Active energy ray curable resin composition and its cured product

Abstract

To provide a curable composition that has high heat resistance and exhibits superior adhesion and mechanical characteristics.SOLUTION: A curable composition comprises two or more functionalized monomers represented by the formula (1). (In the formula (1), n represents a number of 1 or greater, and Z represents an n-valent organic group).SELECTED DRAWING: None

Description

[Technical Field]

[0001] This invention relates to an active energy ray curable resin composition and its cured product. [Background technology]

[0002] In recent years, as high performance is required for various applications, curable compositions have the problem of low heat resistance after curing. To address this problem and improve functions such as heat resistance, it is known that the composition of monomers and additives contained in curable compositions has been investigated. For example, Patent Document 1 discloses a photocurable paste containing at least one epoxy acrylate compound and an epoxy methacrylate compound, each containing multiple ethylenically unsaturated groups in one molecule, along with a photopolymerizable monomer, a photopolymerization initiator, and insulating inorganic particles. [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2011-37986 [Overview of the Initiative] [Problems that the invention aims to solve]

[0004] However, even with curable compositions combining (meth)acrylate containing multiple ethylenically unsaturated groups within a single molecule with inorganic particles, there was still room to improve the heat resistance of the cured product. Therefore, the present invention aims to provide a curable composition that has high heat resistance and can exhibit excellent adhesion and mechanical properties. [Means for solving the problem]

[0005] The inventors of the present invention have conducted various studies to achieve the above objectives and have arrived at the present invention. That is, the present invention is a curable composition comprising two or more compounds represented by the following general formula (1).

[0006] [ka] (In equation (1), n ​​is a number greater than or equal to 1, and Z represents an n-valent organic group.) [Effects of the Invention]

[0007] The curable composition of this disclosure has excellent heat resistance and can provide high adhesion. Therefore, by utilizing its heat resistance and adhesion properties, it can be applied to various fields such as coatings, paints, inks, quantum dot inks, adhesives, adhesives for electrical materials, prepregs, thickeners, thermoplastic resins, thermosetting resins, optical films, resists, electronic information materials, insulating materials, heat insulating materials, conductive adhesives, thermal conductive materials, piezoelectric materials, vibration damping materials, sound insulation materials, soundproofing agents, desiccant agents, antiblocking agents, pore-forming agents, oil absorbents, antibacterial agents, dental materials, ceramic molding materials, cell culture materials, 3D printing materials, and building components. [Modes for carrying out the invention]

[0008] The present invention will be described in detail below. Furthermore, combinations of two or more of the individual preferred embodiments of the present invention described below are also preferred embodiments of the present invention.

[0009] [Curable composition of this disclosure] <Compound represented by the following formula (1)> The curable compositions of this disclosure include compounds having a functional group represented by the following formula (1) (α-allyloxymethylacryloyl group (hereinafter sometimes referred to as AMA group)).

[0010] [ka] (In equation (1), n ​​is a number greater than or equal to 1, and Z represents an n-valent organic group.)

[0011] That is, it has a structure in which an allyloxymethyl group is bonded to the α-carbon atom constituting the double bond in the acrylate within the same molecule.

[0012] (n = 1) In the above formula (1), Z represents an n-valent organic group. When n is 1, Z represents a monovalent organic group, and it is preferably a group represented by -OR1 (where R1 is a hydrogen atom or an organic group having 1 to 40 carbon atoms).

[0013] The number of carbon atoms contained in the organic group of the present disclosure is preferably 1 or more. On the other hand, it is preferably 30 or less, more preferably 25 or less, and even more preferably 20 or less.

[0014] The organic group of the present disclosure may be linear, branched, or cyclic.

[0015] The organic group of the present disclosure preferably has a hydrocarbon skeleton. The hydrocarbon skeleton may be any of a linear or branched aliphatic hydrocarbon group, a cyclic aliphatic hydrocarbon group, and an aromatic hydrocarbon group. These groups may have substituents. For example, an aromatic hydrocarbon group is a group having an aromatic ring and may have an aliphatic portion, and an alicyclic hydrocarbon group is a group having a cyclic aliphatic hydrocarbon portion and may have a linear or branched aliphatic hydrocarbon portion. The hydrocarbon group of the present disclosure may have other substituents. The other substituents are not particularly limited, and examples include a hydroxyl group, an alkoxy group, a halogen atom, a cyano group, and an ether group.

[0016] The linear aliphatic hydrocarbon group is not particularly limited, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, an n-decyl group, an n-undecyl group, an n-dodecyl group, an n-tridecyl group, an n-tetradecyl group, an n-pentadecyl group, an n-hexadecyl group, an n-heptadecyl group, an n-octadecyl group, an n-nonadecyl group, an n-icosyl group, an eicosyl group, a heneicosyl group, a triacontyl group, a tetracontyl group, and the like.

[0017] The branched hydrocarbon group is not particularly limited, and examples thereof include a sec-butyl group, an isobutyl group, a tert-butyl group, a 1-methylbutyl group, a 1-ethylpropyl group, a 2-methylbutyl group, an isoamyl group, a 1,2-dimethylpropyl group, a 1,1-dimethylpropyl group, a tert-amyl group, a 1,3-dimethylbutyl group, a 3,3-dimethylbutyl group, a 1-methylpentyl group, a 1-methylbutyl group, a 1-ethylbutyl group, a 2-ethylbutyl group, a 2-ethyl-2-methylpropyl group, a sec-heptyl group, a tert-heptyl group, an isoheptyl group, a sec-octyl group, a tert-octyl group, an isooctyl group, a 1-ethylhexyl group, a 1-propylpentyl group, a 2-ethylhexyl group, a 2-propylpentyl group, and the like.

[0018] The cyclic hydrocarbon group is not particularly limited, and examples thereof include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, a cyclodecyl group, a cyclododecyl group, a cyclohexadecyl group, a cyclooctadecyl group, and the like. Other groups having a functional group, such as a tetrahydrofurfuryl group, are also included.

[0019] The aromatic hydrocarbon group is not particularly limited, and examples thereof include a phenyl group, a naphthyl group, an anthryl group, a biphenyl group, a phenanthryl group, a fluorenyl group, a benzyl group, a tolyl group, a xylyl group, a cumenyl group, a mesityl group, a biphenyl group, a phenanthryl group, a 2,6-diethylphenyl group, a 2-methyl-6-ethylphenyl group, and the like.

[0020] Specific examples of compounds represented by the above general formula (1) include methyl 2-allyloxymethylacrylate, ethyl 2-allyloxymethylacrylate, n-propyl 2-allyloxymethylacrylate, isopropyl 2-allyloxymethylacrylate, n-butyl 2-allyloxymethylacrylate, sec-butyl 2-allyloxymethylacrylate, tert-butyl 2-allyloxymethylacrylate, n-amyl 2-allyloxymethylacrylate, sec-amyl 2-allyloxymethylacrylate, tert-butyl 2- Amyl, neopentyl 2-allyloxymethylacrylate, n-hexyl 2-allyloxymethylacrylate, sec-hexyl 2-allyloxymethylacrylate, n-heptyl 2-allyloxymethylacrylate, n-octyl 2-allyloxymethylacrylate, sec-octyl 2-allyloxymethylacrylate, tert-octyl 2-allyloxymethylacrylate, ethylhexyl 2-allyloxymethylacrylate, caprylic 2-allyloxymethylacrylate, nonyl 2-allyloxymethylacrylate, 2-allyloxymethyl Decyl acrylate, undecyl 2-allyloxymethylacrylate, lauryl 2-allyloxymethylacrylate, tridecyl 2-allyloxymethylacrylate, myristyl 2-allyloxymethylacrylate, pentadecyl 2-allyloxymethylacrylate, cetyl 2-allyloxymethylacrylate, heptadecyl 2-allyloxymethylacrylate, stearyl 2-allyloxymethylacrylate, nonadecyl 2-allyloxymethylacrylate, eicosyl 2-allyloxymethylacrylate, ceryl 2-allyloxymethylacrylate, 2 - Melicyl allyloxymethylacrylate, clotyl 2-allyloxymethylacrylate, 1,1-dimethyl-2-propenyl 2-allyloxymethylacrylate, 2-methylbutenyl 2-allyloxymethylacrylate, 3-methyl-2-butenyl 2-allyloxymethylacrylate, 3-methyl-3-butenyl 2-allyloxymethylacrylate, 2-methyl-3-butenyl 2-allyloxymethylacrylate, oleyl 2-allyloxymethylacrylate, linolenic acid 2-allyloxymethylacrylate, linolenic acid 2-allyloxymethylacrylate2-Allyloxymethylacrylate cyclopentyl, 2-Allyloxymethylacrylate cyclopentylmethyl, 2-Allyloxymethylacrylate cyclohexyl, 2-Allyloxymethylacrylate cyclohexylmethyl, 2-Allyloxymethylacrylate 4-methylcyclohexyl, 2-Allyloxymethylacrylate 4-tert-butylcyclohexyl, 2-Allyloxymethylacrylate tricyclodecanyl, 2-Allyloxymethylacrylate isobornyl, 2-Allyloxymethylacrylate adamantyl, 2-Allyloxymethylacrylate Dicyclopentanyl lylate, dicyclopentenyl 2-allyloxymethylacrylate, phenyl 2-allyloxymethylacrylate, methylphenyl 2-allyloxymethylacrylate, dimethylphenyl 2-allyloxymethylacrylate, trimethylphenyl 2-allyloxymethylacrylate, 4-tert-butylphenyl 2-allyloxymethylacrylate, benzyl 2-allyloxymethylacrylate, diphenylmethyl 2-allyloxymethylacrylate, diphenylethyl 2-allyloxymethylacrylate, 2-allyloxymethyl acrylate Triphenylmethyl acrylate, cinnamyl 2-allyloxymethylacrylate, naphthyl 2-allyloxymethylacrylate, anthranyl 2-allyloxymethylacrylate, methoxyethyl 2-allyloxymethylacrylate, methoxyethoxyethyl 2-allyloxymethylacrylate, methoxyethoxyethyl 2-allyloxymethylacrylate, 3-methoxybutyl 2-allyloxymethylacrylate, ethoxyethyl 2-allyloxymethylacrylate, ethoxyethoxyethyl 2-allyloxymethylacrylate, 2-allyloxymethyl Cyclopentoxyethyl acrylate, cyclohexyloxyethyl 2-allyloxymethylacrylate, cyclopentoxyethoxyethyl 2-allyloxymethylacrylate, cyclohexyloxyethoxyethyl 2-allyloxymethylacrylate, dicyclopentenyloxyethyl 2-allyloxymethylacrylate, phenoxyethyl 2-allyloxymethylacrylate, phenoxyethoxyethyl 2-allyloxymethylacrylate, glycidyl 2-allyloxymethylacrylate, β-methylglycidyl 2-allyloxymethylacrylate,Examples include β-ethylglycidyl 2-allyloxymethylacrylate, 3,4-epoxycyclohexylmethyl 2-allyloxymethylacrylate, 2-oxetanemethyl 2-allyloxymethylacrylate, 3-methyl-3-oxetanemethyl 2-allyloxymethylacrylate, 3-ethyl-3-oxetanemethyl 2-allyloxymethylacrylate, tetrahydrofuranyl 2-allyloxymethylacrylate, tetrahydrofurfuryl 2-allyloxymethylacrylate, tetrahydropyranyl 2-allyloxymethylacrylate, dioxazolanil, dioxanyl 2-allyloxymethylacrylate, etc.

[0021] (where n is 2 or greater) In formula (1) above, when n is 2 or greater, Z represents an n-valent linking group. This form, where n is a number of 2 or greater, is also one of the preferred embodiments.

[0022] In formula (1) above, n is not particularly limited as long as it is 2 or greater, but it is preferably 2 to 100, and more preferably 2 to 50, in terms of ease of synthesis and storage stability. When the compound represented by formula (1) above is used in applications requiring low viscosity, such as reactive diluents, it is even more preferably 2 to 10, and most preferably 2 to 6.

[0023] In formula (1) above, when n is 2 or greater, Z is not particularly limited as long as it is a linking group that can form two or more covalent bonds with the bonded carbonyl group, i.e., a covalently bonding divalent or higher linking group. It may be a divalent or higher linking group bonded via just one atom, or a divalent or higher linking group bonded via two or more atoms. However, in terms of ease of synthesis and chemical stability, it is preferable that it be a divalent or higher linking group bonded via two or more atoms.

[0024] When Z is a divalent or higher linking group bonded via two or more atoms, Z may be a low molecular weight structure or a high molecular weight structure. The terms low molecular weight structure and low molecular weight skeleton described later generally refer to structures or skeletons that do not have repeating units made up of monomer units, while the terms high molecular weight structure and high molecular weight skeleton described later generally refer to structures or skeletons that have repeating units made up of monomer units. While high molecular weight compounds generally refer to compounds or polymers with a molecular weight of 1000 or more in technical terms, the terms "low molecular weight" and "high molecular weight" are not distinguished or limited by such molecular weights in this invention.

[0025] Examples of Z above include linking groups with a structure obtained by removing two or more hydrogen atoms from a compound having two or more hydroxyl groups. Preferably, examples include linking groups with a structure obtained by removing two or more hydrogen atoms constituting the hydroxyl groups from a compound having two or more hydroxyl groups. Examples of compounds having two or more hydroxyl groups include low molecular weight dihydric alcohols such as ethylene glycol, diethylene glycol, tetraethylene glycol, propylene glycol, tripropylene glycol, butanediol, hexanediol, neopentyl glycol, 1,4-dimethylolcyclohexane, xylylene glycol, hydroquinone, bisphenol A, bisphenol F, bisphenol S, and bisphenol fluorene; low molecular weight trihydric alcohols such as glycerol, trimethylolpropane, and ethylene oxide adducts of isocyanuric acid; low molecular weight tetrahydric alcohols such as pentaerythritol and ditrimethylolpropane; and dipenta Examples include low molecular weight hexavalent alcohols such as erythritol; polyhydric phenol compounds such as phenol novolac resins; hydroxyl group-containing polymers such as polyvinyl alcohol, (meth)acrylate hydroxyethyl copolymer, and (meth)acrylate hydroxypropyl copolymer; compounds obtained by adding one or more molecules of alkylene oxide such as ethylene oxide or propylene oxide or butylene oxide to the above low molecular weight polyhydric alcohols; compounds obtained by adding one or more molecules of cyclic ester compounds such as ε-caprolactone to the above low molecular weight polyhydric alcohols; and sugars such as glucose, fructose, galactose, sucrose, lactose, maltose, cellobiose, starch, and cellulose. The above Z is X(-O-) n The structure may also be represented as follows: (where X represents the residue obtained by removing n oxygen atoms from Z).

[0026] Compounds represented by the above general formula (1) where n is 2 or greater can be produced by reacting a polyfunctional compound with a monofunctional α-(unsaturated alkoxyalkyl) acrylate, etc. Such methods include, for example, transesterification of a polyhydric hydroxyl group-containing compound with an α-(unsaturated alkoxyalkyl) acrylate, dehydration condensation of a polyhydric hydroxyl group-containing compound with α-(unsaturated alkoxyalkyl) acrylic acid, addition of a polyhydric hydroxyl group-containing compound with an α-(unsaturated alkoxyalkyl) acrylate having an epoxy group such as α-allyloxymethylacrylate glycyl, and dehydration condensation of a polyhydric carboxylic acid-containing compound with an α-(unsaturated alkoxyalkyl) acrylate having a hydroxyl group such as α-allyloxymethylacrylate hydroxyethyl. Methods include adding a polyhydric carboxylic acid-containing compound to an α-(unsaturated alkoxyalkyl) acrylate having an epoxy group, adding a polyfunctional epoxy compound to an α-(unsaturated alkoxyalkyl) acrylic acid, reacting a polyhydric isocyanate compound with an α-(unsaturated alkoxyalkyl) acrylate having a hydroxyl group, adding and esterifying a polyhydric isocyanate compound with an α-(unsaturated alkoxyalkyl) acrylic acid, and reacting a polyhydric anhydride compound with an α-(unsaturated alkoxyalkyl) acrylate having a hydroxyl group. Preferably, a transesterification method is used in which a polyhydric alcohol compound is reacted with an α-(unsaturated alkoxyalkyl) acrylate.

[0027] The curable composition of this disclosure may contain two or more compounds represented by the above formula (1), wherein n is a number of 1 or more.

[0028] The curable composition of this disclosure may contain two or more compounds in formula (1) above where n is 1, or it may contain one or more compounds where n is 1 and one or more compounds where n is 2 or more, or it may contain two or more compounds where n is 2 or more.

[0029] The curable composition of this disclosure more preferably contains at least one compound in which n is 1 in formula (1) above.

[0030] The curable composition of this disclosure is preferably satisfied with either (i) or (ii) below from the viewpoint of the heat resistance of the cured product. (i) The above general formula (1) includes one or more compounds in which n is 1 and the glass transition temperature of the homopolymer is less than 50°C, and one or more compounds in which n is 1 and the glass transition temperature of the homopolymer is 50°C or higher. (ii) The compound comprises one or more compounds in which n is 1 in the above general formula (1), and one or more compounds in which n is 2 or more in the above general formula (1).

[0031] In (i) above, as a compound in which n is 1 and the glass transition temperature of the homopolymer is 50°C or higher, the glass transition temperature of the homopolymer is preferably 51°C or higher, more preferably 52°C or higher, and even more preferably 53°C or higher. On the other hand, it is preferably 100°C or lower, more preferably 95°C or lower, and even more preferably 90°C or lower.

[0032] In (i) above, as a compound in which n is 1 and the glass transition temperature of the homopolymer is less than 50°C, the glass transition temperature of the homopolymer is preferably 49°C or lower, more preferably 48°C or lower, and even more preferably 47°C or lower. On the other hand, it is preferably -100°C or higher, more preferably -95°C or higher, and even more preferably -90°C or higher.

[0033] In (ii) above, the compound in which n is 1 is preferably an organic group having 1 or more carbon atoms. On the other hand, it is preferable that Z is an organic group having 30 or fewer carbon atoms, and more preferably an organic group having 20 or fewer carbon atoms.

[0034] In (ii) above, the compound in which n is 1 preferably has a glass transition temperature of -100°C or higher, more preferably -95°C or higher, and even more preferably -90°C or higher. On the other hand, it is preferably 100°C or lower, more preferably 95°C or lower, and even more preferably 90°C or lower.

[0035] In (ii) above, the compound in which n is 2 is preferably an organic group having 2 or more carbon atoms, and more preferably an organic group having 3 or more carbon atoms. On the other hand, Z is preferably an organic group having 30 or fewer carbon atoms, and more preferably an organic group having 20 or fewer carbon atoms.

[0036] A method for producing the compound described in formula (1) above, which is included in the curable composition of this disclosure, can be found in the descriptions in paragraphs

[0057] to

[0084] of Japanese Patent Application Publication No. 2011-74068.

[0037] The curable composition of this disclosure preferably contains, for example, 0.1% by mass or more and 100% by mass or less of the compound represented by the above general formula (1), more preferably 1% by mass or more and 99% by mass or less, and even more preferably 5% by mass or more and 98% by mass or less.

[0038] <Other ingredients> The curable composition of this disclosure may contain components other than the compound represented by formula (1) above. (fine particles) The curable composition of this disclosure preferably contains fine particles such as inorganic particles, organic particles, or organic-inorganic composite particles, with inorganic particles being more preferred. The volume-average particle diameter of the fine particles of this disclosure is preferably 1000 μm or less, more preferably 500 μm or less, and even more preferably 100 μm or less. On the other hand, it is preferably 0 nm or more, more preferably 1 nm, and even more preferably 5 nm or more.

[0039] The types of inorganic particles in this disclosure are not particularly limited. Examples include carbon-based particles such as graphite and carbon black; metal oxides such as silica, alumina, titanium oxide, zirconium oxide, magnesium oxide, and iron oxide; metal hydroxides such as aluminum hydroxide and magnesium hydroxide; complex metal oxides such as barium titanate, strontium titanate, lithium niobate, lithium cobaltate, and lithium iron phosphate; clay minerals such as talc, mica, and bentonite; nitrides such as silicon nitride, boron nitride, and aluminum nitride; sulfates such as aluminum borate, calcium sulfate, and barium sulfate; carbonates such as calcium carbonate and magnesium carbonate; metal particles such as copper particles, aluminum particles, silver particles, gold particles, and silicon particles; and industrially generated particles such as silica fume, fuller ash, blast furnace dust, converter dust, and blast furnace slag (or its pulverized form). Preferably, the particles are metal oxides, complex metal oxides, metal particles, and nitrides, and more preferably, metal oxides and complex metal oxides. The curable composition of this disclosure may contain only one type of inorganic particle, or it may contain two or more types.

[0040] The inorganic particles of this disclosure are preferably present in an amount of 1 part by mass or more, more preferably 5 parts by mass or more, and even more preferably 10 parts by mass or more, per 100 parts by mass of the total amount of the compound represented by the general formula (1) above. On the other hand, it is preferably present in an amount of 9900 parts by mass or less, more preferably 5000 parts by mass or less, and even more preferably 2500 parts by mass or less. The heat resistance and mechanical properties of the cured product of this disclosure tend to be high.

[0041] The shape of the above-mentioned fine particles is not particularly limited. Examples include spherical, polyhedral, large aspect ratio shapes, hollow particles, particles with protrusions, and particles with voids. The fine particles are not particularly limited, but they may be fine particles adjusted to a desired particle size by synthetic methods, or fine particles adjusted to a desired particle size by other methods such as grinding or molding.

[0042] The compound represented by the above general formula (1), which contains the inorganic particles of this disclosure (hereinafter sometimes referred to as the inorganic particle dispersion), tends to maintain a low viscosity compared to other monomers, such as acrylates and methacrylates containing multiple ethylenically unsaturated groups in a single molecule. Therefore, it is expected to be used in a variety of applications.

[0043] The inorganic particle dispersion of this disclosure may contain one or more compounds represented by the above general formula (1), or it may contain two or more compounds (the curable composition of this disclosure).

[0044] The compound represented by the above general formula (1) contained in the inorganic particle dispersion of this disclosure is preferably a compound in which n is a number from 2 to 10, more preferably n is from 2 to 8, and even more preferably n is from 2 to 6. It is preferable that n is an integer.

[0045] The compound represented by the above general formula (1) in the inorganic particle dispersion of this disclosure is preferably an organic group in which Z has 2 or more carbon atoms, and more preferably an organic group in which Z has 3 or more carbon atoms. On the other hand, Z is preferably an organic group in which Z has 30 or fewer carbon atoms, and more preferably an organic group in which Z has 20 or fewer carbon atoms.

[0046] Specifically, the compounds represented by the above general formula (1) contained in the inorganic particle dispersion of this disclosure include the compounds described above. More preferably, the polyhydric hydroxyl group-containing compound is a compound having a structure in which an ester is formed by combining tripropylene glycol and α-(unsaturated alkoxyalkyl)acrylic acid (hereinafter sometimes referred to as AOMA-TPG). However, as long as it has an ester structure, the use of polyhydric hydroxyl group-containing compound and α-(unsaturated alkoxyalkyl)acrylic acid as raw materials is not limited.

[0047] The inorganic particle content in the inorganic particle dispersion of this disclosure is preferably 1% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more, based on the total amount of the inorganic particle dispersion.

[0048] The viscosity of the inorganic particle dispersion of this disclosure is preferably 1 mPa·s or more, more preferably 2 mPa·s or more, and even more preferably 3 mPa·s or more. On the other hand, it is preferably 2500 mPa·s or less, more preferably 2000 mPa·s or less, and even more preferably 1500 mPa·s or less.

[0049] The inorganic particle dispersion of this disclosure can be applied to various fields such as coatings, paints, inks, quantum dot inks, adhesives, bonding agents, adhesives for electrical materials, prepregs, thickeners, thermoplastic resins, thermosetting resins, optical films, resists, electronic information materials, insulating materials, heat insulating materials, conductive adhesives, thermal conductive materials, piezoelectric materials, vibration damping materials, sound insulation materials, soundproofing agents, desiccant agents, antiblocking agents, pore-forming agents, oil absorbents, antibacterial agents, dental materials, ceramic molding materials, cell culture materials, 3D printing materials, and building components by appropriately selecting inorganic particles and compounds represented by the above general formula (1) according to the functions to be imparted or improved.

[0050] (Other monomers) The curable composition of this disclosure may contain any monomer other than the compound represented by the above general formula (1) (hereinafter also referred to as other monomers).

[0051] Other monomers included in the curable composition of this disclosure include monofunctional monomers having one ethylenically unsaturated bond and polyfunctional monomers having two or more ethylenically unsaturated bonds.

[0052] Examples of monofunctional monomers include (meth)acrylates; styrene monomers such as styrene, 4-tert-butylstyrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, p-chlorostyrene, and p-chloromethylstyrene; carboxyl group-containing monomers such as (meth)acrylic acid; and hydroxyl group-containing monomers such as 2-hydroxyethyl (meth)acrylate, 3-hydroxy-2-hydroxypropyl (meth)acrylate, and 3-phenoxy-2-hydroxypropyl (meth)acrylate.

[0053] Examples of (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and lauryl (meth)acrylate.

[0054] Examples of hydroxyl group-containing monomers include hydroxyl group-containing monomers such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate; oxo group-containing monomers such as ethylene glycol methoxy (meth)acrylate and diethylene glycol methoxy (meth)acrylate; fluorine atom-containing monomers such as trifluoroethyl (meth)acrylate and tetrafluoropropyl (meth)acrylate; and epoxy group-containing monomers such as glycidyl (meth)acrylate.

[0055] Examples of polyfunctional monomers include divinylbenzene, 1,3-butadiene, trivinylbenzene, divinylnaphthalene, trivinylcyclohexane, divinyl ether, diallyl ether, and polyvalent (meth)acrylates.

[0056] Examples of polyvalent (meth)acrylates include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and dipentaerythritol hexa(meth)acrylate.

[0057] The other monomers of this disclosure are preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, and even more preferably 1 part by mass or more, based on 100 parts by mass of the total amount of compounds represented by the general formula (1) above. On the other hand, they are preferably 1500 parts by mass or less, more preferably 1000 parts by mass or less, and even more preferably 800 parts by mass or less.

[0058] (Other additives) Examples include radical polymerization initiators, surfactants, curing agents, curing accelerators, colorants, internal mold release agents, coupling agents, reactive diluents, plasticizers, stabilizers, flame retardant aids, crosslinking agents, low shrinkage agents, polymerization inhibitors, antioxidants, UV absorbers, defoaming agents, leveling agents, thixotropes, and thickeners.

[0059] The curable composition of this disclosure may optionally contain a radical polymerization initiator. The radical polymerization initiator is not particularly limited, but may be a photoradical polymerization initiator, a thermal radical polymerization initiator, or both may be used in combination.

[0060] Examples of photoradical polymerization initiators include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin propyl ether; acetophenone compounds such as acetophenone, 2,2-diethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenyl ketone, and 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one; anthraquinone compounds such as 2-ethylanthraquinone, 2-t-butylanthraquinone, 2-chloroanthraquinone, and 2-amylanthraquinone; and 2,4-diethylthioxanthone, 2-isopropylthioxanthone, and 2-chlorothioxant Examples include thioxanthone compounds such as [3-(3,4-dimethyl-9-oxothioxanthene-2-yl)oxy-2-hydroxypropyl]-trimethylazanium chloride; ketal compounds such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenone compounds such as benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, and 4,4'-bismethylaminobenzophenone; and phosphine oxide compounds such as diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, and bis-(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide.

[0061] Examples of thermal radical polymerization initiators include benzoin, benzoin methyl ether, benzoin ethyl ether, and other benzoin and its alkyl ethers; acetophenones such as acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, and 4-(1-t-butyldioxy-1-methylethyl)acetophenone; anthraquinones such as 2-methylanthraquinone, 2-amylanthraquinone, 2-t-butylanthraquinone, and 1-chloroanthraquinone; 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone, and 2 Examples include thioxanthones such as chlorothioxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenones such as benzophenone, 4-(1-t-butyldioxy-1-methylethyl)benzophenone, and 3,3',4,4'-tetrakis(t-butyldioxycarbonyl)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.

[0062] The curable composition of this disclosure preferably contains a radical polymerization initiator in an amount of 0.01 parts by mass or more and 30 parts by mass or less, more preferably 0.05 parts by mass or more and 20 parts by mass or less, and even more preferably 0.1 parts by mass or more and 15 parts by mass or less, per 100 parts by mass of the compound of general formula (1) above. Including a radical polymerization initiator within the above range tends to improve the curability of the curable composition of this disclosure.

[0063] Examples of polymerization inhibitors include phenolic inhibitors such as hydroquinone, methylhydroquinone, trimethylhydroquinone, t-butylhydroquinone, p-methoxyphenol, 6-t-butyl-2,4-xylenol, 2,6-di-t-butylphenol, 2,6-di-t-butyl-4-methoxyphenol, and 2,2'-methylenebis(4-methyl-6-t-butylphenol), as well as copper salts of organic acids and phenothiazines. Among these, phenolic inhibitors are preferred in terms of low coloration and polymerization inhibition ability, and p-methoxyphenol, 6-t-butyl-2,4-xylenol, and 2,6-di-t-butylphenol are particularly preferred in terms of availability and cost-effectiveness.

[0064] The polymerization inhibitor may be a single type, or a mixture of two or more types may be used. The curable composition of this disclosure preferably contains a polymerization inhibitor in an amount of 0.001 parts by mass or more and 20 parts by mass or less, more preferably 0.01 parts by mass or more and 10 parts by mass or less, and even more preferably 0.05 parts by mass or more and 5 parts by mass or less, per 100 parts by mass of the compound of general formula (1). Including a polymerization inhibitor within the above range tends to improve the storage stability of the curable composition of this disclosure.

[0065] The viscosity of the curable composition of this disclosure is preferably 1 mPa·s or more, more preferably 2 mPa·s or more, and even more preferably 3 mPa·s or more. On the other hand, it is preferably 2500 mPa·s or less, more preferably 2000 mPa·s or less, and even more preferably 1500 mPa·s or less.

[0066] <Examples of preferred forms of the curable composition of this disclosure> [1] A curable composition comprising two or more compounds represented by the following general formula (1).

[0067] [ka] (In equation (1), n ​​is a number greater than or equal to 1, and Z represents an n-valent organic group.) [2] The curable composition according to [1], which satisfies at least one of (i) or (ii) below. (i) The above general formula (1) includes one or more compounds in which n is 1 and the glass transition temperature of the homopolymer is less than 50°C, and one or more compounds in which n is 1 and the glass transition temperature of the homopolymer is 50°C or higher. (ii) The compound comprises one or more compounds in which n is 1 in the above general formula (1), and one or more compounds in which n is 2 or more in the above general formula (1). [3] The curable composition according to [1] or [2], comprising fine particles. [4] The curable composition according to [3], wherein the content of fine particles is 1 part by mass or more and 9,900 parts by mass or less per 100 parts by mass of the total compound represented by the general formula (1) above. [5] A cured product of the curable composition described in [1] or [2] above.

[0068] [Cured product of this disclosure] The present invention also includes cured products of the curable compositions disclosed herein. Articles made from the cured products are suitably used in applications such as various coatings, paints, inks, quantum dot inks, adhesives, adhesives for electrical materials, prepregs, thickeners, thermoplastic resins, thermosetting resins, optical films, resists, electronic information materials, insulating materials, heat insulating materials, conductive adhesives, heat conductive materials, piezoelectric materials, vibration damping materials, sound insulation materials, soundproofing agents, desiccant agents, antiblocking agents, pore-forming agents, oil absorbents, antibacterial agents, dental materials, ceramic molding materials, cell culture materials, 3D printing materials, and building components.

[0069] The curable composition of this disclosure exhibits good curability, meaning it can be cured with low irradiation energy, and the resulting cured product also has excellent thermal stability.

[0070] The cured product of this disclosure preferably has a 5% mass loss temperature of 150°C or higher, more preferably 170°C or higher, and even more preferably 200°C or higher, when thermogravimetric analysis (TG) is performed in accordance with the procedure shown in the examples. The storage modulus of the cured product of the present disclosure at -20°C is preferably 1.0×10 8 Pa or more, more preferably 5.0×10 8 Pa or more, and even more preferably 1.0×10 9 Pa or more. On the other hand, it is preferably 1.0×10 10 Pa or less, more preferably 5.0×10 9 Pa or less, and even more preferably 2.5×10 9 Pa or less.

[0071] The storage modulus of the cured product of the present disclosure at 60°C is preferably 1.0×10 5 Pa or more, more preferably 5.0×10 5 Pa or more, and even more preferably 1.0×10 6 Pa or more. On the other hand, it is preferably 1.0×10 8 Pa or less, more preferably 5.0×10 7 Pa or less, and even more preferably 1.0×10 7 Pa or less. Here, the greater the storage modulus, the more excellent the hardness of the cured product tends to be. The storage modulus of the present disclosure can be measured in the manner shown in the examples.

[0072] [Method for producing the cured product of the present disclosure] The method for curing the curable composition of the present disclosure is not particularly limited. For example, it can be cured by irradiation with active energy rays such as heating, electromagnetic waves, and electron beams (hereinafter sometimes referred to as irradiation energy). The curing method of the present disclosure may be used in combination with a curing method by heating and / or a curing method by irradiation with active energy rays. The active energy rays of the present disclosure are not particularly limited, and examples include electromagnetic waves such as gamma rays, X-rays, ultraviolet rays, visible light, and infrared rays, and particle beams such as electron beams, neutron beams, and proton beams. Among these, gamma rays, X-rays, ultraviolet rays, visible light, and electron beams are preferred, ultraviolet rays, visible light, and electron beams are more preferred, and ultraviolet rays are most preferred in terms of the strength of energy, the generator of the energy rays, and the like.

[0073] The amount of polymerization initiator added in this disclosure is preferably 0.01 to 30% by mass, more preferably 0.05 to 20% by mass, and even more preferably 0.1 to 15% by mass, based on the total amount of the curable composition of this disclosure. [Examples]

[0074] The present disclosure will be further described below with reference to examples, but the present disclosure is not limited to these examples. Unless otherwise specified, "parts" means "parts by mass" and "%" means "percent mass". In these examples, various physical properties were measured by the following method.

[0075] <Viscosity measurement method> The viscosity of the curable resin composition was measured at a temperature of 25°C using a cone-plate viscometer (TV-20L, manufactured by Toki Sangyo Co., Ltd.).

[0076] <Thermal decomposition temperature> (Evaluation sample) A curable resin composition was placed in an aluminum pan and irradiated with ultraviolet light under the following conditions to obtain evaluation samples of the cured product. UV irradiation device: HCT400B-28HB (manufactured by Sen Special Light Source Co., Ltd.) Atmosphere: Under the atmosphere Total luminous intensity: 15 J / cm² (Evaluation method) The thermal decomposition temperature of the cured material was measured using a thermogravimetric differential thermal analyzer (TG-DTA2010SA, Bruker) under the following conditions, determining the temperature at which the material lost 5% of its weight. Measurement temperature range: Room temperature to 500℃ Heating rate: 10℃ / min Atmosphere and flow rate: Nitrogen - 100 ml / min

[0077] <Evaluation of thin film curability and adhesion> (Evaluation sample) The curable composition was applied to a copper plate (standard test plate) using a bar coater #4, and cured by ultraviolet irradiation under the following conditions. UV irradiation device: HCT400B-28HB (manufactured by Sen Special Light Source Co., Ltd.) Atmosphere: Under the atmosphere Total luminous intensity: 15 J / cm² (Evaluation method) The thin-film curability of the obtained cured film was evaluated. The curing levels were classified as follows: ○: No stickiness △: Slightly sticky ×: Sticky The adhesion of the resulting cured film was evaluated on a 6-point scale from 0 to 5 according to JIS K 5600-5-6 (cross-cut method). A list of the adhesion level classifications is shown in Table 1.

[0078] [Table 1]

[0079] <Glass transition temperature and storage modulus> (Evaluation sample) A curable resin composition was poured into a mold and irradiated with ultraviolet light under the following conditions to obtain an evaluation sample of the cured material (thickness 1.5 mm x width 4.0 mm). UV irradiation device: 365nm LED Atmosphere: Under the atmosphere Total luminous intensity: 6 J / cm² (Evaluation method) The dynamic viscoelasticity of the obtained cured material was measured under the following conditions, and the storage modulus and loss modulus were determined for each temperature. The temperature at which the value obtained by dividing the loss modulus by the storage modulus (tanδ) was maximized was defined as the glass transition temperature. Equipment: RSA-G2 (manufactured by TA instruments) Measurement mode: Pull Frequency: 1Hz Heating rate: 5°C / min

[0080] <Production of α-allyloxymethyl acrylic acid ester> (Manufacturing Example 1) Manufacturing of AOMA-TPG A stirrer bar, 2.27 g (8 mmol) of titanium tetraisopropoxide (TTIP), 38.5 g (200 mmol) of tripropylene glycol, 124.9 g (800 mmol) of α-allyloxymethylmethyl acrylate (AOMA), 120 mg of polymerization inhibitor (6-t-butyl-2,4-xylenol, manufactured by Tokyo Chemical Industries, Ltd.) (to a concentration of 1000 ppm relative to AOMA), 60 mg of polymerization inhibitor (Polystop 7300P, manufactured by Hakuto Co., Ltd.) (to a concentration of 500 ppm relative to AOMA), and 60.0 g of azeotropic agent toluene were weighed into a separable flask. The mixture (N2 / O2 = 92 / 8 (v / v)) was bubbled through the flask while the pressure inside the system was reduced to 300 Torr and the temperature was raised to 100°C. The reaction was carried out by removing fractions as needed and adding an equal mass of toluene to the system, continuing to heat until the conversion rate of tripropylene glycol reached >99%. After the reaction, the system was depressurized while bubbling a mixed gas (N2 / O2 = 92 / 8 (v / v)) to remove toluene and residual AOMA by distillation. The target fraction was then separated using a medium-pressure preparative liquid chromatograph (YFLC AI-580, manufactured by Yamazen Corporation). To the separated fraction, a polymerization inhibitor (6-t-butyl-2,4-xylenol, manufactured by Tokyo Chemical Industries, Ltd.) was added at a concentration of 300 ppm relative to the target sample, and a polymerization inhibitor (triphenyl phosphite, manufactured by ADEKA Corporation) was added at a concentration of 500 ppm relative to the target sample. The solvent was then removed by distillation, and the target sample AOMA-TPG was isolated.

[0081] (Manufacturing Example 2) Manufacturing of AOMA-THF AOMA-THF was obtained using the same method as in Production Example 1, except that tetrahydrofurfuryl alcohol was used instead of tripropylene glycol.

[0082] (Manufacturing Example 3) Manufacturing of AOMA-L AOMA-L was obtained using the same method as in Production Example 1, except that lauryl alcohol was used instead of tripropylene glycol.

[0083] (Example 1, Comparative Examples 1-2) The monomers and fillers were mixed according to the composition shown in Table 2, and the viscosity of the resulting curable resin composition was evaluated.

[0084] [Table 2] Table 2 shows that curable resin compositions containing AMA groups have lower viscosity and better workability compared to compounds with similar linking groups or compounds with similar molecular weight structures.

[0085] (Examples 2-5, Comparative Examples 3-4) Curable resin compositions were prepared by mixing monomers, oligomers, fillers, and polymerization initiators according to the compositions shown in Table 3, and the viscosity of the samples was measured. Furthermore, the thermal decomposition temperature of the cured product and the thin-film curability and adhesion of the cured film were evaluated. The results are shown in Table 3.

[0086] [Table 3] The results in Table 3 clearly show that the curable composition of this disclosure has excellent heat resistance and can provide high adhesion.

[0087] (Example 6, Comparative Example 5) Curable resin compositions were prepared by mixing monomers and polymerization initiators according to the formulations shown in Table 4, and the viscosity of the samples was measured. Furthermore, the thermal decomposition temperature, glass transition temperature, and storage modulus of the cured products were evaluated. The results are shown in Table 4.

[0088] [Table 4] The results in Table 4 clearly show that the curable composition of this disclosure exhibits excellent heat resistance and elastic modulus.

Claims

1. A curable composition comprising two or more compounds represented by the following general formula (1), 【Chemistry 1】 (In equation (1), n ​​is a number greater than or equal to 1, and Z represents an n-valent organic group.) Furthermore, the curable composition is characterized by containing inorganic particles consisting of metal oxides and / or composite metal oxides in an amount of 1 to 9900 parts by mass per 100 parts by mass of the total compound represented by general formula (1).

2. The claim according to claim 1, satisfying at least one of (i) or (ii) below. Curable composition. (i) The compound comprises one or more compounds in the above general formula (1) where n is 1 and the glass transition temperature of the homopolymer is less than 50°C, and one or more compounds in the above general formula (1) where n is 1 and the glass transition temperature of the homopolymer is 50°C or higher. (ii) The compound comprises one or more compounds in which n is 1 in the above general formula (1), and one or more compounds in which n is 2 or more in the above general formula (1).

3. A cured product of the curable composition according to claim 1 or 2.

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