Polymerizable composition

Abstract

[Problem] To provide a polymerizable composition which has excellent transparency, polymerizability, and curability, exhibits high adhesion to various substrates, and generates very little outgassing during thermal polymerization or thermal curing. In addition, to provide: a polymerized or cured product having heat resistance, water resistance, and impact resistance which have conventionally been difficult to achieve in conjunction with one another; a composition for various applications that has all of these properties; and a polymerized or cured product which is produced from such a composition and has excellent heat resistance, outgassing resistance, water resistance, and impact resistance. [Solution] It has been found that the problem can be effectively solved by using a polymerizable composition containing a (meth)acrylate (A) having an amide group and a cyclic substituent in the molecule and a thermal polymerization initiator (C). This composition has excellent transparency, adhesion, and curability, and can form a cured product having excellent heat resistance, water resistance, and impact resistance, while suppressing outgassing.

Description

polymerizable composition

[0001] This invention relates to a thermopolymerizable composition.

[0002] Generally, polymerizable compositions contain polymerizable compounds having ethylenically unsaturated groups and polymerization initiators. Polymerization or crosslinking reactions occur when exposed to active energy rays such as heat or light, producing high molecular weight polymers or cured products having a three-dimensionally linked crosslinked structure. These cured products are used as adhesives for bonding components of electronic devices such as electronic components, electronic paper, and batteries; as sealing materials for fixing or protecting semiconductor devices such as semiconductor chips and wiring; and for adhesion, temporary fixing, bonding, sealing, surface protection, or surface modification of components of optical devices such as liquid crystal display bodies and optical lenses. Furthermore, polymers obtained by polymerizing and curing polymerizable compositions are being used in a wide range of fields as elastomer-based materials, flexible materials for displays, hard materials for dental applications, optical materials such as optical films and sheets, cosmetic materials, and materials for two-dimensional or three-dimensional molding.

[0003] Polymerizable compositions require various performance characteristics depending on the field and environment in which they are used, necessitating the combination of diverse polymerizable components. Generally, monofunctional monomers, polyfunctional monomers, crosslinking agents, and polymerization initiators containing (meth)acrylate or (meth)acrylamide groups as ethylenically unsaturated groups are the main components, and additives such as fillers, pigments and dyes, leveling agents, viscosity modifiers, and polymerization inhibitors can be added depending on the application. However, (meth)acrylate monomers lack sufficient adhesion to many substrates that are coated, tackled, or bonded, and the resulting polymers or cured products have insufficient hardness, heat resistance, or cohesive strength, which are important properties of adhesives and tacks. On the other hand, (meth)acrylamide monomers have the advantage of excellent adhesion to substrates and high hardness, heat resistance, or cohesive strength of cured products, but they are expensive, have limited industrial product variations, and often have insufficient water resistance in cured products.

[0004] We attempted to prepare a polymerizable composition containing both (meth)acrylate monomers and (meth)acrylamide monomers, and then polymerize and cure it. However, because the polymerization rates of the (meth)acrylate monomers and (meth)acrylamide monomers differed significantly, controlling the polymerization reaction proved difficult, leading to the new problem of not being able to obtain a uniform random copolymer or alternating copolymer. Furthermore, problems such as insufficient heat resistance and outgassing at high temperatures, caused by the (meth)acrylate monomers, made it difficult to use in the fields of electronic devices, optical devices, and semiconductor devices.

[0005] The present invention aims to provide a polymerizable composition that exhibits excellent transparency, polymerizability, and curability, high adhesion to a wide variety of substrates such as glass, resin, metal, metal oxide, and ceramic, while simultaneously generating very little outgassing during thermal polymerization or thermal curing. Furthermore, it aims to provide polymers and cured products that possess heat resistance, water resistance, and impact resistance, which have conventionally been difficult to achieve simultaneously.

[0006] The present invention aims to provide adhesives, sealants, inks, inkjet inks, 3D modeling materials, coatings, paints, photosensitive resins, cosmetics, decorative materials, dental materials, dicing tapes, flexible printed circuit boards, adhesives for dissimilar materials, adhesives for electronic devices, adhesives for optical devices, adhesives for semiconductor devices, sealants for electronic devices, sealants for optical devices, sealants for semiconductor devices, and binder resins for batteries, all of which contain the polymerizable composition and / or its polymers and cured products and possess high polymerizability, curability, and adhesion.

[0007] As a result of diligent research, the inventors of the present invention have found that a polymerizable composition containing a (meth)acrylate (A) having an amide group and a cyclic substituent in the molecule (hereinafter referred to as "component (A)") and a thermal polymerization initiator (C) (hereinafter referred to as "component (C)") can effectively solve the above-mentioned problems, and have completed the present invention.

[0008] The polymerizable composition of the present invention contains component (A) and component (C) as essential components. Component (A) has a (meth)acrylate group, and the polymerizable composition containing it exhibits high polymerizability. Furthermore, even when other polymerizable components are used in combination, it is possible to appropriately control the copolymerizability with component (A), and polymers or cured products suitable for each application can be obtained.

[0009] Component (A) has a cyclic substituent, which results in a high glass transition temperature (Tg) of the homopolymer and excellent heat resistance of the polymerizable composition. Furthermore, component (A) has an amide group, and polymerizable compositions containing it have high cohesive strength and water resistance. Moreover, the balance between the hydrophilicity of the amide group and the hydrophobicity of the cyclic substituent is excellent, resulting in polymerizable compositions with excellent transparency and high wettability and adhesion to various substrates. In addition, due to the heterogeneous effect resulting from the interaction between the amide group and the cyclic substituent, the resulting polymers and cured products exhibit excellent resistance to yellowing, water resistance, and durability in high-temperature and high-humidity environments, even though they contain an amide group, which is usually prone to discoloration and has low water resistance.

[0010] Furthermore, the presence of amide groups significantly reduces outgassing during the curing of (meth)acrylate. This makes it suitable for use as an adhesive, sealant, coating agent, etc., in electronic devices, optical devices, and semiconductor devices. By polymerizing or curing the polymerizable composition of the present invention, polymers or cured products with excellent transparency, hardness or strength, heat resistance, impact resistance, heat cycle resistance, and water resistance can be obtained.

[0011] When (meth)acrylate (A) has an unsaturated cyclic substituent, the unsaturated bonds in the ring undergo partial polymerization upon heat and / or irradiation with active energy rays. As a result, component (A) becomes a special monomer with properties intermediate between monofunctional and polyfunctional monomers, and the resulting cured product exhibits excellent heat resistance and impact resistance.

[0012] The thermal polymerization initiator (C) has good compatibility with the amphiphilic (meth)acrylate (A). In polymerizable compositions containing components (A) and (C), the polymerization rate can be easily controlled during polymerization or curing by heating, and the molecular weight of the polymer can be adjusted according to the purpose.

[0013] The present invention will be described in detail below with reference to embodiments of the invention. The scope of the present invention is not limited to the embodiments described herein, and various modifications can be made without departing from the spirit of the invention. Furthermore, if multiple upper and lower limits are given for a particular parameter, any combination of these upper and lower limits can be used to create a suitable numerical range.

[0014] The polymerizable composition of the present invention is characterized by containing a (meth)acrylate (A) having a specific structure and a thermal polymerization initiator (C). Optionally, it may further contain a binder component (B) (hereinafter referred to as "component (B)"), a polymerizable monomer other than (meth)acrylate (A) (D) (hereinafter referred to as "component (D)"), a filler, a crosslinking agent, a photopolymerization initiator, and other additives. Each component will be described in detail below.

[0015] In this specification, "(meth)acrylate" means both acrylate and methacrylate, "(meth)acrylic" means both acrylic and methacrylic, and "(meth)acryloyl group" means both acryloyl group and methacryloyl group.

[0016] In the present invention, (meth)acrylate (A) is a compound having at least one amide group (-C(=O)NH-, -C(=O)NR-) and at least one cyclic substituent within the molecule, and at least one (meth)acrylate group, i.e., an acrylate group and / or a methacrylate group. The presence of the amide group enhances hydrogen bonding, improving adhesion to various substrates, cohesive force, and the toughness, heat resistance, and mechanical strength of the cured product. Furthermore, the presence of the cyclic substituent introduces a bulky structure, improving the heat resistance, impact resistance, and low dielectric properties of the cured product, while suppressing polymerization shrinkage and resulting in a cured product with excellent dimensional stability. In particular, component (A) exhibits unique amphiphilicity due to having a hydrophilic amide group and a hydrophobic, bulky cyclic substituent within the same molecule. This enhances compatibility with other components in polymerizable compositions, improves wettability and adhesion to various substrates with different polarities, and also reduces outgassing.

[0017] The cyclic substituents of (meth)acrylate (A) are not particularly limited, but are preferably substituents having one or more cyclic structures selected from monocyclic or polycyclic saturated aliphatic rings having 3 to 18 carbon atoms, monocyclic or polycyclic unsaturated aliphatic rings having 3 to 30 carbon atoms, monocyclic or polycyclic aromatic rings having 6 to 30 carbon atoms, monocyclic or polycyclic saturated aliphatic heterocycles having 3 to 30 carbon atoms, monocyclic or polycyclic unsaturated aliphatic heterocycles having 3 to 18 carbon atoms, and monocyclic or polycyclic aromatic heterocycles having 6 to 30 carbon atoms. These cyclic substituents have the effect of improving the heat resistance, water resistance, mechanical strength, low shrinkage, low hygroscopicity, and low dielectric properties of the polymer and cured product. Furthermore, from the viewpoint of easily exhibiting the characteristic amphiphilicity of component (A), it is preferable that the number of carbon atoms of the cyclic substituent is 5 to 18.

[0018] Examples of saturated aliphatic rings include monocyclic groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and cyclododecyl. Among these, the cyclohexyl group is preferred from the viewpoint of availability and heat resistance. Examples of polycyclic saturated aliphatic rings include groups derived from bicycloalkanes, tricycloalkanes, etc. Examples include adamantyl, norbornyl, bornyl, isobornyl, norbornane, dicyclopentanyl, tricyclodecanyl, and tetracyclododecanyl. These bulky aliphatic cyclic structures are preferred because they particularly improve the heat resistance, rigidity, low dielectric properties, and transparency of polymers and cured products. Among these, the adamantyl, isobornyl, dicyclopentanyl, and norbornane groups are particularly preferred.

[0019] Examples of unsaturated aliphatic rings include monocyclic groups such as cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, and cyclooctenyl. Examples of polycyclic unsaturated aliphatic rings include norbornene, norbornadiene, and dicyclopentenyl. These unsaturated aliphatic ring structures are preferred because they particularly improve the heat resistance and impact resistance of polymers and cured products. Among these, norbornene and dicyclopentenyl are particularly preferred.

[0020] Examples of aromatic rings include phenyl, naphthyl, anthryl, phenanthryl, biphenyl, terphenyl, fluorenyl, and pyrenyl groups. These aromatic cyclic structures have the effect of improving the refractive index and heat resistance of polymers and cured products. Among these, phenyl and naphthyl groups are preferred from the viewpoint of availability and cost.

[0021] Examples of saturated aliphatic heterocycles include those containing one or more heteroatoms such as nitrogen, oxygen, and sulfur atoms as ring-forming atoms. Examples include oxanorbornane group, azanorbornane group, pyrrolidinyl group, piperidyl group, piperazinyl group, morpholinyl group, thiomorpholinyl group, tetrahydrofuryl group, tetrahydropyranyl group, dioxolanil group, and dioxanyl group. Among these, oxanorbornane group, azanorbornane group, morpholinyl group, and tetrahydrofuryl group are preferred from the viewpoint of availability and improved adhesion to polar substrates.

[0022] Examples of unsaturated aliphatic heterocycles include those that contain one or more heteroatoms such as nitrogen, oxygen, and sulfur atoms as atoms constituting the ring. Examples include oxanorbornene group, azanorbornene group, dihydrofuryl group, dihydropyranyl group, imidazolinyl group, and pyrazolinyl group.

[0023] Aromatic heterocycles include those that contain one or more heteroatoms such as nitrogen, oxygen, and sulfur atoms as atoms constituting the ring. Examples include furyl, thienyl, pyrrolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, pyrazolyl, triazolyl, tetrazolyl, pyridyl, pyrimidinyl, pyrazinyl, pyridadinyl, triazinyl, quinolyl, isoquinolyl, indolyl, benzofuryl, benzothienyl, benzoxazolyl, benzimidazolyl, carbazolyl, dibenzofuryl, and dibenzothienyl groups.

[0024] Other examples include cyclic substituents having various bisphenol skeletons and bisoxazoline skeletons. The aforementioned cyclic substituents may be present in only one form or in combination of two or more forms.

[0025] These cyclic substituents may have further substituents (R) (hereinafter referred to as "substituents (R)"), to the extent that they do not impair the effects of the present invention. Examples of substituents (R) include linear alkyl groups or hydroxyalkylene groups having 1 to 18 carbon atoms that may be substituted with ethylenically unsaturated bonds; alkenyl groups or alkylene oxyalkyl groups having 2 to 18 carbon atoms that may be substituted with ethylenically unsaturated bonds; branched alkyl groups having 3 to 18 carbon atoms that may be substituted with ethylenically unsaturated bonds; halogen atoms such as fluorine, chlorine, and bromine atoms; cyano groups; nitro groups; hydroxyl groups; mercapto groups; carboxyl groups; amino groups; aryl groups such as phenyl and naphthyl groups; aryloxy groups such as phenoxy groups; aralkyl groups such as benzyl groups; acyl groups such as acetyl and propionyl groups; and acyloxy groups such as acetoxy groups. Furthermore, examples of ethylenically unsaturated groups that the substituent (R) may include one or more groups selected from the group consisting of (meth)acrylate groups, (meth)acrylamide groups, vinyl groups, vinyl ether groups, alkyl vinyl ether groups, allyl groups, (meth)allyl ether groups, and maleimide groups.

[0026] It is preferable that the cyclic substituent of (meth)acrylate (A) is an unsaturated ring, and / or that substituent (R) has an ethylenically unsaturated group. In this case, (meth)acrylate (A) has two or more polymerizable unsaturated groups in the molecule, and a cured product (polymer) having a crosslinked structure can be obtained by thermal polymerization. This further improves the heat resistance, mechanical strength, impact resistance, durability, water resistance, etc. of the resulting cured product.

[0027] It is more preferable when (meth)acrylate (A) also contains polymerizable unsaturated groups of a different type than the (meth)acrylate group it possesses (e.g., a double bond on a norbornene ring, a vinyl ether group, an allyl group, etc.) within the molecule. With such a configuration, multiple unsaturated groups with different polymerizability are present, making it possible to polymerize each unsaturated group stepwise or selectively by selecting a thermal polymerization initiator, using it in combination with a photopolymerization initiator, or adjusting the polymerization temperature and light irradiation conditions. For example, by first polymerizing the (meth)acrylate group by thermal polymerization, and then polymerizing the remaining unsaturated groups by ultraviolet irradiation, a post-curing treatment that further increases the crosslink density is possible. Such a dual curing (hybrid curing) process is extremely effective in mitigating volume shrinkage (curing shrinkage) associated with curing and suppressing the generation of internal stress, ultimately obtaining a cured product with high crosslink density and excellent impact resistance. Furthermore, by partially polymerizing the (meth)acrylate group by thermal polymerization, a polymerizable composition and a mixture containing its polymer can be obtained. In this case, the resulting polymer functions as binder component (B), and the mixture, as a polymerizable composition containing components (A), (C), and (B), can be further polymerized by thermal polymerization and / or photopolymerization to polymerize all remaining unsaturated groups, including (meth)acrylate groups, thereby obtaining a high-performance polymer or cured product.

[0028] The amide groups of (meth)acrylate (A) include primary amide groups, secondary amide groups (N-substituted amides), tertiary amide groups (N,N-disubstituted amides), diacetamide groups, and N-substituted diacetamide groups. Due to their high polarity and hydrogen bonding ability, amide groups enhance the cohesive force of polymerizable compositions, improving the strength of the resulting cured product, and significantly improving wettability and adhesion to polar substrates such as metals, metal oxides, glass, and ceramics. Structurally, it is preferable that component (A) has its amide group in the spacer portion connecting the (meth)acrylate group and the cyclic substituent. That is, a structure of "(meth)acrylate group - (linking group 1) - amide group - (linking group 2) - cyclic substituent" is preferred. This structure allows for effective electronic interactions between the amide group and the (meth)acrylate group, as well as steric and electronic interactions between the amide group and the cyclic substituent, contributing to improved polymerizability and the physical properties of the cured product.

[0029] As linking group 1, linear or branched alkylene groups having 1 to 6 carbon atoms are preferred. As linking group 2, directly bonded or linear or branched alkylene groups having 1 to 6 carbon atoms are preferred. In particular, a structure in which the (meth)acrylate group and the amide group are linked by a linear alkylene group having 2 to 4 carbon atoms (e.g., an ethylene group, a propylene group), and the amide group and the cyclic substituent are directly bonded, is preferred because it can increase the molecular weight of the resulting polymer while maintaining high polymerizability of the (meth)acrylate group. Furthermore, this structure tends to suppress outgassing caused by the (meth)acrylate group and discoloration (yellowing) caused by the amide group, making the resulting polymer and cured product particularly advantageous in fields such as electronic devices, optical devices, and semiconductor devices.

[0030] (Meth)acrylate (A) is composed of a combination of six structural elements, which are described herein in the form of "(meth)acrylate group-(linking group 1)-amide group-(linking group 2)-cyclic substituent". Specific examples, though not limited to them, include (meth)acryloyloxymethylenenorbornanecarboxamide, (meth)acryloyloxyethylenenorbornanecarboxamide, (meth)acryloyloxy(iso)propylenenorbornanecarboxaciamide, (meth)acryloyloxy(iso)butylenenorbornanecarboxamide, (meth)acryloyloxy(iso)amylenenorbornanecarboxamide, (meth)acryloyloxy(iso)hexylenenorbornanecarboxamide, (meth)acryloyloxyalkylenenorbornanecarboxamide; (meth)acryloyloxymethylenebornenecarboxamide, (meth)acryloyloxyethylenenorbornenecarboxamide, (meth)acryloyloxy(iso)propylenenorbornenecarboxaciamide, (meth)acryloyloxy(iso)butylenenor (Meth)acryloyloxyalkylene norbornene carboxyamides, represented by (meth)acryloyloxy(iso)amylene norbornene carboxyamide and (meth)acryloyloxy(iso)hexylene norbornene carboxyamide; (meth)acryloyloxymethylene oxanorbornane carboxyamide, (meth)acryloyloxyethylene oxanorbornane carboxyamide, (meth)acryloyloxy(iso)propylene oxanorbornane carboxaciamide, (meth)acryloyloxy(iso)butylene oxanorbornane carboxyamide, (meth)acryloyloxy(iso)amylene oxanorbornane carboxyamide and (meth)acryloyloxy(iso)hexylene oxanorbornane carboxyamide;(meth)acryloyloxymethyleneoxanorbornene carboxyamide, (meth)acryloyloxyethyleneoxanorbornene carboxyamide, (meth)acryloyloxy(iso)propyleneoxanorbornene carboxaciamide, (meth)acryloyloxy(iso)butyleneoxanorbornene carboxyamide, (meth)acryloyloxy(iso)amyleneoxanorbornene carboxyamide, (meth)acryloyloxy(iso)hexyleneoxanorbornene carboxyamide, (meth)acryloyloxyalkyleneoxanorbornene carboxyamide, (meth)acryloyloxyalkylene(1-6 carbon atoms)norbornene-2-alkyl(1-6 carbon atoms)-2-carboxyamide, (meth)acryloyloxy Examples include siaalkylene (1-6 carbon atoms) dicyclopentenyl carboxyamide; (meth)acryloyloxyalkylene (1-6 carbon atoms) dicyclopentanyl carboxyamide; (meth)acryloyloxyalkylene (1-6 carbon atoms) alkyl (1-6 carbon atoms) dicyclopentanyl dicarboxyamide; bis(meth)acryloyloxyalkylene (1-6 carbon atoms) dicyclopentanyl dicarboxyamide; (meth)acryloyloxyalkylene (1-6 carbon atoms) isobornane carboxyamide; bis(meth)acryloyloxyalkylene (1-6 carbon atoms) cyclohexane dicarboxyamide; N-((meth)acryloyloxyethyl)-N-phenylamide, N-((meth)acryloyloxyethyl)benzamide, etc. These (meth)acrylates (A) may be used individually or in combination of two or more types.

[0031] The content of (meth)acrylate (A) in the entire coincidence composition is 0.1 to 99.9% by mass, preferably 0.5 to 90% by mass, more preferably 1 to 75% by mass with respect to the total mass of the composition. If the content of component (A) is 0.1% by mass or more, effects such as improvement in adhesion and heat resistance due to its content can be sufficiently obtained. On the other hand, if the content of component (A) is 99.9% by mass or less, a margin for blending 0.1% by mass or more of the essential component, the thermal polymerization initiator (C), is secured, and smooth polymerization of the composition becomes possible.

[0032] The polymerizable composition of the present invention contains a thermal polymerization initiator (C) as an essential component. Component (C) is a compound that decomposes upon heating to generate an active species (usually a radical) that initiates polymerization. By containing this component (C), the composition of the present invention can be polymerized and cured by heating.

[0033] As the thermal polymerization initiator (C), known thermal radical polymerization initiators can be used. For example, organic peroxide-based initiators; azo-based initiators; peroxides such as hydrogen peroxide; persulfates such as ammonium persulfate, potassium persulfate, and sodium persulfate; organic boron compounds such as tributylborane, tributylborane partial oxide, sodium tetraphenylborate, sodium tetrakis(p-fluorophenyl)borate, and triethanolamine salt of tetraphenylborate; barbituric acids such as 5-butylbarbituric acid and 1-benzyl-5-phenylbarbituric acid; sulfinates such as sodium benzenesulfinate and sodium p-toluenesulfinate, etc. These are appropriately selected in consideration of the 10-hour half-life temperature, etc., according to the target polymerization and curing temperature.

[0034] Examples of organic peroxide initiators include ketone peroxides such as methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, cyclohexanone peroxide, and acetylacetone peroxide; 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(t-hexylperoxy)cyclohexane, 1,1-bis(t-butylperoxy)cyclohexane, 2,2-bis(t-butylperoxy)butane, and n-butyl-4,4-bis(t-butylperoxy) Peroxyketals such as valerate, 2,2-bis(4,4-di-t-butylperoxycyclohexyl)propane; Hydroperoxides such as t-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, p-menthane hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide; Benzoyl peroxide, isobutylyl peroxide, lauroyl peroxide Diacyl peroxides such as di-t-butyl peroxide, decanoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, succinic acid peroxide, m-toluyl peroxide; dialkylates such as di-t-butyl peroxide, dicumyl peroxide, t-butylcumyl peroxide, α,α'-bis(t-butylperoxy)-p-diisopropylbenzene, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, and 2,5-dimethyl-2,5-di(t-butylperoxy)hexine-3. Peroxides; peroxyesters such as t-butyl peroxyacetate, t-butyl peroxyisobutyrate, t-butyl peroxypivalate, t-butyl peroxyneodecanoate, t-butyl peroxy-2-ethylhexanoate, t-butyl peroxylaurate, t-butyl peroxybenzoate, di-t-butyl peroxyisophthalate, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, t-butyl peroxymalic acid, and t-hexyl peroxybenzoate;Examples of the peroxydicarbonates include di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, di-sec-butyl peroxydicarbonate, di(2-ethylhexyl) peroxydicarbonate, di(2-ethoxyethyl) peroxydicarbonate, di(methoxyisopropyl) peroxydicarbonate, di(3-methoxybutyl) peroxydicarbonate, bis(4-t-butylcyclohexyl) peroxydicarbonate, and the like.;

[0035] Examples of the azo initiators include 2,2'-azobisisobutyronitrile (AIBN), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis(cyclohexane-1-carbonitrile), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2-(carbamoylazo)isobutyronitrile, dimethyl-2,2'-azobis(2-methylpropionate), 4,4'-azobis(4-cyanovaleric acid), and the like.

[0036] These thermal polymerization initiators (C) may be used alone or in combination of two or more. For example, when curing at a low temperature is desired, one with a low 10-hour half-life temperature can be selected, and when a long pot life is desired, one with a high 10-hour half-life temperature can be selected._It is also possible to design a stepwise curing process such as preliminary curing at a low temperature and main curing at a high temperature by using a combination of an initiator that decomposes at a low temperature and an initiator that decomposes at a high temperature. Furthermore, it is also possible to combine with a photopolymerization initiator described later.

[0037] The content of the thermal polymerization initiator (C) is 0.01 to 10% by mass, preferably 0.1 to 7% by mass, and more preferably 0.5 to 5% by mass, based on the total mass of the polymerizable composition. If the content of component (C) is less than 0.01% by mass, polymerization may not proceed sufficiently or may take a long time, and the physical properties of the resulting polymer and cured product may deteriorate. On the other hand, if it exceeds 10% by mass, the improvement in the polymerization rate is limited, and it may even lead to a decrease in the molecular weight of the resulting polymer, a decrease in the mechanical properties and heat resistance of the cured product, outgassing, or discoloration and deterioration of the physical properties of the polymer and cured product due to the large amount of undegraded initiator and decomposition products remaining.

[0038] The polymerizable composition of the present invention may contain (meth)acrylate (A) and a thermal polymerization initiator (C) in liquid or solid form, and these can be mixed and used in a polymerization reaction. For example, when both components (A) and (C) are liquids, they can be easily mixed at room temperature, making it possible to prepare a uniform polymerizable composition. With such a combination of liquids, solvent-free polymerization is possible without the use of solvents, which is expected to reduce environmental impact and improve workability. After mixing, polymerization is initiated by heating upon activation of the thermal polymerization initiator, and a stepwise or selective curing process can also be designed by using a photopolymerization initiator in combination as needed. This results in a cured product with excellent control over coatability and reactivity, exhibiting high performance in applications such as coatings and inks. In particular, when used as an adhesive or encapsulant for semiconductors, its liquid state allows for high penetration into fine details, and after curing, it exhibits high adhesion and heat resistance, functioning as a highly reliable material in chip protection and packaging processes. Furthermore, as a binder resin for batteries, it can be uniformly mixed with electrode materials, achieving both electrochemical stability and mechanical strength.

[0039] When one component (A) and the other (C) are liquid and the other is solid, mixing is performed by dissolving or dispersing the solid component in the liquid component. When the solid component is in the form of fine powder particles, the dispersibility during mixing is high, and homogenization of coating properties and reactivity is achieved. Heating melts or activates the reaction of the solid component, causing a polymerization reaction to proceed, and a solvent-free, high-performance cured product can be obtained. Such a configuration also offers excellent storage stability and handling, and by performing heating and polymerization at the necessary timing, it is possible to achieve both processability and final physical properties. In semiconductor applications, fine powder adhesives and encapsulants are suitable for screen printing and precision coating by dispensers, and offer excellent applicability to fine parts. By proceeding with polymerization simultaneously with melting due to heating, a cured product with high adhesion and heat resistance is obtained, exhibiting high reliability in chip protection and packaging processes. Furthermore, as a binder resin for batteries, the uniform mixing of fine powder with the electrode active material improves processability during electrode formation, and polymerization by heating makes it possible to construct an electrode structure that combines high mechanical strength and electrochemical stability. Furthermore, by controlling the crosslinking density of the cured material through stepwise heat treatment, it is possible to improve the battery's cycle life and capacity retention rate.

[0040] When components (A) and (C) are both solid at room temperature, a polymerizable powder composition can be obtained by mixing them. This powder composition can be used as a so-called powder coating or hot-melt adhesive. When used, it is melted by heating, applied to a substrate in a solvent-free state, and then polymerization and curing can be advanced by continuing to heat it. This process enables environmentally friendly product design that does not use solvents, suppresses volume shrinkage during curing, and reduces the generation of internal stress. Such solid-component compositions undergo polymerization simultaneously with melting by heating, resulting in cured products with high adhesion and heat resistance, exhibiting high reliability in chip protection and packaging processes in the semiconductor field. Furthermore, as a binder resin for batteries, the powder composition can be uniformly mixed with electrode active material, improving processability during electrode formation, and polymerization by heating makes it possible to construct an electrode structure that combines high mechanical strength and electrochemical stability. In addition, by controlling the crosslinking density of the cured product through stepwise heating treatment, it is possible to improve the battery cycle life and capacity retention rate.

[0041] The polymerizable composition of the present invention can be directly used in various applications as a functional material with controllable viscosity, fluidity, and reactivity, even in its unpolymerized state. Specifically, it can be used in any application selected from the group consisting of adhesives, sealants, inks, inkjet inks, 3D modeling materials, coatings, paints, photosensitive resins, cosmetics, decorative materials, dental materials, dicing tapes, flexible printed circuit boards, adhesives for dissimilar materials, adhesives for electronic devices, adhesives for optical devices, adhesives for semiconductor devices, sealants for electronic devices, sealants for optical devices, sealants for semiconductor devices, and binders for batteries. In these applications, polymerization and curing can be performed under the necessary conditions at the time of use to achieve the performance required for the purpose, and it is possible to achieve both processability and final physical properties.

[0042] The polymerizable composition of the present invention may further contain, as needed, a binder component (B), polymerizable monomers other than component (A) (D), fillers, crosslinking agents, photopolymerization initiators, and other additives. Each component is described in detail below. By appropriately blending these components, it is possible not only to adjust the viscosity and curability of the composition, but also to broadly and precisely adjust various physical properties of the cured product, such as hardness, flexibility, adhesion, and heat resistance, according to the intended application.

[0043] Binder component (B) is added to polymerizable compositions to impart film-forming ability, improve tack-free properties and handling in the uncured state, and enhance mechanical properties such as flexibility, toughness, pliability, and impact resistance of the cured product after curing. Binder component (B) also has the function of adjusting the viscosity of the composition, playing a role in improving compatibility with various coating methods such as screen printing, dispensers, and spin coating. Binder component (B) may contain at least one selected from the group consisting of polymerizable oligomers (B1), polymerizable polymers (B2), non-polymerizable oligomers (B3), and non-polymerizable polymers (B4).

[0044] Polymerizable oligomer (B1) and polymerizable polymer (B2) are polymerizable compounds having one or more ethylenically unsaturated groups in their molecules. Examples of these ethylenically unsaturated groups include (meth)acrylate groups, (meth)acrylamide groups, vinyl groups, vinyl ether groups, alkyl vinyl ether groups, allyl groups, (meth)allyl ether groups, maleimide groups, etc., and one or more of these may be included. In particular, from the viewpoint of copolymerization with the essential component (meth)acrylate (A), it is preferable that the ethylenically unsaturated group contains one of (meth)acrylate groups, (meth)acrylamide groups, or vinyl groups. Furthermore, from the viewpoint of increasing the molecular weight of the resulting polymer and improving its mechanical strength, it is even more preferable that it contains one of acrylamide groups, acrylate groups, or vinyl groups. In addition, when the purpose is to improve heat resistance, it is particularly preferable to contain (meth)acrylamide groups and methacrylate groups.

[0045] In this specification, polymerizable oligomers (B1) and polymerizable polymers (B2) are distinguished based on their respective number-average molecular weight (Mn). Specifically, polymerizable oligomers (B1) refer to polymerizable compounds with a number-average molecular weight (Mn) of 1,000 or more and less than 10,000, and polymerizable polymers (B2) refer to polymerizable compounds with a number-average molecular weight (Mn) of 10,000 or more. These polymerizable compounds may be monofunctional compounds having one ethylenically unsaturated group in the molecule, or polyfunctional compounds having two or more unsaturated groups, as described later. In this specification, unless otherwise specified, the number-average molecular weight (Mn) refers to the value measured on a standard polystyrene basis by gel permeation chromatography (GPC).

[0046] In this specification, "polyfunctional compound" refers to a compound having two or more ethylenically unsaturated groups in its molecule. The polymerizable oligomer (B1) and polymerizable polymer (B2) may be monofunctional or polyfunctional compounds, and can be used alone or in combination depending on the purpose. For example, by using a polyfunctional compound as a crosslinking agent, the crosslinking density of the cured product can be increased, improving physical properties such as heat resistance, mechanical strength, and solvent resistance. On the other hand, by using a monofunctional compound in combination, the crosslinking density can be appropriately adjusted, increasing the flexibility and toughness of the cured product, as well as reducing the viscosity of the composition to improve coatability and processability.

[0047] Polymerizable oligomers (B1) and polymerizable polymers (B2) are both polymerizable compounds having one or more ethylenically unsaturated groups in their molecules, and include linear or branched structures with a polyolefin-based backbone such as acrylic, ester, amide, ether, urethane, urea, silicone, or polybutadiene as the main chain structure. These are classified as monofunctional or polyfunctional oligomers and polymers, and compounds having (meth)acrylate groups or (meth)acrylamide groups are preferably used. Specific examples include polyurethane (meth)acrylate, polyester (meth)acrylate, polyether (meth)acrylate, polyamide (meth)acrylate, poly(meth)acrylic acid ester (meth)acrylate, polystyrene (meth)acrylate, polyacrylonitrile (meth)acrylate, epoxy acrylate (bisphenol A type), etc. These monofunctional or polyfunctional oligomers and polymers having (meth)acrylate groups or (meth)acrylamide groups may be used individually or in combination of two or more types.

[0048] The polymerizable oligomer (B1) content is typically in the range of 1 to 80% by mass, preferably 2 to 70% by mass, and more preferably 5 to 60% by mass, relative to the total mass of the polymerizable composition. By blending within this range, the viscosity of the composition can be appropriately adjusted, improving its suitability for application methods such as screen printing, spin coating, and dispensers. Furthermore, it has the effect of imparting flexibility, toughness, and impact resistance to the cured product. In particular, by using a monofunctional oligomer, it is possible to suppress the crosslinking density and improve flexibility and processability. On the other hand, by using a polyfunctional oligomer, a highly crosslinked structure can be formed, improving heat resistance and dimensional stability.

[0049] The incorporation of such polymerizable oligomers (B1) allows for the design of materials with required properties in applications such as adhesives, sealants, inks, inkjet inks, 3D modeling materials, coatings, paints, photosensitive resins, cosmetics, decorative materials, dental materials, dicing tapes, flexible printed circuit boards, adhesives for dissimilar materials, adhesives and sealants for electronic, optical, and semiconductor devices, and battery binders. In particular, in semiconductor sealants requiring flexibility and adhesion, and in dicing tapes and battery binders requiring impact resistance and processability, the amount of B1 incorporated and the selection of its functionalities greatly contribute to performance.

[0050] The polymerizable polymer (B2) content is typically in the range of 0.1 to 50% by mass, preferably 0.5 to 40% by mass, and more preferably 1 to 30% by mass, relative to the total mass of the polymerizable composition. This blending range provides high mechanical strength, heat resistance, and chemical resistance to the cured product. In particular, the use of a polyfunctional polymer increases the crosslinking density of the cured product, improving dimensional stability and durability. Furthermore, the combined use of a monofunctional polymer allows for viscosity adjustment and the addition of flexibility, contributing to improved coatability and processability.

[0051] The incorporation of such polymerizable polymers (B2) is particularly effective in applications requiring high heat resistance and impact resistance, such as adhesives and encapsulants for electronic devices, 3D fabrication materials, photosensitive resins, and battery binders. For example, in semiconductor device encapsulation applications, it is necessary to maintain stable performance against thermal cycling and external stress, and the high molecular weight and multifunctionality of B2 contribute to achieving this performance. Furthermore, as a battery binder, the appropriate incorporation of B2 is essential to achieve both adhesion to electrodes and mechanical strength, and it also contributes to improved long-term stability and cycle life.

[0052] From the viewpoint of readily available commercially available products, the polymerizable oligomer (B1) and polymerizable polymer (B2) can be, for example, the following urethane acrylates can be used: Mitsubishi Chemical Corporation's product names UV-3200B, UV-3000B, UV-6640B, UV-3700B, UV-3310B, UV-7000B; Shin Nakamura Chemical Industry Co., Ltd.'s product name U-4HAU-200PA; Daicel and Cytec Corporation's product names EBECRYL245, EBECRYL1259, EBECRYL8210, EBECRYL284, EBECRYL8402; SARTOMER Corporation's product names CN944, CN969, CN9002, CN9029; Negami Kogyo Co., Ltd.'s product names UN1255, UN-5507; and Kyoeisha Co., Ltd.'s product names AH-600, UA-306I. As urethane acrylamide, Quick Cure® 6100, Quick Cure® 7100, Quick Cure® 8100, etc., manufactured by KJ Chemicals Co., Ltd., can be used.

[0053] Non-polymerizable oligomers (B3) and non-polymerizable polymers (B4) are oligomers or polymers that substantially do not contain ethylenically unsaturated groups in their molecules and do not directly participate in the curing reaction of polymerizable compositions. They mainly exist physically dispersed or miscible within the matrix of the cured product and contribute to adjusting the viscosity of the composition, improving film formation, mitigating volume shrinkage during the curing reaction, reducing internal stress in the cured product, and improving toughness. These components are also effective in adjusting processability, flexibility, impact resistance, adhesion, and optical properties in general applications such as adhesives, sealants, inks, inkjet inks, 3D modeling materials, coatings, paints, photosensitive resins, cosmetics, decorative materials, dental materials, dicing tapes, flexible printed circuit boards, and adhesives for dissimilar materials. In particular, reducing internal stress plays an important role in suppressing warping and cracking in precision components such as semiconductor chips and optical elements, thereby improving product reliability.

[0054] Examples of non-polymerizable oligomers (B3) and non-polymerizable polymers (B4) include (meth)acrylic resins, polyester resins, polyurethane resins, polyolefin resins, polybutadiene resins, vinyl resins, polyamide resins, polyimide resins, epoxy resins (phenoxy resins, etc.), phenol resins, maleimide resins (bismaleimide resins, etc.), silicone resins, oxetane resins, fluororesins, polythiol resins, polyvinyl alcohol resins, vinyl acetate resins, polyvinyl acetal resins, terpene resins, rosin resins, rosin-modified phenol resins, diallyl phthalate resins, and benzoxazine resins. These resins can exhibit a variety of functions depending on the purpose, such as transparency and light resistance in optical applications, low dielectric and insulating properties in electronic materials, moisture resistance and adhesion in battery applications, and even initial tack and flexibility in adhesives and sealants. These non-polymerizable components may be used individually or in combination of two or more types.

[0055] (Meth)acrylic resins used as non-polymerizable oligomers (B3) and non-polymerizable polymers (B4) are suitable for their excellent transparency, weather resistance, and adhesive properties. By incorporating these into polymerizable compositions, the optical properties of the cured product, particularly the total light transmittance, can be enhanced, and haze (cloudiness) can be reduced. Furthermore, they have high stability against ultraviolet and visible light, and are less prone to yellowing and deterioration of physical properties, thus maintaining high reliability even in components used in outdoor environments or under strong light sources. Due to these properties, polymerizable compositions containing (meth)acrylic resins are extremely useful as optical adhesives and sealants for optical films, lenses, light guide plates, and LED elements for liquid crystal displays and organic EL displays. In addition, in fields such as inks, inkjet inks, decorative materials, and cosmetics, it is possible to create high-quality appearances by taking advantage of their high transparency and light resistance.

[0056] Furthermore, because (meth)acrylic resin is polar, it exhibits good wettability and adhesion to a variety of substrates, including glass, metals, and various plastics. This property is effective in ensuring adhesive reliability between semiconductor chips and lead frames or substrates while mitigating stress caused by curing shrinkage when applied to die attach films and underfill materials for semiconductor packaging. This suppresses delamination during temperature cycling tests and high-temperature, high-humidity tests, thereby improving the long-term reliability of semiconductor devices. It also contributes to improved adhesion, weather resistance, and processability in applications such as adhesives, sealants, coatings, paints, flexible printed circuit boards, and adhesives for dissimilar materials. The (meth)acrylic resin used is preferably a copolymer mainly composed of alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate, alicyclic (meth)acrylates such as cyclohexyl (meth)acrylate and isobornyl (meth)acrylate, (meth)acryloylmorpholin, (meth)acrylamide monomers, etc.

[0057] Polyolefin resins possess excellent electrical properties derived from their non-polar chemical structure, and are particularly characterized by their low dielectric constant and low dielectric loss tangent. Polymerizable compositions containing polyolefin resin as a non-polymerizable polymer (B4) are suitable for electronic material applications where reduction of transmission loss in the high-frequency band is required. For example, they are effective as adhesives, sealants, and insulating materials used in antennas for fifth-generation mobile communication systems and subsequent high-speed communication systems, multilayer printed circuit boards, flexible substrates, coaxial cables, etc. This minimizes signal attenuation and enables high-speed and stable signal transmission. Furthermore, because polyolefin resins have excellent flexibility, they contribute to stress relief and improved impact resistance in applications such as dicing tapes, adhesives for dissimilar materials, and flexible printed circuit boards.

[0058] Furthermore, polyolefin resins have extremely low water absorption and excellent moisture resistance. This property is effective in sealing electronic components and semiconductor chips, as it effectively blocks the intrusion of moisture from the outside, preventing failures due to corrosion and migration. This ensures long-term reliability even when used as a battery binder or encapsulant. On the other hand, because polyolefin resins are nonpolar, adhesion to polar materials such as metals and epoxy substrates may be a challenge. However, this can be improved by graft modification using maleic acid, acrylic acid, glycidyl methacrylate, etc. Modified polyolefin resins, with their introduced polar groups functioning as anchors, dramatically improve adhesive strength at dissimilar material interfaces, thus exhibiting high effectiveness in general applications such as adhesives, encapsulants, coatings, and paints.

[0059] Polybutadiene resin is a rubbery polymer with a very low glass transition temperature (Tg) due to its numerous double bonds derived from butadiene in its main chain. By incorporating polybutadiene resin as a non-polymerizable polymer (B4) into polymerizable compositions, excellent flexibility and rubber elasticity can be imparted to the cured product. This property is extremely effective in easing internal stress in the cured product, and in particular, it absorbs thermal stress that occurs when joining materials with significantly different coefficients of thermal expansion, preventing delamination at the interface and fracture of the components. Therefore, by using it as a die attach film for mounting large semiconductor chips onto substrates or as an underfill material in flip-chip mounting, reliability during temperature cycling can be greatly improved. Furthermore, by utilizing its flexibility and stress-relaxing properties, it contributes to improved impact resistance and processability in applications such as adhesives, sealants, dicing tapes, and flexible printed circuit boards.

[0060] Furthermore, due to its excellent low-stress properties, polybutadiene resin is suitable for bonding and potting applications of electronic components used in environments subject to vibration and shock. For example, in electronic control units and sensor modules installed in automobiles, it is expected to protect semiconductor elements and solder joints from vibrations during driving, thereby reducing the failure rate. However, because polybutadiene resin has unsaturated bonds in its main chain, its heat resistance and oxidation resistance may be relatively low. For such applications, it is preferable to use hydrogenated polybutadiene resin, in which the double bonds of polybutadiene are hydrogenated. By converting the unsaturated bonds to saturated bonds through hydrogenation, heat resistance, weather resistance, and ozone resistance are significantly improved, enabling use in more severe environments. This makes it applicable to applications requiring high reliability, such as semiconductor encapsulants, battery binders, high-durability adhesives, and adhesives for fixing electronic components.

[0061] Polyimide resin is a super engineering plastic that possesses a highly rigid and heat-resistant structure consisting of an aromatic backbone and imide rings, exhibiting the highest level of heat resistance among known polymers. By incorporating polyimide resin as a non-polymerizable polymer (B4) into polymerizable compositions, the heat resistance of the cured product can be significantly improved. In particular, in semiconductor package manufacturing processes such as solder reflow processes exposed to high temperatures of 260°C or higher, it is possible to maintain stable performance without decomposition, deformation, or reduction in adhesive strength. For this reason, it is extremely useful as a surface protective film (passivation film) for semiconductor chips requiring heat resistance, an interlayer insulating film, or as a binder component for high-heat-resistant adhesives. Furthermore, in flexible printed circuit board applications, polyimide resin contributes to improved reliability in high-temperature environments due to its flexibility and dimensional stability. In addition, its excellent heat resistance and mechanical properties can be utilized in applications such as battery binders, encapsulants, and coatings.

[0062] Furthermore, polyimide resins possess high mechanical strength and rigidity, contributing to improved dimensional stability, wear resistance, and electrical insulation of cured products. This makes them effective in ensuring insulation reliability in electronic circuits and semiconductor devices where high-density mounting is required. Conventional polyimide resins had low solubility in solvents and were difficult to process. However, in recent years, soluble polyimide resins that are soluble in common organic solvents such as 3-methoxy-N,N-dimethylpropanamide and γ-butyrolactone have been developed by introducing ether bonds, sulfone bonds, and bulky substituents into the main chain. This makes composition preparation and application easier, and allows for applications such as adhesives, encapsulants, photosensitive resins, and 3D molding materials. In addition, a method of forming a polyimide structure by compounding it as a polyamic acid solution and dehydrating and ring-closing it during a heating process after application is also widely adopted, enabling material design that combines high heat resistance and processability.

[0063] Among epoxy resins, those with relatively high molecular weights, that do not substantially react even in the presence of a curing agent at or near room temperature, and that possess film-forming ability are suitably used as non-polymerizable polymers (B4) in polymerizable compositions. A typical example is the high molecular weight solid epoxy resin obtained by the polycondensation of bisphenol A and epichlorohydrin, so-called phenoxy resin. Phenoxy resin has numerous hydroxyl groups in its main chain, and these hydroxyl groups form strong hydrogen bonds with surfaces such as metals, glass, and inorganic fillers, resulting in extremely high adhesion. Furthermore, due to the high rigidity and toughness derived from the bisphenol A skeleton, the cured product exhibits excellent mechanical strength and impact resistance. These properties provide reliable adhesion and protective performance in applications such as semiconductor encapsulants, adhesives for electronic components, and dicing tapes.

[0064] Furthermore, phenoxy resin functions as a toughener when incorporated into thermosetting compositions consisting of liquid epoxy resin and a curing agent, improving the toughness of the cured product. During the curing process, it partially miscibles with the epoxy resin matrix or forms a microscopic phase separation structure, absorbing fracture energy and improving impact resistance and crack resistance. This effect is widely applied in semiconductor encapsulants, prepregs for printed circuit boards, and adhesives for fixing electronic components. Phenoxy resin also has the effect of improving wettability and dispersibility with fillers, and is effective in reducing melt viscosity and improving fluidity (fillability) in molds in polymerizable compositions that highly fill inorganic fillers such as silica. This makes it possible to achieve both processability and physical properties in encapsulants, coatings, and three-dimensional molding materials.

[0065] Phenolic resins are thermosetting resins manufactured from phenols and aldehydes, and are broadly classified into novolac and resol types. When used as a non-polymerizable polymer (B4), thermoplastic novolac-type phenolic resins are mainly selected. Novolac-type phenolic resins do not harden when heated on their own, but they can function as curing agents for epoxy resins. However, in this invention, they are mainly used with an emphasis on their physical effects as a binder component. Because phenolic resins have a rigid structure with densely packed aromatic rings, they can impart high heat resistance, hardness, and chemical resistance to cured products. In particular, they excel at maintaining their elastic modulus in high-temperature ranges and are effective in applications such as semiconductor encapsulants, printed circuit boards, battery binders, and flexible substrates where dimensional stability is required.

[0066] Furthermore, phenolic resins are easily carbonized and form a dense carbonized layer during combustion, resulting in excellent flame retardancy. This property makes it possible to achieve high flame retardancy standards (e.g., UL94 V-0) without using halogen-based or phosphorus-based flame retardants, contributing to a reduction in environmental impact. In semiconductor encapsulants, they are widely used in combination with epoxy resins due to their excellent balance of heat resistance, flame retardancy, electrical insulation, and cost performance. On the other hand, because phenolic resins are hard and brittle, it is preferable to use phenolic resins modified with alkylphenols or cashew oil to improve flexibility and toughness. This makes it possible to achieve both processability and physical properties in applications such as adhesives, encapsulants, coatings, 3D molding materials, and photosensitive resins.

[0067] Maleimide resins, particularly bifunctional bismaleimide resins (BMI), are thermosetting resins with highly reactive maleimide groups at their molecular ends. Upon heating, they undergo addition polymerization or homopolymerization, forming a three-dimensional network structure with extremely high crosslinking density. The resulting cured product exhibits a high glass transition temperature (Tg) exceeding 300°C, excellent heat resistance, a low coefficient of thermal expansion (CTE), and low dielectric properties in the high-frequency range. These properties make them extremely useful as insulating materials for next-generation high-performance electronic materials, especially multilayer printed circuit boards used in servers, routers, and base stations. They are also suitable for applications requiring heat resistance and dimensional stability, such as semiconductor encapsulants, battery binders, flexible substrates, and coatings, contributing to improved reliability in high-temperature environments.

[0068] When bismaleimide resin is incorporated into polymerizable compositions as a non-polymerizable polymer (B4), mitigating its high melting point and brittleness after curing becomes a challenge. Therefore, in practice, it is often used in alloy (blended) with epoxy resins, cyanate ester resins, or various thermoplastic resins. By combining it with these resins, it is possible to maintain the excellent heat resistance and electrical properties of BMI while simultaneously improving the toughness, adhesion, and processability of the cured product in a balanced manner. Furthermore, by using reactive diluents such as diallylbisphenol A, it is possible to reduce the melt viscosity and improve impregnation into glass cloth. Leveraging these properties, maleimide resin is widely used in applications requiring high reliability, such as semiconductor encapsulants, high-temperature resistant adhesives, insulating materials for printed circuit boards, and matrix resins for composite materials in the aerospace field.

[0069] Silicone resins are polymers with a unique structure in which siloxane bonds (-Si-O-) form the main chain, with organic groups such as methyl and phenyl groups bonded to silicon atoms. Because siloxane bonds have high bond energy and are chemically stable, silicone resins exhibit excellent heat resistance, cold resistance, and weather resistance. Furthermore, due to the very high degree of rotational freedom of the molecular chain, they possess an extremely low glass transition temperature and rubber elasticity, significantly reducing internal stress in cured products. By incorporating non-polymerizable polymers (B4), particularly non-reactive silicone oils and silicone gums, into polymerizable compositions, stress relaxation, flexibility, and impact resistance can be improved. These properties contribute to improved reliability against thermal cycling and mechanical loads in applications such as semiconductor encapsulants, die attach materials, battery potting materials, flexible substrates, adhesives, and coatings.

[0070] Typical applications of silicone resin include optical materials, particularly encapsulants for white LEDs. Silicone resins possess extremely high transparency in the visible light range and exhibit very little yellowing due to ultraviolet light or heat, allowing for efficient extraction of light emitted from LED chips and suppression of changes in color and brightness over long periods. Furthermore, grades with precisely controlled refractive indices have been developed, making it possible to further optimize light extraction efficiency. In semiconductor applications, its outstanding stress relaxation capabilities make it suitable for use as a potting and die attach material for power semiconductors and large system-on-a-chip (SoC) devices, preventing chip and solder bump damage due to thermal cycling and improving the long-term reliability of devices. In addition, its flexibility, weather resistance, and low stress properties enable the design of high-performance materials in fields such as inks, decorative materials, 3D printing materials, and cosmetics.

[0071] Rosin resin is an amorphous solid primarily composed of resin acids such as abietic acid and pima acid, obtained from natural resins such as pine resin. It is relatively inexpensive yet exhibits excellent compatibility with many polymers and solvents. By incorporating rosin resin as a non-polymerizable polymer (B4) into polymerizable compositions, it improves wettability to the adherend and imparts tackiness. In particular, when used as an adhesive or sealant, it can effectively enhance initial tack (stickiness) and tackiness. In hot-melt adhesives and pressure-sensitive adhesives (such as adhesive tapes), it is an essential component for adjusting the balance of tackiness properties when combined with the base polymer responsible for cohesive force. It also contributes to improved wettability and dispersibility in applications such as decorative materials, cosmetics, inks, and coatings.

[0072] In the field of electronic materials, rosin resin plays an important role as the main component of soldering flux, utilizing the weak acidity of its carboxyl groups. During soldering, it reduces and removes oxide films from metal surfaces, cleaning them and promoting the wetting and spreading of molten solder. After soldering, it becomes a non-corrosive residue and maintains high electrical insulation properties, making it suitable for use in no-clean fluxes where cleaning is omitted. However, natural rosin has conjugated double bonds in its molecule, making it unstable to heat and light, and prone to oxidation and discoloration. To improve this drawback, modified rosin, such as hydrogenated rosin (achieved by hydrogenation), disproportionated rosin (achieved by isomerization by heating), or polymerized rosin (achieved through stabilization treatment), is suitably used in applications requiring high reliability.

[0073] Rosin-modified phenolic resin is a resin obtained by reacting rosin or modified rosin with phenol and formaldehyde. It exhibits hybrid properties, combining the tackiness and solubility of rosin with the hardness, heat resistance, and chemical resistance of phenolic resin. This makes it possible to achieve a balance of physical properties that cannot be achieved with rosin resin or phenolic resin alone. One of its main applications is as a vehicle (coloring agent) for offset printing inks. It enhances the dispersibility of pigments, aiding in vivid color development, while also giving the ink appropriate viscosity and fluidity, improving transferability to paper and drying properties. Furthermore, it also has the effect of imparting gloss and abrasion resistance to printed materials, making it applicable in fields such as decorative materials, inks, coatings, and sealants.

[0074] Non-polymerizable oligomers (B3) and non-polymerizable polymers (B4) do not directly participate in the curing reaction of the polymerizable composition, but their physical dispersion or compatibility within the matrix brings about multifaceted effects on the physical properties of the composition and the cured product. The content of these components is usually set in the range of 1 to 60% by mass, preferably 3 to 50% by mass, and more preferably 5 to 40% by mass, relative to the total mass of the polymerizable composition. Appropriate content allows for performance design tailored to the purpose, such as viscosity adjustment, improved film formation, mitigation of curing shrinkage, reduction of internal stress, imparting of flexibility and toughness, and even improvement of filler dispersibility and wettability.

[0075] These non-polymerizable components are widely used not only in high-performance fields such as semiconductors, optics, electronic materials, and batteries, but also in general applications such as adhesives, sealants, inks, inkjet inks, 3D modeling materials, coatings, paints, photosensitive resins, cosmetics, decorative materials, dental materials, dicing tapes, flexible printed circuit boards, and adhesives for dissimilar materials. For example, polyimide resins and bismaleimide resins impart high heat resistance, while polybutadiene resins and silicone resins improve stress relaxation and flexibility. Rosin resins and (meth)acrylic resins enhance tackiness and wettability, and phenolic resins and phenoxy resins impart mechanical strength and flame retardancy. By utilizing the properties of various resins in their formulations, it is possible to design high-performance polymerizable compositions tailored to specific applications.

[0076] The polymerizable composition of the present invention may further contain polymerizable monomers (D) in addition to the (meth)acrylate component (A) for the purpose of adjusting viscosity, controlling crosslink density, precisely adjusting the physical properties of the cured product (flexibility, hardness, heat resistance, impact resistance, chemical resistance, etc.), and further improving curing reactivity and expanding the design freedom of the crosslink structure. Polymerizable monomer (D) has a different structure from component (A) and is a low molecular weight polymerizable compound with a number average molecular weight (Mn) of less than 1,000. It is not particularly limited as long as it is a compound having one or more ethylenically unsaturated groups in the molecule, and both monofunctional monomers and polyfunctional monomers can be used.

[0077] Polymerizable monomers (D) may include monomers (d1) having chain substituents with 1 to 36 carbon atoms, monomers (d2) having cyclic substituents with 3 to 20 carbon atoms, and monomers (d3) having one or more ethylenically unsaturated groups and one or more reactive functional groups (excluding ethylenically unsaturated groups) in the molecule, depending on their structure. Monomers (d1) and (d2) may be monofunctional (d1-1, d2-1) or polyfunctional (d1-2, d2-2), respectively. Note that some monomers (d1-1) and (d2-1) may structurally overlap with monomer (d3), in which case they are classified as d3.

[0078] The monomer (d1) has one or more ethylenically unsaturated groups and a chain substituent having 1 to 36 carbon atoms in its molecule. The chain substituent may be linear or branched and may be a saturated alkyl group or an unsaturated alkenyl group. Furthermore, these chain substituents may include or be substituted with functional groups such as hydroxyl groups, primary to tertiary amino groups, thiol groups, ether groups, ester groups, ketone groups, carboxylic acid groups, amide groups, and sulfonic acid groups.

[0079] The ethylenically unsaturated group of monomer (d1) is one or more groups selected from (meth)acrylate, (meth)acrylamide, vinyl, vinyl ether, alkyl vinyl ether, allyl, (meth)allyl ether, and maleimide groups. These groups exhibit high copolymerizability with (meth)acrylate (A), with (meth)acrylamide and (meth)acrylate groups being particularly preferred.

[0080] Among the monomers (d1), monofunctional monomers (d1-1) having a (meth)acrylate group include alkyl (meth)acrylates having a linear or branched chain with 1 to 36 carbon atoms, and compounds having or substituted with one or more functional groups such as tertiary amino groups, ether groups, ester groups, ketone groups, amide groups, and sulfonic acid groups in their structure. In particular, methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate, stearyl (meth)acrylate, isostearyl (meth)acrylate, behenyl (meth)acrylate, 2-(2-ethoxyethoxy)ethyl acrylate, methoxydiethylene glycol (meth)acrylate, and N,N-dimethylaminoethyl (meth)acrylate are preferred. These d1-1s may be used individually or in combination of two or more types.

[0081] Among the monomers (d1), monofunctional monomers (d1-1) having a (meth)acrylamide group include N-substituted alkyl(meth)acrylamides, N,N-disubstituted dialkyl(meth)acrylamides having a linear or branched chain with 1 to 36 carbon atoms, and compounds having one or more functional groups such as tertiary amino groups, ether groups, ester groups, ketone groups, amide groups, sulfonic acid groups, etc., in their structure, or compounds substituted with such groups. Among these, dimethylacrylamide, diethylacrylamide, isopropylacrylamide, t-butylacrylamide, ethylhexylacrylamide, n-octylacrylamide, t-octylacrylamide, methoxybutylacrylamide, butoxymethylacrylamide, dimethyl-3-aminopropylacrylamide, and diacetoneacrylamide are preferred from the viewpoint of being readily available industrially. These d1-1s may be used individually or in combination of two or more.

[0082] Among the monomers (d1), the following compounds are examples of polyfunctional monomers (d1-2) having a (meth)acrylate group. Examples include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, methoxydipropylene glycol (meth)acrylate, methoxytripropylene glycol (meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,6-hexanediol ethylene oxide modified di(meth)acrylate, hydroxypivalate neopentyl glycol di(meth)acrylate, glycerin di(meth)acrylate, trimethylolethane tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol di(meth)acrylate, tri(meth)acrylate, tetra(meth)acrylate, dipentaerythritol tri-hexa(meth)acrylate, etc. Furthermore, polyether-based, polyurethane-based, and polyester-based di(meth)acrylates without cyclic substituents, such as ethylene glycol diglycidyl ether di(meth)acrylate, diethylene glycol diglycidyl ether di(meth)acrylate, polyethylene glycol di(meth)acrylate with a number average molecular weight (Mn) of less than 1,000, polypropylene glycol di(meth)acrylate, polyisopropylene glycol di(meth)acrylate, and polytetramethylene glycol di(meth)acrylate, can also be suitably used. These d1-2 may be used individually or in combination of two or more.

[0083] Among monomers (d1), the following compounds are examples of polyfunctional monomers (d1-2) having a (meth)acrylamide group. For example, methylenebis(meth)acrylamide, ethylenebis(meth)acrylamide, propylenebis(meth)acrylamide, butylenebis(meth)acrylamide, diallyl(meth)acrylamide, N-(tris(3-(meth)acrylamidepropoxymethyl)methyl)(meth)acrylamide, N,N-bis(2-(meth)acrylamideethyl)(meth)acrylamide, 4,7,10-trioxa-1,13-tridecanbis(meth)acrylamide, N,N'-1,2-ethandylbis(N-(2-(meth)acrylamideethyl))(meth)acrylamide, etc. Furthermore, N-(meth)acryloylhexamethyleneimine and its alkyl-substituted derivatives (2-methyl, 3-methyl, 4-methyl, 2-ethyl, 3-ethyl, 4-ethyl, 3-propyl, 4-propyl, 3-isopropyl, 4-isopropyl, 3,5-dimethyl, 4,4-dimethyl), N-(meth)acryloylheptamethyleneimine, N-(meth)acryloyloctamethyleneimine, N-(meth)acryloyldecamethyleneimine, etc. are also suitably used. In addition, polyether-based, polyurethane-based, and polyester-based di(meth)acrylamides without cyclic substituents, such as polyethylene glycol di(meth)acrylamide, polypropylene glycol di(meth)acrylamide, polyisopropylene glycol di(meth)acrylamide, and polytetramethylene glycol di(meth)acrylamide, which have a number average molecular weight (Mn) of less than 1,000, can also be suitably used. These d1-2 may be used individually or in combination of two or more.

[0084] The monomer (d2) has one or more ethylenically unsaturated groups and a cyclic substituent having 3 to 20 carbon atoms in its molecule. The cyclic substituent is one or more substituents selected from monocyclic or polycyclic aliphatic rings, aromatic rings, aliphatic heterocycles, and monocyclic or polycyclic aromatic heterocycles. The aliphatic ring and aliphatic heterocycle of d2 may be saturated or unsaturated rings.

[0085] The ethylenically unsaturated group possessed by monomer (d2) is one or more groups selected from the group consisting of (meth)acrylate group, (meth)acrylamide group, vinyl group, vinyl ether group, alkyl vinyl ether group, allyl group, (meth)allyl ether group, and maleimide group. Among these, (meth)acrylamide group and (meth)acrylate group are preferred from the viewpoint of high copolymerizability with (meth)acrylate (A). Note that monomer (d2) is distinct from (meth)acrylate (A), and specifically, if it has a (meth)acrylate group, it does not have an amide group in the molecule, and if it has a (meth)acrylamide group, it does not have a (meth)acrylate group in the molecule.

[0086] Among monomers (d2), the following compounds can be cited as monofunctional monomers (d2-1) having a (meth)acrylate group: phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, phenoxytetraethylene glycol (meth)acrylate, phenoxyhexaethylene glycol (meth)acrylate, cyclohexyl (meth)acrylate, tert-butylcyclohexyl (meth)acrylate, benzyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, bornyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, and the like.

[0087] Furthermore, dicyclopentanyl di(meth)acrylate, caprolactone-modified dicyclopentenyl di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, ethylene oxide-modified bisphenol A type di(meth)acrylate, propylene oxide-modified bisphenol A type di(meth)acrylate, cyclohexanedimethanol di(meth)acrylate, tris(2-hydroxyethyl) isocyanurate tri(meth)acrylate, and polyether di(meth)acrylate, polyurethane di(meth)acrylate, polyester di(meth)acrylate, etc., having cyclic substituents with a number average molecular weight (Mn) of less than 1,000 can also be suitably used. Among these monomers (d2-1), phenoxyethyl acrylate, cyclohexyl acrylate, tert-butylcyclohexyl acrylate, dicyclopentanyl acrylate, dicyclopentenyl acrylate, isobornyl acrylate, and tetrahydrofurfuryl acrylate are preferred from the viewpoint of being readily available industrially and for their reactivity and property adjustment. These d2-1 may be used individually or in combination of two or more.

[0088] Among monomers (d2), the following compounds are examples of monofunctional monomers (d2-1) having a (meth)acrylamide group. These include compounds having an aliphatic or aromatic ring, such as N-cyclohexyl(meth)acrylamide, N,N-dicyclohexyl(meth)acrylamide, N-cyclohexyl-N-methyl(meth)acrylamide, N-cyclohexyl-N-ethyl(meth)acrylamide, N-cyclohexyl-N-propyl(meth)acrylamide, N-cyclohexyl-N-butyl(meth)acrylamide, and N-phenyl(meth)acrylamide. Furthermore, N-(meth)acryloylmorpholine, N-(meth)acryloylpiperidine, N-(meth)acryloyl-2-methylpiperidine, N-(meth)acryloyl-3-methylpiperidine, N-(meth)acryloyl-4-methylpiperidine, N-(meth)acryloyl-2,6-dimethylpiperidine, N-(meth)acryloyl-3,5-dimethylpiperidine, N-(meth)acryloyl-3,3-dimethylpiperidine, N-(meth)acryloyl-4,4-dimethylpiperidine, N-(meth)acryloyl-2,2,6,6-tetramethylpiperidine, N-(meth)acryloyl-2-methylpiperidine Compounds having aliphatic heterocycles such as ethyl-5-ethylpiperidine, N-(meth)acryloyl-4-methyl-4-ethylpiperidine, N-(meth)acryloyl-2-ethylpiperidine, N-(meth)acryloyl-3-ethylpiperidine, N-(meth)acryloyl-4-ethylpiperidine, N-(meth)acryloyl-2-propylpiperidine, N-(meth)acryloyl-3-propylpiperidine, N-(meth)acryloyl-4-propylpiperidine, N-(meth)acryloyl-3-isopropylpiperidine, and N-(meth)acryloyl-4-isopropylpiperidine are also suitably used. Furthermore, polyether di(meth)acrylamides, polyurethane di(meth)acrylamides, polyester di(meth)acrylamides, etc., having cyclic substituents with a number-average molecular weight (Mn) of less than 1,000 can also be mentioned.

[0089] Among these monomers (d2-1), N-cyclohexylacrylamide, N,N-dicyclohexylacrylamide, N-cyclohexyl-N-methylacrylamide, N-acryloylmorpholine, N-acryloylpiperidine, N-acryloyl-2-methylpiperidine, N-acryloyl-4-methylpiperidine, N-acryloyl-2,6-dimethylpiperidine, N-acryloyl-3,5-dimethylpiperidine, and N-phenylacrylamide are preferred from the viewpoint of ease of industrial availability, stability, reactivity, etc. These d2-1 may be used individually or in combination of two or more.

[0090] The content of polymerizable monomer (D) is adjusted as appropriate depending on the application and required performance of the polymerizable composition, but is preferably 1 to 95% by mass, more preferably 5 to 80% by mass, and even more preferably 10 to 70% by mass, relative to the total mass of the polymerizable composition. If the content of component (D) is less than 1% by mass, the effects of improving physical properties such as viscosity adjustment, control of crosslinking density, and improvement of transparency may not be fully realized. On the other hand, if it exceeds 95% by mass, the proportion of the essential component (meth)acrylate (A) decreases relatively, and the amount of outgassing during thermal polymerization or thermal curing may not be sufficiently suppressed, which may cause problems, especially in fields where high reliability is required, such as electronic devices, optical components, and semiconductor packages. In addition, it may become difficult to achieve both heat resistance and impact resistance in the cured product, and issues may remain regarding mechanical strength and dimensional stability.

[0091] Among the polymerizable monomers (D), monomers (d1) having chain-like substituents with 1 to 36 carbon atoms are effective in applications requiring flexibility and extensibility. In particular, they are suitable for applications requiring flexibility, such as adhesives, sealants, elastomers, and encapsulants for flexible devices, as well as for applications requiring toughness and impact resistance in various devices such as 3D molding materials, decorative materials, and electronic, optical, and semiconductor devices. d1 is easily filled as a flexible chain-like substituent between or around the cyclic substituents of (meth)acrylate (A). This packing effect mitigates volume shrinkage associated with polymerization, keeping curing shrinkage of the polymerizable composition low. Furthermore, by suppressing the generation of internal stress, the resulting cured product exhibits high transparency and durability. In particular, in encapsulation applications for electronic materials and semiconductor devices, it contributes to crack suppression and improved adhesion, enabling highly reliable material design. Moreover, in general applications such as adhesives, potting materials, and coatings, it contributes to improved adhesion to the substrate, impact resistance, and durability, making it a component that can flexibly accommodate a wide range of material designs. From these perspectives, the content of d1 is usually 0.3 to 80% by mass, preferably 1 to 70% by mass, and more preferably 5 to 50% by mass, relative to the total mass of the polymerizable composition. In particular, for applications where flexibility is required, the content of d1 is preferably 20 to 80% by mass, and more preferably 30 to 70% by mass.

[0092] Among the polymerizable monomers (D), monomers (d2) having cyclic substituents with 3 to 20 carbon atoms have a highly rigid structure, contributing to improved heat resistance and dimensional stability of the cured product. The cyclic structure of d2 suppresses volume change during polymerization, reducing curing shrinkage, and the resulting cured product exhibits high heat resistance and dimensional stability. As a result, it exhibits excellent performance in applications requiring dimensional accuracy and thermal stability, such as optical components, semiconductor packages, and structural materials for electronic devices. Furthermore, when used as a coating agent or sealant, it exhibits excellent physical stability in high-temperature environments, contributing to improved long-term reliability. From these viewpoints, the content of d2 is usually 0.2 to 70% by mass, preferably 0.5 to 60% by mass, and more preferably 2 to 50% by mass, relative to the total mass of the polymerizable composition.

[0093] When a polymerizable composition contains both a cyclic (meth)acrylate (A) and a monomer (d2), the resulting polymer and cured product exhibit improved heat resistance and dimensional stability by forming a rigid cyclic network. However, there is a concern that cracks may develop due to an increase in internal stress over time. In such cases, the mass ratio (A / d2) of component (A) to d2 is preferably 1 / 3 to 20 / 1, more preferably 1 / 2 to 10 / 1, and particularly preferably 1 / 1.5 to 7 / 1. Within this range, the effect of (meth)acrylate (A) is fully expressed without being hindered by d2, and d2 plays a supporting role, thus maintaining a good balance of physical properties in the cured product.

[0094] Furthermore, when (meth)acrylate (A), monomer (d1), and monomer (d2) are used in combination as polymerizable monomers, the synergistic effect of each component results in a cured product exhibiting well-balanced properties with excellent transparency, impact resistance, heat cycle resistance, heat resistance, and durability. In such a configuration, it is preferable that the content of d1 be 0.3 to 60 mass%, the content of d2 be 0.2 to 40 mass%, and the total of both be 0.5 mass% or more. By using d1 and d2 in combination, the properties of flexibility and rigidity are complemented, making it possible to improve the physical properties of the cured product in a multifaceted way. The mass ratio of these contents (d1 / d2) is more preferably 30 / 1 to 1 / 10, and particularly preferably 10 / 1 to 1 / 5. This ratio optimizes the balance between flexibility and dimensional stability, enabling material design that achieves both high reliability and performance in electronic, optical, and semiconductor applications.

[0095] One embodiment of the present invention is a polymerizable composition that further contains a crosslinking agent. By incorporating a crosslinking agent, it becomes possible to control the crosslinking density of the cured product, thereby improving physical properties such as mechanical strength, heat resistance, chemical resistance, and durability. In particular, in adhesive and sealant applications, it contributes to improved adhesion to the substrate and environmental resistance, and in the optical, electronic, and semiconductor fields, it is effective in improving dimensional stability and reliability. Furthermore, the inclusion of a crosslinking agent enhances the structural stability of the cured product by forming a three-dimensional network structure, while also suppressing thermal deformation and stress concentration. As a result, excellent durability and dimensional stability can be maintained even in applications where repeated stress is applied, such as flexible printed circuit boards and dicing tapes. In addition, in three-dimensional molding materials and decorative materials, it contributes to improved molding accuracy and surface hardness.

[0096] Examples of crosslinking agents used in the present invention include polyfunctional monomers (d1-2) having chain substituents with 1 to 36 carbon atoms, polyfunctional monomers (d2-2) having cyclic substituents with 3 to 20 carbon atoms, a polyfunctional polymerizable oligomer (B1), and a polyfunctional polymerizable polymer (B2). These crosslinking agents have two or more ethylenically unsaturated groups in their molecules and form a three-dimensional crosslinked structure through a copolymerization reaction when heated in the presence of (meth)acrylate (A) and a thermal polymerization initiator (C). Depending on the application, one of these crosslinking agents may be used alone, or two or more may be used in combination.

[0097] The total content of the crosslinking agent (polyfunctional polymerizable monomers, oligomers, and polymers) relative to the total mass of the polymerizable composition is preferably 1 to 95% by mass. Within this content range, it is possible to balance and adjust the physical properties of the cured product, such as mechanical strength, dimensional stability, heat resistance, impact resistance, and heat cycle resistance. In particular, by controlling the crosslinking density, it is possible to accurately impart the properties required for each application, such as high adhesive strength and durability in adhesive applications, excellent moisture resistance and insulation in sealant applications, and low outgassing, high transparency, and control of the coefficient of thermal expansion in optical, electronic, and semiconductor material applications. From this viewpoint, the crosslinking agent content is more preferably 5 to 90% by mass, and particularly preferably 10 to 80% by mass.

[0098] In addition to the above, monomers (d3) having one or more ethylenically unsaturated groups and one or more reactive functional groups (excluding ethylenically unsaturated groups) in the molecule, and compounds (e) that do not have ethylenically unsaturated groups but have two or more reactive groups in the molecule, can also be suitably used as crosslinking agents. These compounds can form crosslinked structures not only by thermal polymerization, but also by reaction mechanisms other than thermal polymerization, and are extremely useful in the design of functional materials because they enable multi-step curing and structural control by selective reactions.

[0099] For example, monomer (d3) can form a partially crosslinked structure through selective functional group reactions while maintaining the flexibility of the cured product, making it suitable for applications requiring both flexibility and structural stability, such as adhesives and photosensitive resins. Furthermore, residual functional groups react in subsequent processes, contributing to improved adhesion to the substrate and enhanced physical properties through post-curing. On the other hand, compound (e) has reactive groups such as epoxy groups, isocyanate groups, and carboxylic acid groups, and can proceed with crosslinking reactions in response to external stimuli such as heat, moisture, and light. This allows for design tailored to required characteristics, such as improved environmental responsiveness and long-term reliability in encapsulant and adhesive applications, and low outgassing and dimensional stability in optical, electronic, and semiconductor material applications.

[0100] A monomer (d3) is a monomer that has one or more ethylenically unsaturated groups in its molecule, as well as one or more reactive functional groups. These reactive functional groups remain after thermal polymerization and participate in subsequent reactions (e.g., moisture curing, reactions with other compounds) or form chemical bonds with functional groups on the substrate surface. This not only functions as a crosslinking point but also contributes to improved adhesion and durability. Examples of d3s include hydroxyl group-containing (meth)acrylic monomers, carboxyl group-containing (meth)acrylic monomers, amino group-containing (meth)acrylic monomers, isocyanate group-containing (meth)acrylic monomers, glycidyl group-containing (meth)acrylic monomers, and oxazoline group-containing vinyl monomers.

[0101] Examples of the hydroxyl group-containing (meth)acrylic monomers include hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 5-hydroxypentyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, and 8-hydroxyoctyl (meth)acrylate; hydroxyalkyl (meth)acrylamides such as N-hydroxyethyl (meth)acrylamide and N-hydroxypropyl (meth)acrylamide; and other examples such as 2-acryloyloxyethyl 2-hydroxyethyl Examples include primary hydroxyl group-containing (meth)acrylic monomers such as phthalic acid and N-methylol(meth)acrylamide; secondary hydroxyl group-containing (meth)acrylic monomers such as 2-hydroxypropyl(meth)acrylate, 2-hydroxybutyl(meth)acrylate, 2-hydroxy3-phenoxypropyl(meth)acrylate, 3-chloro2-hydroxypropyl(meth)acrylate, and 2-hydroxy3-phenoxypropyl(meth)acrylate; and tertiary hydroxyl group-containing (meth)acrylic monomers such as 2,2-dimethyl2-hydroxyethyl(meth)acrylate. Among these, hydroxyalkyl(meth)acrylates and hydroxyalkyl(meth)acrylamides are preferably used. These hydroxyl group-containing (meth)acrylic monomers may be used individually or in combination of two or more.

[0102] Examples of the carboxyl group-containing (meth)acrylic monomers mentioned above include monocarboxylic acids such as (meth)acrylic acid and crotonic acid; and dicarboxylic acids such as maleic acid, maleic anhydride, fumaric acid, citraconic acid, and itaconic acid. Among these, (meth)acrylic acid is preferably used. These carboxyl group-containing (meth)acrylic monomers may be used individually or in combination of two or more.

[0103] Examples of the amino group-containing (meth)acrylic monomers include aminoalkyl (meth)acrylates such as N,N-dimethylaminoethyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylate, N,N-di-t-butylaminoethyl (meth)acrylate, and N,N-diethylaminoethyl (meth)acrylate; and aminoalkyl (meth)acrylamides such as N,N-dimethylaminoethyl (meth)acrylamide, N,N-diethylaminoethyl (meth)acrylamide, and N,N-dimethylaminopropyl (meth)acrylamide. These amino group-containing (meth)acrylic monomers may be used individually or in combination of two or more.

[0104] Examples of the glycidyl group-containing (meth)acrylic monomers include glycidyl (meth)acrylate, glycidyl (meth)acrylamide, N-hydroxyethyl (meth)acrylamide glycidyl ether, N-methyl-N-hydroxyethyl (meth)acrylamide glycidyl ether, N-ethyl-N-hydroxyethyl (meth)acrylamide glycidyl ether, N-propyl-N-hydroxyethyl (meth)acrylamide glycidyl ether, N-butyl-N-hydroxyethyl (meth)acrylamide glycidyl ether, N-hydroxypropyl (meth)acrylamide glycidyl ether, N-hydroxybutyl (meth)acrylamide glycidyl ether, N-hydroxypentyl (meth)acrylamide glycidyl ether, N-hydroxyhexyl (meth)acrylamide glycidyl ether, N-hydroxyheptyl (meth)acrylamide glycidyl ether, and N-hydroxyoctyl (meth)acrylamide glycidyl ether. These glycidyl group-containing (meth)acrylic monomers may be used individually or in combination of two or more.

[0105] Examples of the oxazoline group-containing vinyl monomers include 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, 4,5-diethyl-2-vinyl-2-oxazoline, and 2-isopropenyl Examples include 2-2-oxazoline, 4-methyl-2-isopropenyl-2-oxazoline, 5-methyl-2-isopropenyl-2-oxazoline, 4-ethyl-2-isopropenyl-2-oxazoline, 5-ethyl-2-isopropenyl-2-oxazoline, 4,4-dimethyl-2-isopropenyl-2-oxazoline, 4,4-diethyl-2-isopropenyl-2-oxazoline, 4,5-dimethyl-2-isopropenyl-2-oxazoline, and 4,5-diethyl-2-isopropenyl-2-oxazoline. Furthermore, from the viewpoint of high reactivity, 2-vinyl-2-oxazoline, 5-methyl-2-vinyl-2-oxazoline, and 4,4-dimethyl-2-vinyl-2-oxazoline are preferred, with 2-vinyl-2-oxazoline being the most preferred among them. These oxazoline group-containing (meth)acrylic monomers may be used individually or in combination of two or more. Furthermore, the monomer (d3) that can introduce these crosslinking sites is not limited to one type, but may be used in combination of multiple types.

[0106] Compound (e) is a compound that does not have an ethylenically unsaturated group but has two or more reactive groups in its molecule. This compound functions as a so-called curing agent, reacting with functional groups of other components in the polymerizable composition (for example, the hydroxyl group or carboxyl group of compound (d3)) to form a crosslinked structure. Examples of compound (e) include isocyanate compounds having two or more isocyanate groups, epoxy compounds having two or more epoxy groups, aziridine compounds having two or more aziridine groups, carboxylic acid compounds having two or more carboxyl groups, oxazoline compounds having two or more oxazoline groups, and amino compounds having two or more amino groups.

[0107] Examples of isocyanate compounds include lower aliphatic polyisocyanates such as butylene diisocyanate and hexamethylene diisocyanate; alicyclic isocyanates such as cyclopentylene diisocyanate, cyclohexylene diisocyanate, and isophorone diisocyanate; aromatic diisocyanates such as 2,4-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, and xylylene diisocyanate; isocyanate adducts such as trimethylolpropane / tolylene diisocyanate trimer adducts, trimethylolpropane / hexamethylene diisocyanate trimer adducts, and isocyanurates of hexamethylene diisocyanate; and polymers having isocyanate groups, such as homopolymers of the aforementioned isocyanate group-containing vinyl monomers and copolymers with other compounds having unsaturated bonds. These isocyanate compounds may be used individually or in combination of two or more.

[0108] Examples of epoxy compounds include polyethylene glycol diglycidyl ether, polyglycerol polyglycidyl ether, glycerin diglycidyl ether, diglycidyl ether, trimethylolpropane triglycidyl ether, diglycidylaniline; and polymers containing glycidyl groups, such as homopolymers of the aforementioned glycidyl group-containing vinyl monomers and copolymers with other compounds having unsaturated bonds. These epoxy compounds may be used individually or in mixtures of two or more.

[0109] Examples of aziridine compounds include commercially available products with trade names HDU, TAZM, and TAZO (all manufactured by Sogo Yakuko Co., Ltd.). These aziridine compounds may be used individually or in combination of two or more.

[0110] Examples of carboxylic acid compounds include aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, 1,4-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, diphenyldicarboxylic acid, diphenoxyethanedicarboxylic acid, diphenyletherdicarboxylic acid, and diphenylsulfondicarboxylic acid; alicyclic dicarboxylic acids such as 1,3-cyclopentanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, and 1,4-cyclohexanedicarboxylic acid; malonic acid, dimethylmalonic acid, succinic acid, 3,3-diethylsuccinic acid, glutaric acid, 2,2-dimethylglutaric acid, adipic acid, 2-methyladipic acid, trimethyladipic acid, and pimeline. Examples of carboxylic acid compounds include aliphatic dicarboxylic acids such as acids, azelaic acid, sebacic acid, and suberic acid; compounds having a hydroxycarboxyl group, such as glycolic acid, 3-hydroxybutyric acid, 4-hydroxyvaleric acid, hydroxypropionic acid, hydroxycaproic acid, and hydroxybenzoic acid, and their ester-forming derivatives or their anhydrides; and polymers having a carboxyl group, such as homopolymers of the aforementioned carboxyl group-containing vinyl monomers or copolymers with other compounds having unsaturated bonds. These carboxylic acid compounds may be used individually or in combination of two or more.

[0111] Examples of oxazoline compounds include alkylene bisoxazolines such as tetramethylenebisoxazoline and hexamethylenebisoxazoline; aromatic bisoxazolines such as 1,3-phenylenebis(2-oxazoline) and 1,4-bis(4,5-dihydro-2-oxazolyl)benzene; and polymers containing oxazoline groups, such as homopolymers of the aforementioned oxazoline group-containing vinyl monomers and copolymers with other compounds having unsaturated bonds. These oxazoline compounds may be used individually or in combination of two or more.

[0112] Examples of amino compounds having two or more amino groups include aliphatic amines such as ethylenediamine, diethylenetriamine, triethylenetotriamine, iminobispropylamine, polyadipoamine, and polyoxyalkylenediamine; cyclic amines such as piperazine, aminoethylpiperazine, and 1,3-diaminocyclohexane; aromatic amines such as m-phenylenediamine, p-phenylenediamine, 4,4-diaminodiphenylmethane, tris(4-aminophenyl)methane, and tris(2-aminophenyl)amine; and polymers having amino groups, such as homopolymers of the aforementioned amino group-containing (meth)acrylic monomers and copolymers with other unsaturated compounds. These amine compounds may be used individually or in combination of two or more.

[0113] The content of compound (e) is 0.01 to 60% by mass, preferably 0.1 to 50% by mass, and more preferably 0.5 to 30% by mass, based on the total mass of the polymerizable composition. Within this content range, it is possible to optimize the balance between the progress of the crosslinking reaction and the physical properties of the cured product (flexibility, adhesion, heat resistance, moisture resistance, etc.), enabling highly reliable performance in high-performance applications such as adhesives, encapsulants, optical, electronic, and semiconductor materials. Compound (e) may be used alone, or two or more types may be used in combination to enable multi-stage curing combining multiple reaction mechanisms (e.g., thermal reaction and moisture reaction, photoreaction and chemical bonding with the substrate) and complex control of physical properties. This allows for high-performance designs tailored to each application, such as achieving both low outgassing and dimensional stability in semiconductor encapsulation applications, improved transparency and environmental resistance in optical materials, and high adhesion and durability to the substrate in adhesive applications.

[0114] The polymerizable composition of the present invention can be cured by active energy rays (photocuring) in addition to thermal polymerization or thermal curing, thereby enabling dual curing (hybrid curing). In dual curing, the synergistic effect of thermal curing and photocuring results in less residual polymerizable components and extremely low shrinkage during curing, thus producing cured products with excellent safety, impact resistance, and heat resistance. This enables improved initial curing speed, shortened manufacturing processes, handling of complex shapes, and partial curing control. In particular, in adhesive and encapsulant applications, it improves reliability through rapid initial fixation and post-curing, and in optical, electronic, and semiconductor material applications, it enables flexible design according to the required performance, such as low-temperature process compatibility and high-precision pattern formation.

[0115] The order of thermal curing and photocuring is arbitrary and can be performed individually or simultaneously. Examples of active energy rays include visible light, ultraviolet (UV), infrared, electron beams (EB), X-rays, gamma rays, alpha rays, and beta rays. When using electron beams, a photopolymerization initiator is not required, but when using ultraviolet or visible light, the use of a photopolymerization initiator is preferable. Examples of active energy ray generators include xenon lamps, low-pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, UV-LED lamps, and microwave excimer lamps, with ultraviolet being particularly preferred from the viewpoint of equipment availability, curing speed, and safety.

[0116] Intramolecular cleavage-type photoradical polymerization initiators are a type that directly generates radical species by cleaving bonds within the molecule upon light irradiation. Because they enable highly efficient and rapid curing, they are suitable for electronic and optical material applications where fine pattern formation and rapid curing are required. Representative compounds include, for example, acetophenone-based compounds such as 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexylphenyl-ketone, and 2-hydroxy-2-methyl-1-phenyl-propane-1-one; benzoin-based compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether; α-aminoketone-based compounds such as 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropane-1-one and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1; acylphosphine oxide-based compounds such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and 2,4,6-trimethylbenzoyl-diphenylphosphine oxide; and oxime ester-based compounds. Furthermore, polymerizable oligomer-type or polymer-type photopolymerization initiators containing ethylenically unsaturated groups can also be suitably used. These are particularly effective in applications requiring low volatility, low outgassing, and high durability, such as semiconductor encapsulants and optical adhesives, because the initiator itself participates in the polymerization reaction and is incorporated as part of the cured product.

[0117] Hydrogen abstraction type photoradical polymerization initiators are excited by light irradiation and abstract hydrogen from surrounding hydrogen donors to generate radicals. They are advantageous for adjusting curing conditions and deep curing in applications where flexibility and tackiness are important, such as adhesives and sealants. Typical compounds include, for example, benzophenone-based compounds such as benzophenone, methylbenzophenone, 4-phenylbenzophenone, hydroxybenzophenone, and acrylic benzophenone; thioxanthone-based compounds such as thioxanthone, 2-chlorothioxanthone, isopropylthioxanthone, and diethylthioxanthone; benzoyl ester-based compounds such as methyl benzoylmate, ethyl benzoylmate, and 3,5-dimethoxybenzoylmate methyl; benzoyl amide-based compounds such as N-methylbenzoylamide, N-phenylbenzoylamide, and benzoylamide groups having an ethylenically unsaturated group or urethane group; and anthraquinone and camphorquinone. Polymerizable oligomer-type or polymer-type photopolymerization initiators containing an ethylenically unsaturated group are also preferably used. Similarly, by using polymerizable oligomer-type or polymer-type photopolymerization initiators containing ethylenically unsaturated groups in combination, improvements in the structural stability and adhesion of the cured product, as well as enhanced environmental resistance, are expected.

[0118] These photopolymerization initiators may be used individually, or multiple initiators with different absorption wavelengths may be used in combination. Commercially available examples include "Omnirad 1173," "Omnirad 184," and "Omnirad TPO" from IGM Resins, "Ebecryl P36" from Daicel Allnex, "Pro22669" and the "SPEEDCURE" series from Arkema, and the "Kohshylex I" series from KJ Chemicals. In particular, from the viewpoint of suppressing migration, "Kohshylex I 3002, 3003, 3101, and 3102," which have a high molecular weight, high activity, or have ethylenically unsaturated groups, are preferably used. The content of the photopolymerization initiator is preferably 0.01 to 20% by mass, more preferably 0.1 to 10% by mass, and even more preferably 0.5 to 5% by mass, relative to the total polymerizable composition. Within this range, sufficient polymerization can be obtained by photocuring, and by combining it with thermal curing, a cured product with high hardness and high impact resistance can be formed.

[0119] The polymerizable composition of the present invention is applicable to a wide range of applications, including adhesives, sealants, inks, inkjet inks, 3D modeling materials, coatings, paints, photosensitive resins, cosmetics, decorative materials, dental materials, dicing tapes, flexible printed circuit boards, adhesives for dissimilar materials, adhesives for electronic devices, adhesives for optical devices, adhesives for semiconductor devices, sealants for electronic devices, sealants for optical devices, sealants for semiconductor devices, and binder resins for batteries. In these applications, fillers may be appropriately included for purposes such as improving mechanical strength, imparting thermal conductivity, reducing thermal expansion, providing flame retardancy, controlling conductivity or insulation, adjusting viscosity, coloring, and reducing costs.

[0120] The fillers used in this invention are broadly classified into inorganic fillers, organic fillers, and inorganic-organic hybrid fillers. Examples of inorganic fillers include silica (fused silica, crystalline silica, fumed silica, precipitated silica), alumina, zirconia, titania, composite metal oxides (barium titanate, strontium titanate, calcium titanate, zirconium titanate, lithium titanate, lithium cobalt oxide, lithium manganese oxide, etc.), carbonates (calcium carbonate, magnesium carbonate), sulfates (barium sulfate, calcium sulfate), clay minerals (talc, kaolin, mica, clay, bentonite, montmorillonite), metal hydroxides (aluminum hydroxide, magnesium hydroxide), nitrides (boron nitride, aluminum nitride, silicon nitride), carbides (silicon carbide, boron carbide), glass products (glass beads, glass flakes, glass fiber, glass balloons), carbon materials (carbon black, graphite, carbon nanotubes, graphene, carbon fiber), and metal powders (silver, copper, gold, nickel, aluminum).

[0121] Examples of organic fillers include polymethyl methacrylate (PMMA) beads, polystyrene beads, polyethylene wax, cross-linked polyurethane particles, core-shell rubber particles, cellulose powder, wood flour, starch particles, chitin, and chitosan particles. Inorganic-organic hybrid fillers include inorganic fillers that have been surface-treated or modified with organic materials. Examples include silane-coated silica, montmorillonite modified with quaternary ammonium salts, polymer-coated titanium dioxide, functionally modified zeolites, alumina coated with polyimide or polyester, and carbon nanotubes modified with oxazoline polymers. These hybrid fillers contribute to improved dispersibility, adhesion, mechanical strength, heat resistance, conductivity, barrier properties, and flame retardancy, and are particularly effective in electronic, optical, and semiconductor applications.

[0122] The particle size of the filler is optimized according to the application. The average particle size (d50) of the inorganic filler is 0.3 μm or more, preferably 0.4 μm or more, more preferably 0.8 μm or more, and even more preferably 1.2 μm or more, from the viewpoint of improving moldability. On the other hand, from the viewpoint of improving narrow gap filling ability, it is desirable to have a particle size of 10 μm or less, preferably 8 μm or less, and more preferably 5 μm or less. When used as a flame retardant, an average particle size of 2.2 μm or less is preferable. In terms of shape, there are spherical, plate-like, needle-like, flake-like, and irregular shapes, and spherical is particularly preferred in applications where moldability and fluidity are important, and spherical silica is particularly suitable for electronic and semiconductor applications.

[0123] The filler content is set within the range of 0.1 to 95% by mass relative to the total mass of the polymerizable composition. For general applications (adhesives, coatings, inks, etc.), 5 to 50% by mass is preferred, while for electronic, optical, and semiconductor applications where high filling is required, 70 to 95% by mass is preferred, and 80 to 90% by mass is particularly preferred. For example, in semiconductor encapsulants, setting the inorganic filler content to 65% by mass or more, preferably 70% by mass or more, and more preferably 75 to 90% by mass, significantly improves the heat resistance, moisture resistance, and dimensional stability of the cured product. On the other hand, in order to ensure fluidity and moldability, it is desirable to set the content to 95% by mass or less, preferably 90% by mass or less.

[0124] These fillers can be used individually or in combination of two or more. By combining multiple types of fillers, the properties of each filler can be synergistically enhanced, enabling advanced material design tailored to specific applications, such as achieving both thermal conductivity and insulation, a balance between heat resistance and flexibility, or both transparency and dimensional stability. In particular, the combined use of inorganic and organic hybrid fillers improves dispersibility and interfacial adhesion in polymerizable compositions, thereby comprehensively improving the physical properties of the resulting cured product.

[0125] (Meth)acrylate (A), an essential component of polymerizable compositions, has an amphiphilic structure with polar amide groups, (meth)acrylate groups, and nonpolar cyclic substituents. This amphiphilicity allows component (A) to have excellent compatibility with various fillers, both inorganic and organic, and facilitates the uniform and stable dispersion of fillers in the composition. As a result, the functions of the fillers (thermal conductivity, dimensional stability, heat resistance, electrical conductivity, flame retardancy, etc.) are fully exhibited, greatly contributing to the improvement of the physical properties of the cured product. In particular, in high-filler designs, the amphiphilicity of component (A) assists in the dispersibility of fillers, maintaining fluidity and filling properties during molding while suppressing the generation of internal stress in the cured product. This leads to improved crack suppression, dimensional stability, durability, and reliability in electronic, optical, and semiconductor applications, and ensures uniformity of appearance and physical properties in general applications.

[0126] The polymerizable composition of the present invention may contain various additives as needed, as long as they do not impair the effects of the present invention. These additives are used to adjust the processability, storage stability, curing behavior, balance of physical properties, appearance, durability, reliability, etc., of the composition, enabling performance design tailored to the application.

[0127] Examples of additives include polymerization inhibitors, degradation inhibitors or storage stabilizers, antioxidants, preservatives, light stabilizers, heat stabilizers, flame retardants, surfactants, sensitizers, curing accelerators, antistatic agents, UV absorbers, weathering improvers, mold release agents, stress reducers, colorants such as pigments or dyes, fragrances, defoaming agents, fillers, coupling agents, silane coupling agents, surface tension modifiers, plasticizers, surface lubricants, leveling agents, and softeners. These additives may be used individually or in combination of two or more. The content is set within a range that does not adversely affect the properties of the polymerizable composition and the cured product, and is 20% by mass or less, preferably 10% by mass or less, and more preferably 5% by mass or less, based on the total mass of the polymerizable composition.

[0128] When the polymerizable composition of the present invention is used as an ink composition, paint composition, coating composition, etc., it is preferable to incorporate a surface tension modifier or leveling agent to improve the smoothness of the coating film and prevent coating defects such as streaks, craters, and orange peel. Furthermore, in applications such as protective films, adhesives, dicing tapes, and encapsulants for electronic devices, it is preferable to incorporate an antistatic agent to prevent static electricity buildup and prevent the adhesion of dust and debris due to static electricity, as well as damage to electronic components (ESD damage).

[0129] Examples of antistatic agents include nonionic surfactant-based antistatic agents such as polyoxyethylene alkyl ethers, polyoxyethylene sorbitan fatty acid esters, and polyoxyethylene nonylphenyl ethers; polymer-based antistatic agents such as polyethylene oxide, polyvinylpyrrolidone, polyquaternium, and polyimide; conductive material-based antistatic agents such as carbon black, conductive polymers (polyaniline, etc.), and metal oxides (zinc oxide, indium oxide); and salt-based antistatic agents such as quaternary ammonium salts, phosphate ester salts, and organic sulfonates. These antistatic agents can be appropriately selected according to the application and environmental conditions, and may be used alone or in combination with other additives to obtain synergistic effects.

[0130] The content of the antistatic agent is preferably set within a range that sufficiently exhibits an electrostatic suppression effect while not adversely affecting the mechanical or electrical properties of the cured product, relative to the total mass of the polymerizable composition. The content is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and even more preferably 0.5% by mass or more. On the other hand, excessive addition may lead to a decrease in insulation properties and deterioration of mechanical strength, so the upper limit is preferably 5% by mass or less, more preferably 3% by mass or less, and even more preferably 2% by mass or less. The optimal content varies depending on the type and dispersibility of the antistatic agent, the humidity and temperature of the usage environment, compatibility with the substrate, etc., and is therefore adjusted as appropriate according to the actual application. In particular, for electronic material applications, it is important to uniformly disperse an antistatic agent with low outgassing properties, low metal content, and high transparency at a low concentration.

[0131] Examples of flame retardants include solid components such as aluminum hydroxide, magnesium hydroxide, zinc molybdate, zinc borate, zinc oxide, and melamine resin. Among these, aluminum hydroxide and zinc molybdate are preferred from the viewpoint of improving narrow gap filling ability and heat resistance, and it is even more desirable to include aluminum hydroxide. The flame retardant content is preferably 1% by mass or more, more preferably 2% by mass or more, and even more preferably 3% by mass or more, relative to the total mass of the polymerizable composition, in order to improve the heat resistance, flame retardancy, dimensional stability, and electrical reliability of the cured product. On the other hand, considering the balance with fluidity and filling ability during molding, viscosity control, and mechanical strength, the content is 25% by mass or less, more preferably 20% by mass or less, and even more preferably 18% by mass or less.

[0132] Examples of stress-reducing agents include silicone oil, silicone rubber, and carboxyl-terminated butadiene acrylonitrile rubber. These improve the fluidity of the resin and contribute to stress relaxation and improved impact resistance of the cured product. Silicone oil and carboxyl-terminated butadiene acrylonitrile rubber are particularly preferred.

[0133] The polymer or cured product of the present invention is obtained by polymerizing or curing the polymerizable composition of the present invention described above, and the polymerization and curing method is not particularly limited. Polymerization can be efficiently advanced by heating above the decomposition temperature of the thermal polymerization initiator (C), and the heating temperature and heating time are appropriately set according to the type and amount of initiator used, the component composition in the composition, and the required physical properties of the cured product (e.g., crosslinking density, flexibility, heat resistance, impact resistance, dimensional stability, etc.). For example, polymerization and curing can be completed by heating in the range of 80 to 200°C for several minutes to several hours. Furthermore, by using a photopolymerization initiator in combination, dual curing (hybrid curing) by combining photocuring with active energy rays such as ultraviolet light and visible light is also possible, which reduces shrinkage of the cured product, suppresses unreacted components, and homogenizes the physical properties. The polymerizable composition can be polymerized without solvents, and has advantages such as reduced environmental impact, avoidance of solvent residue, and control of curing shrinkage, making it extremely effective in the manufacture of high-performance materials.

[0134] One embodiment of the present invention is a polymerizable composition in which the volume shrinkage rate (curing shrinkage rate) that occurs during the polymerization process is 5% or less. More preferably, the curing shrinkage rate is 3% or less, more preferably 2% or less, and even more preferably 1% or less. Such a composition contains 5% by mass or more of (meth)acrylate (A) and 0.5% by mass or more of a thermal polymerization initiator (C) relative to the entire polymerizable composition. When producing a polymer, it is preferable to further contain a non-polymerizable olimer (B3) or a non-polymerizable polymer (B4) as a binder component, and among these, it is more preferable to further contain B4 from the viewpoint of excellent durability of the resulting polymer. When producing a cured product, it is preferable to further contain a polymerizable olimer (B1) or a polymerizable polymer (B2) as a binder component, and among these, it is more preferable to further contain B2 from the viewpoint of excellent heat resistance, impact resistance, and durability of the resulting polymer.

[0135] One embodiment of the present invention is a polymerizable composition in which the resulting polymer and cured product have a saturated water absorption rate of 10% or less. More preferably, the saturated water absorption rate is 5% or less, more preferably 3% or less, and even more preferably 2% or less. Such a composition contains 5% by mass or more of (meth)acrylate (A) and 0.2% by mass or more of a thermal polymerization initiator (C) relative to the entire polymerizable composition. Such a composition preferably further contains a polymerizable monomer (D). Furthermore, monomer D is more preferably a chain or cyclic substituent having 6 or more carbon atoms.

[0136] The polymers or cured products of the present invention can be obtained not only as fully cured bodies, but also as mixtures containing unreacted components in a partially polymerized and cured state. Such partially cured bodies offer design flexibility to balance processability and final physical properties by adjusting viscosity, fluidity, and reactivity. In particular, they are useful in the semiconductor and electronic device fields from the viewpoint of stress relaxation, improved adhesion through stepwise curing, and interface control. Furthermore, polymers obtained by solution polymerization are easy to control in terms of molecular weight and structural design, and can be applied to applications such as adhesives, sealants, inks, coatings, materials for electronic, optical, and semiconductor devices, and binders for batteries by separating and purifying them as needed. These polymers or cured products can be given properties such as flexibility, heat resistance, chemical resistance, transparency, electrical insulation, and dimensional stability depending on the required performance, and have high utility in a wide range of industrial applications.

[0137]

[0138] 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, in the following, "parts" and "%" are all on a mass basis unless otherwise specified. (1) (Meth)acrylate (A) Table 1 shows (meth)acrylates (A-1) to (A-22) used in the examples.

[0139]

[0140] (2) Binder component (B) (Polymerizable oligomer (B1)) B1-1: UV-3000B (bifunctional urethane acrylate, manufactured by Mitsubishi Chemical Corporation) B1-2: UV-6640B (bifunctional urethane acrylate, manufactured by Mitsubishi Chemical Corporation) B1-3: EBECRYL 4740 (bifunctional urethane acrylate, manufactured by Daicel Ornex Co., Ltd.) B1-4: BMI-3000J (linear alkylene group-containing bismaleimide, Mn: 7500, manufactured by Designer Molecules Inc.) B1-5: Epolid PB3600 (epoxidized polybutadiene, Mn: 5900, manufactured by Daicel Chemical Industries, Ltd.) (Polymerizable polymer (B2)) B2-1: Quick Cure 7100 (bifunctional urethane acrylamide, registered trademark "Quick Cure" and [Kohshylex], manufactured by KJ Chemicals Co., Ltd.) B2-2: Quick Cure 8100: (Bifunctional urethane acrylamide, registered trademark "Quick Cure" and [Kohshylex], manufactured by KJ Chemicals Co., Ltd.) (Non-polymerizable oligomer (B3)) B3-1: Pine Crystal ME-D (Liquid rosin derivative, manufactured by Arakawa Chemical Industries, Ltd.) B3-2: Actflow UT-1001 (Liquid acrylic resin, manufactured by Soken Chemical Co., Ltd.) B3-3: RICON 134 (Liquid polybutadiene resin, manufactured by Ray Valley) B3-4: CER-3000L (Polyfunctional epoxy resin, manufactured by Nippon Kayaku Co., Ltd.) (Non-polymerizable polymer (B4)) B4-1: Panlon-Precoat 200 (Acrylic resin, manufactured by Negami Kogyo Co., Ltd.) B4-2: ToughTec H1041 (Thermoplastic elastomer, manufactured by Asahi Kasei Corporation) B4-3: ZX1356-2 (Phenoxy resin, manufactured by Nippon Steel Chemical & Material Co., Ltd.)

[0141] (3) Thermal polymerization initiator (C) C-1: 2-Azobisisobutyronitrile C-2: 2,2'-Azobis(2,4-dimethylvaleronitrile) C-3: Bis(3,5,5-trimethylhexanoyl)peroxide C-4: Benzoyl peroxide C-5: Dicumyl peroxide (manufactured by NOF Corporation, product name Permil D)

[0142] (4) Polymerizable monomers (D) (polymerizable compounds having chain substituents with 1 to 36 carbon atoms (d1)) (monofunctional d1-1) d1-1-1: Dimethylacrylamide (registered trademark "Kohshylmer", "DMAA") d1-1-2: Diethylacrylamide (registered trademark "Kohshylmer", "DEAA") d1-1-3: Isopropylacrylamide (registered trademark "Kohshylmer", "NIPAM") d1-1-4: N-(3-(dimethylamino)propylacrylamide) (registered trademark "Kohshylmer", "DMAPAA") d1-1-5: Diacetone acrylamide (registered trademark "Kohshylmer") d1-1-6: 2-Ethylhexyl acrylate d1-1-7: Lauryl methacrylate d1-1-8: Oleylacrylamide (registered trademark "Kohshylmer") d1-1-9: N-Octylacrylamide (registered trademark "Kohshylmer") (Polyfunctional d1-2) d1-2-1: Pentaerythritol triacrylate d1-2-2: Dipentaerythritol hexaacrylate d1-2-3: 1,6-Hexanediol diacrylate d1-2-4: Tripropylene glycol diacrylate (Cyclic substituents with 3 to 20 carbon atoms are polymerizable compounds (d2)) (Monofunctional d2-1) d2-1-1: N-Methylcyclohexylacrylamide (registered trademark "Kohshylmer") d2-1-2: N-Acryloylmorpholine (registered trademark "Kohshylmer", "ACMO") d2-1-3: N-Phenylacrylamide (registered trademark "Kohshylmer") d2-1-4: Tert-butylcyclohexyl acrylate (registered trademark "Kohshylmer") d2-1-5: Isobornyl acrylate d2-1-6: Tetrahydrofurfurylacrylamide (Polyfunctional d2-2) d2-2-1: 1,4-cyclohexanedimethanol diacrylate d2-2-2: bisphenol A ethoxylate diacrylate (Mn=512) d2-2-3: tricyclodecanedimethanol diacrylate d2-2-4: 4,4'-Bismaleimidediphenylmethane (polymerizable compound (d3)) d3-1: Glycidyl methacrylate d3-2: 2-Vinyl-2-oxazoline d3-3: N-(2-hydroxyethyl)acrylamide (registered trademark "Kohshylmer", "HEAA") d3-4: Acrylic acid d3-5: 4-Hydroxybutyl acrylate

[0143] (5) Others (Compound(e)) e-1: Hexamethylene diisocyanate e-2: Benzyldimethylamine (Photopolymerization initiator) f-1: 2-(4-(2-hydroxy-2-methylpropionyl)phenoxy)ethyl acrylate f-2: Kohshylex I-3101 (High molecular weight, UV curable, registered trademark "Kohshylex", manufactured by KJ Chemicals Co., Ltd.) f-3: Omnirad TPO (manufactured by IGM Resins BV) f-4: Omnirad 1173 (manufactured by IGM Resins BV) (Additives) g-1: Carbon black (Coloring agent, CIPigment Black) g-2: Pigment dispersion (NX-061 Green, manufactured by Dainichi Seika Kogyo Co., Ltd.) g-3: BYK-331 (Leveling agent, Polyether-modified polydimethylsiloxane, manufactured by BYK Chemie) g-4: Titanium dioxide (Inorganic filler) g-5: Silica (inorganic filler, d50 = 1.5 μm) g-6: Aluminum hydroxide pulverized (flame retardant)

[0144] (6) Substrates (substrates or films) PC: Polycarbonate substrates and films PMMA: Polymethyl methacrylate substrates and films PET: Easy-to-adhere polyethylene tereflote substrates and films LCP: Liquid crystal polymer flexible substrates ABS: Acrylonitrile-butadiene-styrene copolymer synthetic resin substrates PI: Polyimide substrates and films PA: Polyamide substrates and films PVC: Polyvinyl chloride substrates SPCC: Cold-rolled steel substrates SUS: Stainless steel substrates Al: Aluminum substrates Cu: Copper substrates Ni: Nickel substrates BT: Barium titanate substrates PO: Polyolefin substrates HDF: Wood substrates (high-density fiberboard) GL: Glass substrates NMC: Li(NiMnCo)O2) substrates (active material substrates)

[0145] (Preparation of Polymerizable Compositions) In Examples 1-24 and Comparative Examples 1-3, (meth)acrylate (A), thermal polymerization initiator (C), binder component (B), polymerizable monomer (D), and other components were weighed in proportions shown in Table 2 and mixed for 30 minutes while maintaining a temperature of 35-45°C to prepare the polymerizable compositions of the Examples and Comparative Examples. Polymerization was carried out using the obtained polymerizable compositions by the following method to obtain polymers or cured products. The hygroscopicity, heat resistance, and curing shrinkage resistance of the obtained polymers or cured products were evaluated by the following method, and the results are shown in Table 2.

[0146] (Preparation of polymerized or cured product) A release film (polyethylene terephthalate (PET) film treated with a release agent) was placed in close contact with a glass plate (50 mm x 50 mm x 5 mm), and a silicone spacer (40 mm x 15 mm x 1 mm) was placed on top of it. The polymerizable compositions prepared in each example and comparative example were poured into the spacer, degassed, and then polymerized or cured by the following methods to obtain a sheet-like polymerized or cured product. (Thermal polymerization) If the polymerizable composition did not contain polyfunctional components A, B, or D, polymerization was carried out by heating at 80°C for 60 minutes to obtain a polymer without a crosslinked structure. (Thermosetting) If the polymerizable composition contained one or more of the polyfunctional components A, B, or D, curing was carried out by heating at 80°C for 60 minutes to obtain a cured product with a crosslinked structure. (Sequential curing with heat and UV) If the polymerizable composition contains one or more polyfunctional components A, B, or D, it is cured by heating at 80°C for 60 minutes, followed by UV irradiation (equipment: iGraphics inverter-type conveyor system ECS-4011GX, light source: metal halide lamp M04-L41, UV irradiance: 700mW / cm²). 2 Total luminous intensity: 1000 mJ / cm² 2) was further carried out to obtain a cured product having a crosslinked structure. In this case, it is written as "(1) thermal curing (2) UV curing". Note that depending on the composition of the polymerizable composition, UV curing may be started before thermal polymerization is complete. (Simultaneous thermal and UV curing) If the polymerizable composition contains one or more polyfunctional components A, B, or D, UV irradiation is performed while heating at 80°C for 60 minutes. UV irradiation device: I-Graphics inverter type conveyor device ECS-4011GX, light source: metal halide lamp M04-L41, UV irradiance: 50 mW / cm 2 Total luminous intensity: 1000 mJ / cm² 2 The following procedure was performed to obtain a cured product having a cross-linked structure. In this case, it is written as "(1) Thermocuring (1) UV curing".

[0147] (Evaluation of moisture absorption resistance) A 30 mm x 30 mm test piece was cut from the obtained sheet-like polymer or cured material, dried under vacuum at 60°C for 24 hours, and then accurately weighed to obtain the weight in the dry state. Next, this dried test piece was left in a high-temperature, high-humidity chamber at 85°C and 85% humidity for 12 hours. After the predetermined time had elapsed, the test piece was accurately weighed immediately after being removed from the high-temperature, high-humidity chamber to obtain the weight in the saturated water absorption state. The water absorption rate of the cured material was calculated according to the following formula, and the moisture absorption was evaluated in four stages. Water absorption rate (%) = (Weight in saturated water absorption state - Weight in dry state) / Weight in dry state × 100 ◎: Water absorption rate was 8% or less. ○: Water absorption rate exceeded 8%, but was 10% or less. △: Water absorption rate exceeded 10%, but was 20% or less. ×: Water absorption rate exceeded 20%.

[0148] (Heat Resistance Evaluation) A 10 mg sample was cut from the obtained polymer or cured product, sealed in an aluminum pan, and the glass transition temperature (Tg) was measured using a differential scanning calorimeter (DSC-60plus, manufactured by Shimadzu Corporation). The heat resistance was evaluated according to the following criteria: ◎: Tg was 100°C or higher. ○: Tg was 80°C or higher and less than 100°C. △: Tg was 60°C or higher and less than 80°C. ×: Tg was less than 60°C.

[0149] (Evaluation of curing shrinkage resistance) The density of the prepared polymerizable composition was measured in accordance with JIS K5600-2-4. The density of the obtained polymer or cured product was measured using an electronic hydrometer (MDS-300 manufactured by Alpha Mirage Co., Ltd.) in accordance with JIS K7112. The curing shrinkage rate was calculated according to the following formula, and the curing shrinkage resistance was evaluated in four stages. Curing shrinkage rate (%) = (Ds - Dl) / Dl × 100 (wherein Ds is the density of the polymer or cured product, and Dl is the density of the polymerizable composition.) ◎: Curing shrinkage rate was 3% or less. ○: Curing shrinkage rate exceeded 3%, but was 5% or less. △: Curing shrinkage rate exceeded 5%, but was 8% or less. ×: Curing shrinkage rate exceeded 8%.

[0150]

[0151] As is clear from the results in Table 2, the polymerizable compositions of each example contained a (meth)acrylate (A) having an amide group and a cyclic substituent in the molecule, and a thermal polymerization initiator (C), and polymers could be easily obtained by heating. Furthermore, by including a binder component (B) and / or a polymerizable compound (D), a wide variety of polymers or cured products could be obtained. In addition, when a thermal polymerization initiator was included, polymers or cured products with high hygroscopicity resistance, heat resistance, and curing shrinkage resistance could be obtained by thermal polymerization or thermal curing. Furthermore, when both a thermal polymerization initiator and a photopolymerization initiator were included, polymers or cured products with high hygroscopicity resistance, heat resistance, and curing shrinkage resistance could be obtained by sequential or simultaneous curing with heat and UV. On the other hand, in Comparative Examples 1 to 3, no polymer could be obtained in Comparative Example 1, which did not contain component C, and although a cured product could be obtained by thermal curing in Comparative Example 2, which did not contain component A, the shrinkage during curing was large. Furthermore, in Comparative Example 3, which did not contain component A but contained small amounts of component C and a photopolymerization initiator, simultaneous curing with heat and UV was performed, but a cured product suitable for physical property evaluation could not be obtained.

[0152] (Preparation and Evaluation of Adhesive Compositions) Examples 25-35 and Comparative Examples 4-5 The polymerizable compositions obtained in Table 2 (indicated by example number), components A, B, C, D, and other components were weighed in the proportions shown in Table 3 and uniformly mixed at room temperature to prepare the adhesive compositions of the examples and comparative examples. Using the obtained adhesive compositions, adhesive layers and adhesive sheets were prepared by the following method, and the curability of the adhesive composition, adhesion to various substrates, and the transparency, adhesive strength, stain resistance (reworkability), durability, and yellowing resistance of the obtained adhesive layers were evaluated. The evaluation results are shown in Table 3. In Example 30, the polymerized adhesive sheet was subjected to an aging treatment by holding it in a constant temperature oven at 40°C for 72 hours to complete the crosslinking reaction, and then the various physical properties of the adhesive layer were evaluated.

[0153] (Evaluation of Adhesive Curing Properties) In the same manner as described above (manufacturing of polymers or cured products), a heavy-release PET film was placed in close contact with a horizontally positioned glass plate, and a spacer with a thickness of 1 mm and an internal dimension of 60 mm x 100 mm was placed inside. After filling the inside of the spacer with the adhesive compositions of each example and comparative example prepared, a light-release PET film was placed on top, and thermal curing, sequential curing with heat and UV, or simultaneous curing with heat and UV was performed in the same manner as described above. The UV irradiation was performed at a wavelength of 385 nm and an output of 100 mW / cm². 2 The process was carried out using a UV LED lamp to achieve an integrated light intensity of 1000 mJ / cm2. After that, the release PET films on both sides were removed, and the curing properties of the resulting cured material (adhesive layer) were evaluated in three stages by touch. ○: A cured material that could maintain its shape was obtained, and tack was observed when touched, but there was no adhesion of liquid uncured material. △: A cured material that could maintain its shape was obtained, and tack was observed when touched, but there was adhesion of liquid uncured material. ×: Curing was insufficient, a cured material that could maintain its shape was not obtained, and a large amount of liquid residue was observed.

[0154] (Adhesive Sheet Preparation and Adhesion Evaluation) Similar to the (Evaluation of Adhesive Curability) above, the prepared adhesive composition was applied to various substrates, and then laminated with a light-release PET film using a desktop roll-type laminator (Royal Sovereign RSL-382S) to a thickness of 5 μm, taking care not to trap air bubbles. Next, thermal curing, sequential thermal and UV curing, or simultaneous thermal and UV curing were performed as described above. For ultraviolet irradiation, the same inverter-type conveyor system and light source were used, with an ultraviolet irradiance of 100 mW / cm². 2 , cumulative light intensity 1000 mJ / cm 2 The experiment was conducted under the following conditions. Afterwards, the light release separator was peeled off to obtain an adhesive sheet consisting of an adhesive layer and a substrate. Using the obtained adhesive sheet, 100 1mm square grids were created in accordance with JIS K 5600, cellophane tape was applied and peeled off in one go, and the number of grids on which the adhesive layer remained on the substrate was counted to evaluate adhesion according to the following criteria: ◎: No peeling was observed. 〇: 1 to 5 grids peeled off. △: 6 to 20 grids peeled off. ×: 21 or more grids peeled off.

[0155] (Adhesion Evaluation) Under conditions of 23°C and 50% relative humidity, the adhesive layer was transferred to various substrates and pressed onto them using a 2kg pressure roller with two passes. The substrates were then left in the same atmosphere for 30 minutes. Subsequently, a 180° peel test was performed using a tensile testing machine (ORIENTEC, Tensilon RTA-100) at a peeling speed of 300 mm / min in accordance with JIS Z 0237, and the peel strength (N / 25 mm) was measured. The evaluation was performed according to the following criteria: ◎: 30 (N / 25 mm) or more ○: 15 (N / 25 mm) or more, less than 30 (N / 25 mm) △: 8 (N / 25 mm) or more, less than 15 (N / 25 mm) ×: Less than 8 (N / 25 mm)

[0156] (Transparency Evaluation of the Adhesive Layer) The total light transmittance of the glass substrate was measured using a haze meter (NDH-2000, manufactured by Nippon Denshoku Industries Co., Ltd.) in accordance with JIS K 7105. Under conditions of a temperature of 23°C and a relative humidity of 50%, the adhesive layer was transferred to the glass substrate, and the total light transmittance of the glass substrate and the adhesive layer was measured. Then, the transmittance of the glass plate was subtracted to calculate the transmittance of the adhesive layer itself, and the transparency was evaluated in four stages as follows: ◎: Transmittance of 90% or more ○: Transmittance of 85% or more and less than 90% △: Transmittance of 50% or more and less than 85% ×: Transmittance of less than 50%

[0157] (Stain Resistance (Reworkability) Evaluation) In the same manner as the adhesive strength measurement described above, adhesive sheets were prepared and left at 80°C for 24 hours. After peeling off the adhesive layer, the surface of the base film was visually inspected for contamination (residual state of the adhesive layer (glue)). The following criteria were used for evaluation: ◎: No contamination was observed (no glue residue). ○: Very slight contamination was observed. △: Slight contamination was observed. ×: Contamination was observed (glue residue was present).

[0158] (Yellowing resistance evaluation) An adhesive sheet was prepared in the same manner as the adhesive strength measurement described above, and set in a xenon fade meter (Suga Test Instruments Co., Ltd., SC-700-WA), measuring 70 mW / cm². 2 After irradiating the adhesive sheet with ultraviolet light of a certain intensity for 120 hours, the discoloration of the adhesive layer was observed visually. The evaluation was performed according to the following criteria: ◎: No yellowing was observed visually. ○: Very slight yellowing was observed visually. △: Yellowing was observed visually. ×: Clear yellowing was observed visually.

[0159] (Durability Evaluation) In the same manner as the adhesive strength measurement described above, adhesive sheets were prepared and held for 100 hours under conditions of 85°C and 85% relative humidity. After that, the presence or absence of lifting, peeling, bubbles, or clouding of the adhesive layer was visually observed and evaluated according to the following criteria. ◎: Transparent, with no lifting, peeling, or bubbles. ○: Very slight clouding, but no lifting, peeling, or bubbles. △: Slight clouding, lifting, peeling, or bubbles. ×: Extreme clouding, lifting, peeling, or bubbles.

[0160]

[0161] As is clear from the results in Table 3, the adhesive compositions of the examples exhibited high curability, and the adhesive layers obtained by curing them were highly transparent and had good adhesion and tackiness (adhesion) to various materials. Furthermore, because the cured product (adhesion layer) obtained from the adhesive compositions of the examples contained (meth)acrylate (A), which has both an amide group and a cyclic substituent, as a constituent component, it exhibited excellent stain resistance when the adhesive layer was peeled off the substrate, as well as excellent resistance to yellowing and durability of the cured product. In particular, such adhesive compositions have the characteristic of developing strong tackiness through thermal curing, and further improving peelability by increasing the crosslinking density through UV irradiation. This property is extremely useful for dicing tape applications in semiconductor manufacturing processes. Specifically, in the dicing process of silicon wafers and molded resin packages, it exhibits stable fixing force when dividing chips, and can be easily peeled off after processing, thus contributing to improved yield and process efficiency. In addition, its high transparency makes it suitable for optical inspection and ensuring alignment accuracy. On the other hand, the comparative adhesive composition and the cured product obtained therefrom were inferior in terms of curability, transparency, adhesion to various materials, and tackiness, and sufficient performance was not obtained in terms of stain resistance, yellowing resistance, and durability. Furthermore, it was confirmed that the adhesive strength between the resulting adhesive layer and various substrates tended to improve when heat and UV curing were used in combination, as well as when a crosslinking reaction using compound e was used in combination. These results indicate that the adhesive composition of the example has high practicality as a high-performance adhesive for semiconductor dicing tapes.

[0162] (Preparation and Evaluation of Adhesive Compositions) For Experiments 36-43 and Comparative Examples 6-7, the polymerizable compositions (indicated by Example Number) obtained in Table 2, components A, B, C, D, and other components were weighed in the proportions shown in Table 4 and uniformly mixed at room temperature to prepare the adhesive compositions for the Examples and Comparative Examples. Using the obtained adhesive compositions, adhesive test specimens were prepared by bonding the same or different types of substrates using the following method. The adhesive strength and impact resistance of the prepared adhesive test specimens were evaluated, and the results are shown in Table 4.

[0163] Two substrates of the same or different types with a size of 100 mm × 25 mm × 1 mm were prepared, and an adhesive composition was uniformly applied to any one of them. According to JIS K 6850, the other substrate was overlapped on the coated surface and bonded so that the overlapping area was 12.5 mm × 25 mm. By using a spacer, the thickness of the adhesive layer was adjusted to 100 μm, and a bonded adhesive test piece was prepared. Then, the bonded test piece was subjected to heat curing, sequential curing of heat and UV, or simultaneous curing of heat and UV in the same manner as described above. The ultraviolet irradiation was carried out from above the transparent substrate using a UVLED lamp with a wavelength of 385 nm and an output of 100 mW / cm2 so that the integrated light amount was 1000 mJ / cm2.

[0164] (Adhesive strength evaluation) Using the obtained adhesive test piece, according to JIS K 6850, a tensile testing machine (Tensilon RTA-100 manufactured by ORIENTEC) was used, and the tensile shear strength was measured under the condition of a tensile speed of 10 mm / min. The higher the tensile shear strength, the higher the adhesive strength is evaluated. ◎: The tensile shear strength was 20 MPa or more. ○: The tensile shear strength was 15 MPa or more and less than 20 MPa. △: The tensile shear strength was 10 MPa or more and less than 15 MPa. ×: The tensile shear strength was less than 10 MPa.

[0165] (Impact resistance evaluation) Using the obtained adhesive test piece, according to JIS K 6855, an impact testing machine No. 511 (manufactured by Mize Testing Machine Co., Ltd.) was used, and the impact peel adhesive strength was measured. The higher the impact peel adhesive strength, the higher the impact resistance is evaluated. ◎: The impact peel adhesive strength was 20 KJ / m 2 or more. ○: The impact peel adhesive strength was 15 KJ / m 2 or more and less than 20 KJ / m 2 △: The impact peel adhesive strength was 10 KJ / m 2 or more and less than 15 KJ / m 2 ×: The impact peel adhesive strength was less than 10 KJ / m 2

[0166] ​(Heat cycle resistance evaluation) The obtained adhesive test specimens were left at -40°C for 30 minutes, followed by a 30-minute period at 120°C. This process constituted one heat cycle, and was repeated 10 times. After that, the tensile shear strength was measured in the same manner as in the adhesive strength evaluation, and the strength retention rate was calculated using the following formula. Based on this strength retention rate, the heat cycle resistance was evaluated in the following four stages: Strength retention rate (%) = (Strength after heat cycle) / (Strength before heat cycle) × 100 ◎: Strength retention rate was 90% or higher. ○: Strength retention rate was 80% or higher and less than 90%. △: Strength retention rate was 60% or higher and less than 80%. ×: Strength retention rate was less than 60%.

[0167]

[0168] As is clear from the results in Table 4, the adhesive compositions of the examples exhibited high curability, with easy thermal curing and high adhesive strength and impact resistance. Furthermore, it was confirmed that the curing reaction continued to proceed by UV irradiation after or simultaneously with thermal curing, making it applicable to bonding transparent substrates and dissimilar materials, as well as dissimilar materials such as opaque and transparent substrates. In particular, when the cyclic substituent of (meth)acrylate (A) has an unsaturated bond, photopolymerization proceeded after the thermal polymerization of (meth)acrylate, and it was shown that the adhesive strength, impact resistance, and heat cycle resistance were further improved by the complete polymerization of the unsaturated bond of the cyclic substituent. Such adhesive compositions exhibit high wettability to active materials used in battery electrodes and also exhibit high adhesive strength when bonding active materials to each other, making them useful as battery binders. On the other hand, the adhesive compositions of the comparative examples and the adhesive test pieces obtained therefrom did not exhibit the above-mentioned excellent properties.

[0169] (Preparation and Evaluation of Adhesive Films) Examples 44-51 and Comparative Examples 8-9 The polymerizable compositions (indicated by example number) obtained in Table 2, components A, B, C, D, and other components were weighed in the proportions shown in Table 5. These were stirred at room temperature for 2 minutes at a rotation speed of 2,000 rpm using a mixer (Thinky Co., Ltd., Awatori Rentaro RARE-310), and then degassed at a rotation speed of 2,200 rpm for 1 minute to prepare a varnish-like adhesive film composition (hereinafter referred to as adhesive varnish). The obtained adhesive varnish was applied to a light-release PET film to a thickness of 200 μm using a tabletop coater, taking care not to introduce air bubbles. After application, heat curing, sequential heat and UV curing, or simultaneous heat and UV curing were performed as described above to obtain a film-like adhesive. UV irradiation was performed using the same inverter-type conveyor device and light source, with an UV irradiance of 100 mW / cm². 2 , cumulative light intensity 1000 mJ / cm 2 The experiment was conducted under the specified conditions. The resulting adhesive films were evaluated for appearance, heat and humidity resistance, and flexibility, and the results are shown in Table 5.

[0170] (Appearance evaluation of adhesive film) The obtained adhesive film was visually inspected and evaluated on the following four-point scale according to its appearance. ◎: No unevenness, bubbles, or cracks were observed. 〇: Slight unevenness was observed, but no bubbles or cracks were observed. △: Bubbles or cracks were observed in some areas. × Bubbles or cracks were observed throughout.

[0171] (Evaluation of moisture and heat resistance of adhesive film) The adhesive film was left for 100 hours under conditions of 85°C and 85% relative humidity, and then the appearance was evaluated in the same manner as above, and the moisture and heat resistance was evaluated on the following four scales. ◎: No change in appearance was observed at all. ○: Slight unevenness was observed. △: Some unevenness or bubbles were observed. ×: Bubbles or cracks were observed throughout.

[0172] (Evaluation of the flexibility of the adhesive film) Test pieces measuring 5 mm in width and 125 mm in length were cut from the adhesive film, and the elongation at break at room temperature (23°C) was measured using the same tensile testing machine as described above, under the conditions of an initial distance of 50 mm between chucks and a tensile speed of 5 mm / min. Based on the obtained elongation at break, the flexibility of the adhesive film was evaluated according to the following criteria: ◎: Elongation at break was 100% or more. ○: Elongation at break was 70% or more and less than 100%. △: Elongation at break was 40% or more and less than 70%. ×: Elongation at break was less than 40%.

[0173]

[0174] As is clear from the results in Table 5, the adhesive varnish of the example was able to easily form an adhesive film by thermal curing, and the resulting adhesive film had a good appearance and exhibited high humidity and heat resistance and flexibility. Furthermore, it was confirmed that UV irradiation after or simultaneously with thermal curing tended to further improve humidity and heat resistance while maintaining flexibility. Such adhesive films possess both humidity and heat resistance that can maintain stable performance even in high temperature and high humidity environments, and flexibility that is excellent in stress relaxation, making them suitable for fixing and protecting components in the manufacturing process of semiconductor devices. In particular, they can be uniformly attached in film form even to semiconductor components with microstructures, and have the function of absorbing stress due to differences in thermal expansion during mounting, so applications in semiconductor packaging and chip-on-film technology are expected. On the other hand, the adhesive composition of the comparative example and the adhesive test pieces obtained therefrom did not yield the above-mentioned excellent properties, and it was determined that application to semiconductor applications is difficult.

[0175] (Preparation and Evaluation of Sealing Agent Compositions) Examples 52-58 and Comparative Examples 10-11 The polymerizable compositions obtained in Table 2 (indicated by example number), components A, B, C, D, and other components were weighed in the proportions shown in Table 6. These were uniformly mixed at room temperature, using a mixer as needed, to prepare the sealing agent compositions of the examples and comparative examples. Using the obtained sealing agent compositions, curing treatment was performed by the following method to produce sealing materials (i.e., cured products of the sealing agent compositions). Various physical properties were evaluated for the produced sealing materials, and the results are shown in Table 6.

[0176] (Preparation of sealing material) A silicone spacer (30 mm long x 15 mm wide x 3 mm thick) was placed on a glass plate (50 mm long x 50 mm wide x 5 mm thick), and a copper foil (5 mm long x 50 mm wide x 80 μm thick) was placed inside the spacer. The prepared sealing agent composition was injected therein, and after thorough degassing, thermal curing, sequential curing with heat and UV, or simultaneous curing with heat and UV was performed as described above to obtain a sheet-like sealing material. Ultraviolet irradiation was performed using the same inverter-type conveyor device and light source, with an ultraviolet irradiance of 700 mW / cm². 2 , cumulative light intensity 1000 mJ / cm 2 The experiment was conducted under the specified conditions. The resulting sealing material was evaluated for water resistance, outgassing resistance, and corrosion resistance.

[0177] (Evaluation of the water resistance of the sealing material) 1 g was cut from the obtained sealing material and placed as a test piece in a constant temperature and humidity chamber at 85°C and 95% relative humidity, and left undisturbed for 48 hours. After that, the weight of the test piece was measured again, and the water absorption rate was calculated using the following formula. Based on the water absorption rate, the water resistance of the sealing material was evaluated on the following four-point scale. The lower the water absorption rate, the higher the water resistance. Water absorption rate (%) = (Weight after water absorption - Weight before water absorption) / Weight before water absorption × 100 ◎: Water absorption rate was less than 1.0%. ○: Water absorption rate was 1.0% or more and less than 2.0%. △: Water absorption rate was 2.0% or more and less than 3.0%. ×: Water absorption rate was 3.0% or more.

[0178] (Evaluation of Outgassing Resistance of Sealing Material) 1 g of the obtained sealing material was cut out and placed as a test specimen in a constant temperature bath set to 100°C. After flowing a dry nitrogen stream for 24 hours, the weight of the test specimen was measured again, and the outgassing rate was calculated using the following formula. Based on the outgassing rate, the outgassing resistance of the sealing material was evaluated in the following four stages. A lower outgassing rate indicates higher outgassing resistance. Outgassing Rate (%) = (Weight after test - Weight before test) / Weight before test × 100 ◎: Outgassing rate was less than 0.1%. ○: Outgassing rate was 0.1% or more and less than 0.3%. △: Outgassing rate was 0.3% or more and less than 1.0%. ×: Outgassing rate was 1.0% or more.

[0179] (Evaluation of Corrosion Resistance of Sealing Material) The obtained sealing material was placed in a constant temperature and humidity chamber set to 85°C and 85% relative humidity for 500 hours. After that, the surface of the copper foil placed inside the sealing material was visually observed, and the corrosion resistance was evaluated in the following four stages based on the presence or absence of corrosion. ◎: No corrosion was observed. ○: Slight corrosion was observed. △ Some corrosion was observed. ×: Significant corrosion was observed.

[0180]

[0181] As is clear from the results in Table 6, the encapsulant obtained from the encapsulant composition of the example exhibited high water resistance, extremely low outgassing, and good resistance to metal corrosion (corrosion resistance). These properties were not fully expressed in the cured product obtained from the comparative composition, and it was confirmed that it was inferior in performance. Due to these excellent properties, the encapsulant composition of the present invention is extremely useful as a protective encapsulant for semiconductor devices. In particular, it is suitable as an encapsulant for ensuring long-term reliability in semiconductor packages with high-density mounting and fine wiring, and can reduce the risk of contamination by outgassing and metal corrosion. Furthermore, it can be used with optical components without impairing transparency or durability, and contributes to the insulation protection and improved environmental resistance of electrical components. Based on these properties, this encapsulant composition can be suitably used as an encapsulant in fields requiring high performance and high reliability, such as semiconductors, optical components, and electrical components.

[0182] (Preparation and Evaluation of Paint Compositions) Examples 59-64 and Comparative Examples 12-13 The polymerizable compositions obtained in Table 2 (indicated by example number), components A, B, C, D, and other components were weighed in the proportions shown in Table 7 and uniformly mixed at room temperature to prepare the paint compositions of the examples and comparative examples. The prepared paint compositions were applied to various substrates and the wettability after application was evaluated. The paint compositions were also applied to ABS boards and cured by heat curing, sequential heat and UV curing, or simultaneous heat and UV curing in the same manner as described above to obtain cured coating films. Ultraviolet irradiation was performed using the same inverter-type conveyor device and light source, with an ultraviolet irradiance of 700 mW / cm². 2 , cumulative light intensity 1000 mJ / cm 2The experiment was conducted under the following conditions. The curability of the polymerizable composition, the appearance of the resulting cured coating, and the abrasion resistance were evaluated using the following methods, and the results are shown in Table 7.

[0183] (Wettability Evaluation) The various paint compositions obtained were applied to various substrates using a bar coater, and the degree of paint repellency of the coating film was observed visually. Wettability was evaluated in the following four stages based on the uniformity of the coating film and the degree of repellency. ◎: No repellency, and the coating film was uniform. ○: Very slight repellency was observed, but the coating film was almost uniform. △: Some repellency was observed, but the coating film as a whole was almost uniform. ×: There was a lot of repellency, and the coating film was uneven.

[0184] (Evaluation of Curability of Paint Compositions) Various paint compositions were applied to a 3 mm thick ABS resin plate using a bar coater to achieve a cured film thickness of 25 μm. After application, cured coatings were obtained by performing thermal curing, sequential curing with heat and UV, or simultaneous curing with heat and UV, as described above. The curability of the obtained cured coatings was evaluated in the following four stages by touching the surface with a finger to check the adhesion of the paint composition and the amount of fingerprint remaining on the coating surface. ◎: No adhesion of the paint composition, and no fingerprints were observed on the coating surface. ○: No adhesion of the paint composition, and slight fingerprints were observed on the coating surface. △: Slight adhesion of the paint composition, or fingerprints were observed on the coating surface. ×: The paint composition adhered to the finger.

[0185] (Appearance Evaluation of Cured Coating Film) The obtained cured coating film was visually observed for surface smoothness and transparency, and an overall appearance evaluation was performed based on these results. In the case where the paint composition contained pigment, only surface smoothness was evaluated, excluding the evaluation of transparency. The appearance evaluation was performed on the following four scales: ◎: The surface was smooth and the coating film was transparent. ○: The surface was smooth and the coating film was generally transparent, but slight cloudiness was observed. △: Irregularities were observed on the surface, or cloudiness was observed in the coating film. ×: The surface was irregular and cloudiness was observed in the coating film.

[0186] (Evaluation of Abrasion Resistance of Cured Coating Film) The obtained cured coating film was evaluated for abrasion resistance in accordance with ISO 20566 using a car wash abrasion test device (Amtec Kistler GmbH, Amtec laboratory Car Wash). The 20° gloss value of the cured coating film before and after the abrasion test was measured using a gloss meter manufactured by BYK Gardner, and the gloss retention rate was calculated based on the following formula. Based on the gloss retention rate, the abrasion resistance of the coating film was evaluated in the following four stages. A higher gloss retention rate indicates higher abrasion resistance. Gloss Retention Rate (%) = (Gloss value after friction) / (Gloss value before friction) × 100 ◎: Gloss retention rate was 90% or higher. ○: Gloss retention rate was 80% or higher and less than 90%. △: Gloss retention rate was 60% or higher and less than 80%. ×: Gloss retention rate was less than 60%.

[0187]

[0188] As is clear from the results in Table 7, the paint composition of the example showed good wettability to various substrates and had excellent curability. The resulting cured coating had a good appearance and excellent abrasion resistance. On the other hand, the paint composition of the comparative example had low curability, and the appearance and abrasion resistance of the resulting cured coating were inferior. It shows excellent wettability to a wide range of substrates, from general-purpose plastics (ABS, PC, PET, etc.) to wood and metals (aluminum, copper, stainless steel, etc.). Furthermore, it has high curability, and the resulting cured coating has high transparency, smoothness, and abrasion resistance, making it suitable for applications where appearance quality and durability are required. Due to these characteristics, the paint composition of the present invention can be suitably used in a wide range of fields as a high-performance coating. For example, coatings for electronic components (enclosures, terminals, protective films, etc.), indoor and outdoor coatings (building materials, furniture, exterior walls, etc.), floor coatings (factory and store floors where abrasion resistance is required, etc.), and vehicle coatings (exterior parts, interior trim, display surrounds, etc.). In these applications, the paint composition of the present invention is expected to provide high reliability and processability, contributing to the improvement of the added value of products.

[0189] (Preparation and Evaluation of Decorative Coating Agents) Examples 65-69 and Comparative Examples 14-15 The polymerizable compositions obtained in Table 2 (indicated by example number), components A, B, C, D, and other components were weighed in the proportions shown in Table 8 and uniformly mixed at room temperature to prepare the decorative coating agents for the examples and comparative examples. The decorative coating agents referred to here are curable compositions used for decorative molding and decorative processing of decorative films, decorative sheets, etc. Laminates were prepared by performing the following decorative processing wp using the obtained decorative coating agents, and the physical properties of the obtained laminates were evaluated. These results are shown in Table 8.

[0190] (Preparation of Laminates) The obtained decorative coating agent was applied to a 180 μm thick PC film (Teijin, Panlite PC-2151) using a bar coater to a film thickness of 5 μm. After application, thermal curing, sequential curing with heat and UV, or simultaneous curing with heat and UV was performed as described above to obtain laminates with a coating layer. The obtained laminates were cut to a predetermined size, and the surface tack resistance, elongation, pencil hardness, scratch resistance, bending resistance, and sunscreen resistance of the hard coat layer were evaluated by the following methods. These results are shown in Table 8.

[0191] (Surface Tack Resistance Evaluation) Using the obtained laminate, the degree of stickiness was visually evaluated by touching the surface of the film with a finger. The evaluation was performed on the following four levels, with the less sticky the surface, the higher the surface tack resistance. ◎: No stickiness was observed at all. 〇: Some stickiness was observed, but no finger marks were left on the surface. △: Stickiness was present, and finger marks were left on the surface. ×: The stickiness was strong, and the finger stuck to the surface.

[0192] (Elongation Evaluation) The obtained laminate was cut to a length of 50 mm and a width of 15 mm, and fixed to a tensile testing machine with a chuck distance of 25 mm as described above. The test was conducted in an oven set to a temperature of 150°C, and the appearance was visually observed while being pulled in one direction at a speed of 250 mm / min. The length (mm) of the test piece was measured when cracks or whitening occurred in the coating layer. The elongation was calculated using the following formula, and the evaluation was carried out in the following four stages: Elongation (%) = (Sample length after test / 25) × 100 ◎: Elongation was 200% or more. 〇: Elongation was 150% or more and less than 200%. △: Elongation was 110% or more and less than 150%. ×: Elongation was less than 110%.

[0193] (Surface Hardness Evaluation) Using laminated test specimens, surface hardness was evaluated in accordance with JIS K 5600 by scratching the surface of the specimen with a pencil at a 45° angle from a distance of approximately 10 mm. The hardness of the hardest pencil that did not scratch the surface was determined as the pencil hardness, and the evaluation was performed on the following four scales. The higher the pencil hardness, the higher the surface hardness. ◎: Pencil hardness was 2H or higher. ○: Pencil hardness was HB to H. △: Pencil hardness was 3B to B. ×: Pencil hardness was 4B or lower.

[0194] (Scratch Resistance Evaluation) The obtained laminate test specimens were rubbed 10 times back and forth with #0000 steel wool under a load of 200g, and the surface condition after friction was visually observed to evaluate scratch resistance. The evaluation was performed on the following four levels: ◎: No delamination or scratching of the film was observed. ○: A few fine scratches were observed on a part of the film. △: Streaky scratches were observed throughout the film. ×: Delamination of the film occurred.

[0195] (Evaluation of bending resistance) A test specimen of the laminate was bent 180° with the coated layer facing outwards, and a 1kg weight was placed on it and left to stand for 10 minutes. After standing, the bending resistance was evaluated by visually observing the surface of the laminate for the presence or absence of cracks. The evaluation criteria were as follows: ◎: No cracks were observed at all. ○: Some whitening was observed in the bent area. △: Some cracks were observed in the bent area. ×: Clear cracks were observed in the bent area.

[0196] (Sunscreen Resistance Evaluation) The coating layer of the laminate test specimen was coated with the sunscreen Ultra Sheer DRY-TOUCH SUNSCREEN SPF100. ＋ A sample of Johnson & Johnson sunscreen was applied to a surface approximately 1 cm in diameter and heated at 80°C for 6 hours. After heating, it was allowed to cool to room temperature, washed with a neutral detergent, and the surface condition was observed to evaluate sunscreen resistance based on the following criteria: ◎: No trace of sunscreen was observed. ○: A slight transparent trace was observed in the area where the sunscreen was applied. △: A white mark remained in the area where the sunscreen was applied, and the surface was swollen. ×: The area where the sunscreen was applied was sticky, and the surface was peeling.

[0197]

[0198] As is clear from the results in Table 8, a laminate having a decorative coating layer (decorative coating film) could be easily obtained by applying the decorative coating agent of the example to the surface of a general-purpose plastic substrate and curing it with heat or heat and UV irradiation. The surface (coating layer) of the obtained laminate had tack resistance, high hardness, and excellent scratch resistance and sunscreen resistance. Furthermore, the elongation and bending resistance of the laminate were also good. In particular, when the cyclic substituent of (meth)acrylate (A) had an unsaturated bond, UV curing progressed due to the unsaturated bond, and the hardness, scratch resistance and sunscreen resistance of the surface (coating layer) were further improved. On the other hand, the curable composition of the comparative example did not show similar decorative performance. The decorative coating agent of the present invention can be suitably used in various decorative molding, decorative processing, and decorative printing applications such as decorative films, decorative sheets, and decorative coatings.

[0199] (Preparation and Evaluation of Dental Material Compositions) Examples 70-75 and Comparative Example 16 The polymerizable compositions obtained in Table 2 (indicated by example number), components A, B, C, D, and other components were weighed in the proportions shown in Table 9 and uniformly mixed at room temperature to prepare the dental material compositions of the examples and comparative examples. For each composition obtained, the solubility or dispersibility (when insoluble inorganic fillers or pigments are included) was observed visually and the storage stability was evaluated. Furthermore, using the prepared dental material compositions, hardened dental materials were prepared by the following method and the hardness of the composition, the surface smoothness and hardness of the obtained hardened dental materials were evaluated. The results of these evaluations are shown in Table 8.

[0200] (Solubility (Dispersibility) Evaluation) ◎: The obtained composition was homogeneous and transparent. 〇: The obtained composition was homogeneous and semi-transparent. △: The obtained composition was cloudy, making it difficult to determine its homogeneity. ×: The obtained composition was not mixed.

[0201] (Storage Stability Evaluation) The obtained compositions were placed in light-shielding screw-top tubes, sealed, and stored under two conditions: 40°C for 1 month and 80°C for 2 weeks. After storage, the dissolution or dispersion state of the compositions was observed, and storage stability was evaluated according to the following criteria. ◎: No change in state was observed after storage under both conditions of 40°C for 1 month and 80°C for 2 weeks. ○: A slight change in state was observed after storage only under the condition of 80°C for 2 weeks. △: A change in state was observed after storage under either the condition of 40°C for 1 month or 80°C for 2 weeks. ×: A change in state was observed after storage under both conditions of 40°C for 1 month and 80°C for 2 weeks.

[0202] (Evaluation of curability of dental material composition) Using the obtained dental material composition, the composition was filled into a polytetrafluoroethylene mold (20 mm × 20 mm × 10 mm) having a 6 mm diameter hole in the center, and after pressing with a polypropylene film, heat curing, sequential heat and UV curing, or simultaneous heat and UV curing were performed as described above. UV irradiation was performed using a dental light curing unit (Tokuyama Dental Co., Ltd., Tokuso Power Light, light output density 700 mW / cm²). 2, Light intensity at the irradiated surface: 640-650 mW / cm² 2 The light source was a halogen lamp (with an irradiation aperture of 8 mm), and the polypropylene film was irradiated for 30 seconds in close contact with the lamp. After irradiation, the polypropylene film was peeled off, and the resulting cured body was touched by hand to check for stickiness and the presence of uncured components. The curability was evaluated according to the following criteria: ◎: No stickiness was observed at all, and it was completely cured. ○: Slight stickiness was observed, but no fingerprints were left on the surface, and wiping off uncured components was not required. △: Stickiness was present, fingerprints were left on the surface, and wiping off uncured components was necessary. ×: Stickiness was severe, and fingers stuck to the surface.

[0203] (Evaluation of surface smoothness of dental materials) The surface of the hardened material obtained by the evaluation of the hardening properties of the dental material composition was visually observed to check for smoothness and gloss, and the surface smoothness was evaluated according to the following criteria. ◎: The surface was smooth and glossy. ○: The surface was almost smooth, with slight cloudiness or minor irregularities. △: The surface was cloudy overall, and some irregularities or granular material were observed. ×: The surface was cloudy overall and covered with granular material.

[0204] (Hardness Evaluation of Dental Materials) The hardened material obtained from the hardening evaluation of the dental material composition described above was buffed, and its Knoop hardness (KHN) was measured using a microhardness tester manufactured by Matsuzawa Seiki under the conditions of a load of 10 g and a holding time of 20 seconds. The measurement was performed at 23°C. The evaluation was performed based on the following criteria: ◎: Knoop hardness was 200 KHN or higher (equivalent to permanent tooth enamel). ○: Knoop hardness was 70 KHN or higher and less than 200 KHN (equivalent to dentin). △: Knoop hardness was less than 70 KHN. ×: Hardening was insufficient, and measurement was not possible.

[0205]

[0206] As is clear from the results in Table 9, the dental material compositions of the examples had high solubility (or dispersibility), excellent curability, and storage stability. The cured products obtained by curing these compositions had good hardness and surface smoothness. On the other hand, the compositions of the comparative examples were inferior in solubility, curability, and storage stability, and sufficient curing did not proceed, resulting in insufficient hardness and surface smoothness of the resulting cured products.

[0207] As shown in the evaluation results of each example and comparative example described above, the polymerizable composition containing the (meth)acrylate (A) and thermal polymerization initiator (C) having a specific structure according to the present invention exhibited high transparency and excellent curability, as well as excellent wettability and adhesion to various substrates. Furthermore, it was confirmed that the cured products obtained by curing these compositions exhibited excellent physical properties such as water resistance, heat resistance, impact resistance, heat cycle resistance, and abrasion resistance. On the other hand, it was found that the polymerizable compositions and cured products of the comparative examples that did not contain component A or component C did not exhibit the above-mentioned physical properties sufficiently, and were inferior in terms of performance.

[0208] The present invention includes the following: (1) A polymerizable composition comprising a (meth)acrylate (A) having an amide group and a cyclic substituent in the molecule, and a thermal polymerization initiator (C). (2) The polymerizable composition according to (1), wherein the cyclic substituent has at least one cyclic structure selected from the group consisting of monocyclic or polycyclic saturated aliphatic rings, monocyclic or polycyclic unsaturated aliphatic rings, monocyclic or polycyclic aromatic rings, monocyclic or polycyclic saturated aliphatic heterocycles, monocyclic or polycyclic unsaturated aliphatic heterocycles, and monocyclic or polycyclic aromatic heterocycles. (3) The polymerizable composition according to (1) or (2), further comprising a binder component (B). (4) The polymerizable composition according to (3), wherein the binder component (B) contains at least one selected from the group consisting of polymerizable oligomers (B1), polymerizable polymers (B2), nonpolymerizable oligomers (B3), and nonpolymerizable polymers (B4). (5) A polymerizable composition according to any one of (1) to (4), further comprising a polymerizable monomer (D) other than the (meth)acrylate (A). (6) A polymerizable composition according to any one of (1) to (5), further comprising a crosslinking agent. (7) A polymerizable composition according to any one of (1) to (6), further comprising a photopolymerization initiator. (8) A polymerizable composition according to any one of (1) to (7), further comprising a filler. (9) A polymer obtained by polymerizing the polymerizable composition according to any one of (1) to (8). (10) A cured product obtained by curing the polymerizable composition according to any one of (1) to (8). (11) A polymerizable composition according to any one of the above (1) to (8), used for any application selected from the group consisting of adhesives, sealants, inks, inkjet inks, three-dimensional molding materials, coatings, paints, photosensitive resins, cosmetics, decorative materials, dental materials, dicing tapes, flexible printed circuit boards, adhesives for dissimilar materials, adhesives for electronic devices, adhesives for optical devices, adhesives for semiconductor devices, sealants for electronic devices, sealants for optical devices, sealants for semiconductor devices, and binders for batteries.(12) A polymer according to (9) above, used in any application selected from the group consisting of adhesives, sealants, inks, inkjet inks, three-dimensional molding materials, coatings, paints, photosensitive resins, cosmetics, decorative materials, dental materials, dicing tapes, flexible printed circuit boards, adhesives for dissimilar materials, adhesives for electronic devices, adhesives for optical devices, adhesives for semiconductor devices, sealants for electronic devices, sealants for optical devices, sealants for semiconductor devices, and binders for batteries. (13) An adhesive containing a polymerizable composition according to any one of (1) to (8) above, or a polymer according to (9) above. (14) An adhesive containing a polymerizable composition according to any one of (1) to (8) above, or a polymer according to (9) above. (15) A sealant containing a polymerizable composition according to any one of (1) to (8) above, or a polymer according to (9) above. (16) An ink containing a polymerizable composition according to any one of (1) to (8) above, or a polymer according to (9) above. (17) An inkjet ink containing the polymerizable composition described in any one of items (1) to (8) above, or the polymer described in item (9) above. (18) A three-dimensional molding ink containing the polymerizable composition described in any one of items (1) to (8) above, or the polymer described in item (9) above. (19) A coating agent containing the polymerizable composition described in any one of items (1) to (8) above, or the polymer described in item (9) above. (20) A paint containing the polymerizable composition described in any one of items (1) to (8) above, or the polymer described in item (9) above. (21) A photosensitive resin containing the polymerizable composition described in any one of items (1) to (8) above, or the polymer described in item (9) above. (22) A cosmetic containing the polymerizable composition described in any one of items (1) to (8) above, or the polymer described in item (9) above. (23) A decorative material containing the polymerizable composition described in any one of items (1) to (8) above, or the polymer described in item (9) above. (24) A dental material containing a polymerizable composition according to any one of items (1) to (8) above, or a polymer according to item (9) above. (25) A dicing tape containing a polymerizable composition according to any one of items (1) to (8) above, or a polymer according to item (9) above.(26) A flexible printed circuit board containing the polymerizable composition described in any one of (1) to (8) above, or the polymer described in (9) above. (27) A nanoimprint ink containing the polymerizable composition described in any one of (1) to (8) above, or the polymer described in (9) above. (28) An adhesive for dissimilar materials containing the polymerizable composition described in any one of (1) to (8) above, or the polymer described in (9) above. (29) An adhesive for electronic devices containing the polymerizable composition described in any one of (1) to (8) above, or the polymer described in (9) above. (30) An adhesive for optical devices containing the polymerizable composition described in any one of (1) to (8) above, or the polymer described in (9) above. (31) An adhesive for semiconductor devices containing the polymerizable composition described in any one of (1) to (8) above, or the polymer described in (9) above. (32) An encapsulant for electronic devices containing the polymerizable composition described in any one of (1) to (8) above, or the polymer described in (9) above. (33) A encapsulant for optical devices containing the polymerizable composition described in any one of (1) to (8) above, or the polymer described in (9) above. (34) A encapsulant for semiconductors containing the polymerizable composition described in any one of (1) to (8) above, or the polymer described in (9) above. (35) A binder resin for batteries containing the polymerizable composition described in any one of (1) to (8) above, or the polymer described in (9) above. (36) A semiconductor device containing a cured product of the polymerizable composition described in any one of (1) to (8) above. (37) An electronic device containing a cured product of the polymerizable composition described in any one of (1) to (8) above. (38) An optical device containing a cured product of the polymerizable composition described in any one of (1) to (8) above. (39) A battery containing a cured product of the polymerizable composition described in any one of (1) to (8) above.

[0209] The polymerizable composition of the present invention, by containing a specific (meth)acrylate (A) and a thermal polymerization initiator, exhibits excellent wettability to various substrates having a wide range of polarities from low to high polarity, and yields cured products with low curing shrinkage and excellent moisture resistance, heat resistance, impact resistance, and durability. The polymerizable composition of the present invention, possessing such properties, is extremely useful in various industrial fields, and its usefulness is particularly remarkable in applications requiring high reliability and durability. Specifically, by containing the polymerizable composition, it can be suitably used in a wide range of applications such as decoration, bonding, protection, sealing, insulation, and reinforcement in adhesives, sealants, coatings, paints, decorative materials, dental materials, adhesive films, dicing tapes, flexible printed circuit boards, dissimilar material adhesives, electronic device adhesives, optical device adhesives, semiconductor device adhesives, electronic device encapsulants, optical device encapsulants, semiconductor device encapsulants, and battery binders. Furthermore, the compositions of the present invention can be processed at room temperature or low temperature and are compatible with various curing methods such as UV curing and thermal curing, resulting in high productivity and process flexibility, as well as contributing to reduced environmental impact and energy conservation. Therefore, the present invention is expected to have a wide range of applications in various industrial fields, including electronic equipment, automobiles, construction, medical, optical, and energy-related fields.

Claims

A polymerizable composition containing a (meth)acrylate (A) having an amide group and a cyclic substituent in the molecule, and a thermal polymerization initiator (C). The polymerizable composition according to claim 1, wherein the cyclic substituent has at least one cyclic structure selected from the group consisting of a monocyclic or polycyclic saturated aliphatic ring, a monocyclic or polycyclic unsaturated aliphatic ring, a monocyclic or polycyclic aromatic ring, a monocyclic or polycyclic saturated aliphatic heterocycle, a monocyclic or polycyclic unsaturated aliphatic heterocycle, and a monocyclic or polycyclic aromatic heterocycle. The polymerizable composition according to claim 1 or 2, further comprising a binder component (B). The polymerizable composition according to claim 3, wherein the binder component (B) contains at least one selected from the group consisting of polymerizable oligomer (B1), polymerizable polymer (B2), non-polymerizable oligomer (B3), and non-polymerizable polymer (B4). The polymerizable composition according to any one of claims 1 to 4, further comprising polymerizable monomer (D) other than the (meth)acrylate (A). A polymerizable composition according to any one of claims 1 to 5, further comprising a crosslinking agent. A polymerizable composition according to any one of claims 1 to 6, further comprising a photopolymerization initiator. A polymerizable composition according to any one of claims 1 to 7, further comprising a filler. A polymer obtained by polymerizing the polymerizable composition according to any one of claims 1 to 8. A cured product obtained by curing a polymerizable composition according to any one of claims 1 to 8. A polymerizable composition according to any one of claims 1 to 8, used in any application selected from the group consisting of adhesives, sealants, coatings, paints, decorative materials, dental materials, adhesive films, dicing tapes, flexible printed circuit boards, dissimilar material adhesives, electronic device adhesives, optical device adhesives, semiconductor device adhesives, electronic device encapsulants, optical device encapsulants, semiconductor device encapsulants, and battery binders. The polymer according to claim 9, which is used in any application selected from the group consisting of adhesives, sealants, coatings, paints, decorative materials, dental materials, adhesive films, dicing tapes, flexible printed circuit boards, dissimilar material adhesives, electronic device adhesives, optical device adhesives, semiconductor device adhesives, electronic device encapsulants, optical device encapsulants, semiconductor device encapsulants, and battery binders. An adhesive containing the polymerizable composition according to any one of claims 1 to 8, or the polymer according to claim 9. An adhesive containing a polymerizable composition according to any one of claims 1 to 8, or a polymer according to claim 9. A sealing agent containing a polymerizable composition according to any one of claims 1 to 8, or a polymer according to claim 9. A paint containing the polymerizable composition according to any one of claims 1 to 8, or the polymer according to claim 9. A decorative material containing a polymerizable composition according to any one of claims 1 to 8, or a polymer according to claim 9. A dental material containing a polymerizable composition according to any one of claims 1 to 8, or a polymer according to claim 9. A dicing tape containing the polymerizable composition according to any one of claims 1 to 8, or the polymer according to claim 9. An electronic device adhesive containing a polymerizable composition according to any one of claims 1 to 8, or a polymer according to claim 9. An optical device adhesive containing the polymerizable composition according to any one of claims 1 to 8, or the polymer according to claim 9. A semiconductor device adhesive containing a polymerizable composition according to any one of claims 1 to 8, or a polymer according to claim 9. An electronic device encapsulant containing the polymerizable composition according to any one of claims 1 to 8, or the polymer according to claim 9. An optical device encapsulant containing the polymerizable composition according to any one of claims 1 to 8, or the polymer according to claim 9. A semiconductor encapsulant containing the polymerizable composition according to any one of claims 1 to 8, or the polymer according to claim 9. A battery binder containing a polymerizable composition according to any one of claims 1 to 8, or a polymer according to claim 9. A semiconductor device comprising a cured product of a polymerizable composition according to any one of claims 1 to 8. An electronic device comprising a cured product of a polymerizable composition according to any one of claims 1 to 8. An optical device comprising a cured product of a polymerizable composition according to any one of claims 1 to 8. A battery comprising a cured product of a polymerizable composition according to any one of claims 1 to 8.

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