(Meth)acrylate, curable resin composition, and cured product

Abstract

The purpose of the present invention is to provide: a novel (meth)acrylate that is a material for forming a cured product capable of maintaining, for a long period of time, a high insulation property under a high temperature and high humidity; a curable resin composition containing said (meth)acrylate; and a cured product obtained by curing the curable resin composition. The novel (meth)acrylate according to the present invention is represented by general formula (1) or (2). (In formula (1), R1-R4 each independently represent H or a methyl group, R5-R7 each independently represent a halogen group, an alkyl group, an alkoxy group, or an aromatic group, AO represents an ethyleneoxy group or a propyleneoxy group, m and n each independently represent an integer of 0-5, p represents an integer of 0-2, and r and s each independently represent an integer of 0-15.) (In formula (2), R1-R4 each independently represent H or a methyl group, R5-R7 each independently represent a halogen group, an alkyl group, an alkoxy group, or an aromatic group, AO represents an ethyleneoxy group or a propyleneoxy group, m and n each independently represent an integer of 0-5, p represents an integer of 0-2, and r and s each independently represent an integer of 0-15.)

Description

[Technical Field]

[0001] The present invention relates to a novel (meth)acrylate, a curable resin composition containing the (meth)acrylate, and a cured product obtained by curing the curable resin composition. [Background technology]

[0002] As electronic components have become smaller in recent years, the distance between wirings on circuit boards has become narrower, and the insulating properties of insulating films used between wirings have become increasingly important for miniaturizing electronic components.In particular, electronic components such as circuit boards are sometimes used in harsh environments such as high temperatures and high humidity, and insulating films used in electronic components are required to maintain high insulating properties even in such harsh environments.

[0003] Conventionally, photosensitive polyimides have been used as insulating films for the above applications, but the film-forming process involves applying heat at 300 to 400°C, which may degrade the performance of electronic components.

[0004] Furthermore, acrylic and epoxy photosensitive materials other than polyimide have the problem that they are prone to insulation deterioration when used in harsh environments such as high temperature and humidity.

[0005] Patent Document 1 describes a thermally conductive sheet that can realize a semiconductor device with high insulation reliability, which contains a thermosetting resin and an inorganic filler dispersed in the thermosetting resin, and which has a volume resistivity of 1.0 × 10 at 175°C when cured, as measured in accordance with JIS K6911 at an applied voltage of 1000V one minute after the voltage application. 8 A thermally conductive sheet having a thermal conductivity of Ω·m or more is disclosed.

[0006] Furthermore, Patent Document 2 discloses a photosensitive resin composition having high resistance and excellent light-shielding and insulating properties, which contains (a) an alkali-soluble resin, (b) a photopolymerizable monomer, (c) a photopolymerization initiator having a specific structure, and (d) high-resistivity carbon black as a coloring material. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] Japanese Patent Application Laid-Open No. 2015-146387 [Patent Document 2] International Publication No. 2019 / 065789 Summary of the Invention [Problem to be solved by the invention]

[0008] However, the thermally conductive sheet described in Patent Document 1 and the cured film obtained from the photosensitive resin composition described in Patent Document 2 cannot maintain high insulating properties for a long period of time under high temperature and high humidity conditions.

[0009] The present invention aims to provide a novel (meth)acrylate that is a material for forming a cured product that can maintain high insulating properties for a long period of time under high temperature and high humidity conditions, a curable resin composition containing the (meth)acrylate, and a cured product obtained by curing the curable resin composition. [Means for solving the problem]

[0010] As a result of extensive research aimed at solving the above-mentioned problems, the present inventors have found that the above-mentioned object can be achieved by the following novel (meth)acrylate, curable resin composition, and cured product, and have thus completed the present invention.

[0011] The present invention relates to a (meth)acrylate represented by the following general formula (1) or (2): [ka] (In the formula, R 1 ~R 4 are each independently H or a methyl group, and R 5 ~R 7are each independently a halogen group, an alkyl group, an alkoxy group, or an aromatic group; AO is an ethyleneoxy group or a propyleneoxy group; m and n are each independently an integer of 0 to 5; p is an integer of 0 to 2; and r and s are each independently an integer of 0 to 15. [ka] (In the formula, R 1 ~R 4 are each independently H or a methyl group, and R 5 ~R 7 are each independently a halogen group, an alkyl group, an alkoxy group, or an aromatic group; AO is an ethyleneoxy group or a propyleneoxy group; m and n are each independently an integer of 0 to 5; p is an integer of 0 to 2; and r and s are each independently an integer of 0 to 15.

[0012] The curable resin composition of the present invention contains at least one of the above-mentioned (meth)acrylates, a base polymer, a polymerization initiator, and a solvent.

[0013] The content of the (meth)acrylate in the curable resin composition is preferably 20 to 100 parts by mass relative to 100 parts by mass of the base polymer.

[0014] The curable resin composition preferably further contains a polyfunctional monomer and / or an epoxy resin.

[0015] The cured product of the present invention is obtained by curing the curable resin composition.

[0016] The water absorption rate of the cured product is preferably 1% or less. [Effects of the Invention]

[0017] The cured product obtained by curing the curable resin composition of the present invention uses the (meth)acrylate represented by the above general formula (1) and / or (2), and therefore has an extremely low water absorption rate and can maintain high insulating properties for a long period of time under high temperature and high humidity conditions. DETAILED DESCRIPTION OF THE INVENTION

[0018] <(Meth)acrylate represented by general formula (1) or (2)> The novel (meth)acrylate of the present invention is represented by the following general formula (1) or (2) (hereinafter, also collectively referred to as (meth)acrylate X). In the present invention, the term "(meth)acrylate" means an acrylate, a methacrylate, or a mixture thereof. The same applies to other compounds described similarly. [ka] (In the formula, R 1 ~R 4 are each independently H or a methyl group, and R 5 ~R 7 are each independently a halogen group, an alkyl group, an alkoxy group, or an aromatic group; AO is an ethyleneoxy group or a propyleneoxy group; m and n are each independently an integer of 0 to 5; p is an integer of 0 to 2; and r and s are each independently an integer of 0 to 15. [ka] (In the formula, R 1 ~R 4 are each independently H or a methyl group, and R 5 ~R 7 are each independently a halogen group, an alkyl group, an alkoxy group, or an aromatic group; AO is an ethyleneoxy group or a propyleneoxy group; m and n are each independently an integer of 0 to 5; p is an integer of 0 to 2; and r and s are each independently an integer of 0 to 15.

[0019] In the above formula, the halogen group is not particularly limited, and examples thereof include fluorine, chlorine, bromine, and iodine.

[0020] In the above formula, the alkyl group is not particularly limited and may be linear, branched, or cyclic, or may be a combination of these. The number of carbon atoms in the alkyl group is not particularly limited and is usually 1 to 10, preferably 1 to 5, and more preferably 1 to 3.

[0021] In the above formula, the alkoxy group is not particularly limited and may be linear, branched, or cyclic, or may be a combination of these. The number of carbon atoms in the alkoxy group is not particularly limited and is usually 1 to 10, preferably 1 to 5, and more preferably 1 to 3.

[0022] In the above formula, the aromatic group is not particularly limited and may be an aromatic hydrocarbon group or an aromatic heterocyclic group. The aromatic group may have a substituent.

[0023] In the above formula, AO is an ethyleneoxy group or a propyleneoxy group, and when m and n are integers of 2 or more, AO may be only an ethyleneoxy group, only a propyleneoxy group, or an ethyleneoxy group and a propyleneoxy group.

[0024] In the above formula, m and n each independently represent an integer of 0 to 5, preferably an integer of 0 to 3, more preferably 0 or 1, and even more preferably 0.

[0025] In the above formula, p is an integer of 0 to 2, preferably 0 or 1, and more preferably 0.

[0026] In the above formula, r and s each independently represent an integer of 0 to 15, preferably an integer of 0 to 10, more preferably an integer of 0 to 5, and even more preferably 0.

[0027] Examples of the (meth)acrylate represented by the above general formula (1) include (meth)acrylate represented by the following formula (3). [ka]

[0028] The (meth)acrylate represented by the above general formula (1) can be synthesized, for example, by reacting a compound represented by the following general formula (4) with (meth)acrylic anhydride in the presence of an alkali catalyst. [ka] (In the formula, R 5 ~R 7 , AO, m, n, p, r and s are the same as above.)

[0029] Examples of alkali catalysts include sodium amide, triethylamine, tributylamine, trioctylamine, pyridine, dimethylaminopyridine, N,N-dimethylaniline, 1,5-diazabicyclo[4,3,0]nonene-5 (DBN), 1,8-diazabicyclo[5,4,0]undecene-7 (DBU), sodium hydroxide, potassium hydroxide, sodium hydride, sodium phosphate, potassium phosphate, sodium carbonate, potassium carbonate, silver oxide, sodium methoxide, and potassium t-butoxide.

[0030] Examples of the (meth)acrylate represented by the above general formula (2) include (meth)acrylate represented by the following formula (5). [ka]

[0031] The (meth)acrylate represented by the above general formula (2) can be synthesized, for example, by reacting a compound represented by the following general formula (6) with (meth)acrylic anhydride in the presence of an alkali catalyst. [ka] (In the formula, R 5 ~R 7 , AO, m, n, p, r and s are the same as above.)

[0032] Examples of the alkali catalyst include those mentioned above.

[0033] <Curable resin composition> The curable resin composition of the present invention contains at least one of the (meth)acrylate X, a base polymer, a polymerization initiator, and a solvent.

[0034] The content of the (meth)acrylate X in the curable resin composition is not particularly limited, but from the viewpoint of reducing the water absorption rate of the obtained cured product and from the viewpoint of film-forming properties, it is preferably 20 to 100 parts by mass, more preferably 20 to 80 parts by mass, and even more preferably 20 to 40 parts by mass relative to 100 parts by mass of the base polymer.

[0035] The base polymer is not particularly limited, and examples thereof include poly(meth)acrylic resins, polyurethane resins, polyvinyl resins, polystyrene resins, polyethylene resins, polypropylene resins, polyimide resins, polyamide resins, polyacetal resins, polycarbonate resins, polyester resins, epoxy resins, phenol resins, urea resins, melamine resins, polyphenylene ether resins, polyphenylene sulfide resins, polyether sulfone resins, and polyether ether ketone resins, which can be used alone or in combination of two or more. Of these, it is preferable to use poly(meth)acrylic resins.

[0036] The monomers forming the poly(meth)acrylic resin are not particularly limited, and examples thereof include alkyl(meth)acrylates, alkoxy group-containing (meth)acrylates, alicyclic group-containing (meth)acrylates, aryl group-containing (meth)acrylates, hydroxyl group-containing (meth)acrylates, epoxy group-containing (meth)acrylates, and carboxy group-containing (meth)acrylates, etc. These may be used alone or in combination of two or more.

[0037] Examples of alkyl(meth)acrylates include methyl(meth)acrylate, ethyl(meth)acrylate, n-propyl(meth)acrylate, isopropyl(meth)acrylate, n-butyl(meth)acrylate, isobutyl(meth)acrylate, tert-butyl(meth)acrylate, sec-butyl(meth)acrylate, n-pentyl(meth)acrylate, n-hexyl(meth)acrylate, n-octyl(meth)acrylate, isooctyl(meth)acrylate, n-octyl(meth)acrylate, and octyl(meth)acrylate. Examples of the acrylates include methyl (meth)acrylate, ...

[0038] Examples of alkoxy group-containing (meth)acrylates include 2-methoxyethyl (meth)acrylate, methoxyethylene glycol (meth)acrylate, 2-ethoxyethyl (meth)acrylate, and ethyl carbitol (meth)acrylate, which can be used alone or in combination of two or more.

[0039] Examples of alicyclic group-containing (meth)acrylates include cyclohexyl (meth)acrylate, tert-butylcyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, and adamantyl (meth)acrylate, which may be used alone or in combination of two or more.

[0040] Examples of aryl group-containing (meth)acrylates include aryl group-containing (meth)acrylates having 6 to 15 carbon atoms, such as phenyl (meth)acrylate, benzyl (meth)acrylate, and phenoxyethyl (meth)acrylate, which can be used alone or in combination of two or more.

[0041] Examples of hydroxyl group-containing (meth)acrylates include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, and 12-hydroxylauryl (meth)acrylate, which may be used alone or in combination of two or more.

[0042] Examples of epoxy group-containing (meth)acrylates include glycidyl (meth)acrylate and epoxycyclohexyl (meth)acrylate, which can be used alone or in combination of two or more.

[0043] Examples of carboxy group-containing (meth)acrylates include acrylic acid, methacrylic acid, carboxyethyl (meth)acrylate, carboxybutyl (meth)acrylate, and carboxypentyl (meth)acrylate, which can be used alone or in combination of two or more.

[0044] In addition, 2-(meth)acryloyloxyethyl succinic acid, maleic acid, itaconic acid, maleic anhydride, itaconic anhydride, vinyl acetate, vinyl propionate, styrene, α-methylstyrene, N-vinylcaprolactam, cyclohexylmaleimide, phenylmaleimide, cyclohexylmaleimide, phenylmaleimide, methylmaleimide, ethylmaleimide, n-butylmaleimide, laurylmaleimide, and silicone-containing monomers may be used as copolymerizable monomers. These may be used alone or in combination of two or more.

[0045] From the viewpoint of reducing the water absorption rate of the cured product, it is preferable to use 20% by mass or more, and more preferably 30% by mass or more, of an alicyclic group-containing (meth)acrylate relative to all monomers forming the poly(meth)acrylic resin. From the same viewpoint, it is preferable to use 10% by mass or more, and more preferably 20% by mass or more, of an aryl group-containing (meth)acrylate relative to all monomers forming the poly(meth)acrylic resin. Furthermore, from the same viewpoint, it is preferable to use 5% by mass or more, and more preferably 10% by mass or more, of a carboxy group-containing monomer relative to all monomers forming the poly(meth)acrylic resin.

[0046] The weight-average molecular weight of the poly(meth)acrylic resin is not particularly limited, but is preferably 5,000 to 100,000, more preferably 10,000 to 30,000, from the viewpoint of facilitating the formation of fine patterns when contained in a curable resin composition (hereinafter referred to as good resolution). The weight-average molecular weights of other types of base polymers are also preferably within the above ranges. The weight-average molecular weight of the base polymer containing the poly(meth)acrylic resin is a value measured using gel permeation chromatography (GPC) in terms of polystyrene, and is a value measured in accordance with JIS 7252-4. The weight-average molecular weights described in the examples below are also values ​​determined according to the description in this section.

[0047] The acid value of the poly(meth)acrylic resin is not particularly limited, but from the viewpoint of resolution, it is preferably 10 to 200 (mgKOH / g), and more preferably 30 to 100 (mgKOH / g).

[0048] As the polymerization initiator, a photopolymerization initiator is preferably used. The photopolymerization initiator is not particularly limited, and examples thereof include benzoin and its alkyl ethers such as benzoin, benzoin methyl ether, and benzoin ethyl ether; acetophenones such as acetophenone, 2,2-dimethoxy-2-phenylacetophenone, and 1,1-dichloroacetophenone; anthraquinones such as 2-methylanthraquinone, 2-amylanthraquinone, 2-t-butylanthraquinone, and 1-chloroanthraquinone; thioxanthones such as 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone, and 2-chlorothioxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenones such as benzophenone; 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propan-1-one and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1; acylphosphine oxides, and xanthones. These photopolymerization initiators may be used alone or in combination of two or more.

[0049] The content of the photopolymerization initiator is not particularly limited, but is preferably 1 part by weight or more, more preferably 5 parts by weight or more, and is preferably 15 parts by weight or less, more preferably 10 parts by weight or less, relative to 100 parts by weight of all polymerizable raw materials in the curable resin composition.

[0050] The curable resin composition may contain a photopolymerization initiation aid. Examples of the photopolymerization initiation aid include trifunctional thiol compounds such as 1,3,5-tris(3-mercaptopropionyloxyethyl)isocyanurate, 1,3,5-tris(3-mercaptobutyloxyethyl)isocyanurate (manufactured by Showa Denko K.K., Karenz MT (registered trademark) NR1), and trimethylolpropane tris(3-mercaptopropionate); tetrafunctional thiol compounds such as pentaerythritol tetrakis(3-mercaptopropionate) and pentaerythritol tetrakis(3-mercaptobutyrate) (manufactured by Showa Denko K.K., Karenz MT (registered trademark) PEI); and polyfunctional thiols such as hexafunctional thiol compounds such as dipentaerythritol hexakis(3-propionate). These photopolymerization initiation aids may be used alone or in combination of two or more.

[0051] The curable resin composition may contain a thermal polymerization initiator. Examples of the thermal polymerization initiator include organic peroxides such as cumene hydroperoxide, diisopropylbenzene peroxide, di-t-butyl peroxide, lauryl peroxide, benzoyl peroxide, t-butylperoxyisopropyl carbonate, t-butylperoxy-2-ethylhexanoate, and t-amylperoxy-2-ethylhexanoate; and azo compounds such as 2,2'-azobis(isobutyronitrile), 1,1'-azobis(cyclohexanecarbonitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), and dimethyl 2,2'-azobis(2-methylpropionate). These thermal polymerization initiators may be used alone or in combination of two or more.

[0052] Examples of solvents include ethers such as tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, and diethylene glycol dimethyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; esters such as ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, and 3-methoxybutyl acetate; alcohols such as methanol, ethanol, isopropanol, n-butanol, ethylene glycol monomethyl ether, and propylene glycol monomethyl ether; aromatic hydrocarbons such as toluene, xylene, and ethylbenzene; chloroform, dimethyl sulfoxide, and the like. These solvents may be used alone or in combination of two or more. The content of the solvent is not particularly limited and may be appropriately adjusted depending on the optimum viscosity of the composition when used.

[0053] The curable resin composition may further contain a polyfunctional monomer other than the (meth)acrylate X. The polyfunctional monomer is not particularly limited, and examples thereof include polyfunctional aromatic vinyl monomers such as divinylbenzene, diallyl phthalate, and diallyl benzene phosphonate; and polyfunctional (meth)acrylates such as (di)ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and tris(hydroxyethyl)isocyanurate tri(meth)acrylate. Among these, (di)pentaerythritol tetra(meth)acrylate, (di)pentaerythritol penta(meth)acrylate, (di)pentaerythritol hexa(meth)acrylate, and tris(hydroxyethyl)isocyanurate tri(meth)acrylate, which have a large number of functional groups, are preferred. These polyfunctional monomers may be used alone or in combination of two or more.

[0054] The content of the polyfunctional monomer in the curable resin composition is not particularly limited, but from the viewpoint of reducing the water absorption rate of the obtained cured product and from the viewpoint of film-forming properties, the content is preferably 20 to 100 parts by mass, more preferably 20 to 50 parts by mass, and even more preferably 20 to 40 parts by mass relative to 100 parts by mass of the base polymer.

[0055] The curable resin composition may further contain an epoxy resin. This epoxy resin is different from the epoxy resin that can be used as the base polymer described above and has a smaller molecular weight than the epoxy resin. Therefore, the curable resin composition includes an epoxy resin as a base polymer and may further contain an epoxy resin. Epoxy resins are typically low-molecular-weight resins, oligomers, and monomers having an epoxy skeleton, and have a weight-average molecular weight of approximately 1,000 or less. The epoxy resin is not particularly limited, and examples thereof include bisphenol A epoxy compounds, bisphenol F epoxy compounds, glycidyl ether epoxy compounds, glycidyl ester epoxy compounds, biphenyl epoxy compounds, phenol novolac epoxy compounds, cresol novolac epoxy compounds, bisphenol A novolac epoxy compounds, aliphatic polyglycidyl ether compounds, cycloaliphatic epoxy compounds, polymers of monomers having epoxy groups, copolymers of monomers having epoxy groups and other monomers, and epoxy compounds having siloxane bond sites. These epoxy resins may be used alone or in combination.

[0056] The content of the epoxy resin in the curable resin composition is not particularly limited, but from the viewpoint of reducing the water absorption rate of the obtained cured product and from the viewpoint of film-forming properties, the content is preferably 10 to 100 parts by mass, more preferably 10 to 50 parts by mass, and even more preferably 10 to 30 parts by mass, relative to 100 parts by mass of the base polymer.

[0057] The curable resin composition may further contain a radical polymerizable oligomer such as an unsaturated polyester, an epoxy acrylate, a urethane acrylate, or a polyester acrylate.

[0058] The curable resin composition may contain known additives such as adhesion imparting agents, coatability improvers, dyes, pigments, defoaming agents, coupling agents, leveling agents, sensitizers, release agents, lubricants, plasticizers, antioxidants, ultraviolet absorbers, flame retardants, thickeners, and dispersants, within the range that does not impair the effects of the present invention.

[0059] The solid content concentration of the curable resin composition is not particularly limited, but from the viewpoint of film formability of the resulting cured product, it is preferably 10 to 60 mass %, more preferably 20 to 50 mass %.

[0060] <Cured product> The cured product of the present invention can be obtained by curing the curable resin composition. Examples of methods for producing the cured product include injecting the curable resin composition into a molding die (resin die), or coating the curable resin composition onto a substrate (substrate) or various layers to form a desired shape, and then curing the curable resin composition by irradiating it with light (e.g., ultraviolet light) and / or heating. Curing conditions are appropriately adjusted depending on the curable resin composition used.

[0061] The cured product of the present invention has an extremely low water absorption rate and is capable of maintaining high insulating properties for a long period of time under high temperature and high humidity conditions. The water absorption rate of the cured product is preferably 1% or less, more preferably 0.9% or less, and even more preferably 0.8% or less.

[0062] The use of the cured product of the present invention is not particularly limited, but it can be suitably used as a member requiring insulation (e.g., an insulating film, an insulating film resist, an insulating sheet, an insulating layer, etc.). Examples of uses include semiconductor elements / integrated circuits (ICs and the like), discrete semiconductors (diodes, transistors, thermistors, etc.), LEDs (LED lamps, chip LEDs, light-receiving elements, lenses for optical semiconductors), sensors (temperature sensors, optical sensors, magnetic sensors), passive components (high-frequency devices, resistors, capacitors, etc.), mechanical components (connectors, switches, relays, etc.), automotive parts (circuit systems, control systems, sensors, lamp seals, etc.), adhesives / pressure-sensitive adhesives (optical components, optical disks, pickup lenses, etc.), surface protection films, and optical films. [Example]

[0063] The present invention will be described below with reference to examples, but the present invention is not limited to these examples in any way.

[0064] [Base polymer manufacturing] Manufacturing Example 1-1 A glass flask equipped with a heating / cooling / stirring device, a reflux condenser, and a nitrogen inlet tube was charged with 20.0 g of methacrylic acid, 34.1 g of dicyclopentanyl methacrylate, and 21.0 g of benzyl acrylate. After purging the gas phase of the system with nitrogen, 4.8 g of 2,2'-azobis(isobutyronitrile) was added, and the mixture was heated to 80°C and reacted at that temperature for 8 hours. Subsequently, 20.3 g of 3,4-epoxycyclohexylmethyl methacrylate, 0.2 g of triphenylphosphine, and 0.1 g of methoxyhydroquinone were added. After purging the gas phase of the system with air, the mixture was heated to 100°C and reacted at that temperature for 20 hours to obtain base polymer (A-1). The acid value of the resulting base polymer, calculated based on the solids content, was 73.3. The weight-average molecular weight (Mw) of the resulting base polymer, as determined by GPC, was 14,000.

[0065] Manufacturing Example 1-2 A glass flask equipped with a heating / cooling / stirring device, a reflux condenser, and a nitrogen inlet tube was charged with 2.6 g of methacrylic acid, 13.1 g of dicyclopentanyl methacrylate, 8.3 g of 3,4-epoxycyclohexylmethyl methacrylate, and 72.3 g of cyclohexanone. After the gas phase in the system was replaced with nitrogen, 3.6 g of 2,2'-azobis(2,4-dimethylvaleronitrile) was added, heated to 65°C, and reacted at the same temperature for 13 hours to obtain base polymer (A-2). The acid value of the resulting base polymer, calculated as solids, was 52.6. The weight-average molecular weight (Mw) of the resulting base polymer, as determined by GPC, was 5,400.

[0066] Manufacturing Example 1-3 A glass flask equipped with a heating / cooling / stirring device, a reflux condenser, and a nitrogen inlet tube was charged with 2.6 g of methacrylic acid, 12.9 g of dicyclopentanyl acrylate, 8.6 g of 3,4-epoxycyclohexylmethyl methacrylate, and 72.3 g of cyclohexanone. After the gas phase in the system was replaced with nitrogen, 3.6 g of 2,2'-azobis(2,4-dimethylvaleronitrile) was added, heated to 65°C, and reacted at the same temperature for 13 hours to obtain base polymer (A-3). The acid value of the resulting base polymer, calculated as solids, was 68.8. The weight-average molecular weight (Mw) of the resulting base polymer, as determined by GPC, was 7,300.

[0067] Manufacturing Example 1-4 A glass flask equipped with a heating / cooling / stirring device, a reflux condenser, and a nitrogen inlet tube was charged with 2.3 g of methacrylic acid, 13.3 g of dicyclopentanyl acrylate, 8.5 g of glycidyl methacrylate, and 72.3 g of cyclohexanone. After the gas phase in the system was replaced with nitrogen, 3.6 g of 2,2'-azobis(2,4-dimethylvaleronitrile) was added, heated to 65°C, and reacted at the same temperature for 13 hours to obtain base polymer (A-4). The acid value of the resulting base polymer, calculated as solids, was 42.7. The weight-average molecular weight (Mw) of the resulting base polymer, as determined by GPC, was 7,200.

[0068] Manufacturing Example 1-5 A glass flask equipped with a heating / cooling / stirring device, a reflux condenser, and a nitrogen inlet tube was charged with 3.0 g of methacrylic acid, 14.1 g of dicyclopentanyl acrylate, 6.9 g of glycidyl methacrylate, and 72.3 g of cyclohexanone. After the gas phase in the system was replaced with nitrogen, 3.6 g of 2,2'-azobis(2,4-dimethylvaleronitrile) was added, heated to 65°C, and reacted at the same temperature for 13 hours to obtain base polymer (A-5). The acid value of the resulting base polymer, calculated as solids, was 57.8. The weight-average molecular weight (Mw) of the resulting base polymer, as determined by GPC, was 7,100.

[0069] Manufacturing Example 1-6 A glass flask equipped with a heating / cooling / stirring device, a reflux condenser, and a nitrogen inlet tube was charged with 9.8 g of methacrylic acid, 20.3 g of dicyclopentanyl methacrylate, and 55.8 g of cyclopentanone. After the gas phase in the system was purged with nitrogen, 2.7 g of 2,2'-azobis(isobutyronitrile) was added, heated to 80°C, and reacted at that temperature for 8 hours. The system was then heated to 100°C and reacted at that temperature for 2 hours. Next, 11.3 g of glycidyl methacrylate, 0.02 g of methoxyhydroquinone, 0.001 g of 4-benzoyloxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical (BTOX), and 0.1 g of dimethylbenzylamine were added. After the gas phase in the system was purged with air, the system was heated to 100°C and reacted at that temperature for 20 hours to obtain base polymer (A-6). The resulting base polymer had an acid value calculated based on the solid content of 47.5, and a weight average molecular weight (Mw) of 7,900 as determined by GPC.

[0070] [Production of (meth)acrylate] Manufacturing Example 2-1 A glass flask equipped with a heating / cooling / stirring device, a reflux condenser, and a nitrogen inlet tube was charged with 10.0 g of Adamantate E201 (Osaka Organic Chemical Industry Co., Ltd.), 6.2 g of methacrylic anhydride, 0.3 g of dimethylaminopyridine, and 24.3 g of toluene. After the gas phase in the system was replaced with air, the system was heated to 90°C and reacted at that temperature for 12 hours. Then, 100.0 g of methanol was added, and the precipitated solid was filtered and dried to obtain methacrylate (C-1) represented by the following formula 3. [ka]

[0071] Manufacturing Example 2-2 A glass flask equipped with a heating / cooling / stirring device, a reflux condenser, and a nitrogen inlet tube was charged with 10.0 g of Adamantate E201 (Osaka Organic Chemical Industry Co., Ltd.), 3.5 g of acrylic acid, 0.3 g of dimethylaminopyridine, and 24.3 g of toluene. After the gas phase in the system was replaced with air, the system was heated to 90°C and reacted at that temperature for 12 hours. Then, 100.0 g of methanol was added, and the precipitated solid was filtered and dried to obtain acrylate (C-3) represented by the following formula 7. [ka]

[0072] [Preparation of Curable Resin Composition] Example 1 A curable resin composition (solids concentration: approximately 40% by mass) was prepared by mixing, in a dark environment, 21.4% by mass of the base polymer (A-1), 6.4% by mass of dipentaerythritol hexaacrylate (B-1) as a polyfunctional monomer, 6.4% by mass of the methacrylate (C-1), 4.3% by mass of dicyclopentadiene dimethanol diglycidyl ether (D-1) as an epoxy resin, 1.2% by mass of a photopolymerization initiator (Omnirad 379EG, manufactured by IGM Resins BV), 0.3% by mass of 3-glycidoxypropylmethyldiethoxysilane (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.) as an adhesion promoter, and 60% by mass of propylene glycol monomethyl ether acetate (PGMEA) as a solvent.

[0073] Example 2, Comparative Examples 1 to 4 A curable resin composition (solid content concentration: approximately 40% by mass) was prepared in the same manner as in Example 1, except that the raw materials shown in Table 1 were used in the amounts shown in Table 1.

[0074] Example 3, Comparative Examples 5 and 6 A curable resin composition (solid content concentration: approximately 35% by mass) was prepared in the same manner as in Example 1, except that the raw materials shown in Table 2 were used in the amounts shown in Table 2.

[0075] Examples 4 to 6, Comparative Example 7 A curable resin composition (solid content: approximately 35% by mass) was prepared in the same manner as in Example 1, except that the raw materials shown in Table 3 were used in the amounts shown in Table 3.

[0076] The raw materials listed in Tables 1 to 4 are as follows. Base polymer (A-1): Base polymer produced in Production Example 1-1 Base polymer (A-2): Base polymer produced in Production Example 1-2 Base polymer (A-3): Base polymer produced in Production Example 1-3 Base polymer (A-4): Base polymer produced in Production Example 1-4 Base polymer (A-5): Base polymer produced in Production Example 1-5 Base polymer (A-6): Base polymer produced in Production Example 1-6 Multifunctional monomer (B-1): Dipentaerythritol hexaacrylate Methacrylate (C-1): methacrylate prepared in Preparation Example 2-1 Acrylate (C-2): Dimethylol-tricyclodecane diacrylate Acrylate (C-3): Acrylate prepared in Preparation Example 2-2 Acrylate (C-4): an acrylate represented by the following formula 8 [ka] Epoxy resin (D-1): Dicyclopentadiene dimethanol diglycidyl ether Epoxy resin (D-2): VG3101L manufactured by Techmore Photopolymerization initiator (E-1): Omnirad 379EG manufactured by IGM Resins BV Photopolymerization initiator (E-2): Irgacure OXE01 manufactured by BASF Japan Adhesion promoter (F-1): 3-glycidoxypropylmethyldiethoxysilane (Shin-Etsu Chemical Co., Ltd., KBM-403) Adhesion promoter (F-2): reaction product of isocyanatepropyltriethoxysilane (KBM9007, manufactured by Shin-Etsu Chemical Co., Ltd.) and ureidopropyltrimethoxysilane (T1915, manufactured by Tokyo Chemical Industry Co., Ltd.) (prepared in accordance with Example 1 described in International Publication WO2014 / 104195). Polymerization inhibitor: methoxyhydroquinone Surfactant: Silicone oil (FZ2122, manufactured by Toray Dow Corning Co., Ltd.) PGMEA: Propylene glycol monomethyl ether acetate

[0077] [Resolution evaluation] Examples 1 and 2, Comparative Examples 1 to 4 Each of the prepared curable resin compositions was uniformly coated on a glass substrate using a spin coater, and then dried on a hot plate at 90°C for 2 minutes. The resulting coating film was irradiated with light from an ultra-high pressure mercury lamp at 300 mJ / cm through a mask having a hole pattern light-shielding portion. 2 The substrate was irradiated with light (illuminance: 30 mW in i-line equivalent). The distance between the mask and the substrate (exposure gap) was 50 μm. The substrate was then developed using a 2.38% TMAH aqueous solution. After rinsing with water, the substrate was baked at 230°C for 30 minutes to produce a resist pattern with a film thickness of 8 μm. The resolution was evaluated according to the size of the resolved through-holes using the following criteria. The results are shown in Table 1. A: The size of the resolved through-hole is 30 μm or less in diameter. B: The size of the resolved through-hole is greater than 30 μm and less than 50 μm in diameter. C: The size of the resolved through-hole is 50 μm or more in diameter.

[0078] [Insulation evaluation] Examples 1 and 2, Comparative Examples 1 to 4 A glass substrate having a predetermined copper wiring pattern was prepared. Each of the prepared curable resin compositions was uniformly applied to the glass substrate with copper wiring using a spin coater, and then dried on a hot plate at 90°C for 2 minutes. The resulting coating film was irradiated with light from an ultra-high pressure mercury lamp at 300 mJ / cm2 while shielding the electrodes on both ends of the copper wiring. 2 The substrate was irradiated with light (the illuminance was 30 mW in i-line equivalent). It was then developed using a 2.38% TMAH aqueous solution. After rinsing with water, it was baked at 230°C for 30 minutes to form a hardened film with a film thickness of 8 μm. This substrate was used as an evaluation substrate. The obtained substrate was placed in a HAST evaluation device (manufactured by ESPEC) and tested under conditions of a temperature of 130°C, humidity of 85%, and an applied voltage of 12 V. The insulation properties were reduced and the resistance value was 10 6 The time it took for the resistance to drop below Ω was measured, and the insulation was evaluated according to the following criteria. The results are shown in Table 1. A: Resistance value is 10 6 Time below Ω for more than 100 hours B: Resistance value is 10 6 The time when the value is below Ω is between 80 and 100 hours. C: Resistance value is 10 6The time when the value is below Ω is between 50 and 80 hours. D: Resistance value is 10 6 Time below Ω for less than 50 hours

[0079] [Water absorption measurement] Examples 1 and 2, Comparative Examples 1 to 4 Each of the curable resin compositions prepared in Examples 1 and 2 and Comparative Examples 1 to 4 was uniformly applied to a glass substrate using a spin coater, and then dried on a hot plate at 90°C for 2 minutes. The entire surface of the resulting coating film was irradiated with light from an ultra-high pressure mercury lamp at 300 mJ / cm. 2 The substrate was irradiated with light (illuminance: 30 mW in i-line equivalent). It was then developed using a 2.38% TMAH aqueous solution. After rinsing with water, it was baked at 230°C for 30 minutes to form a cured film with a thickness of 8 μm. The resulting substrate was immersed in water at 23°C for 24 hours, after which the water content in the cured film was measured using Tg-DTA to determine the water absorption (%). The results are shown in Table 1.

[0080] [Measurement of ion migration] Example 3, Comparative Examples 5 and 6 A first substrate (copper wiring width: 1500 μm, wiring distance: 350 μm, wiring film thickness: 35 μm) having a copper wiring pattern conforming to IPC-B24 specified in ISO 9455-17 was prepared. Each curable resin composition was uniformly applied to the substrate with the electrodes provided at both ends of the copper wiring protected using a spin coater, and then dried on a hot plate at 100°C for 2 minutes. The resulting coating film was irradiated with light from an ultra-high pressure mercury lamp at 1000 mJ / cm. 2 The substrates were irradiated with light (illuminance: 20 mW in i-line equivalent). They were then baked at 120°C for 45 minutes to form a cured film with a thickness of 35 μm, which was used as each evaluation substrate. The obtained evaluation substrates were placed in a migration tester (Kusumoto Chemicals Co., Ltd., SIR13-SLIM) and tested under conditions of a temperature of 85°C, humidity of 85%, and an applied voltage of 100 V, and the change in resistance value over time was evaluated. The results are shown in Table 2.

[0081] Examples 4 to 6, Comparative Example 7 Each evaluation board was prepared in the same manner as above, except that a second substrate having a copper wiring pattern (copper wiring width: 100 μm, wiring spacing: 100 μm, wiring thickness: 0.1 μm) was used and the thickness of the cured film was adjusted to 6 μm. Tests were conducted in the same manner as above, except that the applied voltage was 12 V, and the change in resistance value over time was evaluated. The results are shown in Table 3.

[0082] [Measurement of relative permittivity] Each monomer composition (solid content concentration: 45% by mass) was prepared by mixing 100 parts by mass of the methacrylate (C-1), acrylate (C-2), or acrylate (C-4) monomer, 3 parts by mass of a photopolymerization initiator (Irgacure OXE04, manufactured by BASF Japan Ltd.), and a solvent (cyclohexanone / propylene glycol monomethyl ether acetate = 75 / 25) under light shielding. Each prepared monomer composition was uniformly applied to an ITO substrate (manufactured by EHC Co., Ltd., 10 cm x 10 cm) using a spin coater, and then dried on a hot plate at 90 °C for 90 seconds to form a coating film. The resulting coating film was then irradiated with light from an ultra-high pressure mercury lamp at 90 mJ / cm. 2 The ITO substrate was irradiated with light (illuminance: 30 mW in i-line equivalent) and then baked at 230°C for 30 minutes to obtain a cured film. The ITO substrate on which the cured film had been formed was then cut to a size of 2.5 cm x 5 cm, a metal mask with an opening was attached to the cured film with polyimide tape, and gold was evaporated six times onto the cured film in the opening using a gold evaporation machine to form gold electrodes (3 mm x 3 mm, film thickness: 1500 Å), and a sample for measuring the dielectric constant was prepared. The capacitance of the prepared samples was measured under the following measurement conditions using an impedance analyzer (Keysight Technologies, E4990A), and the relative dielectric constant was calculated. The results are shown in Table 4. <Measurement conditions> Resonance measurement fixture: 16047E Start: 1kHz End:1000kHz 500mV <Calculation method of relative dielectric constant> The capacitance (C) value was obtained using an impedance analyzer. The relative permittivity was calculated using the following formula: ε r =Cd / ε0S ε r : relative permittivity ε0: Dielectric constant of vacuum C: Capacitance [pF] S: Electrode area [m 2 ] d: Film thickness [m]

[0083] [Table 1]

[0084] [Table 2]

[0085] [Table 3]

[0086] [Table 4] [Industrial Applicability]

[0087] The cured product obtained from the curable resin composition of the present invention can be suitably used as a member that requires insulation properties (for example, an insulating film, an insulating film resist, an insulating sheet, an insulating layer, etc.).

Claims

1. A (meth)acrylate represented by the following general formula (1) or (2): 【Chemical 1】 (In general formula (1), R 1 ~R 4 are each independently H or a methyl group, and R 5 ~R 7 are each independently a halogen group, an alkyl group, an alkoxy group, or an aromatic group; AO is an ethyleneoxy group or a propyleneoxy group; m and n are each independently an integer of 0 to 5; p is an integer of 0 to 2; and r and s are each independently an integer of 0 to 15. 【Chemistry 2】 (In general formula (2), R 1 ~R 4 are each independently H or a methyl group, and R 5 ~R 7 are each independently a halogen group, an alkyl group, an alkoxy group, or an aromatic group; AO is an ethyleneoxy group or a propyleneoxy group; m and n are each independently an integer of 0 to 5; p is an integer of 0 to 2; and r and s are each independently an integer of 0 to 15.

2. A curable resin composition comprising at least one (meth)acrylate according to claim 1, a base polymer, a polymerization initiator, and a solvent.

3. 3. The curable resin composition according to claim 2, wherein the content of the (meth)acrylate is 20 to 100 parts by mass per 100 parts by mass of the base polymer.

4. The curable resin composition according to claim 2 or 3, which contains a polyfunctional monomer.

5. The curable resin composition according to any one of claims 2 to 4, which contains an epoxy resin.

6. A cured product obtained by curing the curable resin composition according to any one of claims 2 to 5.

7. The cured product according to claim 6, wherein the cured product has a water absorption rate of 1% or less.

Images