Composition

Abstract

The objective is to provide a composition containing an ether-based monomer that is less susceptible to the effects of oxygen, particularly inhibits the progression of oxidation reactions accelerated by heat and light, and prevents unintended thickening or gelation during storage or use. Furthermore, the objective is to provide compositions for various applications that have excellent heat resistance, light resistance, and good stability, as well as products using these compositions. [Solution] A composition containing a polymerizable compound having one or more ether bonds and one or more ethylenically unsaturated bonds in its molecule, and an antioxidant was discovered.

Description

[Technical Field]

[0001] The present invention relates to a composition containing a polymerizable compound having one or more ether bonds and one or more ethylenically unsaturated bonds in its molecule, and an antioxidant, and uses thereof. [Background technology]

[0002] Compounds containing ether bonds and ethylenically unsaturated bonds (hereinafter referred to as "ether monomers") have high compatibility with general-purpose monomers, oligomers, etc., and can be suitably used in thermal polymerization or photopolymerization compositions, and are therefore widely used in various fields. However, because these compounds contain ether bonds, they are prone to gradual auto-oxidation into peroxides under the influence of oxygen, and the oxidation reaction is particularly accelerated in the presence of heat and light. Since the peroxides produced by auto-oxidation can act as triggers (initiators) for polymerization reactions, compositions containing ether monomers may experience increased viscosity or gelation over time.

[0003] For example, when a composition containing ether monomers is used in inkjet ink, it may cause nozzle clogging and lead to poor ejection. In addition, when the same composition is used in adhesives or coatings, the composition itself or the polymer obtained by polymerizing or curing the composition may yellow over time. Such yellowing poses a problem in fields such as optics, as it adversely affects quality and performance.

[0004] Patent Document 1 discloses a method for producing isocyanate compounds containing ether bonds and ethylenically unsaturated groups. In this document, a technique is proposed to control the polymerization reaction of ethylenically unsaturated groups while maintaining the stability of the ether bond, by using a specific reaction solvent in which the solubility of hydrogen chloride at 25°C is 0.1 mol% or less, and carrying out the reaction within a predetermined temperature range. While such a technique is effective in the production process of ether monomers, it does not solve the problems of increased viscosity, gelation, and yellowing over time due to oxidation during storage of high-purity ether monomer products. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] International Publication No. 2008 / 143207 [Overview of the Initiative] [Problems that the invention aims to solve]

[0006] The present invention aims to provide a composition containing an ether-based monomer that is less susceptible to the effects of oxygen, particularly inhibits the progression of oxidation reactions accelerated by heat and light, and prevents unintended thickening or gelation during storage or use. Furthermore, the invention aims to provide compositions for various applications that, by containing this composition, have excellent heat resistance, light resistance, and good stability, as well as products using these compositions. [Means for solving the problem]

[0007] The present inventors conducted extensive research to solve the aforementioned problems and, as a result, discovered a composition containing an ether monomer and an antioxidant, leading to the present invention.

[0008] The present invention includes the following: (1) A composition containing a polymerizable compound having one or more ether bonds and one or more ethylenically unsaturated bonds in its molecule, and an antioxidant. (2) The composition according to (1), wherein the antioxidant comprises a phenolic compound and / or an amine compound. (3) The composition according to (1) or (2), wherein the antioxidant comprises a tertiary amine compound having an amide group and / or an ester group. (4) The composition according to any one of (1) to (3), wherein the molecular weight of the antioxidant is 100 to 2000. (5) A composition according to any one of (1) to (4) containing a thermal polymerization initiator and / or a photopolymerization initiator. (6) A composition according to any one of (1) to (6) containing an oligomer and / or polymer. (7) A coating agent composition containing the composition described in any one of the above items (1) to (6). (8) An ink composition containing the composition described in any one of the above items (1) to (6). (9) A three-dimensional printing ink composition containing the composition described in any one of the above items (1) to (6). (10) An adhesive composition containing the composition described in any one of the above items (1) to (6). (11) An adhesive composition containing the composition described in any one of the above items (1) to (6). (12) A paint composition containing the composition described in any one of the above items (1) to (6). (13) A sealing agent composition containing the composition described in any one of the above items (1) to (6). (14) A cosmetic composition for nails containing the composition described in any one of the above items (1) to (6). (15) A decorative coating agent composition containing the composition described in any one of the above items (1) to (6). (16) A dental material composition containing the composition described in any one of the above items (1) to (6). (17) A photosensitive resin composition containing the composition described in any one of the above items (1) to (6). [Effects of the Invention]

[0009] According to the present invention, by coexisting an ether monomer and an antioxidant, the autoxidation of the ether monomer can be effectively suppressed. As a result, the generation of peroxides that can serve as initiators for the polymerization reaction is prevented, and a composition containing an ether monomer and an antioxidant exhibits high stability during storage or use, and even under harsh environments such as heating or light irradiation.

[0010] The composition has excellent stability against heat and light, and by containing this, it is possible to provide a composition that is excellent in heat resistance, light resistance, and has high stability, and is suitable for various applications such as coating agents, inks, inks for three-dimensional modeling, adhesives, adhesives, paints, sealants, nail cosmetics, decorative coating agents, dental materials, photosensitive resins, etc.

[0011] Furthermore, the antioxidant does not inhibit the progress of the polymerization reaction in the composition, and the composition and various compositions for applications containing this can obtain a uniform polymer or cured product. The obtained cured product is excellent in physical properties such as transparency, yellowing resistance, coating property, surface smoothness, and curability.

Embodiments for Carrying Out the Invention

[0012] Embodiments of the present invention will be listed below and described in detail. However, the scope of the present invention is not limited to the embodiments shown below, and can be changed without departing from the gist of the present invention. Also, for specific parameters, when a plurality of upper limit values and lower limit values are described, a suitable numerical range can be set by any combination of these upper limit values and lower limit values.

[0013] In this specification, the “(meth)acryloyl group” means both an acryloyl group and a methacryloyl group, the “(meth)acrylate” means both an acrylate and a methacrylate, and the “(meth)acrylamide” means both an acrylamide and a methacrylamide.

[0014] The composition of the present invention contains an ether monomer (A) (hereinafter referred to as "compound A") and an antioxidant (B) (hereinafter referred to as "component B"). Compound A is a compound having one or more ether bonds and one or more ethylenically unsaturated bonds in its molecule.

[0015] The ether bond contained in compound A is not particularly limited and may be either a linear ether structure or a cyclic ether structure. Compound A may have only one type of ether structure, or it may have two or more different structures.

[0016] Examples of chain-like ether structures include ethylene oxide units represented by (-CH2CH2O-), propylene oxide units represented by (-CH(CH3)CH2O-), and tetramethylene oxide units represented by -(CH2)4O-. Furthermore, polyether structures ((poly)oxyalkylene structures) formed by the linkage of multiple such units may also be present.

[0017] Examples of cyclic ether structures include oxirane rings, oxetane rings, furan rings, tetrahydrofuran rings, dioxolane rings, oxathiolane rings, tetrahydropyran rings, dioxane rings, and morpholine rings.

[0018] Compound A has high molecular chain flexibility due to the presence of ether bonds, allowing for the adjustment of the composition's viscosity to a low level. This makes it possible to reduce the amount of solvent used or design solvent-free compositions. Furthermore, polymers obtained by polymerizing or curing a composition containing compound A exhibit excellent flexibility and extensibility, as well as superior adhesion to substrates, due to the flexible backbone derived from the ether bonds within the polymer. On the other hand, a large number of ether bonds increases the likelihood of auto-oxidation. From this viewpoint, the number of ether bonds contained within the molecule of compound A is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 4.

[0019] The ethylenically unsaturated bond in compound A is not particularly limited as long as it is a polymerizable functional group. Specifically, any functional group that initiates radical polymerization upon heat or light and forms a polymer or cured product can be suitably used.

[0020] Examples of ethylenically unsaturated bonds include (meth)acryloyl groups, (meth)acrylate groups, (meth)acrylamide groups, vinyl groups, allyl groups, and maleimide groups. Among these, (meth)acryloyl groups, (meth)acrylate groups, and (meth)acrylamide groups are preferred due to their high polymerization reactivity. Compound A may have one type of ethylenically unsaturated bond, or it may have two or more different types of bonds.

[0021] The more ethylenically unsaturated bonds there are, the higher the crosslinking density, and the better the hardness, heat resistance, chemical resistance, and glass transition temperature (Tg) of the cured product obtained from the composition. On the other hand, a large number of ethylenically unsaturated bonds tends to reduce the flexibility and extensibility of the polymer obtained by polymerization or curing, and increase the curing shrinkage rate. From this viewpoint, the number of ethylenically unsaturated bonds contained in the molecule of compound A is preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 3.

[0022] The ether bond and ethylenically unsaturated bond in compound A may be directly linked or linked by any linking group. Examples of linking groups include linear or branched alkylene groups such as methylene, ethylene, and propylene; alkenylene groups such as vinylene and propenylene; alkynylene groups such as ethynylene and propynylene; alicyclic hydrocarbon groups such as cyclohexylene and cyclohexanedimethylene; aromatic hydrocarbon groups such as phenylene, naphthylene, and biphenylene; and linking groups with branched structures such as neopentyl residues (2-branched) derived from neopentyl glycol, trimethylol residues (3-branched) derived from trimethylolpropane and glycerin, pentaerythritol residues (4-branched) derived from pentaerythritol, ditrimethylolpropane residues (4-branched) derived from ditrimethylolpropane, and dipentaerythritol residues (6-branched) derived from dipentaerythritol.

[0023] The following are specific examples of compound A, but the present invention is not limited to these. Examples of chain-like ether monomers having one (meth)acrylate group in the molecule include (methoxymethyl)(meth)acrylate, (methoxyethyl)(meth)acrylate, (methoxypropyl)(meth)acrylate, (methoxybutyl)(meth)acrylate, (ethoxymethyl)(meth)acrylate, (ethoxyethyl)(meth)acrylate, (ethoxypropyl)(meth)acrylate, (ethoxybutyl)(meth)acrylate, (butoxymethyl)(meth)acrylate, (butoxyethyl)(meth)acrylate Relate, (butoxypropyl)(meth)acrylate, (butoxybutyl)(meth)acrylate, (isobutoxymethyl)(meth)acrylate, (isobutoxyethyl)(meth)acrylate, (isobutoxypropyl)(meth)acrylate, (isobutoxybutyl)(meth)acrylate, ethylene glycol monomethyl ether (meth)acrylate, diethylene glycol monomethyl ether (meth)acrylate, triethylene glycol monomethyl ether (meth)acrylate, ethylene glycol mono Ethyl ether (meth)acrylate, diethylene glycol monoethyl ether (meth)acrylate, triethylene glycol monoethyl ether (meth)acrylate, ethylene glycol monopropyl ether (meth)acrylate, diethylene glycol monopropyl ether (meth)acrylate, triethylene glycol monopropyl ether (meth)acrylate, ethylene glycol monobutyl ether (meth)acrylate, diethylene glycol monobutyl ether (meth)acrylate, triethylene glycol monobutyl ether (meth)acrylate, phenoxyethylene glycol (meth)acrylate, propylene glycol monomethyl ether (meth)acrylate, dipropylene glycol monomethyl ether (meth)acrylate, propylene glycol monoethyl ether (meth)acrylate, dipropylene glycol monoethyl ether (meth)acrylate, propylene glycol monopropyl ether (meth)acrylate, dipropylene glycol monopropyl ether (meth)acrylate,Examples include propylene glycol monobutyl ether (meth)acrylate, dipropylene glycol monobutyl ether (meth)acrylate, and phenoxypropylene glycol (meth)acrylate.

[0024] Examples of chain-like ether monomers having two or more (meth)acrylate groups in the molecule include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, and dipentaerythritol hexaacrylate.

[0025] Examples of chain-like ether monomers having one (meth)acrylamide group in the molecule include N-(methoxymethyl)(meth)acrylamide, N-(methoxyethyl)(meth)acrylamide, N-(methoxypropyl)(meth)acrylamide, N-(methoxybutyl)(meth)acrylamide, N-(ethoxymethyl)(meth)acrylamide, N-(ethoxyethyl)(meth)acrylamide, N-(ethoxypropyl)(meth)acrylamide, N-(ethoxybutyl)(meth)acrylamide, and N-(butoxymethyl)(meth)acrylamide. Amides, N-(butoxyethyl)(meth)acrylamide, N-(butoxypropyl)(meth)acrylamide, N-(butoxybutyl)(meth)acrylamide, N-(isobutoxymethyl)(meth)acrylamide, N-(isobutoxyethyl)(meth)acrylamide, N-(isobutoxypropyl)(meth)acrylamide, N-(isobutoxybutyl)(meth)acrylamide, ethylene glycol monomethyl ether (meth)acrylamide, diethylene glycol monomethyl ether (meth)acrylamide, triethylene glycol Polyethylene glycol monoethyl ether (meth)acrylamide, ethylene glycol monoethyl ether (meth)acrylamide, diethylene glycol monoethyl ether (meth)acrylamide, triethylene glycol monoethyl ether (meth)acrylamide, ethylene glycol monopropyl ether (meth)acrylamide, diethylene glycol monopropyl ether (meth)acrylamide, triethylene glycol monopropyl ether (meth)acrylamide, ethylene glycol monobutyl ether (meth)acrylamide, diethylene glycol monobutyl ether (meth)acrylamide, triethylene glycol monobutyl ether (meth)acrylamide, phenoxyethylene glycol (meth)acrylamide, propylene glycol monomethyl ether (meth)acrylamide, dipropylene glycol monomethyl ether (meth)acrylamide, propylene glycol monoethyl ether (meth)acrylamide, dipropylene glycol monoethyl ether (meth)acrylamide, propylene glycol monopropyl ether (meth)acrylamide,Examples include dipropylene glycol monopropyl ether (meth)acrylamide, propylene glycol monobutyl ether (meth)acrylamide, dipropylene glycol monobutyl ether (meth)acrylamide, and phenoxypropylene glycol (meth)acrylamide.

[0026] Examples of chain-like ether monomers having two or more (meth)acrylamide groups in the molecule include ethylene glycol di(meth)acrylamide, diethylene glycol di(meth)acrylamide, triethylene glycol di(meth)acrylamide, propylene glycol di(meth)acrylamide, dipropylene glycol di(meth)acrylamide, tripropylene glycol di(meth)acrylamide, N,N'-[oxybis(2,1-ethanediyloxy-3,1-propanediyl)]bisacrylamide, and N-[tris(3-acrylamidepropoxymethyl)methyl](meth)acrylamide.

[0027] Examples of cyclic ether monomers having a (meth)acryloyl group include (meth)acryloylmorpholine, (meth)acryloyloxyethylmorpholine, and (meth)acryloyloxypropylmorpholine.

[0028] Examples of cyclic ether monomers having a (meth)acrylate group include glycidyl (meth)acrylate, (methyloxyranyl)methyl (meth)acrylate, furfuryl (meth)acrylate, furfuryl ethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, tetrahydrofurfuryl ethyl (meth)acrylate, dioxolane (meth)acrylate, (2-methyl-2-ethyl-1,3-dioxolane-4-yl)methyl acrylate, dioxolanedi (meth)acrylate, 2-(tetrahydropyran-2-yl)methyl (meth)acrylate, 2-(tetrahydropyran-2-yl)ethyl (meth)acrylate, 1,3-dioxan-5-ylmethyl (meth)acrylate, and cyclic trimethylolpropaneformal (meth)acrylate.

[0029] Examples of cyclic ether monomers having a (meth)acrylamide group include N-glycidyl(meth)acrylamide, N-furfuryl(meth)acrylamide, N-furfurylethyl(meth)acrylamide, N-tetrahydrofurfuryl(meth)acrylamide, N-tetrahydrofurfurylethyl(meth)acrylamide, dioxolane(meth)acrylamide, 2-(tetrahydropyran-2-yl)methyl(meth)acrylamide, 2-(tetrahydropyran-2-yl)ethyl(meth)acrylamide, and 1,3-dioxan-5-ylmethyl(meth)acrylamide.

[0030] Component B is not particularly limited, as long as it exerts the desired effect. The presence of component B makes compound A less susceptible to the effects of oxygen, and in particular, it can suppress the progress of auto-oxidation of ether bonds, which is accelerated by heat and light. This effectively prevents unintended thickening or gelation during storage or use. Furthermore, it exhibits high stability even under harsh conditions such as heating and light irradiation.

[0031] During the oxidation of compound A, peroxides are generated, and their decomposition produces radical species. These radicals can trigger oxidation chain reactions with other organic compounds, particularly those containing ether groups. Therefore, component B is preferably a compound that has the function of stopping radical chain reactions, and antioxidants with radical scavenging ability are particularly effective.

[0032] Specific examples of component B include phenolic compounds and amine compounds. These effectively halt the oxidation chain reaction by reacting with radical species to form stable non-radical species. Component B may be used alone or in combination with other components. It is preferable to use antioxidants in combination, as a synergistic effect can be expected, and the stability of compound A is further improved by using at least a phenolic compound or an amine compound.

[0033] The amount of component B added is determined appropriately depending on the type of compound A, the usage conditions, the storage period, etc. Since excessive addition may affect the polymerization reaction, it is desirable to obtain a sufficient oxidation inhibitory effect with the minimum necessary amount.

[0034] The molecular weight of component B is not particularly limited and should be appropriately selected according to the properties of compound A and the conditions of use. Antioxidants with low molecular weight are highly volatile and tend to be lost easily during long-term storage. On the other hand, antioxidants with high molecular weight are less volatile and remain stably present in compound A, so a long-term antioxidant effect can be expected. In addition, antioxidants with high molecular weight often have excellent compatibility and dispersibility with compound A, making it easier to exert a uniform antioxidant effect.

[0035] From this perspective, the molecular weight of component B is preferably 100 to 2000, more preferably 120 to 1200, even more preferably 150 to 800, and most preferably 150 to 400. Component B within this molecular weight range has a good balance of volatility and stability and is particularly suitable for compound A.

[0036] Component B can include radical chain arresters, hydrogen peroxide decomposers, and metal deactivators. Each of these inhibits oxidation reactions through different mechanisms, but radical chain arresters and peroxide decomposers are preferred, with radical chain arresters being even more preferred. Radical chain arresters are highly effective in improving the oxidative stability of compound A by breaking the oxidation reaction chain.

[0037] Phenolic compounds used as radical chain arresters are classified into monophenol, bisphenol, and hindered phenol types according to their structure. Monophenol compounds are relatively low molecular weight compounds with one phenol group and tend to be highly volatile, but are effective in suppressing initial oxidation. Bisphenol compounds have two phenol groups and exhibit higher stability and antioxidant effect. Hindered phenol compounds have bulky substituents around the phenol group, resulting in high stability of phenoxy radicals and excellent long-term oxidation suppression. These phenolic compounds are preferably used alone or in combination with other antioxidants to effectively suppress the oxidation reaction of compound A.

[0038] Monophenol types include simple alkylphenols such as 4-methoxyphenol, hydroquinone, methylhydroquinone, tert-butyl-hydroquinone, 2,6-diisobutylphenol, 2,6-di-t-butyl-4-methylphenol, styrene-phenol, 2,5-di-t-amylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol, DL-α-tocopherol (vitamin E), phenol esters such as 2-ethylhexyl-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate, iso-octyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, stearyl(3,5-di-t-butyl-4-hydroxyphenyl)propionate, and tridecyl-3,5-di-t- Examples include phenol thioethers such as butyl-4-hydroxybenzylthioacetate, 2-methyl-4,6-bis(octylsulfanylmethyl)phenol, and 4,6-bis(octylthiomethyl)-o-cresol; phenol acrylates such as 2-t-butyl-6-(3-t-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate and 2-(1-(2-hydroxy-3,5-di-t-pentylphenyl)ethyl)-4,6-di-t-pentylphenyl acrylate; and triazine-bonded compounds such as 2,6-di-t-butyl-4-(4,6-bis(octylthio)-1,3,5-triazine-2-ylamino)phenol and 2-octylthio-4,6-di(3,5-di-t-butyl-4-hydroxyphenoxy)-s-triazine.

[0039] Examples of bisphenol types include alkylene bisphenol types such as 1,6-hexanediol-bis(3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate), 2,2'-methylenebis(4-ethyl-6-t-butylphenol), and 2,2'-methylenebis(6-(1-methylcyclohexyl)-p-cresol), thiobisphenol types such as thiodiethylenebis(3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate), 2,2'-thiobis(6-t-butyl-4-methylphenol), and 4,4'-thiobis(6-t-butyl-m-cresol), triethylene glycol-based bisphenol propionates, and ethylenebis(oxyethylene Examples include polyether types such as bisphenol propionate and bis(2-t-butyl-4-methyl-6-(2-hydroxy-3-t-butyl-5-methylbenzyl)phenyl) terephthalate, phosphonate types such as diethyl((3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl)methyl)phosphonate, calcium diethylbis((3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl)methyl)phosphonate, and distearyl(3,5-di-t-butyl-4-hydroxybenzyl)phosphonate, and amide types such as N,N'-hexane-1,6-diylbis(3-(3,5-di-t-butyl-4-hydroxyphenyl)propionamide).

[0040] Hindered phenol types include polyfunctional ester structures such as glycerin tris(3-(3,5-di-t-butyl-4-hydroxyphenyl)-propionate), pentaerythritol tetrakis(3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate), and tetrakis(methylene-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate)methane; isocyanurate skeleton types such as 1,3,5-tris(2,6-dimethyl-3-hydroxy-4-t-butylbenzyl)isocyanurate; and 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione. Examples include triazine skeleton types, aromatic ring polysubstituted types such as 3,3',3”,5,5',5”-hexa-t-butyl-α,α',α”-(mesitylene-2,4,6-tolyl)tri-p-cresol and 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, aliphatic and cyclic ester types such as octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, and amide and urea types such as N,N'-hexane-1,6-diyrbis(3-(3,5-di-t-butyl-4-hydroxyphenyl)propionamide) and 2,2'-oxamide-bis(ethyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate).

[0041] Amine compounds are classified into primary or secondary amines, tertiary amines, and high molecular weight amines (including primary to tertiary amines) based on differences in their structure and functional groups. These amine compounds react with active radicals derived from peroxides generated by the auto-oxidation of compound A, thereby stopping the radical chain reaction and preventing the chain oxidation of compound A.

[0042] In particular, the use of tertiary amines is preferred. Primary and secondary amines have active hydrogen atoms on their nitrogen atoms, and therefore may react with compound A or other components in the composition. In contrast, tertiary amines do not have hydrogen atoms on their nitrogen atoms, thus suppressing side reactions with other components and preventing unintended reactions. Furthermore, among tertiary amines, those with certain structures, such as compounds with a piperidyl ring, that have multiple hydrogen atoms (α-hydrogens) on the carbon adjacent to the nitrogen atom (α-carbon), are effective as hydrogen donors that contribute to oxidation prevention and exhibit excellent sustained antioxidant effects. On the other hand, while primary and secondary amines have active hydrogen atoms that react rapidly with peroxides, etc., the number of α-hydrogens available for oxidation prevention is limited, and therefore they tend to have inferior sustained antioxidant effects.

[0043] Examples of primary or secondary amines include 1,2-diaminocyclohexane, 1,6-hexanediamine, 2-methyl-1,5-pentanediamine, N,N'-diphenyl-p-phenylenediamine, N-phenyl-N'-isopropyl-p-phenylenediamine, N-cyclohexyl-N'-phenyl-p-phenylenediamine, N-1,3-dimethylbutyl-N'-phenyl-p-phenylenediamine, N-phenyl-N'-benzyl-p-phenylenediamine, 4,4'-diamino-3,3'-dimethyldicyclohexylmethane, diaminecyclohexane, isophoronediamine, and 3-amino-N-[(tetrahydro-2-furyl)methyl]propanamide.

[0044] Tertiary amines include N-(3-dimethylaminopropyl)acrylamide, 2-(dimethylamino)ethyl acrylate, N-methyl-N-(3,5-di-tert-butyl-4-hydroxyphenyl)aniline, N-methyl-N-benzylaniline, N-phenyl-N-(2-naphthyl)amine, diphenylamine, N-methyldiphenylamine, triphenylamine, N-phenyl-1-naphthylamine, 4-isopropoxydiphenylamine, bis(4-t-butylphenyl)amine, bis(4-nonylphenyl)amine, bis(4-butyl Examples include bis(4-methoxyphenyl)amine, trimethylamine, triethylamine, triisopropylamine, tributylamine, tricyclohexylamine, trioctylamine, tristearylamine, diisopropylmethylamine, dimethylstearylamine, dimethyloleylamine, dimethylbenzylamine, N-methylmorpholine, N-ethylmorpholine, N-benzylmorpholine, methyl 3-(morpholinyl)propionate, morpholide 3-(morpholino)propionate, and N-methylpiperazine.

[0045] Examples of high molecular weight amines include 1,6,11-tris(2,4-bis(N-butyl-N-(2,2,6,6-tetramethyl-4-piperidyl)amino)-s-triazine-6-yl)aminoundecane, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, bis(2,2,6,6-tetramethyl-4-piperidyl)di(tridecyl)-1,2,3,4-butanetetracarboxylate, 1,5,8,12-tetrakis(2,4-bis(N-butyl-N-(2,2,6,6-tetramethyl-4-piperidyl)amino)-s-triazine-6-yl)-1,5,8,12-tetraazadodecane, and high molecular weight tertiary amines such as poly(N-methylacrylamide) derivatives.

[0046] Amine compounds preferably have electron-withdrawing structures within their molecules. Having electron-withdrawing structures increases the acidity of hydrogen atoms bonded to carbon atoms adjacent to nitrogen (α-carbons), making these hydrogens more reactive to radicals derived from peroxides. This enhances the function of amine compounds as radical scavengers, improving their antioxidant effect. Examples of such electron-withdrawing structures include carbonyl groups, amide groups, ester groups, and acryloyl groups. These functional groups reduce the electron density within the molecule and promote α-hydrogen abstraction, effectively halting the oxidation chain reaction.

[0047] The electron-withdrawing effect of a structure is stronger the closer it is to the α-carbon, and it is preferable that it is located within three bonds from the α-carbon, and more preferably within two bonds. In particular, carbonyl groups, amide groups, ester groups, acryloyl groups, oxygen atoms, nitrogen atoms, etc., are strongly electron-withdrawing and contribute to the activation of the α-hydrogen, so they are preferred, and among these, ester groups or amide groups are more preferred because they have an excellent balance between structural stability and reactivity.

[0048] The ester group has a structure represented as RC(=O)-O-R'. Hereafter, R will be represented as the carboxylic acid side structure and R' as the alcohol side structure. Tertiary amine compounds having an ester group in the molecule include methyl 3-(N,N-dimethylamino)propionate, methyl 4-(N,N-dimethylamino)butyrate, methyl 3-(N-ethyl-N-methylamino)propionate, methyl 5-(N,N-dimethylamino)valerate, ethyl 4-(N,N-dimethylamino)butyrate, propyl 3-(N,N-dimethylamino)propionate, methyl 3-(N,N-diethylamino)propionate, methyl 6-(N,N-dimethylamino)hexanoate, ethyl 5-(N,N-dimethylamino)valerate, 3 -(N,N-dimethylamino)propionate butyl, 3-(N,N-dimethylamino)propionate tert-butyl, 3-(N-tert-butyl-N-methylamino)propionate methyl, 3-(N-cyclopentyl-N-methylamino)propionate methyl, 3-(N,N-dimethylamino)propionate cyclopentyl, 3-(N-cyclohexyl-N-methylamino)propionate methyl, 3-(N,N-dimethylamino)propionate cyclohexyl, 3-(N-methyl-N-phenylamino)propionate methyl, 3-(N,Phenyl N-dimethylamino)propionate, methyl 3-(pyrrolidinyl)propionate, ethyl 3-(pyrrolidinyl)propionate, butyl 3-(pyrrolidinyl)propionate, methyl 4-(pyrrolidinyl)butyrate, ethyl 4-(pyrrolidinyl)butyrate, ethyl 6-(pyrrolidinyl)hexanoate, phenyl 3-(pyrrolidinyl)propionate, methyl 3-(piperidinyl)propionate, butyl 3-(piperidinyl)propionate, tert-butyl 4-(piperidinyl)butyrate, 3-(piperidinyl)propionate Compounds having a tertiary amine in the carboxylic acid structure, such as cyclohexyl benzoate, phenyl 3-(piperidinyl)propionate, methyl 3-(morpholinyl)propionate, ethyl 3-(morpholinyl)propionate, methyl 4-(morpholinyl)butyrate, methyl 4-(morpholinyl)pentanoate, phenyl 3-(morpholinyl)propionate, and cyclohexyl 4-(morpholinyl)butyrate; 2-dimethylaminoethyl acetate, 3-dimethylaminopropyl acetate, and 2-dimethylaminoethylpropanoate. , 2-dimethylaminoethyl butyrate, 4-dimethylaminobutyl acetate, 2-dimethylaminoethylcyclopropane carboxylate, 2-dimethylaminoethylcyclopentane carboxylate, 2-dimethylaminoethylcyclohexane carboxylate, cyclohexylmethylaminoethyl acetate, pyrrolidine-1-ethanol acetate, pyrrolidine-1-propanol acetate, piperidine-1-ethyl acetate, pyrrolidine-1-ethylcyclopropane carboxylate, pi Examples include compounds having a tertiary amine in the alcohol side of the structure, such as loridine-1-ethylneopentate, 2-(piperidine-1-yl)ethyl, 2,2-dimethylpropanoate, 3-(piperidine-1-yl)propylbenzoate, 2-(morpholinyl)ethyl acetate, 2-(morpholinyl)ethylpropionic acid, 3-(morpholinyl)propyl acetate, 2-(4-morpholinyl)ethylcyclopentanecarboxylic acid, and 2-(morpholinyl)ethylbenzoate.

[0049] The amide group has a structure represented as RC(=O)-N-R'. Hereafter, R will be represented as the carboxylic acid side structure and R' as the amine side structure. Tertiary amine compounds having an amide group in the molecule include 2-(dimethylamino)-N-methylacetamide, 3-(dimethylamino)-N-methylpropanamide, 2-(ethylmethylamino)-N-methylacetamide, N-methyl-2-(cyclopropylmethylamino)acetamide, 2-(dimethylamino)-N-cyclopropylacetamide, 2-(dimethylamino)-N-butylacetamide, 2-(dimethylamino)-N,N-diethylacetamide, N-(1H-pyrrole-1-yl)-2-(dimethylamino)acetamide, N-methyl-1-pyrrolidineacetamide, N-methyl-1-piperidineacetamide, N,N-dimethyl-1-pyrrolidineacetamide, N-cyclopropyl-1-pyrrolidineacetamide, N-3-azetidinyl-1-pyrrolidineacetamide, N-methyl-1-piperidinebutanamide, N-cyclopentyl-1-pyrrolidineacetamide, N-(1,1-dimethylethyl)-1-piperidineacetamide, N,N-diethyl-1-piperidineacetamide, N-methyl-4-morpholineacetamide, N-methyl-4-morpholinepropanamide, N,N-dimethyl-4-morpholineacetamide, N-cyclopropyl-4-morpholineacetamide, N-ethyl-4-morpholinepropanamide, N,N-dimethyl-4-morpholinepropanamide, N-ethyl-N-methyl-4-morpholinepropanamide, N,Compounds having a tertiary amine in the structure of a carboxylic acid such as N-diethyl-4-morpholinepropanamide, 3-(morpholino)propionate morpholide, N-(2-pyridinyl)-4-morpholineacetamide, N-(dimethylaminomethyl)acetamide, N-(2-dimethylaminoethyl)acetamide, N-(3-dimethylaminopropyl)acetamide, N-(2-diethylaminoethyl)acetamide, N-(2-diethylaminoethyl)propanamide, N-(dimethylaminomethyl)-2-pyrazinecarboxamide, N-(2-pyrrolidinylethyl)acetamide Examples include amides, N-(1-piperidinylmethyl)acetamide, N-(3-pyrrolidinylpropyl)acrylamide, N-(2-pyrrolidinylethyl)cyclopropanecarboxamide, N-(4-morpholinylmethyl)acetamide, N-(2-morpholinylethyl)acetamide, N-(2-morpholinylethyl)propanamide, N-(morpholinomethyl)benzamide, N-(4-morpholinylmethyl)-3-pyridinecarboxamide, 1H-pyrrole-3-carboxamide-N-morpholinylethyl, and other compounds having a tertiary amine in the amine-side structure.

[0050] Hydrogen peroxide decomposers promote the decomposition of peroxides generated during the oxidation process of compound A, thereby preventing the generation of radicals. Typical examples include phosphate ester compounds, thioester compounds, and thioether compounds. Specifically, the following compounds are examples: Phenyl phosphites such as diphenyl phosphite, triphenyl phosphite, trisnonylphenyl phosphite, diphenylisodecyl phosphite, tris(2,4-di-tert-butylphenyl) phosphite, mono(dinonylphenyl)mono-p-nonylphenyl phosphite, tetraalkyl(C12~C16)-4,4'-isopropylidene-(bisphenyl) diphosphite, alkyl phosphites such as triisooctyl phosphite, tridecyl phosphite, trilauryl phosphite, pentaerythritol skeleton types such as distearyl pentaerythritol diphosphite and bis(2,4-di-t-butylphenyl)pentaerythritol diphosphite, heptakis( Examples include polyol phosphites such as dipropylene glycol triphosphite, tris(dipropylene glycol)phosphite, and poly(dipropylene glycol)phenyl phosphite; thioester compounds such as tetrakis(methylene-3-(laurylthio)propionate)methane, bis(methyl-4-(3-n-alkyl(C12~C14)thiopropionyloxy)-5-t-butylphenyl)sulfide, didodecylthiodipropionate, and lauryl / stearylthiodipropionate; and thioether compounds such as pentaerythritoltetrakis(3-laurylthiopropionate), dialkyl-3,3'-thiodipropionate, and 2-mercaptobenzimidazole.

[0051] Metal deactivators are used to prevent metal ions from catalyzing oxidation reactions. These include chelating agents and metal sequestering agents, which inhibit the progression of oxidation reactions by binding to metal ions and reducing their catalytic activity. Typical examples include hydrazine compounds and amide compounds. Specifically, the following compounds are examples: N'1,N'12-bis(2-hydroxybenzoyl)dodecanedihydrazide, 1,2-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propanoyl]hydrazine, N,N'-diphenyloxamide, N,N'-bis(salicyl)hydrazine, N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine, bis(benzylidene)oxalyldihydrazide, isophthaloyldi Examples include hydrazides, sebacoylbisphenylhydrazide, N,N'-diacetyladipoyldihydrazide, N,N'-bis(salicyroyl)thiopropionyldihydrazide, and amide compounds such as N-2-ethylphenyl-N'-2-ethoxyphenyloxalamide, N-(1,2,4-triazole-3-yl)salicylamide, and N-(1,2,4-triazole-3-yl)-3-methylsalitchlamide.

[0052] The amounts of compound A and component B in the composition of the present invention are not particularly limited. Specifically, compound A is preferably 10 to 99.999% by mass of the whole composition, more preferably 12 to 95% by mass, and even more preferably 15 to 90% by mass. By adjusting the amount of compound A, it is possible to easily control the balance between the flexibility and hardness of the resulting polymer and impart mechanical properties according to the application. Furthermore, since the crosslinking density and reactivity can be adjusted depending on the type and number of functional groups of compound A, it also has a positive effect on polymerizability and curability.

[0053] Component B is preferably present in an amount of 0.001 to 10% by mass, more preferably 0.02 to 8% by mass, and even more preferably 0.1 to 5.0% by mass, relative to the total composition. Uniform dispersion of component B in the composition maintains high transparency, resulting in less appearance defects such as discoloration and cloudiness in the resulting polymer. Furthermore, an appropriate amount of component B improves the persistence of the antioxidant effect, contributing to the long-term quality stability of the product.

[0054] The viscosity of the composition of the present invention is not particularly limited and can be appropriately adjusted depending on the type and proportion of the components included, as well as the intended use of the composition. Furthermore, by including a specific antioxidant (component B), the composition of the present invention can suppress thickening and gelation caused by heat and light.

[0055] The composition of the present invention may contain a third component (C) (hereinafter referred to as "component C") in addition to compound A and component B. Component C is added for the purpose of improving the functionality, processability, curability, appearance, and functionality of the resulting polymer and cured product of the composition, and is selected as appropriate according to the desired performance.

[0056] Component C includes polymerization initiators, polymerizable compounds (excluding compound A), non-polymerizable compounds (excluding component B), and other additives. These may be used individually or in combination of two or more. Polymerizable compounds participate in the polymerization reaction together with compound A and are used to adjust the physical properties and structure of the polymer. On the other hand, non-polymerizable compounds are used to impart auxiliary functions such as plasticity, fluidity, surface properties, and dispersibility.

[0057] Examples of polymerization initiators include photopolymerization initiators and thermal polymerization initiators. Photopolymerization initiators generate radicals upon irradiation with ultraviolet or visible light, while thermal polymerization initiators decompose upon heating and generate radicals. By using these in combination, dual curing utilizing both photopolymerization and thermal polymerization becomes possible, improving the flexibility of curing conditions and the controllability of curing depth. In dual curing, the order of thermal polymerization and photopolymerization is not particularly limited, but performing photopolymerization first followed by thermal polymerization is preferable because it allows for uniform curing from the surface to the interior. The mixing ratio of photopolymerization initiator and thermal polymerization initiator can be appropriately adjusted depending on the type of initiator used, irradiation conditions, temperature conditions, etc.

[0058] <Photopolymerization initiator> Examples of photopolymerization initiators include radical polymerization initiators, cationic polymerization initiators, and anionic polymerization initiators. Among these, the use of radical polymerization initiators is preferred. Examples of radical polymerization initiators include acetophenone-based, benzoin-based, thioxanthone-based, acylphosphine oxide-based, and benzoyl glyceride-based initiators. One type of photopolymerization initiator may be used alone, or two or more types may be used in combination.

[0059] Examples of acetophenone-based photoinitiators include α-hydroxy-α,α'-dimethylacetophenone, methoxyacetophenone, 2-hydroxy-2-cyclohexylacetophenone, 1-hydroxycyclohexylphenyl ketone, 4-t-butyl-dichloroacetophenone, 2-hydroxy-2-methylpropiophenone, and 2-hydroxy-4'-isopropyl-2-methylpropiophenone. Examples of benzoin-based photoinitiators include benzoin, benzoin methyl ether, and anisole methyl ether. Examples of benzophenone-based photoinitiators include benzophenone, p-dimethylaminobenzophenone, benzophenone carboxylic acid, and 4-hydroxybenzophenone. Examples of thioxanthone-based photoinitiators include thioxanthone, 2-isopropylthioxanthone, 2,4-dichlorothioxanthone, dodecylthioxanthone, and 2,4-diethylthioxanthone. Examples of acylphosphine oxide-based photoinitiators include bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-2,4-di-n-butoxyphenylphosphine oxide, and bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphenylphosphine oxide.

[0060] Commercially available products include those manufactured by IGM Resins BV, such as Omnirad 1116, Omnirad 1173, Omnirad 184, Omnirad 369, Omnirad 500, Omnirad 651, Omnirad 754, Omnirad 819, Omnirad 907, Omnirad 1300, Omnirad 1800, Omnirad 1870, Omnirad 2959, Omnirad 4265, and Omnirad TPO, as well as products manufactured by UCB, such as Yubekrill P36.

[0061] The amount of photopolymerization initiator in the composition of the present invention is adjusted as appropriate depending on the composition, the reactivity of the monomer used, the irradiation conditions, etc. For example, it is preferably 0.1 to 10% by mass of the total composition, more preferably 0.5 to 7.0% by mass, and even more preferably 1.0 to 5.0% by mass. If the photopolymerization initiator is blended within this range, the composition will have sufficient curability, and the risk of curing failure or unreacted residue can be reduced. In addition, excessive blending may cause yellowing or odor.

[0062] The light irradiation conditions in the photopolymerization reaction can be appropriately set according to the absorption wavelength of the photopolymerization initiator used, the film thickness of the composition, the curing rate, etc. For example, high-pressure mercury lamps, metal halide lamps, xenon lamps, UV-LEDs, laser light sources, etc., can be used as irradiation methods. The irradiation wavelength is usually selected in the range of 200 nm to 405 nm, and UV-LEDs and laser light sources in particular have excellent wavelength controllability, enabling selective curing. The irradiation intensity and time also affect the curing depth and surface curability, so it is preferable to optimize them according to the characteristics of the composition.

[0063] <Thermal polymerization initiator> Examples of thermal polymerization initiators include azo compound initiators, organic peroxide initiators, and persulfate initiators. Examples of azo compound initiators include 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride, dimethyl-2,2'-azobis(2-methylpropionate), 2,2'-azobis(N-methyl-2-imidazoline), and 2,2'-azobis(2-amidinopropane)dihydrochloride. Examples of organic peroxide initiators include benzoyl peroxide, lauroyl peroxide, dicumyl peroxide, t-butyl peroxybenzoate, and methyl ethyl ketone peroxide. Examples of persulfate initiators include ammonium persulfate and sodium persulfate.

[0064] Examples of thermal polymerization methods include emulsion polymerization, solution polymerization, suspension polymerization, bulk polymerization, stepwise polymerization, and continuous polymerization. These methods are appropriately selected according to the structure, molecular weight, dispersibility, viscosity, etc., of the target polymer. The heating conditions in the thermal polymerization reaction are set based on the decomposition temperature of the thermal polymerization initiator used. Generally, it is preferable to heat at a temperature at least 10°C higher than the decomposition temperature of the initiator, and the temperature can usually be adjusted in the range of 60 to 120°C. The heating time is appropriately set in the range of 2 to 20 hours depending on the progress of the reaction and the desired degree of polymerization. The solvent used in the solution polymerization method is not particularly limited, and common organic solvents such as toluene, methyl ethyl ketone, ethyl acetate, butyl acetate, acetone, and ethanol can be used as appropriate.

[0065] Thermosetting is a process that uses heating to induce a chemical reaction in a composition containing a thermal polymerization initiator or crosslinking agent, thereby forming a three-dimensional network structure. Cured products obtained through thermosetting possess excellent mechanical strength, heat resistance, and chemical resistance, making them suitable for applications such as adhesives, paints, and molding materials. Thermosetting conditions are set according to the type of initiator, the viscosity of the composition, the film thickness, and the desired degree of curing. Generally, uniform and complete curing is achieved by heating in the range of 60 to 150°C for 30 minutes to several hours.

[0066] <Polymerizable and non-polymerizable compounds> In the present invention, polymerizable and non-polymerizable compounds are classified into monomers, oligomers, and polymers according to their molecular weight and molecular structure. Structurally, low-molecular-weight compounds without repeating units are monomers, medium-molecular-weight compounds with a small number (usually 2 to several tens) of repeating units are oligomers, and high-molecular-weight compounds with a large number of repeating units are polymers. Polymerizable compounds are used to adjust the curability, mechanical properties, and crosslinking density of compositions, while non-polymerizable compounds are used to impart auxiliary functions such as plasticity, fluidity, dispersibility, and surface properties. Examples of polymerizable functional groups found in polymerizable compounds include (meth)acrylate groups, (meth)acrylamide groups, vinyl groups, allyl groups, and maleimide groups.

[0067] <Monofunctional monomers> The monofunctional monomers used in this invention are low-molecular-weight compounds having one polymerizable functional group within the molecule, and are components other than compound A. These have structures without repeating units and often participate in terminal reactions in polymerization reactions, contributing to the adjustment of curability and control of the polymer's terminal structure. Furthermore, the monofunctional monomers may have reactive functional groups such as isocyanate groups, epoxy groups, hydroxyl groups, amino groups, carboxyl groups, oxazoline groups, and norbornene groups. Examples of monofunctional monomers are listed below.

[0068] Monofunctional (meth)acrylates include alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, tert-butyl (meth)acrylate, neopentyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclohexyl (meth)acrylate, tert-butylcyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl ( Examples include cyclic alkyl(meth)acrylates such as meth)acrylate, norbornyl(meth)acrylate, isobornyl(meth)acrylate, and 2-methyl-2-adamantyl(meth)acrylate; aromatic alkyl(meth)acrylates such as benzyl(meth)acrylate, naphthyl(meth)acrylate, and benzoyl(meth)acrylate; and (meth)acrylates having a hydroxyl group such as hydroxyethyl(meth)acrylate, hydroxypropyl(meth)acrylate, 2-hydroxybutyl(meth)acrylate, 4-hydroxybutyl(meth)acrylate, and hydroxyhexyl(meth)acrylate.

[0069] Monofunctional (meth)acrylamides include alkyl (meth)acrylamides such as N-methyl(meth)acrylamide, N,N-dimethyl(meth)acrylamide, N-ethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, N-butyl(meth)acrylamide, N-(2-ethylhexyl)acrylamide, N-octyl(meth)acrylamide, N-lauryl(meth)acrylamide, N-stearyl(meth)acrylamide, N-oleyl(meth)acrylamide, cyclic alkyl(meth)acrylamides such as N-cyclopentyl(meth)acrylamide, N-cyclohexyl(meth)acrylamide, N-bornyl(meth)acrylamide, N-adamantyl(meth)acrylamide, N-benzyl(meth)acrylamide, N-phenylethyl(meth)acrylamide, aromatic alkyl(meth)acrylamide, N-(2-hydroxyethyl)acrylamide, N-(hydroxyethyl) Examples include (meth)acrylamides having a hydroxyl group such as roxypropyl)acrylamide, N-(hydroxybutyl)acrylamide, and N-(hydroxyhexyl)acrylamide; (meth)acrylamides having an amino group such as N-(2-aminoethyl)acrylamide, N-(3-aminopropyl)acrylamide, N-(4-aminobutyl)acrylamide, N-(2-(methylamino)ethyl)acrylamide, N-(3-(methylamino)propyl)acrylamide, N-(2-(ethylamino)ethyl)acrylamide, N-(2-(dimethylamino)ethyl)acrylamide, N-(3-(dimethylamino)propyl)acrylamide, N-(2-(diethylamino)ethyl)acrylamide, N-(3-(diethylamino)propyl)acrylamide, N-(2-(dimethylamino)ethyl)methacrylamide, and N-(3-(dimethylamino)propyl)methacrylamide; and diacetone (meth)acrylamide.

[0070] Examples of monofunctional vinyls include aromatic vinyls such as styrene, α-methylstyrene, vinyltoluene, vinylphenol, vinylnaphthalene, vinylfluorene, and vinylanthracene; heteroaromatic vinyls such as vinylpyridine, vinylpyrazine, vinylimidazole, vinylthiazole, vinylthiophene, and vinylcarbazole; heterocyclic vinyls such as vinyloxazoline, vinyloxazine, N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylphosphoramide, and N-vinylsulfonamide; and acrylonitrile.

[0071] Examples of substances having reactive functional groups include (meth)acrylates / acrylamides having hydroxyl groups such as 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, 12-hydroxydodecyl (meth)acrylate, N-hydroxyethyl (meth)acrylamide, N-hydroxybutyl (meth)acrylamide, and N-hydroxyoctyl (meth)acrylamide; (meth)acrylates / acrylamides having amino groups such as N,N-dimethylaminoethyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, and N,N-di-t-butylaminoethyl (meth)acrylate; (meth)acrylic acid, crotonic acid, maleic acid, maleic anhydride, fumaric acid, and citraco acid. Carboxyl unsaturated acids such as nic acid and itaconic acid, 2-vinyl-2-oxazoline, 4-methyl-2-vinyl-2-oxazoline, 5-methyl-2-vinyl-2-oxazoline, 4-ethyl-2-vinyl-2-oxazoline, 5-ethyl-2-vinyl-2-oxazoline, 4,4-dimethyl-2-vinyl-2-oxazoline, 4,4-diethyl-2-vinyl-2-oxazoline, 4,5-dimethyl-2-vinyl-2-oxazoline, Examples include vinyl derivatives having an oxazoline group, such as 4,5-diethyl-2-vinyl-2-oxazoline, 2-isopropenyl-2-oxazoline, and 2-isopropenyl-2-oxazoline derivatives; norbornene derivatives, such as 2-norbornene, 5-norbornene-2-methacrylate, 5-norbornene-2-acrylate, 5-norbornene-2-carboxylic acid, 5-norbornene-2-amide, and 5-norbornene-2-alcohol.

[0072] The amount of monofunctional monomer in the composition of the present invention is not particularly limited. For example, it is preferably 0.1 to 90% by mass, more preferably 1.0 to 85% by mass, and even more preferably 1.0 to 55% by mass, based on the total amount of the composition. Within this range, the viscosity of the composition can be easily adjusted, and various properties such as flexibility and transparency can be imparted to the resulting polymer.

[0073] <Polyfunctional monomers> The polyfunctional monomers used in this invention are low-molecular-weight or medium-molecular-weight compounds having two or more polymerizable functional groups in their molecule, and are components other than compound A. These compounds have multiple reaction sites, which promotes crosslinking reactions during polymerization and forms a three-dimensional network structure, thereby improving the mechanical strength, heat resistance, and other properties of the cured product. In addition to polymerizable functional groups such as (meth)acrylate groups, vinyl groups, and allyl groups, the polyfunctional monomers may also have reactive functional groups such as isocyanate groups, epoxy groups, hydroxyl groups, amino groups, carboxyl groups, oxazoline groups, and norbornene groups. These functional groups influence the reactivity with other components and the structure of the cured product.

[0074] Examples of polyfunctional monomers include 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate and its derivatives, dicyclopentanyl di(meth)acrylate, tricyclodecanedimethanol di(meth)acrylate, cyclohexanedimethanol di(meth)acrylate, glycerin di(meth)acrylate, pentaerythritol di(meth)acrylate, isocyanurate ethylene oxide modified diacrylate, caprolactone modified type, aliphatic diol-based (1,3-1,10) di(meth)acrylate and other bifunctional (meth)acrylate monomers, glycerin tri(meth)acrylate, pen Trifunctional (meth)acrylate monomers such as erythritol tri(meth)acrylate and its derivatives, dipentaerythritol tri(meth)acrylate, trimethylol derivatives, isocyanurate derivatives, pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol derivatives (4-6 functional), and other tetrafunctional or more (meth)acrylate monomers, N,N-methylenebisacrylamide, N,N-bis(acrylamide)ethylenediamine, N-acrylamide-2-hydroxyethyl-N-acrylamide, N-acrylamide-2-methylpropane-1,3-diamine, N-acrylamido-2-aminoethyl-N-acrylamido, N-acrylamido-2-aminopropyl-N-acrylamido, N-acrylamido-2-methoxyethyl-N-acrylamido, N-acrylamido-2-ethoxyethyl-N-acrylamido, N-acrylamido-2-(acryloylamino)ethyl-N-acrylamido, and other bifunctional (meth)acrylamidoamides, tris(2-acrylamidoethyl)isocyanurate, tris(2-acrylamidoethyl)amine, tris(3-acrylamidopropoxymethyl)methylacrylamide, glycerin Examples include trifunctional (meth)acrylamides such as triacrylamide, trimethylolpropanetriacrylamide, tris(2-acrylamideethyl)glycerin derivatives, tris(2-acrylamideethyl)melamine derivatives, and tris(2-acrylamideethyl)triazine derivatives; and tetrafunctional or more (meth)acrylamides such as pentaerythritol tetraacrylamide, dipentaerythritol pentaacrylamide, dipentaerythritol hexacrylamide, polyfunctional acrylamides with a polycarbodiimide skeleton, and polyfunctional acrylamides with a polyisocyanurate skeleton.

[0075] The amount of polyfunctional monomer in the composition of the present invention is not particularly limited and can be adjusted as appropriate depending on the curability, mechanical properties, shrinkage behavior, etc. of the composition. For example, it is preferably 0.5 to 60% by mass of the total composition, more preferably 2.0 to 50% by mass, and even more preferably 5.0 to 40% by mass. Within this range, an appropriate crosslinked structure is formed in the polymerization reaction, and the resulting polymer exhibits high hardness and heat resistance. Furthermore, since the crosslinking density is not excessively high, it has an excellent balance between hardness and flexibility, and volume shrinkage and stress concentration during curing can be effectively avoided.

[0076] <Multifunctional oligomers> The polyfunctional oligomers used in the present invention are medium-molecular-weight compounds having repeating units within the molecule and possessing two or more polymerizable functional groups within the molecule, which can contribute to polymerization reactions and the formation of crosslinked structures. Examples of polyfunctional oligomers include urethane di(meth)acrylate oligomers, epoxy di(meth)acrylate oligomers, polyester di(meth)acrylate oligomers, polyether di(meth)acrylate oligomers, and polybutadiene di(meth)acrylate oligomers. These are used to impart physical properties such as flexibility, hardness, strength, and heat resistance. Polyfunctional oligomers may be used individually or in combination of two or more types.

[0077] The amount of polyfunctional oligomer in the composition of the present invention is not particularly limited, as it is appropriately set according to the intended use of the composition, the required physical properties, curing conditions, etc. For example, the amount of polyfunctional oligomer is preferably 0.1 to 70% by mass, and more preferably 2.0 to 60% by mass, relative to the total composition. Within this range, a good balance between curability and physical properties can be achieved, and a uniform cured product can be obtained.

[0078] <Additives> Additives used in the present invention include thermal polymerization inhibitors, radical scavenging agents, diluents, antistatic agents, plasticizers, fillers, surface modifiers, colorants, fragrances, preservatives, flame retardants, and defoaming agents. These may be used individually or in combination of two or more. The amount of additives used in the present invention can be adjusted as appropriate within a range that does not adversely affect each application. For example, it is preferable that the amount is 30% by mass or less of the total composition. [Examples]

[0079] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to the following examples. The abbreviations for each component described in the examples and comparative examples are as follows. In addition, unless otherwise specified, "parts" and "%" below are all on a mass basis.

[0080] The materials used in the examples and comparative examples are as follows: (1) Ether monomer (A) A-1 (Methoxymethyl)acrylate A-2 Triethylene glycol monobutyl ether methacrylate A-3 N-(methoxymethyl)acrylamide A-4 Ethylene glycol monomethyl ether acrylamide A-5 Ethylene glycol dimethacrylate A-6 Dipentaerythritol hexaacrylate A-7 Triethylene glycol diacrylamide A-8 Ditrimethylolpropanetetraacrylamide A-9 Acryloylmorpholin A-10 Tetrahydrofurfuryl methacrylate A-11 Tetrahydrofurfurylacrylamide (2) Antioxidant (B) B-1 4-Methoxyphenol B-2 2,6-di-t-butyl-4-methylphenol B-3 Pentaerythritol tetrakis(3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionate) B-4 N,N'-diphenyl-p-phenylenediamine B-5 N-ethylmorpholin B-6 Methyl 3-(dimethylamino)propionate B-7 3-(dimethylamino)-N-[(tetrahydro-2-furanyl)methyl]propanamide B-8 3-(morpholinyl)propionate methyl B-9 3-(N-methyl-N-phenylamino)propionate methyl B-10 3-(diethylamino)-N,N-diethylpropanamide B-11 Tristearylamine B-12 3-(morpholino)propionate morpholide B-13 Trisnonylphenylphosphite B-14 Didodecylthiodipropionate B-15 Isophthaloyl dihydrazide (3) Other ingredients (C) Polymerization initiator (C1) C1-1 Omnirad184 (manufactured by IGMresins B.V.) C1-2 Omnirad 1173 (manufactured by IGMresins B.V.) C1-3 Omnirad TPO (manufactured by IGMresins B.V.) C1-4 Benzoyl peroxide (BPO) C1-5 Azobisisobutyronitrile (AIBN) Monofunctional or polyfunctional monomers (C2) C2-1 Dimethylacrylamide C2-2 Diethylacrylamide C2-3 N-isopropylacrylamide C2-4 N-(2-hydroxyethyl)acrylamide C2-5 Diacetone acrylamide C2-6 N-Octylacrylamide C2-7 tert-butylcyclohexyl acrylate C2-8 Isobornyl acrylate C2-9 Acrylic Acid C2-10 Hydroxyethyl Acrylate C2-11 1,6-Hexanediol diacrylate C2-12 Trimethylol Prohunt Acrylate Polyfunctional oligomer (C3) C3-1 UV-3000B (Bifunctional urethane acrylate (manufactured by Shiko, Mitsubishi Chemical Corporation)) C3-2 UV-6640B (Bifunctional urethane acrylate (manufactured by Shiko, Mitsubishi Chemical Corporation)) Polymerization inhibitor (C4) C4-1 2,2,6,6-tetramethylpiperidine-N-oxyl (TEMPO) Light stabilizer (C5) C5-1 Tinuvin384-2 (benzotriazole-based UV absorber, manufactured by BASF)

[0081] Examples 1-19 and Comparative Examples 1-3 <Preparation of composition and evaluation of stability> Compound A, component B, and component C were precisely weighed according to the mass ratios shown in Table 1, and 300 g of each composition corresponding to Examples 1-16 and Comparative Examples 1-4 was prepared by uniformly mixing and dissolving them. For each prepared composition, the viscosity and hue at 25°C were measured, and these values ​​were recorded as "pre-test viscosity" and "pre-test hue." Next, 100 mL of each composition was dispensed into 500 mL lidded brown glass screw-top tubes (hereinafter referred to as "light-shielding containers") and 500 mL lidded clear glass screw-top tubes (hereinafter referred to as "clear containers"), sealed, and then heat resistance and light resistance tests were performed. After each test, the viscosity and hue at 25°C were measured again, and these values ​​were recorded as "post-test viscosity" and "post-test hue." Furthermore, the rate of change in viscosity and hue before and after the test was calculated, and the heat resistance and light resistance of each composition were evaluated based on this rate of change.

[0082] Approximately 50 mL was taken from each prepared composition, its mass was precisely measured, and then photo-curable compositions were obtained by adding photo-initiator C1-1 to the mass in an amount of 3% by mass. The photocurability of the obtained photocurable compositions was evaluated. Similarly, approximately 50 mL was taken from each prepared composition, its mass was precisely measured, and then thermo-curable compositions were obtained by adding thermal initiator C1-5 to the mass in an amount of 2% by mass. The thermo-curability of the obtained thermo-curable compositions was evaluated.

[0083] <Heat resistance testing and heat stability evaluation> The light-shielding containers filled with the composition were left standing in a 60°C incubator for 30 days. The viscosity of the composition before and after the test was measured using a cone-plate viscometer (RE550 viscometer, manufactured by Toki Sangyo Co., Ltd.). Viscosity change rate (%) = ((Viscosity after test - Viscosity before test) / Viscosity before test) × 100% ◎: The viscosity change rate was less than 50%. ○: The viscosity change rate was 50% or more and less than 100%. △: The viscosity change rate was 100% or more, but less than 200%. ×: The viscosity change rate was 200% or more.

[0084] <Lightfastness Test and Lightstability Evaluation> The transparent containers filled with the composition were placed on a tabletop rotator in a constant temperature room at 25°C, and continuously irradiated with light from a xenon lamp (simulated sunlight) while rotating the containers for 30 days. The hue (APHA) of the composition before and after the test was measured using a transmission color meter (TZ6000, manufactured by Nippon Denshoku Industries Ltd.). A higher APHA value indicates a darker color. Hue change rate (%) = ((APHA after test - APHA before test) / APHA before test) × 100% ◎: The hue change rate was less than 50%. ○: The hue change rate was between 50% and 100%. △: Hue change rate is between 100% and 200%, or a slight decrease in transparency was observed visually. ×: Hue change rate was 200% or more, or a clear decrease in transparency was observed visually.

[0085] <Photocuring and evaluation of photocurability> A PET film (E5100, manufactured by Toyobo Co., Ltd.) was placed in close contact with a horizontally positioned glass plate, with the corona-treated side facing outwards. Next, the photocurable compositions of the examples and comparative examples were applied to a thickness of 20 μm using a bar coater, and the photocurable compositions were cured by ultraviolet irradiation with a metal halide lamp under a nitrogen atmosphere. For ultraviolet irradiation, an inverter-type conveyor device ECS-4011GX and a metal halide lamp M04-L41 manufactured by I-Graphics were used, with an ultraviolet irradiance of 500 mW / cm². 2 The following criteria were used to evaluate the photocurability after curing. The presence or absence of tack on the surface of the cured film was checked, and the photocurability was evaluated based on the cumulative amount of light required for the tack to disappear, according to the following standards. ◎: Cumulative light intensity 1000 mJ / cm 2 The tack disappeared below a certain value. ○: Cumulative light intensity 1000~2000 mJ / cm 2 Then Tack disappeared. △: Cumulative light intensity 2000~5000 mJ / cm 2 Then Tack disappeared. ×: Total luminous intensity 5000 mJ / cm 2 Despite these factors, Tuck remained with the team.

[0086] <Thermosetting properties evaluation> The thermosetting compositions of the examples and comparative examples were coated to a thickness of 20 μm onto a horizontally positioned aluminum plate using a bar coater to prepare thermosetting test specimens. These test specimens were heat-treated at 80°C under a nitrogen atmosphere. Every two hours after the start of heating, the test specimens were returned to room temperature, and the presence or absence of tack on the film surface was checked. Based on the heating time required for the tack to disappear, the thermosetting properties were evaluated according to the following criteria. ◎: The tack disappeared when the heating time was less than 2 hours. ○: The tack disappeared when the heating time was less than 2-4 hours. △: The tack disappeared when the heating time was less than 4-8 hours. ×: Tack remained even after heating for more than 8 hours.

[0087] [Table 1]

[0088] As is clear from the results in Table 1, the compositions of each example were found to have good stability against heat and light due to the inclusion of a polymerizable compound (A) having an ether bond and an ethylenically unsaturated bond in the molecule, and an antioxidant (B). Furthermore, when a photopolymerization initiator was added to the compositions of the examples, they showed high photocurability, and when a thermal polymerization initiator was added, they showed high thermophotocurability. This confirmed that the presence of component B does not inhibit the polymerizability or curability of the compositions. On the other hand, in Comparative Examples 1 to 3, even when compound A and a polymerization inhibitor or light stabilizer were present together, the self-oxidation of the ether group of compound A could not be suppressed, and the heat and light resistance of the compositions were low. Moreover, the compositions of the comparative examples did not satisfy either thermal or photopolymerizability. The differences in physical properties and curability between the examples and comparative examples are considered to be the result of the antioxidant B contained in the compositions of the present invention acting appropriately on the ether monomer A, as described above.

[0089] Examples 20-34 and Comparative Examples 4-5 <Preparation and evaluation of coating compositions> Compound A, component B, and component C were precisely weighed according to the mass ratios shown in Table 2 and uniformly mixed at room temperature to prepare the coating compositions for the examples and comparative examples. The coating compositions were subjected to heat resistance and light resistance evaluations in the same manner as the polymerizable compositions.

[0090] <Evaluation of the applicability of coating compositions> A PET film (E5100, manufactured by Toyobo Co., Ltd.) was placed in close contact with a horizontally positioned glass plate, with the corona-treated side facing outwards. Next, the photocurable compositions of the examples and comparative examples were applied to a thickness of 10 μm using a bar coater, and the coated surface was observed 10 seconds after application to evaluate the coatability based on the following criteria. ◎: The coated surface was smooth. ○: There were slight streaks, but the coated surface was almost smooth. △: There was a slight flaw. ×: A continuous coated surface was not formed.

[0091] <Appearance evaluation of coating films> A PET film (E5100, manufactured by Toyobo Co., Ltd.) was placed in close contact with a horizontally positioned glass plate, with the corona-treated side facing outwards. Next, the photocurable compositions of the examples and comparative examples were applied to a thickness of 20 μm using a bar coater, and the photocurable compositions were cured by ultraviolet irradiation with a metal halide lamp under a nitrogen atmosphere. For ultraviolet irradiation, an inverter-type conveyor device ECS-4011GX and a metal halide lamp M04-L41 manufactured by I-Graphics were used, with an ultraviolet irradiance of 500 mW / cm². 2 , cumulative light intensity 3000 mJ / cm 2 Subsequently, the appearance of the cured coating film was visually observed for surface smoothness and transparency, and evaluated based on the following criteria. The results of these evaluations are shown in Table 2. ◎: The surface was smooth, and a transparent film was obtained. ○: The surface was smooth, but slight cloudiness was observed in the film. △: The surface was uneven and partially cloudy. ×: The surface was uneven, and the entire film was cloudy white.

[0092] <Evaluation of yellowing resistance of coating films> The coating film was prepared in the same manner as the visual evaluation of the coating film. The obtained coating film was left to stand for 24 hours in an environment of 40°C and 50% relative humidity, and the initial b value was measured using a TZ-6000 manufactured by Nippon Denshoku Industries. Next, the cured product was placed in a constant temperature and humidity chamber set to 85°C and 85% relative humidity and left to stand for 500 hours, and the b value (b value after moist heat) was measured in the same manner. The difference from the initial b value was defined as Δb (Δb = b value after moist heat - initial b value), and the resistance to yellowing due to moist heat was evaluated based on the following criteria. These evaluation results are shown in Table 2. ◎: No yellowing was observed. ○: Slightly yellowed. △: There was some slight yellowing. ×: Clear yellowing was observed.

[0093] [Table 2]

[0094] Examples 35-44 and Comparative Examples 6-7 <Preparation and Evaluation of Inkjet Ink Compositions> Compound A, component B, and component C were precisely weighed according to the mass ratios shown in Table 3 and uniformly mixed at room temperature to prepare the inkjet ink compositions for the examples and comparative examples. The inkjet ink compositions underwent heat resistance and light resistance evaluations, similar to those performed on the polymerizable compositions. The ejection stability of the inkjet ink compositions was also evaluated. The results of these evaluations are shown in Table 3.

[0095] <Evaluation of ejection stability of inkjet ink compositions> The obtained inkjet ink composition was loaded into an inkjet printer (Fujifilm LuxelJetUV350GTW) and solid printing was performed on the entire surface of A4 coated paper. The print quality of the obtained printed material was visually observed, and the ink ejection stability was evaluated according to the following criteria. ◎: Printed evenly with no unevenness in the printing. ○: There were slight printing inconsistencies. △: There were printing inconsistencies in multiple places. ×: A printing failure occurred, and printing was not possible.

[0096] [Table 3]

[0097] Examples 45-55 and Comparative Examples 8-9 <Preparation and Evaluation of Compositions for Three-Dimensional Modeling> Compound A, Component B, and Component C were precisely weighed according to the mass ratios shown in Table 4 and uniformly mixed at room temperature to prepare the three-dimensional shaping compositions for the examples and comparative examples. For the three-dimensional shaping compositions, heat resistance stability evaluation and light resistance stability evaluation were carried out in the same manner as for the polymerizable compositions. In addition, the ejection stability and shaping accuracy of the three-dimensional shaping compositions were also evaluated, and furthermore, the yellowing resistance evaluation of the obtained shaped objects was carried out. The results of these evaluations are shown in Table 4.

[0098] <Evaluation of Ejection Stability of Three-Dimensional Shaping Composition> The three-dimensional shaping composition was filled into a syringe container (capacity 10 mL) of a dispenser. Under the conditions of an ejection pressure of 0.2 MPa, an ejection speed of 10 mm / s, and an ejection distance of 2 mm, using a stainless steel needle with a nozzle inner diameter of 0.2 mm, with an ejection distance of 2 mm, the three-dimensional shaping composition was ejected linearly onto a horizontally installed glass plate. The ejection was stopped for one hour, and then ejection was carried out again, and the continuity of the initial ejection line, the fluctuation of the line width, and the presence or absence of dot missing were observed. In addition, the tip of the nozzle after ejection was observed with a stereomicroscope to confirm the presence or absence of clogging due to ink residue, drying, or gelation. If necessary, the film thickness of the ejected material was measured with a film thickness gauge to quantitatively evaluate the reproducibility of the ejection amount. ◎: Both the initial and re-ejection showed good continuity. ○: There was a slight variation in the line width. Minute residues adhered to the nozzle. △: Dot missing or line break occurred during re-ejection. Dried matter adhered to the tip of the nozzle. ×: Nozzle clogging occurred and ejection was impossible.

[0099] <Evaluation of Shaping Accuracy of Three-Dimensional Shaping Composition> An overpeeled PET film (E7001) was adhered to a horizontally installed glass plate, and a spacer with a thickness of 10 mm and an inner dimension of 10 mm × 10 mm was installed. The three-dimensional shaping composition was filled into the spacer to a thickness of 1 mm, and after keeping it warm at 60 °C for 30 seconds to smooth the liquid surface, a UV-LED lamp (wavelength 405 nm, illuminance 10 mW / cm 2 , integrated light quantity 1,000 mJ / cm 2The material was cured by irradiation with ) . This process was repeated 10 times to obtain a 10 x 10 x 10 mm object. The height of the obtained object was measured and the sides were visually inspected. The printing accuracy was evaluated according to the following criteria. ◎: Height less than 10mm ± 0.1mm, with no irregularities on the sides. ○: Height was less than 10mm ± 0.1~0.2mm, with slight irregularities on the sides. △: Height less than 10mm ± 0.2~0.3mm, with slight unevenness on the sides. ×: Height 10mm ± 0.3mm or more, or obvious irregularities on the sides.

[0100] <Evaluation of yellowing resistance of molded objects> The yellowing resistance of the molded object was evaluated under the same conditions as described in the <Evaluation of yellowing resistance of the coating film> above.

[0101] [Table 4]

[0102] Examples 56-77 and Comparative Examples 10-13 <Preparation and Evaluation of Adhesive Compositions and Drill Compositions> Compound A, component B, and component C were precisely weighed according to the mass ratios shown in Tables 5 and 6, and uniformly mixed at room temperature to prepare the adhesive compositions of the examples and comparative examples. The adhesive compositions were subjected to heat stability and light stability evaluations, similar to those performed on the polymerizable compositions. Sheets were also prepared using the following method, and their moldability was evaluated. Furthermore, the resulting adhesive sheets were used to evaluate adhesive strength and resistance to yellowing. These results are shown in Tables 5 and 6.

[0103] <Sheet fabrication and evaluation of sheet moldability> A heavy-release film was placed in close contact with a horizontally positioned glass plate, and a spacer with a thickness of 1 mm and inner dimensions of 60 mm x 100 mm was installed. The spacer was filled without any gaps with an adhesive composition, and the moldability of the sheet was evaluated based on the time required for the surface to become smooth, according to the following criteria. ◎: Filling was completed in about 30 seconds. ○: Filling was completed within 1 minute. △: Filling was completed within 3 minutes. ×: The surface was not smooth, or gelation occurred, preventing filling. After the above evaluation, a release film was placed on top of the adhesive composition or a spacer filled with the adhesive composition and irradiated with ultraviolet light. For adhesive sheets, the wavelength was 405 nm and the irradiation intensity was 100 mW / cm². 2 With this UV-LED lamp, the cumulative light output is 1,000 mJ / cm². 2 The material was cured by irradiating it with ultraviolet light under the following conditions: for adhesive sheets, wavelength 405nm, irradiance 50mW / cm². 2 The material was cured by irradiating it with ultraviolet light using a UV-LED lamp. Finally, after irradiation, the light release film was peeled off to obtain an adhesive sheet or bonding sheet on the heavy release film.

[0104] <Evaluation of adhesive strength of adhesive sheets> Adhesive sheets were cut to a width of 25 mm and attached to a stainless steel plate substrate under constant pressure. After attachment, they were peeled off at a speed of 300 mm / min in a 180-degree direction, and the maximum or average load at the time of peeling was measured. The adhesive strength of the adhesive sheets was evaluated according to the following criteria. ◎: Very strong (≧2.5 N / 25 mm) ○: Strong (1.5~2.4 N / 25 mm) △: Moderate (0.8~1.4 N / 25 mm) ×: Weak (<0.8 N / 25 mm)

[0105] <Bonding strength of adhesive sheets> The adhesive sheet was attached to an aluminum plate, cured by UV irradiation or heating, and then the bonding area was set to 25 mm x 10 mm. A tensile load was applied and the breaking load was measured. The obtained load was divided by the bonding area (N / cm²). 2 The adhesive strength of the adhesive sheets was evaluated according to the following criteria, with adhesive strength defined as (or MPa). ◎: Very strong ≥2.5MPa ○: Strong 1.5~2.4MPa △: Moderate 0.8~1.4MPa ×: Weak <0.8MPa

[0106] <Evaluation of yellowing resistance of adhesive sheets and bonding sheets> The yellowing resistance of the adhesive sheet and the bonding sheet was evaluated under the same conditions as in the <Evaluation of yellowing resistance of the coating film> described above.

[0107] [Table 5]

[0108] [Table 6]

[0109] Examples 78-86 and Comparative Examples 14-15 <Preparation and evaluation of sealing agent compositions> Compound A, component B, and component C were precisely weighed according to the mass ratios shown in Table 7 and uniformly mixed at room temperature to prepare the encapsulant compositions for the examples and comparative examples. The obtained encapsulant compositions were subjected to heat stability evaluation and light stability evaluation in the same manner as the polymerizable compositions. Furthermore, the degassing properties of the encapsulant material obtained by curing the encapsulant composition were evaluated using the following method. These results are shown in Table 7.

[0110] <Evaluation of degassing properties of sealing materials> Except for changing the dimensions of the spacer to 30mm x 15mm x 3mm, the sealing agent composition was filled into the spacer in the same manner as in the <Sheet Preparation and Sheet Moldability Evaluation> described above, and left to stand for 3 minutes. After that, ultraviolet light was irradiated (wavelength 405nm, illuminance 500mW / cm²). 2 UV-LED lamp, cumulative luminous flux: 1,000 mJ / cm² 2 The cured sealant composition was obtained. Next, the obtained cured material (sealant) was cut out with a microtome, and the cross-section was observed with a scanning electron microscope. The degassing properties of the sealant were evaluated based on the proportion of voids present in the cross-section according to the following criteria. ◎: Bubble rate ~1.0% (Good) ○: Bubble rate 1.0~2.0% (fairly good) △: Bubble content 2.0~5.0% (acceptable range) ×: Bubble rate 5.0%~ (Poor degassing)

[0111] [Table 7]

[0112] Examples 86-96 and Comparative Examples 16-17 <Preparation and Evaluation of Nail Cosmetic Compositions> Compound A, component B, and component C were precisely weighed according to the mass ratios shown in Table 8 and uniformly mixed at room temperature to prepare the nail cosmetic compositions of the examples and comparative examples. The obtained nail cosmetic compositions were subjected to heat stability evaluation and light stability evaluation in the same manner as the polymerizable compositions. In addition, the applicability of the nail cosmetic compositions was evaluated by the following method. Furthermore, the appearance and resistance to yellowing of the obtained nail hardened film were evaluated. These results are shown in Table 8.

[0113] <Evaluation of the applicability of nail cosmetic compositions> The nail cosmetic composition was applied to nail tips using a 6mm wide flat brush. The uniformity of the application surface, including unevenness, streaks, and thickness, was observed, and the applicability of the nail cosmetic composition was evaluated according to the following criteria. ◎: The surface was smooth and the coating thickness was uniform. ○: The coating thickness was uniform, but slight unevenness and streaks were observed. △: Multiple uneven areas and streaks were observed, and the surface did not become smooth even after time had passed. ×: It was not possible to apply the coating evenly, resulting in many uneven areas and streaks.

[0114] <Visual evaluation of nail hardening film> A UV-LED lamp for gel nails (manufactured by Beauty Nailer, wavelength 405nm, output 48W) was used to irradiate nail tips coated with a nail cosmetic composition with ultraviolet light to create a nail hardening film. The prepared nail hardening film was left to stand overnight under a fluorescent light source in an environment of 40°C and 50% humidity, and then its appearance was observed according to the following criteria. ◎: No discoloration or clouding was observed, and it remained unchanged from immediately after curing. ○: Some bubbles formed, but no discoloration or cloudiness was observed. △: Small bubbles appeared throughout, and the overall transparency decreased. ×: Significant clouding was observed, and discoloration was present.

[0115] <Evaluation of photochromic yellowing resistance of nail hardening film> A hardened film was prepared in the same manner as described in the <Appearance Evaluation of Hardened Nail Film>, set in a xenon fade meter, and measured at an intensity of 70 mW / cm². 2 The film was irradiated with ultraviolet light for 120 hours. After that, the discoloration of the cured film was visually observed, and the light resistance to yellowing was evaluated according to the following criteria. ◎: No yellowing was observed at all. ○: Very slight yellowing was observed. △: Yellowing was observed. ×: Clear yellowing was observed.

[0116] [Table 8]

[0117] Examples 96-107 and Comparative Examples 18-19 <Preparation and evaluation of compositions for decorative coating materials> Compound A, component B, and component C were precisely weighed according to the mass ratios shown in Table 9 and uniformly mixed at room temperature to prepare the decorative coating compositions for the examples and comparative examples. The obtained decorative coating compositions were subjected to heat stability evaluation and light stability evaluation in the same manner as the polymerizable compositions. Furthermore, the coatability of the coating compositions was evaluated by the following method. In addition, laminated films were prepared and the yellowing resistance of the obtained laminated films was evaluated. These results are shown in Table 9.

[0118] <Evaluation of the applicability of decorative coating compositions> A decorative coating composition was applied to a 180 μm thick polycarbonate film (Teijin's "Panlight PC-2151") using a bar coater to a dry thickness of 5 μm. The coated surface was visually observed 10 seconds after application, and the coatability of the decorative coating composition was evaluated according to the following criteria. ◎: The coated surface was smooth. ○: There were slight streaks, but the coated surface was almost smooth. △: There was a slight flaw. ×: A continuous coated surface was not formed.

[0119] <Fabrication of laminated films> After heating the coating film obtained from the coating properties evaluation at 80°C for 3 minutes, a high-pressure mercury lamp (illumination intensity 300 mW / cm²) was used. 2 Cumulative irradiation dose: 1,000 mJ / cm² 2 The film was cured by ultraviolet irradiation using [a specific method]. This resulted in a laminated film consisting of a polycarbonate film and a decorative cured coating.

[0120] <Evaluation of yellowing resistance of laminated films> The yellowing resistance of the laminated film was evaluated under the same conditions as described in the <Evaluation of Yellowing Resistance of Coating Film>.

[0121] [Table 9]

[0122] Examples 108-117 and Comparative Examples 20-21 <Preparation and Evaluation of Dental Material Compositions> Compound A, component B, and component C were precisely weighed according to the mass ratios shown in Table 10 and uniformly mixed at room temperature to prepare the dental material compositions for the examples and comparative examples. The obtained dental material compositions were subjected to heat stability evaluation and light stability evaluation in the same manner as the polymerizable compositions. Furthermore, the curability of the dental material compositions was evaluated using the following method. These results are shown in Table 10.

[0123] <Evaluation of the curing properties of dental material compositions> A polytetrafluoroethylene mold (20mm x 20mm x 10mm) with a 6mm diameter hole in the center was filled with a dental material composition and then pressed with a polypropylene film. A dental light curing unit (Tokuso Power Light, manufactured by Tokuyama Dental Co., Ltd., light output density 700mW / cm²) was used. 2 , irradiation surface light intensity 640~650mW / cm 2 A halogen lamp (light source: 8mm aperture) was placed in close contact with the film and irradiated for 30 seconds to obtain a hardened dental material. The hardened dental material was checked by hand to confirm the presence or absence of unhardened components, and the hardening properties of the dental material composition were evaluated according to the following criteria. ◎: It was completely hardened and could not be removed from the mold even when pulled. ○: It was almost hardened, but it detached from the mold when pulled strongly. △: A small amount of uncured material adhered to the finger, and it easily detached from the mold. ×: It had not hardened and was not in the state of a hardened material.

[0124] [Table 10]

[0125] Examples 118-124 and Comparative Examples 22-23 <Preparation of photosensitive resin composition> Compound A, component B, and component C were precisely weighed according to the mass ratios shown in Table 11 and uniformly mixed at room temperature to prepare the photosensitive resin compositions of the examples and comparative examples. The obtained photosensitive resin compositions were subjected to heat resistance stability evaluation and light resistance stability evaluation in the same manner as the polymerizable compositions. Furthermore, patterns were formed using the photosensitive resin compositions by the following method, and the developability of the obtained photosensitive resins was evaluated. These results are shown in Table 11.

[0126] <Developability of photosensitive resins> A photosensitive resin composition was applied to a glass substrate, whose surface had been thoroughly cleaned, using a spin coater to a thickness of 5 μm in a wet application. After application, it was heated on a hot plate at 80°C for 1 minute. Then, using a photomask, it was irradiated with ultraviolet light for 3 minutes (wavelength 405 nm, irradiance 0.5 mW / cm²). 2 , cumulative light intensity 80 mJ / cm 2 Pattern formation was performed. The edge shape and pattern defects (disconnections and pinholes) of the obtained patterns were observed using a scanning electron microscope, and the developability of the photosensitive resin was evaluated according to the following criteria. ◎: The edges are clear, and no pattern defects are observed. ○: The edges were slightly rounded, and several pattern defects were observed. △: Edges were unclear, and numerous pattern defects were observed. ×: Edge could not be confirmed.

[0127] [Table 11]

[0128] As is clear from the results in Tables 2-11, the compositions of the examples for each application were found to have good stability against heat and light due to the inclusion of a polymerizable compound (A) having an ether bond and an ethylenically unsaturated bond in the molecule, and an antioxidant (B). Furthermore, the high stability of these compositions for each application confirmed that they exhibited excellent properties in their respective applications. On the other hand, in the comparative examples for various applications, even when compound A and a polymerization inhibitor or light stabilizer were present together, the self-oxidation of the ether group of compound A could not be sufficiently suppressed, and the heat resistance and light resistance of the various compositions were low. Moreover, these comparative examples could not fully exhibit the desired properties. The differences in physical properties and curability between the examples and comparative examples are considered to be the result of the antioxidant B contained in the composition of the present invention acting appropriately on the ether monomer A, as described above. [Industrial applicability]

[0129] The compositions of the present invention, by containing a compound having an ether bond and an ethylenically unsaturated bond (compound A) and an antioxidant (component B), are less susceptible to the effects of oxygen, particularly suppressing the progression of oxidation reactions accelerated by heat and light, and preventing unintended thickening or gelation during storage or use. Furthermore, compositions for various applications exhibit excellent heat resistance and light resistance, and their polymers can be suitably used as coating compositions, ink compositions, adhesive compositions, paint compositions, encapsulating material compositions, ink compositions for 3D modeling, nail cosmetic compositions, decorative coating compositions, dental material compositions, photosensitive resin compositions, hydrogel compositions, intraocular implant material compositions, skin adhesive compositions, biocompatible adhesive compositions, automotive paint repair compositions, and the like.

Claims

1. A composition containing a polymerizable compound having one or more ether bonds and one or more ethylenically unsaturated bonds in its molecule, and an antioxidant.

2. The composition according to claim 1, wherein the antioxidant comprises a phenolic compound and / or an amine compound.

3. The composition according to claim 1 or 2, wherein the antioxidant comprises a tertiary amine compound having an amide group and / or an ester group.

4. The composition according to claim 1 or 2, wherein the molecular weight of the antioxidant is 100 to 2000.

5. The composition according to claim 1 or 2, comprising a thermal polymerization initiator and / or a photopolymerization initiator.

6. The composition according to claim 1 or 2, comprising an oligomer and / or polymer.

7. A coating agent composition containing the composition described in claim 1 or 2.

8. An ink composition containing the composition described in claim 1 or 2.

9. A composition for three-dimensional molding containing the composition described in claim 1 or 2.

10. A viscous adhesive composition containing the composition described in claim 1 or 2.

11. A encapsulant composition containing the composition described in claim 1 or 2.

12. A nail cosmetic composition containing the composition described in claim 1 or 2.

13. A decorative coating agent composition containing the composition described in claim 1 or 2.

14. A dental material composition containing the composition described in claim 1 or 2.

15. A photosensitive resin composition containing the composition described in claim 1 or 2.

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