (trade name; IBXMA: Kyoeisha Chemical Co., Ltd.), and 1-adamantyl methacrylate (trade name; Adamantate M-104: Idemitsu Kosan Co., Ltd.), etc.

[0079] [Monofunctional polymerizable monomer having a monocyclic hydrocarbon group (a-2)]

[0080] The "monocyclic hydrocarbon group" refers to a hydrocarbon group having one ring (including an aromatic ring).

[0081] As the monomer (a-2), a compound produced by a known method can be used. In addition, commercially available products such as benzyl acrylate, cyclohexyl acrylate (trade name: V#155: Osaka Organic Chemical Industry Co., Ltd.), and cyclohexyl methacrylate (trade name: Light Ester CH: Kyoeisha Chemical Co., Ltd.) can also be used.

[0082] [Multifunctional acrylic monomer (B)]

[0083] Composition (X) contains a polyfunctional acrylic monomer (B). A "polyfunctional acrylic monomer" refers to a monomer having two or more (meth)acryloyl groups in one molecule. When component (B) is used, the amount of component (B) can be, for example, 10% to 50% by weight relative to 100% by weight of the total weight of composition (X).

[0084] Specific examples of the component (B) include tricyclodecane dimethanol di(meth)acrylate, bisphenol F ethylene oxide-modified di(meth)acrylate, bisphenol A ethylene oxide-modified di(meth)acrylate, isocyanuric acid ethylene oxide-modified di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, pentaerythritol di(meth)acrylate, dipentaerythritol di(meth)acrylate, pentaerythritol di(meth)acrylate, and dipentaerythritol di(meth)acrylate. Ester monostearate, trimethylolpropane di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,4-cyclohexanedimethanol di(meth)acrylate, 2-n-butyl-2-ethyl-1,3-propanediol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tri(meth)acrylate Ester, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, trimethylolpropane tri(meth)acrylate, ethylene oxide modified trimethylolpropane tri(meth)acrylate, propylene oxide modified trimethylolpropane tri(meth)acrylate, epichlorohydrin modified trimethylolpropane tri(meth)acrylate, glycerol tri(meth)acrylate, ethylene oxide modified glycerol tri(meth)acrylate, propylene oxide Alkane-modified glycerol tri(meth)acrylate, epichlorohydrin-modified glycerol tri(meth)acrylate, di-trimethylolpropane tetra(meth)acrylate, diglycerol tetra(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate, ethylene oxide-modified phosphoric acid tri(meth)acrylate, tris[(meth)acryloyloxyethyl]isocyanurate, caprolactone-modified tris[(meth)acryloyloxyethyl]isocyanurate, and the compound represented by formula (6).

[0085] From the viewpoint of improving the ion migration resistance of the cured product formed from the photocurable composition (Z), it is preferred that R in the formula (6) 5 is a compound represented by any one of the formulas (7) to (10), more preferably a compound represented by the formula (7). B , preferably 0 or 1.

[0086] Component (B) may be one compound selected from the above-mentioned compounds, etc., or a mixture of two or more thereof.

[0087] Component (B) improves the light curing properties of the composition (X). Furthermore, component (B) is suitable for forming a cured product with an excellent balance of heat resistance and adhesion to substrates. From these viewpoints, the content of component (B) is preferably 10% to 50% by weight, more preferably 13% to 30% by weight, and even more preferably 15% to 25% by weight, relative to 100% by weight of the composition (X).

[0088] [Radical polymerizable compound (C)]

[0089] From the perspective of improving the ion migration resistance of the cured product of composition (X) itself and its adhesion to various substrates, the hydroxyl value of composition (X) is preferably adjusted to 1 mgKOH / g to 100 mgKOH / g. To achieve this adjustment, a radically polymerizable compound (C) having a hydroxyl value of 100 mgKOH / g to 300 mgKOH / g can be used. When component (C) is used, it may be part or all of component (A), part or all of component (B), or a radically polymerizable compound other than component (A) and component (B) may be included. Component (C) may be used alone or as a mixture of two or more.

[0090] When a radically polymerizable compound (C) is used in addition to the components (A) and (B), the component (C) functions as a hydroxyl value adjuster. Therefore, as the components (A) and (B), a compound having a lower hydroxyl value than the component (C) can be used, or a compound having no hydroxyl group can be used.

[0091] In this embodiment, the composition (X) may include, for example, a monofunctional acrylic monomer without a hydroxyl group as component (A), or a polyfunctional acrylic monomer without a hydroxyl group as component (B), and a radically polymerizable compound having a hydroxyl group as component (C) to adjust the hydroxyl value of the entire composition (X). In this case, from the perspective of forming a cured product with excellent ion migration resistance, the content of component (C) is preferably 0.1% to 30% by weight, more preferably 0.3% to 25% by weight, and even more preferably 0.5% to 20% by weight, relative to 100% by weight of the composition (X).

[0092] When the amount of component (C) is within the above range, the hydroxyl value of composition (X) can be easily adjusted to the specified range. The hydroxyl value of component (C) is preferably 100 mgKOH / g to 300 mgKOH / g, more preferably 150 mgKOH / g to 200 mgKOH / g.

[0093] From the perspective of forming a cured product with excellent ion migration resistance, component (C) preferably contains an acrylic oligomer. The weight average molecular weight of component (C) is preferably 100 to 5,000, more preferably 300 to 3,000, and even more preferably 500 to 1,500. From the same perspective, the glass transition point (Tg) of the radically polymerizable compound (C) is preferably 85°C or higher, more preferably 90°C or higher.

[0094] [Photopolymerization initiator (D)]

[0095] The composition (X) may further contain a photopolymerization initiator (D).

[0096] The photopolymerization initiator may be any compound that can initiate polymerization of the monomer components contained in the composition (X) and generate free radicals upon irradiation with ultraviolet rays, visible light, electromagnetic waves, etc., and commonly used photopolymerization initiators may be used. Specific examples of photopolymerization initiators include benzophenone, Michler's ketone, ketone), 4,4'-bis(diethylamino)benzophenone, xanthone, thioxanthone, isopropyl xanthone, 2,4-diethylthioxanthone, 2-ethylanthraquinone, acetophenone, 2-hydroxy-2-methylpropiophenone, 2-hydroxy-2-methyl-4'-isopropylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, isopropyl benzoin ether, isobutyl benzoin ether, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1,1'-(methylene-di-4,1-phenylene)bis(2-hydroxy-2-methyl-1-propanone), camphorquinone, benzanthrone, 2-methyl-1-[4-(methylthio)phenyl] -2-morpholinopropane-1-one, 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4-morpholinophenyl)butan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,4-dimethylaminobenzoic acid ethyl ester, 4-dimethylaminobenzoic acid isopentyl ester, 4,4'-di(tert-butylperoxycarbonyl)benzophenone, 3,4,4'-tri(tert-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2-(4'-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(3',4'-dimethoxyphenyl)- 4,6-bis(trichloromethyl)-s-triazine, 2-(2',4'-dimethoxyphenylvinyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(2'-methoxyphenylvinyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4'-pentyloxyphenylvinyl)-4,6-bis(trichloromethyl)-s-triazine, 4-[p-N,N-bis(ethoxycarbonylmethyl)]-2,6-bis(trichloromethyl)-s-triazine, 1,3-bis(trichloromethyl)-5-(2'-chlorophenyl)-s-triazine, 1,3-bis(trichloromethyl)-5-(4'-methoxyphenyl)-s-triazine, 2-(p-dimethylaminophenylvinyl) benzoxazole, 2-(p-dimethylaminophenyl)benzothiazole, 2-mercaptobenzothiazole, 3,3'-carbonylbis(7-diethylaminocoumarin), 2-(o-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(4-ethoxycarbonylphenyl)-1,2'-biimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4-dibromophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4-dibromophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole,4,6-trichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 3-(2-methyl-2-dimethylaminopropionyl)carbazole, 3,6-bis(2-methyl-2-morpholinylpropionyl)-9-n-dodecylcarbazole, bis(η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium, 3,3',4,4 '-Tetra(tert-butylperoxycarbonyl)benzophenone, 3,3',4,4'-tetra(tert-hexylperoxycarbonyl)benzophenone, 3,3'-bis(methoxycarbonyl)-4,4'-bis(tert-butylperoxycarbonyl)benzophenone, 3,4'-bis(methoxycarbonyl)-4,3'-bis(tert-butylperoxycarbonyl)benzophenone, 4,4'-bis(methoxycarbonyl)-3,3'-bis(tert-butylperoxycarbonyl)benzophenone, etc. Examples of commercially available products include Irgacure 379EG, Irgacure 127, and Irgacure 184 manufactured by BASF, and Omnirad 379EG, Omnirad 127, and Omnirad 184 manufactured by IGM Resins BV. Among these, 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4-morpholinophenyl)butan-1-one is preferred.

[0097] From the perspective of forming a cured product with good ion migration resistance, the content of the photopolymerization initiator (D) is preferably 5 to 15% by weight, more preferably 7 to 12% by weight, relative to 100% by weight of the composition (X). The photopolymerization initiator (D) may be a single compound or a mixture of two or more compounds.

[0098] [Ion scavenger (Y)]

[0099] In the present invention, an ion scavenger (Y) is further added to the composition (X) to prepare a photocurable composition (Z). The ion scavenger (Y) used in the composition (X) has at least one selected from the group consisting of Zr (zirconium), Bi (bismuth), Mg (magnesium) and Al (aluminum). The so-called "ion scavenger" refers to a substance that can capture ions, and there is no particular limitation as long as it has the function of capturing at least one of cations and anions. In the present invention, the ions to be captured are ions introduced into the photocurable composition (Z) that reacts by irradiation with light, electron beams, etc. and changes its solubility in the solvent, such as sodium ions (Na + ), chloride ion (Cl - ), bromide ion (Br - ), copper ions (Cu + 、Cu2+ ) plasma, and by capturing these ions, electrical insulation and electrical corrosion resistance are improved.

[0100] Examples of such ion capture agents that capture ions include cation capture agents that capture cations, anion capture agents that capture anions, and two-ion capture agents that capture cations and anions.

[0101] (Cation scavenger)

[0102] Examples of cation scavengers for catching cations include inorganic ion exchangers such as metal oxides of zirconium phosphate, zirconium tungstate, zirconium molybdate, zirconium antimonate, zirconium selenate, zirconium tellurate, zirconium silicate, zirconium phosphosilicate, and zirconium polyphosphate. Examples of these cation scavengers (also referred to as "inorganic ion exchangers") include IXE-100 (Zr-containing compound) and IXE-150 (Zr-containing compound) marketed by Toagosei Co., Ltd.

[0103] (Anion Scavenger)

[0104] Examples of anion scavengers for capturing anions include inorganic ion exchangers such as bismuth oxide hydrate and hydrotalcites. Examples of these anion scavengers (also referred to as "inorganic ion exchangers") include IXE-500 (Bi-containing compound), IXE-530 (Bi-containing compound), IXE-550 (Bi-containing compound), IXE-700 (Mg- and Al-containing compound), IXE-700F (Mg- and Al-containing compound), IXE-770D (Mg- and Al-containing compound), IXE-702 (Al-containing compound), and IXE-800 (Zr-containing compound), all of which are marketed by Toagosei Co., Ltd.

[0105] (Two-ion capture agent)

[0106] Examples of two-ion scavengers that capture cations and anions include inorganic ion exchangers such as hydrous metal oxides such as alumina hydrate and zirconium oxide hydrate. Furthermore, these two-ion scavengers (also referred to as "inorganic ion exchangers") include IXE-1320 (a compound containing Mg and Al), IXE-600 (a compound containing Bi), IXE-633 (a compound containing Bi), IXE-680 (a compound containing Bi), IXE-6107 (a compound containing Zr and Bi), IXE-6136 (a compound containing Zr and Bi), IXEPLAS-A1 (a compound containing Zr, Mg, and Al), IXEPLAS-A2 (a compound containing Zr, Mg, and Al), and IXEPLAS-B1 (a compound containing Zr and Bi) marketed by Toagosei Co., Ltd.

[0107] In the present invention, the component (Y) may be used alone or in combination with the cation scavenger, anion scavenger, and two ion scavenger. + 、Cl - Br - 、Cu + 、Cu 2+ It is preferable to use a two-ion scavenger that functions independently of the cation and the anion.

[0108] From the viewpoint of improving electrical insulation and electrical corrosion resistance, the amount of the ion scavenger (Y) added is preferably 0.1 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, and even more preferably 0.5 to 2 parts by weight, relative to 100 parts by weight of the composition (X).

[0109] A dispersant may be further added to the composition (X) for the purpose of improving the dispersibility of the ion scavenger (Y). The dispersant that can be used is not limited and can be appropriately selected based on the dispersibility of the ion scavenger (Y) and the effect on the adhesion between the photocurable composition (Z) and the substrate.

[0110] When a dispersant is added, the amount of the dispersant added is preferably 0.1 to 100 parts by weight, more preferably 0.1 to 50 parts by weight, based on 100 parts by weight of the ion scavenger (Y). From the perspective of sufficiently dispersing the ion scavenger (Y) and maintaining good printability, the amount is preferably 0.1 parts by weight, while from the perspective of fully utilizing the ion-capturing function of the ion scavenger (Y), the amount is preferably 100 parts by weight or less.

[0111] [Inkjet ink composition, active energy ray-curable ink composition]

[0112] When the photocurable composition (Z) of the present invention is used as an inkjet ink composition, the viscosity at 25° C. is preferably 1 to 150 mPa·s, more preferably 3 to 70 mPa·s, from the viewpoint of improving discharge properties.

[0113] The present invention can also be implemented as an inkjet ink composition containing the photocurable composition (Z) of the present invention, or an active energy ray-curable ink composition containing the inkjet ink composition. The term "active energy ray" herein refers to energy rays that can decompose a compound that generates active species to generate active species. Examples of such active energy rays include light energy rays such as visible light, ultraviolet light, infrared light, X-rays, α-rays, β-rays, γ-rays, and electron beams.

[0114] In order to improve various properties, the photocurable composition (Z) of the present invention may contain other components such as a flame retardant, a resin containing a phenolic hydroxyl group, a melamine resin, an epoxy compound, an oxetane compound, a hardener, a surfactant, a colorant, a polymerization inhibitor, and a solvent, within a range that does not impair the effects of the present invention.

[0115] [Hardened material]

[0116] The cured product of the present invention is obtained by photocuring the photocurable composition (Z) of the present invention.

[0117] When the photocurable composition (Z) of the present invention is used as an inkjet ink, a cured product can be produced by a method including the following steps 1 and 2.

[0118] (Step 1) A step of applying the photocurable composition (Z) of the present invention on a substrate by an inkjet method to form a coating film

[0119] (Step 2) A step of irradiating the coating film obtained in step 1 with light to cure the coating film and form a cured product on the substrate.

[0120] The inkjet method is not particularly limited, and a known inkjet method can be used. The substrate is not particularly limited as long as it can be coated with the ink of the present invention, and its shape is not limited to a flat plate, and may be curved.

[0121] In addition, although the substrate is not particularly limited, examples thereof include: polyester resin substrates including polyethylene terephthalate (PET) and polybutylene terephthalate (PBT); polyolefin resin substrates including polyethylene and polypropylene; organic polymer films including polyvinyl chloride, fluororesin, acrylic resin, polyamide, polycarbonate and polyimide; cellophane; metal foil; a laminated film of polyimide and metal foil; transparent paper (glassine paper) with a sealing effect, parchment paper, paper treated with sealing using polyethylene, clay adhesive, polyvinyl alcohol, starch or carboxymethyl cellulose (CMC); silicon substrate; and glass substrate.

[0122] By using the inkjet method, the ink of the present invention can be easily applied in a predetermined pattern, and a uniform pattern can be formed on a large substrate.

[0123] The temperature during discharge from an inkjet coating device is preferably 10 to 120° C. The viscosity of the ink of the present invention at this temperature is preferably 1 to 30 mPa·s, more preferably 2 to 25 mPa·s, and even more preferably 3 to 20 mPa·s.

[0124] When using an ink with a viscosity exceeding 30 mPa·s at 25°C, the viscosity of the ink can be reduced by heating the inkjet head during ejection, thereby achieving more stable ejection. When ejecting using a heated inkjet head, the heating temperature is preferably 40°C to 120°C. When using a heated inkjet head, it is preferable to use an ink that does not contain a solvent.

[0125] The thickness of the obtained coating film can be appropriately selected depending on the intended use, and is preferably 1 μm to 20 μm, and more preferably 5 μm to 15 μm.

[0126] When irradiating with ultraviolet rays or visible rays, the exposure dose can be appropriately adjusted according to the composition of the photocurable composition (Z) of the present invention. When measured using an ultraviolet monitor ("UV-Pad" manufactured by Opsytec, wavelength: UV-A (315 nm-400 nm)), it is preferably 100 to 10,000 mJ / cm 2 More preferably, 150 to 5,000 mJ / cm 2 About 180 to 3,000 mJ / cm 2 About 200 to 2,000 mJ / cm 2 The wavelength of the ultraviolet rays or visible rays to be irradiated is preferably 200 to 500 nm, more preferably 300 to 450 nm.

[0127] Furthermore, an exposure machine can be used for light irradiation, which is preferably equipped with a UV-light emitting diode (LED) lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, a halogen lamp or a black light lamp, and is a device that irradiates ultraviolet rays or visible light in the range of 200nm to 500nm.

[0128] The cured product cured by light irradiation may be further heated and calcined as needed. Generally, heating and calcining at 80 to 250° C. for 10 to 60 minutes can produce a stronger cured product.

[0129] The thickness of the cured product of the present invention can be appropriately selected depending on the intended use, and is preferably 1 μm to 20 μm, and more preferably 5 μm to 15 μm.

[0130] From the perspective of producing highly reliable electronic circuit boards, etc., the glass transition temperature of the cured product of the present invention, as measured using a DMS6000 (Hitachi High-Technologies Co., Ltd.), is preferably 85°C or higher, and more preferably 90°C to 150°C. As a reliability test for electronic circuit boards, a voltage-applied insulation resistance test (hereinafter referred to as an ion migration resistance test) is sometimes performed under a constant temperature and humidity environment. In this ion migration resistance test, a specific voltage is applied for a specific time under a specific constant temperature and humidity environment, and the resistance value at that time is checked for abnormalities. In particular, evaluation is often performed at high temperatures of 85 to 130°C. Therefore, in order to obtain highly reliable electronic circuit boards, etc., it is ideal that the glass transition temperature of the cured product is within this range.

[0131] The cured product of the present invention exhibits excellent heat resistance, adhesion to substrates, and ion migration resistance, making it suitable for use as protective films or insulating films for display elements such as liquid crystal displays and electroluminescent (EL) displays, printed wiring boards, flexible wiring boards, semiconductor package substrates, and electronic circuit boards such as solar cell substrates. Furthermore, the cured product of the present invention can be suitably used as a coverlay film or solder resist for protecting conductors such as metal wiring and electrodes that form a predetermined circuit pattern.

[0132] [Electronic components]

[0133] The electronic component of the present invention preferably comprises the cured product of the present invention and is produced by a method comprising steps 1 and 2. Since the cured product of the present invention exhibits excellent heat resistance, adhesion to substrates, and ion migration resistance, the electronic component of the present invention exhibits excellent electrical properties and long-term reliability.

[0134] Example

[0135] Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.

[0136] The following components were used in the Examples and Comparative Examples. The following symbols are used to represent each component as appropriate.

[0137] [Monofunctional acrylic monomer (A)]

[0138] FA-513AS: Dicyclopentanyl acrylate (trade name: Fancryl FA-513AS, Hitachi Chemical Industries, Ltd., hydroxyl value 0 mgKOH / g, homopolymer glass transition point (Tg) 120°C)

[0139] FA-513M: Dicyclopentanyl methacrylate (trade name: Fancryl FA-513M, Hitachi Chemical Industries, Ltd., hydroxyl value 0 mgKOH / g, homopolymer glass transition point (Tg) 175°C)

[0140] IB-XA: Isobornyl acrylate (trade name: IB-XA, Kyoeisha Chemical Co., Ltd., hydroxyl value 0 mgKOH / g, Tg 97°C)

[0141] CHMA: Cyclohexyl methacrylate (trade name: CH, Kyoeisha Chemical Co., Ltd., hydroxyl value 0 mgKOH / g, Tg 65°C)

[0142] [Multifunctional acrylic monomer (B)]

[0143] IRR214-K: Tricyclodecane dimethanol diacrylate (hydroxyl value 0 mgKOH / g, Tg 190°C)

[0144] [Radical polymerizable compound (C)]

[0145] OT-2503: Acrylic acid oligomer (ARONIX OT-2503; trade name, Toa Gosei Co., Ltd., weight average molecular weight 1,000, hydroxyl value 172 mgKOH / g, Tg 94°C)

[0146] [Photopolymerization initiator (D)]

[0147] Irg379: 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4-morpholinophenyl)butan-1-one (IRGACURE 379; trade name, BASF JAPAN)

[0148] [Ion scavenger (Y)]

[0149] IXEPLAS-A1: Two-ion scavenger (trade name: IXEPLAS-A1, Toagosei Co., Ltd., a compound containing Zr, Mg, and Al)

[0150] IXEPLAS-A2: Two-ion scavenger (trade name: IXEPLAS-A2, Toagosei Co., Ltd., a compound containing Zr, Mg, and Al)

[0151] <Example 1>

[0152] <Preparation of Composition 1>

[0153] The following components (A), (B), (C), (D), and (Y) were mixed and dissolved to obtain a composition 1.

[0154]

[0155] <Fabrication of substrate 1>

[0156] Composition 1 was spin-coated at 620 rpm onto a substrate with a facing comb-shaped electrode pattern (manufactured by Connectec Japan, L / S = approximately 30 μm / 40 μm). The substrate was then irradiated with a UV-LED transfer device "LSS-08A" (manufactured by Sun-Energy, lamp wavelength 365 nm) at 5,000 mJ / cm 2 The substrate was then irradiated with ultraviolet light of 365 nm for photocuring after a UV exposure dose of 100 nm (measured using a UV monitor ("UV-Pad") manufactured by Opsytec, wavelength: UV-A (315 nm-400 nm). The substrate was then heated and calcined in a clean oven DT-610 (manufactured by Yamato Scientific Co., Ltd.) at 200°C for 60 minutes to obtain a cured product having a thickness of 16 μm. Furthermore, the film thickness of the cured product on the opposing comb-shaped electrodes was measured using a laser microscope VK-X100 (manufactured by KEYENCE Co., Ltd.).

[0157] <Examples 2 to 4, Comparative Example 1>

[0158] Compositions 2 to 5 were prepared in the same manner as in Example 1 except that the components of Example 1 were changed to those shown in Table 1. Substrates 2 to 5 were prepared in the same manner as in Example 1 using the obtained compositions 2 to 5.

[0159] (Ion migration resistance test)

[0160] The ion migration resistance (IMG (ion migration) resistance) of the substrates (1 to 5) obtained above was evaluated by the following method.

[0161] The obtained substrate was connected to the ion migration tester MIG-87 (manufactured by IMV Co., Ltd.) using wiring and placed in a highly accelerated life tester EHS-411 (manufactured by Espec Co., Ltd.). Then, a DC voltage of 100 V was applied to the opposing comb-shaped electrode patterns for 96 hours under an environment of 130°C×100%.

[0162] (Evaluation Criteria)

[0163] IMG resistance: resistance value of the facing comb-shaped electrode pattern after 96 hours

[0164] ○: Resistance value is displayed as 1×106 Ω or above

[0165] ×: The resistance value is displayed as less than 1×10 6 Ω

[0166] Electrode discoloration: The electrode was observed for discoloration after 96 hours using a laser microscope VK-X100 (manufactured by KEYENCE Co., Ltd.).

[0167] ○: No discoloration of the electrode

[0168] ×: Electrode discoloration

[0169] The Tg of the cured product was calculated using the Fox equation based on the weight ratio of each component. The hydroxyl value of the composition (X) was calculated based on the hydroxyl value of each component. The viscosity of the photocurable composition (Z) was measured at 25°C using an E-type viscometer (TV-22, manufactured by Toki Sangyo Co., Ltd., hereinafter referred to as the same).

[0170] [Table 1]

[0171]

[0172] As shown in Table 1, the inclusion of an ion scavenger (Y) improves the ion migration resistance (hereinafter, appropriately referred to as "IMG resistance") of the cured product in the temperature range of 100°C or higher. These results indicate that the ion scavenger (Y) effectively captures ions that reduce IMG resistance in order to improve IMG resistance. Comparative Example 1, which does not contain an ion scavenger (Y), exhibits low IMG resistance, suggesting that one of the reasons for this is the failure to capture ions that reduce IMG resistance.

[0173] Industrial applicability

[0174] The photocurable composition of the present invention can form a cured product that exhibits excellent reliability in a high-temperature, constant-humidity environment, particularly excellent ion migration resistance in a temperature range of 100°C or higher. Therefore, the composition can be suitably used in the production of electronic circuit boards such as display devices, printed wiring boards, flexible wiring boards, semiconductor package substrates, and solar cell substrates.

Claims

1. A photocurable composition (Z), wherein an ion scavenger (Y) is added to a composition (X) containing a monofunctional acrylic monomer (A) and a polyfunctional acrylic monomer (B), wherein The content of the monofunctional acrylic monomer (A) is 40 to 80% by weight relative to 100% by weight of the composition (X). The content of the multifunctional acrylic monomer (B) is 10 to 50% by weight relative to 100% by weight of the composition (X). The hydroxyl value of the composition (X) is 1 to 100 mgKOH / g. 2 . The photocurable composition (Z) according to claim 1 , wherein the amount of the ion scavenger (Y) added is 0.1 to 10 parts by weight based on 100 parts by weight of the composition (X). The photocurable composition (Z) according to claim 1 or 2, wherein the ion scavenger (Y) is an inorganic particle. The photocurable composition (Z) according to claim 1 or 2, wherein the ion scavenger (Y) is an inorganic particle containing any one of a zirconium compound, a magnesium compound, and an aluminum compound. The photocurable composition (Z) according to claim 1 or 2, wherein the ion scavenger (Y) is a mixture of a zirconium compound, a magnesium compound, and an aluminum compound. 6 . The photocurable composition (Z) according to claim 1 , further comprising a radically polymerizable compound (C) having a hydroxyl value of 100 to 300 mgKOH / g in the composition (X). 7 . The photocurable composition (Z) according to claim 6 , wherein the radical polymerizable compound (C) has a weight average molecular weight of 100 to 5,000. 8 . The photocurable composition (Z) according to claim 6 , wherein the content of the radically polymerizable compound (C) is 0.1 to 30% by weight relative to 100% by weight of the composition (X). 9 . The photocurable composition (Z) according to claim 6 , wherein the radical polymerizable compound (C) has a hydroxyl value of 150 to 200 mgKOH / g. 10 . The photocurable composition (Z) according to claim 6 , wherein the radical polymerizable compound (C) is an acrylic oligomer. The photocurable composition (Z) according to claim 1 or 2, wherein the monofunctional acrylic monomer (A) contains a (meth)acrylate having one or more selected from the group consisting of a condensed cyclic hydrocarbon group, a polycyclic hydrocarbon group, and a monocyclic hydrocarbon group.

12. The photocurable composition (Z) according to claim 11, wherein the monofunctional acrylic monomer (A) is a monofunctional acrylic monomer represented by the following formula (1): In formula (1), R 1 is hydrogen or methyl, R 2 is a monovalent organic group having 4 to 30 carbon atoms and having a condensed cyclic hydrocarbon group, a polycyclic hydrocarbon group or a monocyclic hydrocarbon group, n A An integer from 0 to 10.

13. The photocurable composition (Z) according to claim 12, wherein R in the formula (1) 2 is a group represented by any one of the following formulas (2) to (5), In formulas (2) to (5), R 3 Each independently represents hydrogen or an alkyl group having 1 to 6 carbon atoms, and * represents a bonding bond.

14. The photocurable composition (Z) according to claim 1 or 2, wherein the multifunctional acrylic monomer (B) is a difunctional acrylic monomer represented by the following formula (6): In formula (6), R 4 are independently hydrogen or methyl, R 5 is a divalent organic group having 4 to 30 carbon atoms and having a condensed cyclic hydrocarbon group, a polycyclic hydrocarbon group or a monocyclic hydrocarbon group, n B Each independently represents an integer from 0 to 10.

15. The photocurable composition (Z) according to claim 14, wherein R in the formula (6) 5 is a group represented by any one of the following formulas (7) to (10), In formulas (7) to (10), * represents a bonding bond.

16. The photocurable composition (Z) according to claim 1 or 2, further comprising 5 to 15 wt% of a photopolymerization initiator (D) based on 100 wt% of the composition (X). The photocurable composition (Z) according to claim 1 or 2, which has a viscosity at 25°C of 1 to 100 mPa·s. 18 . The photocurable composition (Z) according to claim 1 , wherein the composition (X) has a hydroxyl value of 5 to 40 mgKOH / g. 19 . An inkjet ink composition comprising the photocurable composition (Z) according to claim 1 . 20 . An active energy ray-curable ink composition comprising the inkjet ink composition according to claim 19 .

21. A cured product obtained by photocuring the photocurable composition (Z) according to any one of claims 1 to 18, the inkjet ink composition according to claim 19, or the active energy ray-curable ink composition according to claim 20.

22. A cured product obtained by photocuring the photocurable composition (Z) according to any one of claims 1 to 18, the inkjet ink composition according to claim 19, or the active energy ray-curable ink composition according to claim 20 and then thermally curing the photocurable composition (Z).

23. An electronic component comprising the cured product according to claim 21 or 22.

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