Polymerizable composition containing (METH)acrylamide compound having cyclic structure, polymer thereof, and various compositions containing same

Abstract

[Problem] Provided is a polymerizable composition having high curability to heat and / or active energy rays and curing shrinkage resistance and capable of providing a cured product having low odor, high transparency and excellent bending resistance. [Solution] A polymerizable composition containing a specific N-substituted (meth)acrylamide or containing the same as a constituent unit was found. Said N-substituted (meth)acrylamide is a compound having a structure in which a cyclic structure is linked to a nitrogen atom of a (meth)acrylamide group via a divalent chain organic group.

Description

Polymerizable composition containing a (meth)acrylamide compound having a cyclic structure, polymers thereof, and various compositions containing these

[0001] The present disclosure relates to a polymerizable composition containing a (meth)acrylamide compound having a cyclic structure, a polymer thereof, and various compositions containing these.

[0002] (Meth)acrylates and (meth)acrylamides having a cyclic structure are used in a wide range of applications, including inks, coatings, adhesives, and photopolymerization resins. Generally, these compounds have a structure in which a cyclic substituent is directly bonded to the oxygen atom of the ester group of the (meth)acrylate or the nitrogen atom of the amide group of the (meth)acrylamide. In such structures, the bulky cyclic structure is directly bonded to the (meth)acrylate group or (meth)acrylamide group, resulting in polymers and cured products with low flexibility and elongation. Furthermore, it is difficult to increase the molecular weight or the density of the cured product, making them difficult to apply to applications requiring high strength and durability. Furthermore, (meth)acrylate monomers have a distinctive odor, and the introduction of a cyclic structure does not improve this odor.

[0003] The present disclosure provides a (meth)acrylamide-based monomer (compound E) having a cyclic structure and a polymerizable composition containing the same. Compound E has a low odor, is highly soluble in a wide variety of solvents, from polar to non-polar, has excellent compatibility with monomers and oligomers, and exhibits high polymerizability and curability against heat or actinic energy rays. Polymerizable compositions containing the compound exhibit high transparency, curability, and cure shrinkage resistance, and the cured products obtained by curing the compositions exhibit excellent flex resistance.

[0004] The present disclosure provides a polymer (including a homopolymer and / or a copolymer) containing, as a structural unit, the compound E. The present disclosure also provides a polymerizable composition, a curable composition, an ink, an ink for three-dimensional modeling, a coating agent, a pressure-sensitive agent, an adhesive, a photosensitive resin, a sealant, a dental material, a paint composition, a decorative coating agent, and the like, which contain the compound and / or its polymer.

[0005] As a result of intensive research to solve the above-mentioned problems, the present inventors have found a polymerizable composition containing a compound (hereinafter also referred to as the compound) having a structure in which a cyclic structure is linked to a nitrogen atom of a (meth)acrylamide group via a divalent chain organic group and / or a polymer thereof (hereinafter also referred to as the polymer).

[0006] The present disclosure includes the following: (1) A polymerizable composition containing an N-substituted (meth)acrylamide represented by general formula [1]. In the general formula [1], R 1 is a hydrogen atom or a methyl group, and L 1 is an organic group having a cyclic structure A ring represented by the general formula [2], and L 2 is a hydrogen atom, an organic group having a cyclic structure A ring represented by general formula [2], or an organic group represented by general formula [3], and L 1 and L 2 When both of them have ring A, they may be the same or different, and R 2 is an alkylene group having 1 to 18 carbon atoms, an alkyleneoxyalkylene group having 2 to 36 carbon atoms, or a poly(alkyleneoxy)alkylene group having 2 to 36 carbon atoms; ring A is a saturated or unsaturated aliphatic hydrocarbon group having 5 to 18 carbon atoms, or a saturated or unsaturated heterocycle containing 2 to 18 carbon atoms and 1 to 12 oxygen atoms; R 3 is an alkyl group having 1 to 18 carbon atoms, an alkyleneoxyalkyl group having 2 to 36 carbon atoms, or a poly(alkyleneoxy)alkyl group having 2 to 36 carbon atoms.

[0007] The N-substituted (meth)acrylamides according to the present disclosure have a low odor and are easy to handle. Furthermore, they have both a hydrophilic (meth)acrylamide group and a hydrophobic cyclic structure, and as an amphiphilic monomer, they are highly soluble in a variety of solvents, from polar to non-polar, and have excellent compatibility with monomers and oligomers. The compounds have (meth)acrylamide groups and exhibit high polymerizability and curability against heat and active energy rays. The compounds have a cyclic structure and exhibit excellent heat resistance and cure shrinkage resistance. The compounds are also divalent chain organic groups (R 2It has a structure in which a cyclic structure (ring A) and a (meth)acrylamide group are linked via an alkyl group, giving it high molecular flexibility.

[0008] The polymers and cured products obtained from polymerizable compositions containing the compounds and / or polymers can be adjusted to have high molecular weights and have high strength and durability. The polymers and cured products also have high flex resistance. The present inventors have found that the compositions can be suitably used in a variety of applications.

[0009] The present disclosure will be described in detail below. The scope of the present disclosure is not limited to the embodiments described herein, and various modifications can be made without departing from the spirit of the present disclosure. Furthermore, when multiple upper and lower limit values ​​are listed for a specific parameter, any upper and lower limit values ​​can be combined to form a suitable numerical range.

[0010] In this disclosure, a monofunctional compound is a compound having one ethylenically unsaturated group in the molecule. A polyfunctional compound is a compound having two or more ethylenically unsaturated groups in the molecule. Among these compounds, those having a weight average molecular weight (Mw) of less than 1,000 are considered monomers, those having a weight average molecular weight (Mw) of 1,000 or more but less than 10,000 are considered oligomers, and those having a weight average molecular weight of 10,000 or more are considered polymers.

[0011] In the present disclosure, a crosslinking agent is a compound having two or more ethylenically unsaturated groups, two or more crosslinkable reactive groups, or one or more ethylenically unsaturated groups and one or more crosslinkable reactive groups in the molecule. Examples of the crosslinkable reactive groups include hydroxyl groups, thiol groups, amino groups, carboxyl groups, isocyanate groups, oxazoline groups, carbodiimide groups, glycidyl groups, epoxy groups, halogen groups, and hydrazine groups.

[0012] In the present disclosure, a polymer is a polymer compound formed by bonding a plurality of monomers (including monofunctional monomers or monofunctional oligomers), and does not have a cross-linked structure between molecules.

[0013] In the present disclosure, a cured product is a product formed by bonding a plurality of monomers together, similar to a polymer, and has a cross-linked structure between molecules.

[0014] In the present disclosure, an alkyl group (including when simply referred to as "alkyl") is a linear or branched monovalent chain-like saturated hydrocarbon group (also referred to as a chain-like alkyl group) having 1 to 18 carbon atoms, or a monovalent cyclic saturated hydrocarbon group (also referred to as a cyclic alkyl group) having 3 to 18 carbon atoms. Examples of the chain-like alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, and structural isomers thereof. Examples of cyclic alkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl, cyclododecyl, cyclotridecyl, cyclotetradecyl, cyclopentadecyl, cyclohexadecyl, cycloheptadecyl, cyclooctadecyl, and structural isomers thereof. In the present disclosure, when "having alkyl groups," any one or more alkyl groups can be selected. When multiple alkyl groups are present, they may be the same or different.

[0015] In the present disclosure, an alkylene group (including when simply referred to as "alkylene") refers to a linear or branched, divalent, chain-like saturated hydrocarbon group (also referred to as a chain-like alkylene group) having 1 to 18 carbon atoms, or a divalent, cyclic, saturated hydrocarbon group (also referred to as a cyclic alkylene group) having 3 to 18 carbon atoms. Examples of the chain-like alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decylene group, an undecylene group, a dodecylene group, a tridecylene group, a tetradecylene group, a pentadecylene group, a hexadecylene group, a heptadecylene group, an octadecylene group, and structural isomers thereof. Examples of the cyclic alkylene group include a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cycloheptylene group, a cyclooctylene group, a cyclononylene group, a cyclodecylene group, a cycloundecylene group, a cyclododecylene group, a cyclotridecylene group, a cyclotetradecylene group, a cyclopentadecylene group, a cyclohexadecylene group, a cycloheptadecylene group, a cyclooctadecylene group, and structural isomers thereof.

[0016] In the present disclosure, an alkenyl group refers to a linear or branched, monovalent, chain-like unsaturated hydrocarbon group (also referred to as a chain alkenyl group) having 3 to 18 carbon atoms, or a monovalent, cyclic, saturated hydrocarbon group (also referred to as a cyclic alkenyl group) having 3 to 18 carbon atoms. Examples of the chain alkenyl group include a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, a decenyl group, an undecenyl group, a dodecenyl group, a tridecenyl group, a tetradecenyl group, a pentadecenyl group, a hexadecenyl group, a heptadecenyl group, an octadecenyl group, and structural isomers thereof. Examples of cyclic alkenyl groups include cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, cyclooctenyl, cyclononenyl, cyclodecenyl, cycloundecenyl, cyclododecenyl, cyclotridecenyl, cyclotetradecenyl, cyclopentadecenyl, cyclohexadecenyl, cycloheptadecenyl, cyclooctadecenyl, and structural isomers thereof. In the present disclosure, when "having alkenyl groups," any one or more can be selected. When multiple alkenyl groups are present, they may be the same or different.

[0017] In the present disclosure, the ethylenically unsaturated group refers to a (meth)acrylamide group, a (meth)acrylate group, a vinyl group, an aromatic vinyl group, a vinyl ether group, an allyl group, a (meth)allyl ether group, or a maleimide group. Furthermore, in the present disclosure, when "having an ethylenically unsaturated group," any one or more of these can be selected. When multiple ethylenically unsaturated groups are present, they may be the same or different.

[0018] In the present disclosure, a substituent refers to an alkyl group, an alkenyl group, an ethylenically unsaturated group, or a group having a structure in which a hydrogen atom of these groups has been substituted with the following group. That is, it includes groups substituted with one or more of a hydroxy group, an alkoxy group having 1 to 18 carbon atoms, a poly(alkyleneoxy)alkyl group having 2 to 36 carbon atoms, an alkenyl group, or an ethylenically unsaturated group. Furthermore, when "having a substituent," any one or more substituents can be selected. When having multiple substituents, these may be the same or different.

[0019] One embodiment of the present disclosure relates to a polymerizable composition containing an N-substituted (meth)acrylamide represented by general formula [1]. The compound has an organic group (L) having a specific cyclic structure in the molecule. 1 ), and by polymerizing this compound, a polymer material with desired physical properties can be obtained.

[0020] In the general formula [1], R 1 is a hydrogen atom or a methyl group. 1 is an organic group having a cyclic structure A ring represented by the general formula [2]. 2 is a hydrogen atom, an organic group having a cyclic structure A ring represented by general formula [2], or an organic group represented by general formula [3]. 1 and L 2 When both of them have ring A, they may be the same or different.

[0021] In the general formula [2], R 2 is a divalent chain organic group, specifically an alkylene group having 1 to 18 carbon atoms, an alkyleneoxyalkylene group having 2 to 36 carbon atoms, or a poly(alkyleneoxy)alkylene group having 2 to 36 carbon atoms. The alkylene group preferably has 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, even more preferably 1 to 4 carbon atoms, and most preferably 1 to 2 carbon atoms. The alkyleneoxyalkylene group and poly(alkyleneoxy)alkylene group preferably have 2 to 24 carbon atoms, more preferably 2 to 16 carbon atoms, even more preferably 2 to 8 carbon atoms, and most preferably 2 to 4 carbon atoms.

[0022] As a result, the N-substituted (meth)acrylamide according to the present disclosure has superior molecular flexibility compared to compounds having a structure in which a cyclic substituent is directly bonded to the nitrogen atom of the amide group of (meth)acrylamide. In addition, the cyclic structure of the compound rotates relatively freely due to the chain organic group, so the molecular chains tend to align in a certain direction, resulting in increased impact resistance and strength. Furthermore, due to the rotation, the compound has a high space occupancy and excellent resistance to cure shrinkage.

[0023] In general formula [2], ring A is a saturated or unsaturated alicyclic hydrocarbon group (also referred to as an aliphatic hydrocarbon ring) or a saturated or unsaturated heterocycle. The cyclic structure of ring A can be exemplified by a monocyclic structure (one ring) or a polycyclic structure (two or more rings). Examples of polycyclic structures include spiro rings bonded together by sharing one atom, fused rings bonded together by sharing two atoms, bridged rings bonded together by sharing three or more atoms, and rings linked via a divalent chain linking group. In the case of a polycyclic structure, the types of rings constituting the polycyclic structure may be the same or different.

[0024] The atoms constituting Ring A are preferably only carbon atoms or a combination of carbon atoms and oxygen atoms. The total number of atoms constituting the ring is preferably 5 to 30. When Ring A has a monocyclic structure, it is preferably a 5- to 18-membered ring, more preferably a 5- to 12-membered ring, even more preferably a 5- to 8-membered ring, and most preferably a 5- to 6-membered ring. When Ring A has a polycyclic structure consisting of only alicyclic hydrocarbon rings, the number of carbon atoms constituting the ring is preferably 5 to 18, more preferably 5 to 12, and even more preferably 5 to 10. When Ring A has a polycyclic structure consisting of only heterocycles, the total number of carbon atoms and oxygen atoms is preferably 5 to 18, more preferably 5 to 12, and even more preferably 5 to 10. When Ring A has a polycyclic structure consisting of any combination of alicyclic hydrocarbon rings and heterocycles, the total number of carbon atoms and oxygen atoms is preferably 5 to 30, more preferably 5 to 24, and even more preferably 5 to 20.

[0025] The N-substituted (meth)acrylamide according to the present disclosure has a cyclic structure, resulting in high molecular rigidity. Furthermore, polymerizable compositions containing the compound and / or its polymers exhibit little cure shrinkage when cured with heat or active energy rays, and the resulting cured products exhibit high strength, hardness, and durability. Furthermore, the A ring is R 2 can be rotated around an axis, and properties such as space occupancy can be imparted to the compound.

[0026] Examples of saturated alicyclic hydrocarbon groups having 5 to 18 carbon atoms include monocyclic structures such as cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl, cyclododecyl, cyclotridecyl, cyclotetradecyl, cyclopentadecyl, cyclohexadecyl, cycloheptadecyl, and cyclooctadecyl groups, norbornane (bicyclo[2.2.1]heptyl), bornane (1,7,7-trimethylbicyclo[2.2.1]heptyl), bicyclo[3.2.1]octyl, decahydronaphthyl, adamantyl, and tricyclo[5.2.1.0]heptyl. 2,6 ]decyl group and polycyclic structures such as 4,7-methanooctahydro-1H-indenyl group.

[0027] Examples of the unsaturated alicyclic hydrocarbon group having 5 to 18 carbon atoms include monocyclic structures such as a cyclopentenyl group, a cyclohexenyl group, a cyclohexadienyl group, a cycloheptenyl group, a cyclooctenyl group, a cyclooctatrienyl group, a cyclonenyl group, a cyclodecenyl group, a cycloundecenyl group, a cyclododecenyl group, a cyclotridecenyl group, a cyclotetradecenyl group, a cyclopentadecenyl group, a cyclohexadecenyl group, a cycloheptadecenyl group, and a cyclooctadecenyl group, and polycyclic structures such as an indene group, a dihydroindene group, a dicyclopentadiene group, a norbornene group, and a bicyclo[2.2.1]heptenyl group.

[0028] Examples of saturated heterocycles having 5 to 30 carbon atoms include monocyclic structures such as tetrahydrofuran, tetrahydropyran, hexamethylene oxide, oxocane, oxepane, 1,3-dioxolane, and 1,4-dioxane, and polycyclic structures such as hexahydrobenzodioxole and octahydrobenzofuran. Other examples include crown ethers such as 9-crown-3, 12-crown-4, 15-crown-5, 18-crown-6, and 21-crown-7, and cyclic polyether structures such as dibenzofuran. These heterocycles also include structural isomers with different bonding positions of the heteroatoms.

[0029] Examples of unsaturated heterocycles having 5 to 30 carbon atoms include pyrans such as a furyl group, a pyran group, and a dihydropyran group, monocyclic structures such as a dioxin group, an oxycycloheptatriene group, and an oxonine group, benzopyrans such as a benzofuran group, a benzopyran group, and a dihydrobenzopyran group, and polycyclic structures such as a xanthene group. These heterocycles also include structural isomers in which the bonding position of the heteroatom is different.

[0030] In the general formula [2], R 2 and ring A are formed by appropriately combining the above. 2 is preferably an alkylene group having 1 to 8 carbon atoms, an alkyleneoxyalkylene group having 2 to 16 carbon atoms, or a poly(alkyleneoxy)alkylene group having 2 to 16 carbon atoms, and the number of atoms constituting the A ring is preferably 5 to 12; R 2 is more preferably an alkylene group having 1 to 4 carbon atoms, an alkyleneoxyalkylene group having 2 to 8 carbon atoms, or a poly(alkyleneoxy)alkylene group having 2 to 8 carbon atoms, and the number of constituent atoms of the A ring is 5 to 10; R 2 is more preferably an alkylene group having 1 to 4 carbon atoms, an alkyleneoxyalkylene group having 2 to 6 carbon atoms, or a poly(alkyleneoxy)alkylene group having 2 to 6 carbon atoms, and the number of atoms constituting the A ring is 5 to 6. When general formula [2] has the above structure, the compound has an excellent balance of hydrophilicity and hydrophobicity and is highly compatible with other components in the composition. The compound also has an excellent balance of rigidity and flexibility, and the molecular weight and heat resistance of the resulting polymer can be easily controlled. Furthermore, the resulting cured product has excellent flex resistance.

[0031] In the general formula [3], R 3 is an alkyl group having 1 to 18 carbon atoms, an alkyleneoxyalkyl group having 2 to 36 carbon atoms, or a poly(alkyleneoxy)alkyl group having 2 to 36 carbon atoms. 3 The number of carbon atoms in the alkyl group and / or alkylene group in R is preferably 1 to 12, more preferably 1 to 8, even more preferably 1 to 4, and most preferably 1 or 2. 3The total number of carbon atoms in the alkyleneoxyalkyl group or poly(alkyleneoxy)alkyl group having 2 to 36 carbon atoms is preferably 2 to 24, more preferably 2 to 16, even more preferably 2 to 8, and most preferably 2 to 4. 3 The types of A ring and R 2 For example, in order to improve the hydrophobicity of the compound, R 3 The number of carbon atoms may be increased.

[0032] In the general formula [1], L 2 is a hydrogen atom, the N-substituted (meth)acrylamide of the present disclosure has an N-monosubstituted structure. The secondary amide group contained in this structure easily forms hydrogen bonds and has high wettability and adhesion to polar materials. Inks, inks for three-dimensional modeling, pressure-sensitive adhesives, adhesives, photosensitive resins, sealants, and dental materials using this compound exhibit strong cohesion and high polymerizability and curability. Furthermore, the characteristic structure of this compound can impart or improve properties required for each application, such as adhesive strength, adhesion, durability, heat resistance, strength, and hardness. The secondary amide group is biodegradable, and is expected to have the effect of reducing the environmental burden of the compound. Furthermore, since the secondary amide group is a major component of the peptide bond that constitutes proteins, this compound is expected to exhibit high biocompatibility.

[0033] In the general formula [1], L 2 When is an organic group represented by general formula [2] or general formula [3], the N-substituted (meth)acrylamide of the present disclosure has an N,N-disubstituted structure. The tertiary amide group contained in this structure does not form intermolecular hydrogen bonds, so the viscosity of the compound is relatively low. Furthermore, since the compound has multiple organic groups, the balance between the hydrophilicity and hydrophobicity of the compound can be more easily adjusted according to the purpose, and the compound has excellent resistance to cure shrinkage. The resulting polymer and cured product have excellent heat resistance, high strength, and hardness.

[0034] In the N-substituted (meth)acrylamides according to the present disclosure, L 1 and L 2When both are general formula [2], the compound has an excellent balance of hydrophilicity and hydrophobicity and is highly compatible with other components in the composition. The compound also has an excellent balance of rigidity and flexibility, making it easy to control the molecular weight and heat resistance of the resulting polymer. In addition, the resulting cured product has excellent flex resistance.

[0035] In the N-substituted (meth)acrylamides according to the present disclosure, R 2 , R 3 And / or the A ring may have a substituent. If the substituent is an ethylenically unsaturated group, the compound has multiple polymerizable functional groups, and the curable composition containing it exhibits high curability. Furthermore, the resulting cured product has high strength and hardness.

[0036] If the substituent is a group having an oxygen atom, oxygen inhibition that occurs during photopolymerization by irradiation with active energy rays such as ultraviolet light or visible light can be suppressed, improving the surface curability of the polymerizable composition. In particular, if the substituent is a hydroxyl group, an alkoxy group, or an ether group, the hydrophilicity of the compound is improved and compatibility with other components is enhanced. In addition, the flexibility of the polymerized product and cured product obtained using the compound is enhanced.

[0037] Groups carrying oxygen atoms, such as hydroxyl groups and ether groups, can function as hydrogen donors. When these substituents are present, radicals generated from an initiator in a photopolymerization reaction abstract hydrogen from the groups carrying oxygen atoms, stabilizing the radicals themselves and promoting the generation of new highly active radicals, thereby accelerating the progress of the polymerization reaction. Due to these unique effects, photopolymerizable compositions containing the compounds exhibit high polymerizability, and active energy ray-curable compositions containing the compounds exhibit high curability.

[0038] Examples of N-substituted (meth)acrylamides according to the present disclosure include the following compounds, although the present disclosure is not limited to these compounds.

[0039] R 2Examples of compounds in which is an alkylene group and ring A is a saturated alicyclic hydrocarbon group include N-(cyclopentyl alkyl)(meth)acrylamide, N,N-alkyl-(cyclopentyl alkyl)(meth)acrylamide, N-(cyclohexyl alkyl)(meth)acrylamide, N,N-alkyl-(cyclohexyl alkyl)(meth)acrylamide, N-(cycloheptyl alkyl)(meth)acrylamide, N,N-alkyl-(cycloheptyl alkyl)(meth)acrylamide, N-(cyclooctyl alkyl)(meth)acrylamide, and N,N-alkyl-(cyclohexyl alkyl)(meth)acrylamide. Alkyl-(cyclooctylalkyl)(meth)acrylamide, N-(cyclononylalkyl)(meth)acrylamide, N,N-Alkyl-(cyclononylalkyl)(meth)acrylamide, N-(cyclodecylalkyl)(meth)acrylamide, N,N-Alkyl-(cyclodecylalkyl)(meth)acrylamide, N-(cycloundecylalkyl)(meth)acrylamide, N,N-Alkyl-(cycloundecylalkyl)(meth)acrylamide, N-(cyclododecylalkyl)(meth)acrylamide, N,N-Alkyl-(cyclo N-(cyclopentadecylalkyl)(meth)acrylamide, N,N-alkyl-(cyclopentadecylalkyl)(meth)acrylamide, N-(cyclohexadecylalkyl)(meth)acrylamide, N,N-alkyl-(cyclohexadecylalkyl)(meth)acrylamide, N,N- Alkyl-(cyclohexadecylalkyl)(meth)acrylamide, N-(cycloheptadecylalkyl)(meth)acrylamide, N,N-Alkyl-(cycloheptadecylalkyl)(meth)acrylamide, N-(cyclooctadecylalkyl)(meth)acrylamide, N,N-Alkyl-(cyclooctadecylalkyl)(meth)acrylamide, N-(norbornanealkyl)(meth)acrylamide, N,N-Alkyl-(norbornanealkyl)(meth)acrylamide, N-(isobornylalkyl)(meth)acrylamide, N,Examples include N-alkyl-(isobornylalkyl)(meth)acrylamide, N-(adamantylalkyl)(meth)acrylamide, N,N-alkyl(adamantylalkyl)(meth)acrylamide, N-(dicyclopentanylalkyl)(meth)acrylamide, N,N-alkyl(dicyclopentanylalkyl)(meth)acrylamide, N-(dodecahydrodimethanobenzoindenealkyl)(meth)acrylamide, and N,N-alkyl(dodecahydrodimethanobenzoindenealkyl)(meth)acrylamide.

[0040] Among these, N-(cyclohexylmethyl)(meth)acrylamide (E-1 and E-2 in Table 1), N,N-methyl-(cyclohexylmethyl)(meth)acrylamide (E-3 in Table 1), N,N-ethyl-(cyclohexylmethyl)(meth)acrylamide, N-(cyclohexylethyl)(meth)acrylamide, N,N-methyl-(cyclohexylethyl)(meth)acrylamide, N,N-ethyl-(cyclohexylethyl)(meth)acrylamide, N-(isobornyl) N,N-methyl-(isobornylmethyl)(meth)acrylamide (E-16 in Table 1), N,N-methyl-(isobornylmethyl)(meth)acrylamide, N-(adamantylmethyl)(meth)acrylamide (E-17 in Table 1), N,N-methyl(adamantylmethyl)(meth)acrylamide, N-(dicyclopentanylmethyl)(meth)acrylamide (E-18 in Table 1), and N,N-methyl(dicyclopentanylmethyl)(meth)acrylamide are preferred because the effects of the present invention can be easily obtained.

[0041] R 2Compounds in which is an alkyleneoxyalkylene group and ring A is a saturated alicyclic hydrocarbon group include N-(cyclohexylmethyleneoxymethyl)(meth)acrylamide, N-(cyclohexylmethyleneoxyethyl)(meth)acrylamide, N-(cyclohexylethyleneoxymethyl)(meth)acrylamide, N-(cyclohexylethyleneoxyethyl)(meth)acrylamide, N,N-methyl-(cyclohexylmethyleneoxymethyl)(meth)acrylamide, N,N-methyl-(cyclohexyl N,N-methyl-(cyclohexylethyleneoxymethyl)(meth)acrylamide, N,N-methyl-(cyclohexylethyleneoxyethyl)(meth)acrylamide, N-(isobornylmethyleneoxymethyl)(meth)acrylamide, N-(isobornylmethyleneoxyethyl)(meth)acrylamide, N-(isobornylethyleneoxymethyl)(meth)acrylamide, -(isobornylethyleneoxyethyl)(meth)acrylamide, N ,N-Methyl-(isobornylmethyleneoxymethyl)(meth)acrylamide, N,N-Methyl-(isobornylmethyleneoxyethyl)(meth)acrylamide, N,N-Methyl-(isobornylethyleneoxymethyl)(meth)acrylamide, N,N-Methyl-(isobornylethyleneoxyethyl)(meth)acrylamide, N-(dicyclopentanylmethyleneoxymethyl)(meth)acrylamide, N-(dicyclopentanylmethyleneoxyethyl)(meth)acrylamide, N-(dicyclopentanylmethyleneoxyethyl)(meth)acrylamide

[0033] Examples of the methacrylamide include N-(dicyclopentanylethyleneoxymethyl)(meth)acrylamide, N-(dicyclopentanylethyleneoxyethyl)(meth)acrylamide, N-methyl((dicyclopentanylmethyleneoxymethyl)(meth)acrylamide, N,N-methyl((dicyclopentanylmethyleneoxyethyl)(meth)acrylamide, N,N-methyl(dicyclopentanylethyleneoxymethyl)(meth)acrylamide, and N,N-methyl(dicyclopentanylethyleneoxyethyl)(meth)acrylamide.

[0042] R 2Examples of the compound in which is an alkylene group and ring A is a saturated alicyclic hydrocarbon group having an alkyl group include N-(alkylcyclopentylalkyl)(meth)acrylamide, N-(alkylcyclopentylalkyl)(meth)acrylamide, N-(alkylcyclohexylalkyl)(meth)acrylamide, and N-(alkylcyclohexylalkyl)(meth)acrylamide.

[0043] Among these, N-(i-propylcyclohexylmethyl)(meth)acrylamide, N-(i-propylcyclohexylethyl)(meth)acrylamide, N-(i-propylcyclohexylpropyl)(meth)acrylamide, N-(i-propylcyclohexylbutyl)(meth)acrylamide, N-(t-butylcyclohexylmethyl)(meth)acrylamide (E-4 in Table 1), N-(t-butylcyclohexylethyl)(meth)acrylamide, N-(t-butylcyclohexylpropyl)(meth)acrylamide, N-(t-butylcyclohexylbutyl)(meth)acrylamide, N,N-methyl-(i-propylcyclohexylmethyl)(meth)acrylamide )acrylamide, N,N-methyl-(i-propylcyclohexylethyl)(meth)acrylamide, N,N-methyl-(i-propylcyclohexylpropyl)(meth)acrylamide, N,N-methyl-(i-propylcyclohexylbutyl)(meth)acrylamide, N,N-methyl-(t-butylcyclohexylmethyl)(meth)acrylamide, N,N-methyl-(t-butylcyclohexylethyl)(meth)acrylamide, N,N-methyl-(t-butylcyclohexylpropyl)(meth)acrylamide, and N,N-methyl-(t-butylcyclohexylbutyl)(meth)acrylamide are preferred because the effects of the present invention can be easily achieved.

[0044] R 2is an alkylene group and ring A is a saturated alicyclic hydrocarbon group having an ethylenically unsaturated group, examples of which include N,N'-(cyclohexanediyl)alkylenebis(meth)acrylamide, N,N'-(cyclohexanediyl)bisalkylene(meth)acrylamide, N-((propenoyloxy)cyclohexane)alkylene(meth)acrylamide, N-((propenoyloxyalkyl)cyclohexane)alkylene(meth)acrylamide, N-(vinylcyclohexane)alkylene(meth)acrylamide, and N-(vinyl ether alkylcyclohexane)alkylene(meth)acrylamide.

[0045] Among these, N,N'-(cyclohexanediyl)bismethylene(meth)acrylamide (E-30 in Table 1), N,N'-(cyclohexanediyl)bisethylenemethylene(meth)acrylamide, N,N'-(cyclohexanediyl)bispropylene(meth)acrylamide, N,N'-(cyclohexanediyl)bisbutylene(meth)acrylamide, N-((propenoyloxymethyl)cyclohexane)methylene(meth)acrylamide, N-((propenoyloxymethyl)cyclohexane)ethylene(meth)acrylamide, N-((propenoyloxymethyl)cyclohexane)ethylene(meth)acrylamide, N-((propenoyloxymethyl)cyclohexane) )cyclohexane)propylene(meth)acrylamide, N-((propenoyloxymethyl)cyclohexane)butylene((meth)acrylamide, N-((propenoyloxyethyl)cyclohexane)methylene(meth)acrylamide, N-((propenoyloxyethyl)cyclohexane)ethylene(meth)acrylamide, N-((propenoyloxyethyl)cyclohexane)propylene(meth)acrylamide, and N-((propenoyloxyethyl)cyclohexane)butylene((meth)acrylamide are preferred because the effects of the present invention can be easily achieved.

[0046] R 2Examples of compounds in which is an alkylene group and ring A is a saturated alicyclic hydrocarbon group having a hydroxyl group include N-(hydroxycyclopentylalkyl)(meth)acrylamide, N-((alkylhydroxy)cyclopentylalkyl)(meth)acrylamide, N,N-alkyl-(hydroxycyclopentylalkyl)(meth)acrylamide, N,N-alkyl-((alkylhydroxy)cyclopentylalkyl)(meth)acrylamide, -(hydroxycyclohexylalkyl)(meth)acrylamide, N-((alkylhydroxy)cyclohexylalkyl) )(meth)acrylamide, N,N-alkyl-(hydroxycyclohexylalkyl)(meth)acrylamide, N,N-alkyl-((alkylhydroxy)cyclohexylalkyl)(meth)acrylamide, N-(dihydroxycyclopentylalkyl)(meth)acrylamide, N,N-alkyl-(dihydroxycyclopentylalkyl)(meth)acrylamide, N-(dihydroxycyclohexylalkyl)(meth)acrylamide, N,N-alkyl-(dihydroxycyclohexylalkyl)(meth)acrylamide, and the like.

[0047] Among them, N-(hydroxycyclohexylmethyl)(meth)acrylamide (E-12 in Table 1), N-((hydroxymethyl)cyclohexylmethyl)(meth)acrylamide, N-((hydroxyethyl)cyclohexylmethyl)(meth)acrylamide, N-(hydroxycyclohexylethyl)(meth)acrylamide, N-((hydroxymethyl)cyclohexylethyl)(meth)acrylamide, N-((hydroxyethyl)cyclohexylethyl)(meth)acrylamide, N,N-methyl-(hydroxycyclohexylmethyl)(meth)acrylamide N,N-methyl-((hydroxymethyl)cyclohexylmethyl)(meth)acrylamide (E-13 in Table 1), N,N-methyl-((hydroxyethyl)cyclohexylmethyl)(meth)acrylamide, N,N-methyl-(hydroxycyclohexylethyl)(meth)acrylamide, N,N-methyl-((hydroxymethyl)cyclohexylethyl)(meth)acrylamide, and N,N-methyl-((hydroxyethyl)cyclohexylethyl)(meth)acrylamide are preferred because the effects of the present invention can be easily achieved.

[0048] R 2 is an alkylene group and the A ring is a saturated alicyclic hydrocarbon group having an alkoxy group, examples of which include N-(alkoxycyclopentylalkyl)(meth)acrylamide, N,N-alkyl-(alkoxycyclopentylalkyl)(meth)acrylamide, N-(alkoxycyclohexylalkyl)(meth)acrylamide (E-26 in Table 1), N,N-alkyl-(alkoxycyclohexylalkyl)(meth)acrylamide, N-(dialkoxycyclopentylalkyl)(meth)acrylamide, N,N-alkyl-(dialkoxycyclopentylalkyl)(meth)acrylamide, N-(dialkoxycyclohexylalkyl)(meth)acrylamide, and N,N-alkyl-(dialkoxycyclohexylalkyl)(meth)acrylamide.

[0049] R 2is an alkylene group and the A ring is a saturated alicyclic hydrocarbon group having two or more different substituents, such as N-(alkoxycyclopentanol alkyl)(meth)acrylamide, N,N-alkyl-(alkoxycyclopentanol alkyl)(meth)acrylamide, N-(alkoxycyclohexanol alkyl)(meth)acrylamide, N,N-alkyl-(alkoxycyclohexanol alkyl)(meth)acrylamide, N-(alkoxycyclopentadiol alkyl)(meth)acrylamide, N,N-alkyl-(alkoxycyclopentadiol alkyl)(meth)acrylamide,

[0033] Examples of the alkyl esters include N-(alkoxycyclohexadiol alkyl)(meth)acrylamide, N-(alkoxycyclohexadiol alkyl)(meth)acrylamide, N,N-alkyl-(alkoxycyclohexadiol alkyl)(meth)acrylamide, N-(dialkoxycyclopentanol alkyl)(meth)acrylamide, N,N-alkyl-(dialkoxycyclopentanol alkyl)(meth)acrylamide, N-(dialkoxycyclohexanol alkyl)(meth)acrylamide, and N,N-alkyl-(dialkoxycyclohexanol alkyl)(meth)acrylamide.

[0050] Among them, N-(methoxycyclohexanolmethyl)(meth)acrylamide (E-25 in Table 1), N-(methoxycyclohexanolethyl)(meth)acrylamide, N-(butoxycyclohexanolmethyl)(meth)acrylamide, N-(butoxycyclohexanolethyl)(meth)acrylamide, N,N-methyl-(methoxycyclohexanolmethyl)(meth)acrylamide, N,N-methyl-(methoxycyclohexanolethyl)(meth)acrylamide, N,N-methyl- (Butoxycyclohexanol methyl) (meth)acrylamide, N,N-methyl-(butoxycyclohexanol ethyl) (meth)acrylamide, N-(methoxycyclohexadiol methyl) (meth)acrylamide, N-(methoxycyclohexadiol ethyl) (meth)acrylamide, N-(butoxycyclohexadiol methyl) (meth)acrylamide, N-(butoxycyclohexadiol ethyl) (meth)acrylamide, N,N-methyl-(methoxycyclohexadiol methyl) N,N-methyl-(methoxycyclohexadiol ethyl)(meth)acrylamide, N,N-methyl-(butoxycyclohexadiol methyl)(meth)acrylamide, N,N-methyl-(butoxycyclohexadiol ethyl)(meth)acrylamide, N-(dimethoxycyclohexanol methyl)(meth)acrylamide (E-24 in Table 1), N-(dimethoxycyclohexanol ethyl)(meth)acrylamide, N-(diethoxycyclohexanol methyl)

[0043] The effects of the present invention can be easily obtained by using N,N-methyl-(dimethoxycyclohexanolmethyl)(meth)acrylamide, N-(diethoxycyclohexanolethyl)(meth)acrylamide, N,N-methyl-(dimethoxycyclohexanolethyl)(meth)acrylamide, N,N-methyl-(diethoxycyclohexanolmethyl)(meth)acrylamide, and N,N-methyl-(diethoxycyclohexanolethyl)(meth)acrylamide, which are preferred.

[0051] R 2is an alkylene group and ring A is an unsaturated alicyclic hydrocarbon group, examples of which include N-(cyclopentenyl alkyl)(meth)acrylamide, N,N-alkyl(cyclopentenyl alkyl)(meth)acrylamide, N-(cyclohexenyl alkyl)(meth)acrylamide, N,N-alkyl-(cyclohexenyl alkyl)(meth)acrylamide, N-(norbornene alkyl)(meth)acrylamide, N,N-alkyl-(norbornene alkyl)(meth)acrylamide, N,N-(norbornene dialkylene)bis(meth)acrylamide, N-(dicyclopentenyl alkyl)(meth)acrylamide, N,N-alkyl(dicyclopentenyl alkyl)(meth)acrylamide, N-(tricyclopentenyl alkyl)(meth)acrylamide, and N,N-alkyl(tricyclopentenyl alkyl)(meth)acrylamide.

[0052] Among these, N-(norbornenemethyl)(meth)acrylamide, N,N-methyl-(norbornenemethyl)(meth)acrylamide, N-(dicyclopentenylmethyl)(meth)acrylamide (E-19 in Table 1), and N,N-methyl(dicyclopentenylalkyl)(meth)acrylamide are preferred because they are more likely to achieve the effects of the present invention.

[0053] R 2 Examples of the compound in which is an alkylene group and ring A is an unsaturated alicyclic hydrocarbon group having an alkyl group include N-(alkylcyclopentenylalkyl)(meth)acrylamide, N,N-alkyl(alkylcyclopentenylalkyl)(meth)acrylamide, N-(alkylcyclohexenylalkyl)(meth)acrylamide, and N,N-alkyl-(alkylcyclohexenylalkyl)(meth)acrylamide.

[0054] R 2Examples of the compound in which is an alkylene group and ring A is an unsaturated alicyclic hydrocarbon group having an ethylenically unsaturated group include N,N'-(norbornenediyl)bisalkylene(meth)acrylamide, N-((propenoyloxyalkyl)norbornenediyl)(meth)acrylamide, N-((vinyl alkyl)norbornene)alkylene(meth)acrylamide, and N-((vinyl ether alkyl)norbornene)alkylene(meth)acrylamide.

[0055] Among these, N,N'-(norbornene-diyl)bismethylene(meth)acrylamide, N,N'-(norbornene-diyl)bisethylene(meth)acrylamide, N-((propenoyloxyalkyl)norbornene)methylene(meth)acrylamide, and N-((propenoyloxyalkyl)norbornene)ethylene(meth)acrylamide are preferred because they make it easier to achieve the effects of the present invention.

[0056] R 2 is an alkylene group and ring A is an unsaturated alicyclic hydrocarbon group having a hydroxyl group, examples of which include N-(hydroxycyclopentenylalkyl)(meth)acrylamide, N-((alkylhydroxy)cyclopentenylalkyl)(meth)acrylamide, N,N-alkyl-(hydroxycyclopentenylalkyl)(meth)acrylamide, N,N-alkyl-((alkylhydroxy)cyclopentenylalkyl)(meth)acrylamide, N-(hydroxycyclohexenylalkyl)(meth)acrylamide, N-((alkylhydroxy)cyclohexenylalkyl)(meth)acrylamide, N,N-alkyl-(hydroxycyclohexenylalkyl)(meth)acrylamide, N,N-alkyl-(hydroxycyclohexenylalkyl)(meth)acrylamide, and N,N-alkyl-((alkylhydroxy)cyclohexenylalkyl)(meth)acrylamide.

[0057] R 2Examples of the compound in which is an alkylene group and ring A is an unsaturated alicyclic hydrocarbon group having an alkoxy group include N-(alkoxycyclopentenylalkyl)(meth)acrylamide, N,N-alkyl-(alkoxycyclopentenylalkyl)(meth)acrylamide, N-(alkoxycyclohexenylalkyl)(meth)acrylamide, and N,N-alkyl-(alkoxycyclohexenylalkyl)(meth)acrylamide.

[0058] R 2 Examples of the compound in which is an alkylene group and ring A is a saturated heterocyclic group include N-(tetrahydrofurylalkyl)(meth)acrylamide, N,N-alkyl(tetrahydrofurylalkyl)(meth)acrylamide, N-(tetrahydropyranalkyl)(meth)acrylamide, N,N-alkyl(tetrahydropyranalkyl)(meth)acrylamide, N-(dioxanealkyl)(meth)acrylamide, and N,N-alkyl(dioxanealkyl)(meth)acrylamide.

[0059] Among these, N-(tetrahydrofurfuryl)(meth)acrylamide (E-6 and E-8 in Table 1), N,N-methyl(tetrahydrofurfuryl)(meth)acrylamide (E-7 and E-9 in Table 1), N-(tetrahydrofurylethyl)(meth)acrylamide, N,N-methyl(tetrahydrofurylethyl)(meth)acrylamide, N-(tetrahydrofurylpropyl)(meth)acrylamide, N,N-methyl(tetrahydrofurylpropyl)(meth)acrylamide, N-(tetrahydrofurylbutyl)(meth)acrylamide, N-(tetrahydrofurylbutyl)(meth)acrylamide and N,N-methyl(tetrahydrofurylbutyl)(meth)acrylamide are preferred because the effects of the present invention can be easily obtained.

[0060] R 2 Examples of compounds in which is an alkylene group and ring A is a saturated heterocyclic group having an alkyl group include N-(alkyltetrahydrofurylalkyl)(meth)acrylamide and N,N-alkyl(alkyltetrahydrofurylalkyl)(meth)acrylamide.

[0061] Among these, N-(methyltetrahydrofurfuryl)(meth)acrylamide, N-(ethyltetrahydrofurfuryl)(meth)acrylamide, N,N-methyl(methyltetrahydrofurfuryl)(meth)acrylamide, and N,N-methyl(ethyltetrahydrofurfuryl)(meth)acrylamide are preferred because they are more likely to achieve the effects of the present invention.

[0062] R 2 is an alkylene group and ring A is a saturated heterocyclic group having an ethylenically unsaturated group, examples of which include N,N'-(tetrahydrofurandiyl)bisalkylene(meth)acrylamide, N-((propenoyloxyalkyl)tetrahydrofuran)alkylene(meth)acrylamide, N-(vinyltetrahydrofuran)alkylene(meth)acrylamide, and N-((vinyl ether alkyl)tetrahydrofuran)alkylene(meth)acrylamide.

[0063] Among these, N,N'-(tetrahydrofurandiyl)bismethylene(meth)acrylamide (E-34 in Table 1), N,N'-(tetrahydrofurandiyl)bisethylene(meth)acrylamide, N,N'-(tetrahydrofurandiyl)bispropylene(meth)acrylamide, N,N'-(tetrahydrofurandiyl)bisbutylene(meth)acrylamide, N-((propenoyloxymethyl)tetrahydrofurfuryl)(meth)acrylamide (E-32 and E-33 in Table 1), N-((propenoyloxyethyl)tetrahydrofurfuryl) (Meth)acrylamide, N-((propenoyloxypropyl)tetrahydrofurfuryl)(meth)acrylamide, N-((propenoyloxybutyl)tetrahydrofurfuryl)(meth)acrylamide, N-((propenoyloxymethyl)tetrahydrofurylethylene)(meth)acrylamide, N-((propenoyloxymethyl)tetrahydrofurylpropylene)(meth)acrylamide, and N-((propenoyloxymethyl)tetrahydrofurylbutylene)(meth)acrylamide are preferred because the effects of the present invention can be easily achieved.

[0064] R 2Examples of the compound in which is an alkylene group and ring A is a saturated heterocyclic group having a hydroxyl group include N-(hydroxytetrahydrofuryl)(meth)acrylamide, N-((alkylhydroxy)tetrahydrofuryl)(meth)acrylamide, N,N-alkyl(hydroxytetrahydrofuryl)(meth)acrylamide, and N,N-alkyl((alkylhydroxy)tetrahydrofuryl)(meth)acrylamide.

[0065] Among these, N-(hydroxytetrahydrofurfuryl)(meth)acrylamide (E-20 in Table 1), N,N-methyl(hydroxytetrahydrofurfuryl)(meth)acrylamide, N-((hydroxymethyl)tetrahydrofurfuryl)(meth)acrylamide (E-21 in Table 1), N,N-methyl((hydroxymethyl)tetrahydrofurfuryl)(meth)acrylamide, N-((hydroxyethyl)tetrahydrofurfuryl)(meth)acrylamide, and N,N-methyl((hydroxyethyl)tetrahydrofurfuryl)(meth)acrylamide are preferred because the effects of the present invention are easily achieved.

[0066] R 2 As the compound in which is an alkylene group and ring A is a saturated heterocyclic group having an alkoxy group, N-(alkoxytetrahydrofurylalkyl)(meth)acrylamide and N,N-alkyl(alkoxytetrahydrofurylalkyl)(meth)acrylamide are preferred because they make it easier to achieve the effects of the present invention.

[0067] R 2 Examples of the compound in which is an alkylene group and ring A is a saturated heterocyclic group having two or more different substituents include N-(alkoxytetrahydrofuryl alcohol alkyl)(meth)acrylamide, N,N-alkyl-(alkoxytetrahydrofuryl alcohol alkyl)(meth)acrylamide, N-(alkoxytetrahydrofuryl alcohol alkyl)(meth)acrylamide, and N,N-alkyl-(alkoxytetrahydrofuryl alcohol alkyl)(meth)acrylamide.

[0068] R 2Examples of the compound in which is an alkylene group and ring A is an unsaturated heterocyclic group include N-(furylalkyl)(meth)acrylamide, N,N-alkyl(furylalkyl)(meth)acrylamide, N-(pyranalkyl)(meth)acrylamide, N,N-alkyl(pyranalkyl)(meth)acrylamide, N-(dioxenealkyl)(meth)acrylamide, and N,N-alkyl(dioxenealkyl)(meth)acrylamide.

[0069] Among these, N-(furylmethyl)(meth)acrylamide (E-14 and E-15 in Table 1), N-(furylethyl)(meth)acrylamide, N-(furylpropyl)(meth)acrylamide, N-(furylbutyl)(meth)acrylamide, N,N-methyl(furylmethyl)(meth)acrylamide, N,N-methyl(furylethyl)(meth)acrylamide, N,N-methyl(furylpropyl)(meth)acrylamide, and N,N-methyl(furylbutyl)(meth)acrylamide are preferred because they make it easier to achieve the effects of the present invention.

[0070] R 2 Examples of compounds in which is an alkylene group and ring A is an unsaturated heterocyclic group having an alkyl group include N-(alkylfurylalkyl)(meth)acrylamide and N,N-alkyl(alkylfurylalkyl)(meth)acrylamide.

[0071] Among these, N-(methylfurylmethyl)(meth)acrylamide, N-(ethylfurylmethyl)(meth)acrylamide, N-(methylfurylethyl)(meth)acrylamide, N-(ethylfurylethyl)(meth)acrylamide, N,N-methyl(methylfurylmethyl)(meth)acrylamide, N,N-methyl(ethylfurylmethyl)(meth)acrylamide, N,N-methyl(ethylfurylmethyl)(meth)acrylamide, and N,N-ethyl(ethylfurylmethyl)(meth)acrylamide are preferred because the effects of the present invention are more easily achieved.

[0072] R 2Examples of the compound in which is an alkylene group and ring A is an unsaturated heterocyclic group having an ethylenically unsaturated group include N,N'-(furandiyl)bisalkylene(meth)acrylamide, N-((propenoyloxyalkyl)furyl)alkylene(meth)acrylamide, N-(vinylfuryl)alkylene(meth)acrylamide, and N-((vinyl ether alkyl)furyl)alkylene(meth)acrylamide.

[0073] Among these, N,N'-(furandiyl)bismethylene(meth)acrylamide, N,N'-(furandiyl)bisethylene(meth)acrylamide, N,N'-(furandiyl)bispropylene(meth)acrylamide, N,N'-(furandiyl)bisbutylene(meth)acrylamide, N-((propenoyloxymethyl)furylmethylene)(meth)acrylamide (E-31 in Table 1), N-((propenoyloxyethyl)furylmethylene)(meth)acrylamide N-((propenoyloxypropyl)furylmethylene)(meth)acrylamide, N-((propenoyloxybutyl)furylmethylene)(meth)acrylamide, N-((propenoyloxymethylfurylethylene)(meth)acrylamide, N-((propenoyloxymethyl)furylpropylene)(meth)acrylamide, and N-((propenoyloxymethyl)furylbutylene)(meth)acrylamide are preferred because the effects of the present invention can be easily achieved.

[0074] R 2 Examples of the compound in which is an alkylene group and ring A is an unsaturated heterocyclic group having a hydroxyl group include N-(hydroxyfuryl)(meth)acrylamide, N-((alkylhydroxy)furyl)(meth)acrylamide, N,N-alkyl(hydroxyfuryl)(meth)acrylamide, and N,N-alkyl((alkylhydroxy)furyl)(meth)acrylamide.

[0075] Among these, N-(hydroxyfurylmethyl)(meth)acrylamide (E-23 in Table 1), N,N-methyl(hydroxyfurylmethyl)(meth)acrylamide, N-((hydroxymethyl)furylmethyl)(meth)acrylamide, N,N-methyl((hydroxymethyl)furylmethyl)(meth)acrylamide, N-((hydroxyethyl)furylmethyl)(meth)acrylamide, and N,N-methyl((hydroxyethyl)furylmethyl)(meth)acrylamide are preferred because they make it easier to achieve the effects of the present invention.

[0076] R 2 As the compound in which is an alkylene group and ring A is an unsaturated heterocyclic group having an alkoxy group, N-(alkoxyfurylalkyl)(meth)acrylamide and N,N-alkyl(alkoxyfurylalkyl)(meth)acrylamide are preferred because the effects of the present invention can be easily achieved.

[0077] R 2 Examples of the compound in which is an alkylene group and ring A is a saturated heterocyclic group having two or more different substituents include N-(alkoxyfuryl alcohol alkyl)(meth)acrylamide, N,N-alkyl-(alkoxyfuryl alcohol alkyl)(meth)acrylamide, N-(alkoxyfuryl alcohol alkyl)(meth)acrylamide, and N,N-alkyl-(alkoxyfuryl alcohol alkyl)(meth)acrylamide.

[0078] Compounds having two A rings include bis(cyclohexylmethyl)(meth)acrylamide (E-5 in Table 1), bis(cyclohexylethyl)(meth)acrylamide, bis(cyclohexylpropyl)(meth)acrylamide, bis(cyclohexylbutyl)(meth)acrylamide, bis(hydroxycyclohexylmethyl)(meth)acrylamide, bis(hydroxycyclohexylethyl)(meth)acrylamide, bis(hydroxycyclohexylpropyl)(meth)acrylamide, and bis(hydroxycyclohexylbutyl)(meth)acrylamide. )(meth)acrylamide, bis(tetrahydrofurfuryl)(meth)acrylamide (E-10 in Table 1), bis(tetrahydrofurylethyl)(meth)acrylamide, bis(tetrahydrofurylpropyl)(meth)acrylamide, bis(tetrahydrofurylbutyl)(meth)acrylamide, bis(furylmethyl)(meth)acrylamide, bis(furylethyl)(meth)acrylamide, bis(furylpropyl)(meth)acrylamide, bis(furylbutyl)(meth)acrylamide, N,N-(cyclohexanemethyl)-(hydroxycyclohexanemethyl)-(meth)acrylamide N,N-(cyclohexaneethyl)-(hydroxycyclohexanemethyl)(meth)acrylamide, N,N-(cyclohexanemethyl)-(hydroxycyclohexaneethyl)(meth)acrylamide, N,N-(cyclohexaneethyl)-(hydroxycyclohexaneethyl)(meth)acrylamide, N,N-(cyclohexaneethyl)-(hydroxycyclohexaneethyl)(meth)acrylamide, N,N-(cyclohexanemethyl)-(tetrahydrofurfuryl)(meth)acrylamide, N,N-(cyclohexaneethyl)-(tetrahydrofurfuryl)(meth)acrylamide, N,N-( N,N-(cyclohexanemethyl)-(furylmethyl)(meth)acrylamide, N,N-(cyclohexaneethyl)-(furylmethyl)(meth)acrylamide, N,N-(cyclohexanemethyl)-(furylethyl)(meth)acrylamide, N,N-(cyclohexaneethyl)-(furylethyl)(meth)acrylamide, N,N-(hydroxycyclohexanemethyl)-(tetrahydrofurfuryl)(meth)acrylamide, N,N-(hydroxycyclohexaneethyl)-(tetrahydrofurfuryl)(meth)acrylamide (E-11 in Table 1), N,Examples include N-(hydroxycyclohexanemethyl)-(furylmethyl)(meth)acrylamide, N,N-(hydroxycyclohexaneethyl)-(furylmethyl)(meth)acrylamide, N,N-(hydroxycyclohexanemethyl)-(furylethyl)(meth)acrylamide, N,N-(hydroxycyclohexaneethyl)-(furylethyl)(meth)acrylamide, N,N-(tetrahydrofurfuryl)-(furylmethyl)(meth)acrylamide, and N,N-(tetrahydrofurfuryl)-(furylethyl)(meth)acrylamide.

[0079] The N-substituted (meth)acrylamides according to the present disclosure can be produced by reacting an amine compound represented by general formula [4] (hereinafter referred to as the amine compound) with one or more compounds selected from (meth)acrylic acid halide, (meth)acrylic anhydride, (meth)acrylic acid, and (meth)acrylic acid ester (hereinafter referred to as the acrylic acid-based compound).

[0080] The amine compound is a divalent chain organic group (R 2 ) through a cyclic structure (ring A). The structures of R², R³, and ring A are as described above.

[0081] The acrylic acid compound may be commercially available or may be synthesized by a known method. The acrylic acid compound may be used alone or in combination of two or more. Examples of (meth)acrylic acid halides include methacrylic acid chloride, acrylic acid chloride, methacrylic acid bromide, and acrylic acid bromide. Examples of (meth)acrylic acid anhydrides include methacrylic acid anhydride and acrylic acid anhydride. Examples of (meth)acrylic acid esters include alkyl methacrylate and alkyl acrylate.

[0082] The method for producing the N-substituted (meth)acrylamide according to the present disclosure is not particularly limited, and the compound can be synthesized by a known method. A catalyst and / or a solvent may be used as needed. The type of catalyst is not particularly limited, and is appropriately selected depending on the raw materials used. Examples include basic catalysts, acidic catalysts, inorganic catalysts, and organic catalysts. The type of solvent is not particularly limited, and is appropriately selected depending on the raw materials used. An aprotic organic solvent is preferred as the solvent used. The resulting compound may be separated and / or purified by a known method such as extraction, crystallization, precipitation, or distillation.

[0083] One example of the production method is the amidation reaction of the amine with the acrylic acid compound, which can proceed without a catalyst or solvent and is preferred from the viewpoints of simple operability and reduced environmental impact.

[0084] The polymer according to one embodiment of the present disclosure is a homopolymer or copolymer containing an N-substituted (meth)acrylamide as a structural unit (collectively referred to as a polymer). The polymer can be obtained by polymerizing the compound or a polymerizable composition described below using a known method. Examples of polymerization methods include thermal polymerization, photopolymerization using active energy rays, and hybrid polymerization combining these methods in any order. In these polymerization reactions, any polymerization initiator described below can be used as needed.

[0085] A homopolymer of the N-substituted (meth)acrylamide compound can be obtained by polymerizing or curing the compound alone, or a copolymer of the compound can be obtained by polymerizing or curing two or more N-substituted (meth)acrylamide compounds having different structures, or by polymerizing or curing the compound in combination with a monomer, oligomer, or polymer having one or more ethylenically unsaturated groups.

[0086] The polymer preferably contains structural units of the N-substituted (meth)acrylamide compound in a range of 0.5 to 100% by mass, more preferably 1.0 to 99.5% by mass. Due to the cyclic structure, the polymer has a high glass transition temperature (Tg) and excellent thermal stability. Furthermore, due to the presence of both hydrophilic (meth)acrylamide groups and hydrophobic cyclic substituents, the polymer is an amphiphilic polymer with high solubility in a variety of solvents, from polar to nonpolar, and excellent compatibility with monomers and oligomers.

[0087] The molecular weight of the polymer is preferably 1,000 to 2,000,000 in weight average molecular weight (Mw), more preferably 5,000 to 1,000,000, and even more preferably 10,000 to 500,000. A molecular weight of 1,000 or more can suppress migration of low molecular weight compounds. Furthermore, a molecular weight of 2,000,000 or less can provide a polymer that is easy to handle.

[0088] The solution viscosity of the polymer can be adjusted appropriately depending on the application. For example, in a solution diluted with ethyl acetate having a solids content of 30%, the viscosity at 25°C is preferably 1 to 200,000 mPa·s, more preferably 3 to 100,000 mPa·s, and even more preferably 10 to 60,000 mPa·s. The polymer has high solubility in a variety of solvents, from polar to nonpolar, and excellent compatibility with monomers and oligomers, making it suitable for use as a component of the polymerizable composition described below.

[0089] A polymerizable composition according to one embodiment of the present disclosure is characterized by containing the N-substituted (meth)acrylamide and / or a polymer thereof. The compound and polymer have high solubility in a variety of solvents, from polar to nonpolar, excellent compatibility with monomers and oligomers, and a high degree of freedom in formulation design into the composition. Because the compound has high polymerizability, a polymer can be obtained by polymerizing it using a method such as electron beam irradiation, even if the compound-derived structural unit is incorporated in an amount of 100% by mass.

[0090] The polymerization or curing conditions can be adjusted appropriately depending on the purpose. When polymerizing or curing a polymerizable composition using active energy rays, the irradiation temperature is preferably 10 to 200°C, more preferably 20 to 100°C. The higher the irradiation temperature, the faster the polymerization rate and the more likely the polymerization reaction of the compound will proceed completely. On the other hand, the lower the irradiation temperature, the more effectively the coloration and thermal degradation of the polymerized and cured product can be suppressed. The irradiation time is preferably 0.1 seconds to 60 minutes, more preferably 1 second to 30 minutes. Compositions containing the compound and its polymers have excellent polymerizability and curability and are less susceptible to curing inhibition by oxygen, so the irradiation atmosphere is not particularly limited. For example, good polymerization or curing can be achieved in air, in an inert gas atmosphere such as nitrogen gas or carbon dioxide gas, or in an atmosphere with a low oxygen concentration.

[0091] When an electron beam is used as the active energy ray for photopolymerization of the polymerizable composition, a photopolymerization initiator is not essential, but when ultraviolet light is used, the addition of a photopolymerization initiator is necessary. The photopolymerization initiator is preferably a substance that generates radicals when irradiated with ultraviolet light of an appropriate wavelength, i.e., a photoradical polymerization initiator.

[0092] The content of the compound and / or its polymer in the polymerizable composition can be adjusted appropriately depending on the application. Specifically, the content of the compound is preferably 0.1 to 100% by mass, more preferably 0.3 to 99.5% by mass, even more preferably 0.5 to 99.0% by mass, and most preferably 1.0 to 95.0% by mass, based on the total polymerizable composition. The content of the polymer is preferably 0.1 to 80% by mass, more preferably 0.3 to 70% by mass, and even more preferably 0.5 to 60% by mass, based on the total polymerizable composition. New polymers and cured products obtained from polymerizable compositions and curable compositions containing the polymer have high flex resistance.

[0093] The polymerizable composition may contain optional components in addition to the N-substituted (meth)acrylamide compound, thereby imparting various properties to the polymerizable composition, polymer, and cured product. Examples of optional components include polymerizable compounds (excluding the N-substituted (meth)acrylamides), non-polymerizable oligomers, non-polymerizable polymers, and polymerization initiators. These components may be used singly or in combination. The content of each component in the polymerizable composition may be adjusted appropriately depending on the application.

[0094] Examples of polymerizable compounds include monofunctional or polyfunctional monomers, oligomers, and polymers. The use of monofunctional monomers, oligomers, and polymers allows the viscosity of the composition to be adjusted to a low viscosity. The monofunctional monomer is preferably present in an amount of 1 to 95% by mass, more preferably 5 to 90% by mass, and even more preferably 10 to 85% by mass, based on the total polymerizable composition. The monofunctional oligomer is preferably present in an amount of 1 to 40% by mass, more preferably 3 to 35% by mass, and even more preferably 5 to 30% by mass, based on the total polymerizable composition. The monofunctional polymer is preferably present in an amount of 0.5 to 35% by mass, more preferably 1 to 30% by mass, and even more preferably 2 to 25% by mass, based on the total polymerizable composition.

[0095] Examples of the monofunctional monomer include monofunctional (meth)acrylate, monofunctional (meth)acrylamide (excluding the N-substituted (meth)acrylamide compounds), vinyl group-containing monomer, allyl group-containing monomer, maleimide group-containing monomer, etc. Any of these monofunctional monomers can be selected and used alone or in combination.

[0096] Examples of monofunctional (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, hydroxyethyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, and isostearate. Tearyl (meth)acrylate, tridecyl (meth)acrylate, methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, propoxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, methoxydiethylene glycol (meth)acrylate, methoxytriethylene glycol (meth)acrylate, methoxytetraethylene glycol (meth)acrylate, 2-(2-ethoxyethoxy)ethyl acrylate, phenoxyethyl (meth)acrylate acrylate, phenoxydiethylene glycol (meth)acrylate, phenoxytetraethylene glycol (meth)acrylate, phenoxyhexaethylene glycol (meth)acrylate, methoxydipropylene glycol (meth)acrylate, methoxytripropylene glycol (meth)acrylate, cyclohexyl (meth)acrylate, tert-butylcyclohexyl (meth)acrylate, benzyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, bornyl (meth)acrylate, isobornyl (meth)acrylate, tetrahydrofurfuryl acrylate, 2-methyl-2-adamantyl (meth)acrylate, allyl (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, hydroxyhexyl (meth)acrylate, and the like.

[0097] Examples of monofunctional (meth)acrylamides include N-methyl(meth)acrylamide, N-ethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, N-butyl(meth)acrylamide, N-hexyl(meth)acrylamide, N-ethylhexyl(meth)acrylamide, N-octyl(meth)acrylamide, N-lauryl(meth)acrylamide, N-stearyl(meth)acrylamide, N-oleyl(meth)acrylamide, N-cyclohexyl(meth)acrylamide, N-methoxymethyl(meth)acrylamide, and N-ethoxymethyl(meth)acrylamide. amide, N-methoxyethyl(meth)acrylamide, N-ethoxyethyl(meth)acrylamide, Nn-butoxymethyl(meth)acrylamide, N-isobutoxymethyl(meth)acrylamide, N-(2-hydroxyethyl)(meth)acrylamide, N-(2-hydroxyethyl)-N-methyl(meth)acrylamide, N-(3-(dimethylamino))propyl(meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, diacetone(meth)acrylamide, (meth)acryloylmorpholine, and the like.

[0098] Examples of vinyl group-containing monomers include N-vinylpyrrolidone, N-vinylcaprolactam, acrylonitrile, vinyl acetate, styrene, and vinyloxazoline.

[0099] The use of polyfunctional monomers, oligomers, and polymers results in the formation of crosslinked structures in the resulting cured product, improving mechanical strength. The polyfunctional monomer is preferably present in an amount of 0.1 to 50% by mass, more preferably 0.3 to 40% by mass, and even more preferably 0.5 to 30% by mass, based on the total polymerizable composition. The polyfunctional oligomer is preferably present in an amount of 0.1 to 40% by mass, more preferably 0.1 to 35% by mass, and even more preferably 0.2 to 30% by mass, based on the total polymerizable composition. The polyfunctional polymer is preferably present in an amount of 0.1 to 50% by mass, more preferably 0.2 to 40% by mass, and even more preferably 0.5 to 30% by mass, based on the total polymerizable composition.

[0100] Examples of polyfunctional monomers include monomers having two or more ethylenically unsaturated groups selected from (meth)acrylate groups, (meth)acrylamide groups, vinyl groups, allyl groups, and maleimide groups. Polyfunctional monomers having 10 or fewer ethylenically unsaturated groups in the molecule are preferred. The ethylenically unsaturated groups are more preferably (meth)acrylate and / or (meth)acrylamide. These polyfunctional monomers can be used alone or in combination.

[0101] Examples of the (meth)acrylate which is a polyfunctional monomer include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, ditetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, and polypropylene glycol di(meth)acrylate. acrylate, polytetramethylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,6-hexanediol ethylene oxide modified di(meth)acrylate, 1,7-heptanediol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,9-Nonanediol di(meth)acrylate, hydroxypivalic acid neopentyl glycol di(meth)acrylate, dicyclopentanyl di(meth)acrylate, caprolactone-modified dicyclopentenyl di(meth)acrylate, ethylene oxide-modified phosphate di(meth)acrylate, glycerin di(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipenta Erythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol tetra(meth)acrylate, ethylene glycol diglycidyl ether di(meth)acrylate, diethylene glycol diglycidyl ether di(meth)acrylate, phthalic acid diglycidyl ester di(meth)acrylate, glycerin polyglycidyl ether poly(meth)acrylate, trimethylolethane tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, tricyclodecane dimethicone Methanol di(meth)acrylate, ethylene oxide modified bisphenol A di(meth)acrylate, propylene oxide modified bisphenol A di(meth)acrylate, cyclohexanedimethanol di(meth)acrylate, acrylate ester (dioxane glycol diacrylate), alkoxylated hexanediol di(meth)acrylate, alkoxylated cyclohexanedimethanol di(meth)acrylate, epoxy (meth)acrylate, urethane (meth)acrylate, isocyanuric acid ethylene oxide modified di acrylate, isocyanuric acid ethylene oxide modified tri(meth)acrylate, tri(meth)acryloyloxyethoxytrimethylolpropane, ethylene oxide modified dipentaerythritol penta(meth)acrylate, ethylene oxide modified dipentaerythritol hexa(meth)acrylate, ethylene oxide modified pentaerythritol tri(meth)acrylate, ethylene oxide modified pentaerythritol tetra(meth)acrylate, succinic acid modified pentaerythritol tri(meth)acrylate, etc.

[0102] Examples of the polyfunctional (meth)acrylamide monomer include methylene bis(meth)acrylamide, ethylene bis(meth)acrylamide, diallyl (meth)acrylamide, N-(tris(3-(meth)acrylamidopropoxymethyl)methyl)(meth)acrylamide, N,N-bis(2-(meth)acrylamideethyl)(meth)acrylamide, 4,7,10-trioxa-1,13-tridecane bis(meth)acrylamide, and N,N'-1,2-ethanedyl bis(N-(2-(meth)acrylamideethyl))(meth)acrylamide.

[0103] The use of non-polymerizable oligomers and polymers can increase the flexibility and elongation of the polymerized product and cured product. The content of the non-polymerizable oligomer in the polymerizable composition can be adjusted appropriately depending on the application. For example, the content of the non-polymerizable oligomer is preferably 0.1 to 40% by mass, more preferably 0.5 to 35% by mass, and even more preferably 1.0 to 30% by mass, based on the total polymerizable composition. The content of the non-polymerizable polymer is preferably 0.1 to 30% by mass, more preferably 0.3 to 25% by mass, and even more preferably 0.5 to 20% by mass, based on the total polymerizable composition.

[0104] The polymerizable composition according to the present disclosure may contain a non-polymerizable oligomer and / or polymer. This allows the viscosity of the polymerizable composition to be adjusted to a higher level, reducing shrinkage during curing. It also improves the flexibility of the resulting cured product. The non-polymerizable oligomer and polymer may be natural or synthetic. Specific examples include rosin-based resins, polyvinyl alcohol, hydroxyethyl cellulose, hydroxypropyl cellulose, acrylic resins, cyclic polyolefin resins, cellulose resins, polyester resins, and polyurethane resins. These non-polymerizable oligomers and polymers may be used alone or in combination of two or more. The content of the non-polymerizable oligomer and / or non-polymerizable polymer can be adjusted appropriately depending on the purpose, and is preferably 0.1 to 10% by mass, more preferably 0.5 to 8% by mass, and even more preferably 1 to 5% by mass, of the total polymerizable composition.

[0105] Examples of monofunctional oligomers, monofunctional polymers, polyfunctional oligomers, and polyfunctional polymers include polyurethane (meth)acrylate, polyurethane (meth)acrylamide, polyester (meth)acrylate, polyester (meth)acrylamide, polyether (meth)acrylate, polyether (meth)acrylamide, polyamide (meth)acrylate, polyamide (meth)acrylamide, polyamide imide (meth)acrylate, polyamide imide (meth)acrylamide, poly(meth)acrylic acid ester (meth)acrylate, poly(meth)acrylic acid ester (meth)acrylamide, epoxy (meth)acrylate, epoxy (meth)acrylamide, etc. Any of these monofunctional or polyfunctional oligomers or polymers can be selected and used alone or in combination.

[0106] The polymerizable compound more preferably has a crosslinkable reactive group. Examples include a cyclic ether, a hydroxyl group, an amino group, a carboxyl group, an isocyanate group, an oxazoline group, and a glycidyl group. The total number of ethylenically unsaturated groups and crosslinkable reactive groups in the polymerizable compound is preferably 10 or less, more preferably 6 or less, and even more preferably 4 or less.

[0107] Examples of polymerization initiators include radical polymerization initiators, cationic polymerization initiators, anionic polymerization initiators, and thermal polymerization initiators. The use of a polymerization initiator can accelerate the polymerization reaction. The content of the polymerization initiator in the polymerizable composition can be adjusted appropriately depending on the application. For example, the content of the polymerization 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, based on the total mass of the polymerizable composition.

[0108] The polymerizable composition of the present disclosure can be polymerized or cured by any method, such as thermal polymerization, photopolymerization using active energy rays, or hybrid polymerization that combines thermal polymerization and photopolymerization in any order. One example of hybrid polymerization is photopolymerization followed by thermal polymerization, which achieves both surface curing and deep curing and reduces cure shrinkage. Examples of active energy rays include visible light, electron beams, ultraviolet rays, infrared rays, X-rays, α-rays, β-rays, and γ-rays. Among these, ultraviolet rays (UV) are preferred from the standpoints of availability of active energy ray generators, curing speed, safety, and the like. Examples of ultraviolet light sources include xenon lamps, low-pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, UV-LED lamps, and microwave excimer lamps.

[0109] Examples of the photopolymerization initiator include acetophenone-based initiators such as α-hydroxy-α,α'-dimethylacetophenone and 2-hydroxy-2-cyclohexylacetophenone; benzoin-based initiators such as benzoin, benzoin methyl ether, and benzoin isopropyl ether; benzophenone-based initiators such as benzophenone, methylbenzophenone, and a benzophenone derivative having an acrylate group; benzoyl formate-based initiators such as methyl benzoylformate, ethyl benzoylformate, and 3,5-dimethoxybenzoylmethylformate; benzoyl formate-based initiators such as N-methylbenzoylformamide, N-phenylbenzoylformamide, N-monosubstituted benzoylformamide derivatives having an unsaturated bond, and N-substituted benzoylformamide derivatives having a urethane bond; thioxanthone-based initiators such as 2-isopropylthioxanthone and 2,4-dichlorothioxanthone; and acylphosphine oxide-based initiators such as bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide and 2,4,6-trimethylbenzoyldiphenylphosphine oxide. These initiators may be used alone or in combination of two or more. Initiators having absorption at different wavelengths may be appropriately selected and used in combination.

[0110] These photopolymerization initiators may be used alone or in combination of two or more. Commercially available products include "Omnirad 1173," "Omnirad 184," and "Omnirad TPO" manufactured by IGM Resins BV, "Ebecryl P36" manufactured by Daicel Allnex, "Pro22669" and "SPEEDCURE" series manufactured by Arkema, and "Kohshylex I" series manufactured by KJ Chemicals. From the viewpoint of preventing migration caused by the photopolymerization initiator, it is preferable to use Kohshylex I 3002, 3003, 3101, or 3102, which has high activity, a high molecular weight, or an unsaturated group.

[0111] 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, based on the total mass of the polymerizable composition. When the content of the photopolymerization initiator is within this range, the polymerizable composition can be sufficiently polymerized, and a cured product with high hardness can be obtained.

[0112] When polymerizing or curing a polymerizable composition by heat, it is preferable to use a thermal polymerization initiator as needed. The heating temperature can be adjusted appropriately depending on the decomposition temperature of the thermal polymerization initiator used. The heating temperature is preferably 40 to 150°C, more preferably 50 to 120°C, and even more preferably 60 to 100°C. The higher the heating temperature, the faster the polymerization rate and the more rapidly the polymerization reaction progresses. On the other hand, the lower the heating temperature, the more effectively the coloration and thermal degradation of the polymerized and cured products can be suppressed. The heating time can be adjusted appropriately depending on the half-life of the thermal polymerization initiator used, and is preferably 10 minutes to 30 hours, more preferably 30 minutes to 20 hours, and even more preferably 1 to 10 hours. The longer the heating time, the more effectively the polymerization reaction progresses completely. On the other hand, the shorter the heating time, the more effectively the coloration and thermal degradation of the polymerized and cured products can be suppressed.

[0113] Examples of the thermal polymerization initiator include thermal radical polymerization initiators, such as azo compound catalysts such as azobisisobutyronitrile, azobisvaleronitrile, and azobis(isobutyrate)dimethyl; peroxide catalysts such as benzoyl peroxide and hydrogen peroxide; and persulfate catalysts such as ammonium persulfate and sodium persulfate. The content of the thermal polymerization initiator is 0.01 to 10% by mass based on the total polymerizable composition. Furthermore, conventional radical polymerization techniques, such as molecular weight adjustment using a chain transfer agent, can be applied.

[0114] Thermal polymerization of the polymerizable composition can be carried out by known methods. Examples include emulsion polymerization, solution polymerization, suspension polymerization, and bulk polymerization. In solution polymerization, any solvent capable of dissolving the polymerized product of the polymerizable composition can be used as the polymerization solvent without any particular limitation. Examples of solvents include aromatic hydrocarbons such as benzene, toluene, ethylbenzene, and xylene; aliphatic hydrocarbons such as hexane, heptane, octane, decane, and cyclohexane; esters such as ethyl acetate, butyl acetate, and 2-hydroxyethyl acetate; aliphatic alcohols such as ethyl alcohol, n-propyl alcohol, and isopropyl alcohol; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; acetonitrile, N,N-dimethylformamide, 3-methoxydimethylpropionic acid amide, and 3-butoxydimethylpropionic acid amide. These solvents can be used alone or in combination. From the viewpoint of ease of removal from the polymer, it is preferable to use low-boiling-point solvents such as ethyl acetate, methyl ethyl ketone, and acetone.

[0115] A curable composition according to one embodiment of the present disclosure is characterized by containing a crosslinking agent. By incorporating a crosslinking agent, a cured product having a crosslinked structure can be obtained. The cured product has excellent physical properties such as strength, hardness, and durability (heat resistance, water resistance, etc.). The content of the crosslinking agent can be adjusted as appropriate, and is preferably 0.1 to 15% by mass, more preferably 0.5 to 10% by mass, and even more preferably 1 to 5% by mass, based on the total mass of the polymerizable composition.

[0116] The polymerizable composition and the curable composition may contain additives as needed. Examples of additives include thermal polymerization inhibitors, antioxidants, UV sensitizers, preservatives, flame retardants (phosphate esters, etc.), surfactants, antistatic agents, colorants (pigments, dyes, etc.), fragrances, antifoaming agents, fillers (organic fillers, inorganic fillers, etc.), silane coupling agents, plasticizers, surface lubricants, leveling agents, and softeners. These additives may be used singly or in combination. The content of the additives is not particularly limited, as long as it does not adversely affect the properties of the polymerizable composition and its polymerized product, and the curable composition and its cured product. For example, the content is preferably 30% by mass or less of the total polymerizable composition.

[0117] The polymerizable composition and the curable composition may contain a solvent such as water or an organic solvent, if necessary. Any solvent may be used alone or in combination. The content of the solvent is not particularly limited as long as it does not adversely affect the properties of the polymerizable composition and its polymerized product, and the curable composition and its cured product. For example, the content of the solvent is preferably 95% by mass or less of the total polymerizable composition.

[0118] The polymerizable composition of the present disclosure can be applied to the surface of any substrate. Examples of the substrate include paper, cloth, nonwoven fabric, glass, polyethylene terephthalate (PET), diacetate cellulose, triacetate cellulose, acrylic polymers, polyvinyl chloride, cellophane, celluloid, polycarbonate, polyimide, metals, metal oxides, and ceramics. Examples of methods for applying the composition to a substrate include known methods such as spin coating, spray coating, dipping, gravure roll coating, knife coating, reverse roll coating, screen printing, and bar coater coating. The applied film can be exposed to active energy rays and / or heat to form a hard coat layer, pressure-sensitive adhesive layer, adhesive layer, or sealant layer.

[0119] One embodiment of the present disclosure is an inkjet ink containing one or more of a polymerizable composition, a polymer, and a curable composition. The inkjet ink contains structural units derived from an N-substituted (meth)acrylamide compound (including the compound itself, the polymerizable composition, and a portion carried over from the polymer). The content of the structural units is preferably 3 to 90% by mass, more preferably 5 to 80% by mass, and even more preferably 8 to 70% by mass, based on the total mass of the inkjet ink. The N-substituted (meth)acrylamide compound has amphiphilic properties, providing excellent dispersibility of pigments and compatibility with oligomers and the like incorporated into the inkjet ink. As a result, a uniform inkjet ink can be obtained, improving ejection stability and print clarity during printing. Furthermore, the compound has a cyclic structure, thereby exhibiting high water resistance as an inkjet ink. Furthermore, the compound contains a (meth)acrylamide group, which provides the inkjet ink with excellent polymerizability and curability, and also provides excellent surface drying of the printed surface. In addition, the inkjet ink can exhibit excellent wettability and adhesion to various substrates. The compound contains a chain organic group (R 2 ), the interaction with components such as pigments is enhanced, further improving dispersibility and transparency. This improves the ink ejection stability during printing and also shows excellent performance in terms of print clarity. In addition, the compound has sufficient dispersibility for pigments and is useful as a pigment dispersant.

[0120] In addition to structural units derived from the compound, the inkjet ink may contain any component selected from monofunctional monomers, polyfunctional monomers, polyfunctional oligomers, polyfunctional polymers, non-polymerizable oligomers, polymers, photopolymerization initiators, pigments, dispersants, and additives. The content of the monofunctional monomer is preferably 5 to 60% by mass, and more preferably 10 to 50% by mass. The content of the polyfunctional monomer is preferably 5 to 80% by mass, and more preferably 10 to 60% by mass. The total content of the polyfunctional oligomers or polymers is preferably 5 to 60% by mass, and more preferably 10 to 55% by mass. When the composition of the inkjet ink is within the above ranges, an inkjet ink can be obtained that has an excellent balance of wettability and adhesion to the substrate and high surface drying properties.

[0121] The viscosity of the inkjet ink can be adjusted appropriately from low to high depending on the printing method and application, such as inkjet printing, screen printing, offset printing, flexographic printing, etc. Generally, the viscosity of the ink at 25°C is preferably 1,000 mPa·s or less, more preferably 500 mPa·s or less, and even more preferably 100 mPa·s or less from the viewpoint of suitable use in inkjet methods.

[0122] One embodiment of the present disclosure is an ink for three-dimensional modeling containing one or more of a polymerizable composition, a polymer, and a curable composition. The ink for three-dimensional modeling contains a structural unit derived from an N-substituted (meth)acrylamide, and the content of the structural unit is preferably 3 to 70 mass% of the total ink for three-dimensional modeling, more preferably 5 to 60 mass%, and even more preferably 8 to 50 mass%. The compound is amphiphilic, exhibiting high dispersibility for fillers and other additives incorporated into the ink for three-dimensional modeling, and high compatibility with oligomers, polymers, and other additives. The compound has a cyclic structure, and the ink for three-dimensional modeling has high water resistance and strength. Furthermore, the ink for three-dimensional modeling has excellent resistance to shrinkage upon curing and high modeling accuracy. The compound contains a (meth)acrylamide group, and the ink for three-dimensional modeling has high polymerizability and curability, allowing for easy production of modeled objects. Furthermore, the chain organic group provides the ink with an excellent balance of strength and flexibility, and exhibits impact resistance. By having both a chain linking group and a cyclic structure, distortion during molding is easily alleviated and dimensional stability is also excellent.

[0123] In addition to structural units derived from the compound, the ink for three-dimensional modeling can contain optional components selected from monofunctional monomers, polyfunctional monomers, polyfunctional oligomers, polyfunctional polymers, non-polymerizable oligomers, polymers, photopolymerization initiators, pigments, dispersants, and additives. The content of these components is preferably 5 to 30% by mass of monofunctional monomers, 10 to 80% by mass of polyfunctional monomers, 5 to 60% by mass of the total of polyfunctional oligomers or polymers, and 0.5 to 20% by mass of the total of non-polymerizable oligomers or polymers. By having the composition of the ink for three-dimensional modeling within these ranges, it is possible to obtain an ink for three-dimensional modeling that has an excellent balance between strength and impact resistance in the modeled object and high modeling precision.

[0124] One embodiment of the present disclosure is a coating agent containing one or more of a polymerizable composition, a polymer, and a curable composition. The coating agent contains structural units derived from N-substituted (meth)acrylamide, preferably in an amount of 5 to 80 mass%, more preferably 8 to 70 mass%, and even more preferably 10 to 60 mass%, based on the total weight of the coating agent. The compound exhibits amphiphilic properties, high dispersibility of fillers and other additives incorporated into the coating agent, and high compatibility with oligomers, polymers, and other additives. As a result, the resulting cured film exhibits high transparency and surface smoothness. The compound has a cyclic structure, which provides excellent resistance to cure shrinkage of the coating agent, and high water resistance and surface hardness of the resulting cured film. Additionally, the compound contains a (meth)acrylamide group, and coating agents containing the compound exhibit excellent polymerizability and curability, as well as excellent wettability and adhesion to various substrates. The compound contains a chain organic group, which provides a good balance of hardness and flexibility and excellent flex resistance, making the coating agent suitable for application to curved surfaces and flexible substrates. Furthermore, when the chain linking group is long, a cured film having high flexibility while maintaining surface hardness can be obtained, making it particularly useful for applications where decorativeness and design are important. The compound or its structural unit having both a chain linking group and a cyclic structure can be arranged at high density during coating, further improving the strength of the resulting coating film. As described above, the coating agent according to this embodiment has an excellent balance of various properties and is useful as a high-performance film-forming material for a wide range of applications.

[0125] In addition to the structural units derived from the compound, the coating agent can contain optional components selected from monofunctional monomers, polyfunctional monomers, polyfunctional oligomers, polyfunctional polymers, non-polymerizable oligomers, polymers, photopolymerization initiators, and additives. The content of these components is preferably 2 to 50% by mass of monofunctional monomers, 5 to 60% by mass of polyfunctional monomers, 0.5 to 60% by mass of the total content of polyfunctional oligomers or polymers, and 0.1 to 10% by mass of the total content of non-polymerizable oligomers or polymers. By having the composition of the coating agent within these ranges, the coating agent exhibits excellent wettability and adhesion to the substrate and, after curing, can form a cured film with high transparency and a smooth surface. Therefore, the coating agent of the present invention is particularly useful in fields where the appearance quality of the film is important, such as optical applications and decorative applications.

[0126] One embodiment of the present disclosure is a pressure-sensitive adhesive containing one or more of a polymerizable composition, a polymer, and a curable composition. The content of structural units derived from N-substituted (meth)acrylamide in the pressure-sensitive adhesive is preferably 3 to 60 mass% of the total pressure-sensitive adhesive, more preferably 5 to 55 mass%, and even more preferably 8 to 50 mass%. The compound is amphiphilic and has good compatibility with other components incorporated into the pressure-sensitive adhesive. As a result, the cured pressure-sensitive adhesive layer has high transparency. The compound has a cyclic structure, which improves the pressure-sensitive adhesive's resistance to humidity and heat. The compound contains a (meth)acrylamide group, which contributes to the pressure-sensitive adhesive's high cohesive strength and excellent contamination resistance. In addition, the pressure-sensitive adhesive exhibits excellent adhesion to various substrates, and the compound's chain organic group further improves adhesion. This also contributes to the pressure-sensitive adhesive's excellent ability to conform to the irregularities of substrate surfaces. Pressure-sensitive adhesives with these properties are suitable for a wide range of applications, including pressure-sensitive adhesive layers and sheets in the optical and automotive fields, as well as electronic materials and semiconductor components.

[0127] In addition to the structural units derived from the compound, the PSA may contain any component selected from monofunctional monomers, polyfunctional monomers, polyfunctional oligomers, polyfunctional polymers, non-polymerizable oligomers, polymers, photopolymerization initiators, and additives. Examples of additives include tackifiers such as rosin-based, terpene-based, and aromatic-modified resins. The content of the monofunctional monomer is preferably 1 to 60% by mass, the content of the polyfunctional compound is preferably 0.5 to 50% by mass, the total content of the polyfunctional oligomers or polymers is preferably 1 to 50% by mass, and the total content of the non-polymerizable oligomers or polymers is preferably 0.1 to 20% by mass. When the PSA composition is within the above ranges, a highly transparent PSA layer can be obtained, with an excellent balance of basic physical properties such as initial tackiness, adhesive strength, and holding power. Furthermore, the PSA layer exhibits high adhesion even to uneven substrates and excellent impact absorption.

[0128] The adhesive layer is formed by applying the adhesive to a separator or substrate and then curing it with active energy rays, heat, or a combination of these. If the adhesive contains an organic solvent, the adhesive may be dried after application to the separator or substrate to volatilize the organic solvent. The drying process can be adjusted as needed to ensure that the performance of the adhesive layer is not affected. For example, the adhesive may be heated at 60 to 120°C for 1 to 30 minutes. The adhesive can be applied using any commonly used method. Examples include spin coating, spray coating, knife coating, dip coating, gravure roll coating, reverse roll coating, screen printing, and bar coating. The thickness of the adhesive layer can be adjusted to a thin type (5 to 25 μm) suitable for optical films and screen protectors, a medium-thick type (20 to 50 μm) suitable for removable tapes and temporary fixation applications, or a thick type (50 to 180 μm) suitable for automotive interior materials and cushioning applications.

[0129] One embodiment of the present disclosure is an adhesive containing one or more of a polymerizable composition, a polymer, and a curable composition. The content of structural units derived from N-substituted (meth)acrylamide in the adhesive is preferably 5 to 70 mass% of the total adhesive, more preferably 7 to 60 mass%, and even more preferably 10 to 50 mass%. The compound is amphiphilic, exhibiting good compatibility with other components incorporated into the adhesive and providing a cured film with high transparency. The compound has a cyclic structure, resulting in high water resistance and cure shrinkage resistance. Furthermore, the compound contains a (meth)acrylamide group, which allows the adhesive to exhibit high curability and excellent adhesion to various substrates, demonstrating high adhesive strength not only between homogeneous materials but also between dissimilar materials. Furthermore, the compound contains a chain organic group, which provides a good balance between strength and flexibility of the adhesive and further improves impact resistance and cure shrinkage resistance. These properties allow the formed adhesive layer to have high transparency and cure shrinkage resistance, making it extremely suitable for use as an adhesive in optical applications such as semiconductors, polarizing plates, and optical laminate films.

[0130] In addition to the structural units derived from the compound, the adhesive may contain optional components selected from monofunctional monomers, polyfunctional monomers, polyfunctional oligomers, polyfunctional polymers, non-polymerizable oligomers, polymers, photopolymerization initiators, and additives. The content of these components is preferably 5 to 30% by mass for monofunctional monomers, 3 to 50% by mass for polyfunctional monomers, 1 to 40% by mass for the total content of polyfunctional oligomers or polymers, and 0.1 to 50% by mass for the total content of non-polymerizable oligomers or polymers. The content of fillers is preferably 0.5 to 20% by mass, more preferably 0.5 to 15% by mass, and even more preferably 1 to 10% by mass. Examples of additives include silica, alumina, silica-alumina, zinc oxide, titanium oxide, zirconium oxide, calcium carbonate, cerium oxide, boron nitride, cellulose nanofibers, and carbon nanotubes.

[0131] Furthermore, the adhesive has excellent resistance to shrinkage on cure, and can be suitably used in fields where misalignment of the adhesive position cannot be tolerated, such as sensors and lenses, etc. In addition, the adhesive can be suitably used in applications where adhesive reliability and adhesive durability are required, such as semiconductors, electrical components, and automotive components.

[0132] One embodiment of the present disclosure is a photosensitive resin containing one or more of a polymerizable composition, a polymer, and a curable composition. The content of structural units derived from N-substituted (meth)acrylamide in the photosensitive resin is preferably 1 to 60% by mass, more preferably 3 to 55% by mass, and even more preferably 5 to 50% by mass, based on the total mass of the photosensitive resin. The compound has a cyclic structure and a (meth)acrylamide group, and exhibits high affinity with both aqueous and organic solvent developers. This facilitates pattern formation. Furthermore, the compound has a cyclic structure, allowing the photosensitive resin to form a pattern with high hardness, with minimal edge chipping and precise pattern formation. Furthermore, the compound contains a (meth)acrylamide group, and the photosensitive resin has excellent curability. Additionally, the compound contains a chain organic group, which allows the photosensitive resin to exhibit excellent wettability and high moldability of pattern details, particularly corners. Photosensitive resins with such properties can be suitably used in various optical applications, such as circuit pattern formation in the photolithography process in semiconductor manufacturing, protective films for semiconductor surfaces such as passivation layers and insulating layers, and packaging materials for semiconductor chips.

[0133] A wide range of lasers can be used for exposure, including g-line (436 nm), i-line (365 nm), KrF excimer laser (248 nm), ArF excimer laser (193 nm), F2 laser (157 nm), and visible light laser (488-514 nm). In addition to structural units derived from N-substituted (meth)acrylamide, the photosensitive resin can contain optional components selected from monofunctional monomers, polyfunctional monomers, polyfunctional oligomers, polyfunctional polymers, non-polymerizable oligomers or polymers, photopolymerization initiators, and additives. The content of these components is preferably 5-70% by mass of monofunctional monomers, 5-60% by mass of polyfunctional monomers, 1-50% by mass of the total of the polyfunctional oligomers and polymers, and 0.1-10% by mass of the total of the non-polymerizable oligomers and polymers. When the composition of the photosensitive resin falls within the above ranges, it exhibits high curability over a wide range of light sources. Furthermore, the exposed areas are completely cured, while the unexposed areas are completely removed by washing, allowing for extremely precise pattern formation. If necessary, alkali-soluble resins such as novolac resins, polyhydroxystyrene resins, polyacrylic resins, polyimide resins, and poly(acrylamide-acrylic acid) resins may also be used.

[0134] One embodiment of the present disclosure is a sealant containing one or more of a polymerizable composition, a polymer, and a curable composition. The content of structural units derived from N-substituted (meth)acrylamide in the sealant is preferably 5 to 60 mass%, more preferably 8 to 55 mass%, and even more preferably 10 to 50 mass%, based on the total sealant. The compound has a cyclic structure, and sealants containing this compound exhibit excellent resistance to cure shrinkage. Furthermore, the cured product (sealant) obtained by curing the sealant exhibits excellent water resistance and moist heat resistance. Due to the compound's (meth)acrylamide group, the sealant has high curability. Furthermore, due to the compound's chain organic group, the sealant has excellent impact resistance and resistance to thermal cycling, and can maintain stable performance even in harsh environments. Additionally, the sealant exhibits high adhesion to various materials and low outgassing, making it extremely suitable for use as a sealing material for electronic components, semiconductor devices, and the like.

[0135] In addition to structural units derived from N-substituted (meth)acrylamides, the sealant may contain optional components selected from monofunctional monomers, polyfunctional monomers, polyfunctional oligomers, polyfunctional polymers, non-polymerizable oligomers or polymers, photopolymerization initiators, and additives. The content of these components is preferably 5 to 70% by mass of monofunctional monomers, 5 to 80% by mass of polyfunctional monomers, 5 to 50% by mass of the total of polyfunctional oligomers and polymers, and 1 to 30% by mass of the total of non-polymerizable oligomers and polymers. If necessary, fillers such as silica, alumina, silica-alumina, zinc oxide, titanium oxide, calcium carbonate, cerium oxide, boron nitride, cellulose nanofibers, and carbon nanotubes can be used appropriately. The filler content is preferably 0.5 to 20% by mass, more preferably 0.5 to 15% by mass, and even more preferably 1 to 10% by mass. When the sealant composition is within the above ranges, the sealant exhibits excellent adhesion and cure shrinkage resistance, and can optimize the properties required for a sealing material, such as low outgassing. This allows the film to be suitably used in applications requiring sealing reliability and sealing durability, such as semiconductor applications such as protection of semiconductor chips and packaging of semiconductors, electronic components, automotive components, etc. In addition, the film can be suitably used in applications where decorativeness and design are important.

[0136] One embodiment of the present disclosure is a dental material containing one or more of a polymerizable composition, a polymer, and a hardenable composition. The content of structural units derived from N-substituted (meth)acrylamide in the dental material is preferably 1 to 80% by mass, more preferably 2 to 70% by mass, and even more preferably 5 to 60% by mass, based on the dental material. The compound is amphiphilic and exhibits excellent dispersibility and solubility in components such as inorganic fillers incorporated into the dental material, thereby improving the storage stability of the dental material. Furthermore, the compound has a cyclic structure, which allows the dental material to exhibit high adhesiveness even in a humid environment and excellent performance in suppressing shrinkage during hardening. Furthermore, the compound contains a (meth)acrylamide group, which allows the dental material to exhibit high adhesion to inorganic materials and dentin materials and excellent hardening properties. Additionally, the compound contains a chain organic group, which allows the dental material to exhibit an excellent balance of hardness and flexibility, high hardness, and further improved compatibility and dispersibility. In addition, the compound has both a cyclic structure and a chain organic group, and thus the cured surface of the dental material containing the compound exhibits high smoothness and excellent properties in terms of aesthetics and operability. These properties make the dental material suitable for use in a wide range of dental fields, including dental restorative materials, dental adhesives, and denture base materials.

[0137] In addition to structural units derived from N-substituted (meth)acrylamides, dental materials can contain optional components selected from monofunctional monomers, polyfunctional monomers, polyfunctional oligomers, polyfunctional polymers, non-polymerizable oligomers or polymers, photopolymerization initiators, and additives. The content of these components is preferably 0.5 to 70% by mass of monofunctional monomers, 1 to 60% by mass of polyfunctional monomers, 1 to 50% by mass of the total of polyfunctional oligomers and polymers, and 1 to 20% by mass of the total of non-polymerizable oligomers and polymers. If necessary, fillers such as silica, alumina, silica-alumina, zinc oxide, titanium oxide, calcium carbonate, cerium oxide, boron nitride, metal nanofibers, and metal nanotubes can be used as appropriate. The filler content is preferably 2 to 40% by mass, more preferably 5 to 30% by mass, and even more preferably 8 to 20% by mass.

[0138] When the composition of the dental material is within the above range, the dental material has high resistance to hardening shrinkage and low deformation during hardening and over time after hardening, allowing the dental material to be produced as designed. In addition, the surface is less likely to become uneven and has good surface smoothness, making it suitable for use in the production of composite resins for treating and restoring natural teeth, fillings, crowns, dentures, bridges, implants, etc.

[0139] The N-substituted (meth)acrylamides of the specific structure disclosed herein have a low odor and are extremely easy to handle. The compounds contain (meth)acrylamide groups and exhibit high polymerizability and curability against heat and actinic radiation. The compounds have a cyclic structure, and the resulting polymers or cured products have excellent heat resistance, durability, and mechanical strength. Furthermore, the compounds contain both hydrophilic (meth)acrylamide groups and hydrophobic cyclic substituents, functioning as amphiphilic monomers. They are highly soluble in a variety of solvents, from polar to nonpolar, and have excellent compatibility with monomers and oligomers. Polymerizable compositions containing the compounds or their polymers with these properties can be suitably used in inks, inkjet inks, inks for three-dimensional modeling, coating agents, pressure-sensitive adhesives, adhesives, photosensitive resins, sealants, dental materials, and the like.

[0140] 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 the following, "parts" and "%" are all based on mass unless otherwise specified.

[0141] The products obtained in the synthesis examples were confirmed to be the intended products using the following instruments: Fourier transform infrared spectrophotometer (FT-IR): Nicolet iS50 (manufactured by Thermo Fisher Scientific K.K.) Gas chromatography (GC): GC-2025 (manufactured by Shimadzu Corporation) Gas chromatography mass spectrometer (GC-MS): GCMS-QP2010 Ultra (manufactured by Shimadzu Corporation) Nuclear magnetic resonance spectrometer (FT-NMR): JNM-ECZ400s (manufactured by JEOL Ltd.)

[0142] Synthesis Example 1 (Synthesis of Compound E-1) 150 mL of tetrahydrofuran (THF), 0.04 g of 4-methoxyphenol (MeHQ), 48.0 g of triethylamine (TEA), and 57.0 g of cyclohexylmethylamine were added to a 1 L flask equipped with a reflux condenser, a stirrer, a thermometer, and a dropping funnel. The reaction solution was cooled to -10°C with stirring. 43.0 g of acrylic acid chloride (AC) was added to the dropping funnel, and AC was slowly added dropwise while maintaining the reaction solution at -10 to 0°C. After the addition was completed, the reaction solution was brought to 0 to 10°C and stirred for an additional 3 hours. After confirming the disappearance of the raw materials by GC analysis, the precipitated TEA hydrochloride was filtered off, and low-boiling components such as THF were removed by distillation under reduced pressure to obtain a pale yellow solid product. The resulting solid was purified by recrystallization to obtain a white solid product. GC-MS analysis (CI method) revealed that the protonated molecular ion (M+H) was 168, and the molecular weight of the product was calculated to be 167. From these results, the product was confirmed to be the target compound, N-(cyclohexylmethyl)acrylamide (compound E-1). Furthermore, GC analysis confirmed that the purity of the product was 98% and the yield was 90%.

[0143] Synthesis Example 2 (Synthesis of Compound E-2) Reaction and purification were carried out using the same charge ratio and conditions as in Synthesis Example 1, except that AC in Synthesis Example 1 was replaced with methacrylic acid chloride (MC), to obtain a white solid product. Similarly, GC-MS analysis revealed that the protonated molecular ion (M+H) was 182, and the molecular weight of the product was calculated to be 181. From these results, the product was confirmed to be the target compound, N-(cyclohexylmethyl)methacrylamide (Compound E-2). Furthermore, GC analysis confirmed that the purity of the product was 99% and the yield was 80%.

[0144] Synthesis Example 3 (Synthesis of Compound E-6) A reaction was carried out using the same charge ratio and conditions as in Synthesis Example 1, except that cyclohexylmethylamine was replaced with tetrahydrofurfurylamine, yielding a pale yellow liquid product. The resulting liquid was purified by distillation to yield a colorless liquid product. GC-MS analysis revealed a protonated molecular ion (M+H) of 156, and the molecular weight of the product was calculated to be 551. From these results, the product was confirmed to be the target compound, N-(tetrahydrofurfuryl)acrylamide (Compound E-6). Furthermore, GC analysis confirmed that the purity of the product was 99% and the yield was 77%.

[0145] Synthesis Example 4 (Synthesis of Compound E-30) A 1 L flask equipped with a reflux condenser, stirrer, thermometer, and dropping funnel was charged with 150 mL of THF, 0.14 g of MeHQ, 60.7 g of TEA, and 51.0 g of N-(4-aminomethylcyclohexyl)methylamine. The reaction mixture was cooled to 0°C with stirring. 54.3 g of AC was added to the dropping funnel, and AC was slowly added dropwise while maintaining the reaction mixture at 0-10°C. After the addition was complete, the reaction mixture was brought to 10-20°C and stirred for an additional 3 hours. The reaction mixture was then purified to obtain a white solid product. GC analysis confirmed that the product had a purity of 97% and a yield of 92%. Furthermore, FT-NMR and FT-IR analyses identified the product as the target compound, N,N'-(cyclohexanediyl)bismethyleneacrylamide (Compound E-30). 1 The H-NMR data and IR data are as follows: 1H-NMR(CDCl3)δ(ppm):6.68(dd,2H,CH2=CH-C=O),6.19(dd,2H,CH2=CH-C=O), 5.86(dd,2H,CH2=CH-C=O),3.10(d,4H,CON(CH3)-CH2-cHex),2.74(s,6H,-N-CH3),1.71(m,2H,N-CH2-C6H10),1.38-1.48(m,8H,N-CH2-C6H10) FT-IR:C=C(790cm -1 ), C=O(1,750cm -1 )

[0146] Synthesis Example 5 (Synthesis of Compound E-32) The reaction and purification were carried out using the same charge ratio and conditions as in Synthesis Example 4, except that the raw material amine was changed to N-(2-hydroxymethyl)tetrahydrofurfurylamine, to obtain a colorless liquid product. GC analysis confirmed that the purity of the product was 99% and the yield was 77%. Furthermore, FT-NMR analysis and FT-IR analysis identified the product as the target compound, N-((propenoyloxymethyl)tetrahydrofurfuryl)acrylamide (Compound E-32). 1 The H-NMR data and IR data are as follows: 1 H-NMR(CDCl3)δ(ppm):6.87(dd,1H,CH2=CH-COO),6.54(dd,1H,CH2=CH-CONH), 6.32(dd,1H,CH2=CH-COO),6.16(dd,1H,CH2=CH-CONH),6.02(dd,1H,CH2=CH-COO), 5.86(dd,1H,CH2=CH-CONH),4.46(d,2H,CH2=COO),4.09-4.22(m,2H,CH-O-CH),3.36(d,2H, CH2=CONH),1.72-2.20(m,4H, CH2-CH-O-CH-CH2) FT-IR:C=C(790cm -1 ,810cm -1 ), C=O(1,750cm -1 ,1,770cm -1 ),NH(1,540cm -1 ), COC(1,140cm -1 )

[0147] Other N-substituted (meth)acrylamides were also synthesized by the above method. The obtained products were subjected to GC-MS analysis, FT-NMR analysis, and FT-IR analysis to identify the target compounds. The purity and yield of each product were also confirmed by GC analysis. The synthesized N-substituted (meth)acrylamides are shown in Table 1-1 and Table 1-2.

[0148]

[0149]

[0150] (Odor evaluation of compounds) Compounds E-1 to E-34 were placed in a wide-mouth glass bottle, sealed, and left to stand at room temperature for 30 minutes. The lid was then slightly opened, and the odor intensity was measured using a four-point scale. The evaluation was based on the average of the scores of six people with a normal sense of smell. ◎: No odor was detected. ◯: A slight odor was detected, but it was not bothersome. △: An odor was detected. ×: A strong odor was detected.

[0151] (Evaluation of Solubility of Compounds) Compounds E-1 to E-34 (5 g) were mixed with the solvent or monomer (5 g) shown in Table 2 and stirred for 30 minutes at 25°C. The state of the mixture was then visually inspected to evaluate the solubility. ○: Completely dissolved, resulting in a homogeneous mixture. △: Partially dissolved, or resulting in a cloudy mixture. ×: Insoluble, or resulting in a two-layered mixture.

[0152] Odor and solubility evaluations were also performed on isobornyl acrylate (IBOA), tetrahydrofurfuryl acrylate (THFA), glycidyl acrylamide (GAM), 2-ethylhexyl acrylate (2HEA), and dipentaerythritol hexaacrylate (DPHA), and the results are summarized in Table 2.

[0153]

[0154] All of the N-substituted (meth)acrylamides E of the present disclosure had no or only a slight odor. In contrast, the monofunctional and polyfunctional (meth)acrylate compounds used as comparative examples all had a strong odor. Furthermore, it was confirmed that E, as an amphiphilic monomer, has excellent solubility in polar to nonpolar general-purpose solvents and compatibility with other monomers.

[0155] The polymerizable composition containing the N-substituted (meth)acrylamide of the present disclosure and various compositions containing the same were tested. The compounds used are as follows: (Monofunctional Monomers) IBOA: Isobornyl acrylate IBAM: Isobornyl acrylamide THFA: Tetrahydrofurfuryl acrylate THFMA: Tetrahydrofurfuryl methacrylate GAM: Glycidyl acrylamide ADAM: Adamantyl acrylamide DCPTEA: Dicyclopentenyl acrylate DCPTAA: Dicyclopentanyl acrylate POA: Phenoxyethyl acrylate DMAA: Dimethyl acrylamide (registered trademarks "Kohshylmer" and "DMAA") DEAA: Diethyl acrylamide (registered trademarks "Kohshylmer" and "DEAA") ACMO: Acryloylmorpholine (registered trademarks "Kohshylmer" and "ACMO") TBCHA: 4-tert-butylcyclohexyl acrylate (registered trademark "Kohshylmer") DAAM: Diacetone acrylamide (registered trademark "Kohshylmer") NOAM: N-Octyl acrylamide (registered trademark "Kohshylmer") DMAPAA: N-(3-(dimethylamino)propyl)acrylamide (registered trademarks "Kohshylmer" and "DMAPAA") NIPAM: N-isopropylacrylamide (registered trademarks "Kohshylmer" and "NIPAM") 2EHA: 2-ethylhexyl acrylate EEEA: ethyl carbitol acrylate BA: n-butyl acrylate LA: lauryl acrylate HEA: hydroxyethyl acrylate HEMA: hydroxyethyl methacrylate 4HBA: 4-hydroxybutyl acrylate P1M: 2-methacryloyloxyethyl acid phosphate TBA: tert-butyl acrylate HPPA: 2-hydroxy-3-phenoxypropyl acrylate (polyfunctional compound) QC7100: urethane acrylamide (Quick Cure 7100) (registered trademark "Quick Cure", manufactured by KJ Chemicals Co., Ltd.) QC7300: urethane acrylamide (Quick Cure 7300) (registered trademark "Quick Cure" manufactured by KJ Chemicals Co., Ltd.) Cure" manufactured by KJ Chemicals Co., Ltd.QC8100: Urethane acrylamide (Quick Cure 8100) (registered trademark "Quick Cure", manufactured by KJ Chemicals Co., Ltd.) QC8400: Urethane acrylamide (Quick Cure 8400) (registered trademark "Quick Cure", manufactured by KJ Chemicals Co., Ltd.) UV6630: Difunctional urethane acrylate (medium / hard type, Shikoh UV-6630B) UV3000: Difunctional urethane acrylate (soft / elastic type, Shikoh UV-3000B) PEGDA: Polyethylene glycol 600 diacrylate HDDA: 1,6-hexanediol diacrylate DPHA: Dipentaerythritol hexaacrylate PETA: Pentaerythritol (tri / tetra)acrylate TMPTA: Trimethylolpropane triacrylate BPE-200: Ethoxylated bisphenol A dimethacrylate (BPE-200, manufactured by Shin-Nakamura Chemical Co., Ltd.) A-BPE-10: Ethoxylated bisphenol A diacrylate (A-BPE-10, manufactured by Shin-Nakamura Chemical Co., Ltd.) DCPA: Dimethylol-tricyclodecane diacrylate PPGDAM: Polypropyleneoxydiacrylamide (number average molecular weight = 400) (registered trademark "Kohshylmer", manufactured by KJ Chemicals Co., Ltd.) (Initiator) D-1: 2-(4-(2-hydroxy-2-methylpropionyl)phenoxy)ethyl acrylate D-2 [pro22669] manufactured by Arkema Co., Ltd. D-3: 4-Acryloyloxybenzophenone D-4: Kohshylex I-3102 (polymer type) (registered trademark "Kohshylex", manufactured by KJ Chemicals Co., Ltd.) D-5: Omnirad TPO D-6: Omnirad 2595 D-7: Omnirad 1173 D-8: 2,2-Azobisisobutyronitrile D-9: 2,2-Azobis(2-methylbutyronitrile) D-10: Benzoyl peroxide D-11: Diisopropyl peroxydicarbonate (additive) H-1: Carbon black (CI Pigment Black) H-2: Pigment Blue 15:4 (manufactured by Toyo Color Co., Ltd.) H-3: Solsperse 6000 (manufactured by Lubrizol Japan Co., Ltd.) H-4: BYKJET-9151 (manufactured by BYK Corporation) H-5: Terpene resin (YS Resin PX 1150)H-6: Rosin ester resin (Harie Star DS-70L, manufactured by Harima Chemical Co., Ltd.)

[0156] (Preparation and Evaluation of Polymerizable Compositions) Examples 1 to 15 and Comparative Examples 1 to 3 (UV Curing Method) N-substituted (meth)acrylamide E, monofunctional monomer, polyfunctional compound, and initiator D were weighed out in the mass ratios shown in Table 3-1 and mixed for 30 minutes at 25°C to prepare compositions F-1 to F-15 as example compositions F and compositions G-1 to G-3 as comparative compositions G. The transparency and UV curability of the resulting compositions were evaluated by the following methods. The evaluation results are shown in Table 3-1.

[0157] (Transparency Evaluation) The obtained compositions were allowed to stand overnight at 23°C, and then the appearance and state of the compositions were visually observed. ⊚: High transparency, with no cloudiness or separation observed. ◯: High transparency, but slight cloudiness observed. Δ: No layer separation, but cloudiness observed. ×: Cloudiness and layer separation observed.

[0158] (UV Curability Evaluation) Using a real-time FT-IR equipped with a UV irradiation device (measuring instrument: Nicolet 6700, detector: MCT-A), polymerizable composition F or G was subjected to UV-LED lamp (wavelength: 365 nm, 130 mW / cm 2 Before and after UV irradiation, the CH out-of-plane bending vibration band (800 cm) derived from the unsaturated bond of the (meth)acrylamide group or the (meth)acrylate group was observed. -1 The intensity at the point (near the center of the sample) was measured, and the polymerization conversion rate was calculated using the following formula. The evaluation criteria are as follows: Polymerization conversion rate = (intensity before irradiation - intensity after irradiation) / intensity before irradiation x 100% ◎: Polymerization conversion rate is 95% or more ○: Polymerization conversion rate is 90% or more but less than 95% △: Polymerization conversion rate is less than 90%

[0159] UV-cured films were prepared using polymerizable compositions F-1 to F-15 and compositions G-1 to G-3 by the method described below, and the cure shrinkage resistance of each composition was evaluated. The resulting cured films were also evaluated for flex resistance by the method described below. The evaluation results are shown in Table 3-1.

[0160] (Preparation of UV-cured film) Composition F or G was uniformly applied onto a 100 μm-thick PET film using a bar coater so that the thickness after curing would be 20 μm. After application, a light-release PET film was attached to prevent air from entering. Then, using a UV irradiation device (manufactured by iGraphics, product name "ECS-4011GX," equipped with the same company's metal halide lamp "M04-L41"), UV irradiation was carried out on the coated film under conditions set at a lamp height of 200 mm and a conveyor speed of 540 cm / min. The irradiation was carried out with an integrated light dose of 400 mJ / cm per pass. 2 Three passes were performed under the above conditions to obtain a cured film by UV curing.

[0161] (Evaluation of cure shrinkage resistance) The cured film of each composition obtained was cut into a 10 cm square, and the average lift amount of the four corners was measured to evaluate cure shrinkage resistance (curl resistance). A larger lift amount indicates more pronounced curling of the film and lower cure shrinkage resistance. ⊚: The lift amount was 0.5 mm or less. ○: The lift amount was 1 mm or less. △: The lift amount was 3 mm or less. ×: The lift amount was more than 3 mm.

[0162] (Evaluation of Flex Resistance) The flex resistance of the cured films obtained from each composition was evaluated by the cylindrical mandrel method in accordance with JIS K 5600-5-1. The prepared cured films were wound around a mandrel with a diameter of 3 mm, and after the test, the state of the film was visually observed. ⊚: No cracks or cracks. ◯: Slight cracks were observed. Δ: Cracks were observed. ×: The film peeled off.

[0163]

[0164] Preparation Example 1 (Preparation of Polymer P-1) 200 g of methanol, 100 g of Compound E-6, and 1 g of initiator D-8 (AIBN) were added to a reactor equipped with a thermometer, stirrer, reflux condenser, and nitrogen inlet tube. Nitrogen gas was introduced while stirring to replace the air in the reactor with nitrogen. The reaction solution was then heated to the reflux temperature and reacted for 7 hours under a nitrogen atmosphere. After completion of the reaction, the reaction solution was added dropwise to 2 L of a mixed solution of ethyl acetate and hexane (1:1 by mass ratio) to cause reprecipitation. The resulting precipitate was filtered and dried to obtain 92 g of E-6 homopolymer (P-1). Gel permeation chromatography (GPC) analysis confirmed that the weight-average molecular weight (Mw) of the resulting P-1 was 60,000. The GPC analysis conditions were as follows: Measurement equipment: Prominence-I LTMPTA030C (Shimadzu Corporation); guard column: Shodex KF-G (Showa Denko) x 1; separation column: Shodex KF-803 (Showa Denko) x 1; column temperature: 40°C; mobile phase: THF, flow rate: 0.5 mL / min; standard sample: polystyrene

[0165] Production Example 2 (Production of Polymer P-2) Polymerization was carried out in the same manner as in Production Example 1 using 200 g of ethyl acetate, 50 g of compound E-1, 50 g of LA as a monofunctional monomer, and 0.1 g of initiator D-9 (V-59). After polymerization was completed, the reaction solution was added dropwise to 2 L of methanol to cause reprecipitation, and the resulting precipitate was filtered and dried to obtain 90 g of polymer P-2, a copolymer of E-1 and LA. The Mw of the resulting P-2 was 150,000, and the GPC measurement conditions were the same as in Production Example 1.

[0166] Production Example 3 (Production of Polymer P-3) Polymerization was carried out in the same manner as in Production Example 1 using 200 g of ethyl acetate, 15 g of compound E-7, 75 g of BA as a monofunctional monomer, and 0.5 g of initiator D-10 (BPO). After polymerization was completed, the reaction solution was added dropwise to 2 L of methanol to cause reprecipitation, and the resulting precipitate was filtered and dried to obtain 75 g of polymer P-3, a copolymer of E-7 and BA. The Mw of the resulting P-3 was 86,000, and the GPC measurement conditions were the same as in Production Example 1.

[0167] Production Example 4 (Production of Polymer P-4) Polymerization was carried out in the same manner as in Production Example 1 using 200 g of ethyl acetate, 15 g of compound E-12, 50 g of NIPAM as a monofunctional monomer, and 0.1 g of initiator D-9 (V-59). After polymerization was completed, the reaction solution was dropped into 2 L of methanol to cause reprecipitation, and the resulting precipitate was filtered and dried to obtain 89 g of polymer P-4, a copolymer of E-12 and NIPAM. The Mw of the resulting P-4 was 123,000, and the GPC measurement conditions were the same as in Production Example 1.

[0168] Production Example 5 (Production of Polymer Q-1) Polymerization was carried out in the same manner as in Production Example 1 using 200 g of N,N-dimethylformamide, 100 g of GAM as a monofunctional monomer, and 1 g of initiator D-8 (AIBN). After polymerization was completed, the reaction solution was added dropwise to 2 L of ethyl acetate and hexane (1:1 mass ratio) to cause reprecipitation. The resulting precipitate was filtered and dried to obtain 78 g of Polymer Q-1, a GAM homopolymer. The Mw of the resulting Q-1 was 55,000, and the GPC measurement conditions were the same as in Production Example 1.

[0169] Examples 16-23 and Comparative Examples 4-6 (Thermal Curing Method, Electron Beam (EB) Curing Method, Hybrid Thermal and UV Curing Method) N-substituted (meth)acrylamide E, polymer P or Q, monofunctional monomer, polyfunctional compound, and initiator D were weighed out in the mass ratios shown in Table 3-2 and mixed for 30 minutes at 25°C to prepare polymerizable compositions F of the examples F-16 to F-23 and comparative compositions G-4 to G-6. The transparency of the resulting compositions was evaluated as described above. The evaluation results are shown in Table 3-2.

[0170] For compositions F-16, F-17, F-22, and G-4 containing a photopolymerization initiator, UV-cured films were prepared under the same UV irradiation conditions as in the UV curing method described above. Each cured film was evaluated for its resistance to cure shrinkage and its flex resistance. The evaluation results are shown in Table 3-2.

[0171] For compositions F-18, F-19, F-21, and G-6, which contained a thermal polymerization initiator, thermally cured films were prepared according to the thermal curing method described below. For compositions F-20 and G-5, which contained both a photopolymerization initiator and a thermal polymerization initiator, hybrid cured films were prepared according to the UV and thermal curing method described below. Furthermore, for composition F-23, which did not contain an initiator, EB-cured films were prepared according to the EB curing method described below. Furthermore, the cure shrinkage resistance of each composition and the flex resistance of the resulting cured films were evaluated using the same procedures as for the UV-cured products described above. The evaluation results are shown in Table 3-2.

[0172] (Preparation of Thermosetting Film) Composition F or G was uniformly applied onto a 100 μm-thick PET film using a bar coater so that the thickness after drying would be 20 μm. After application, a light-release PET film was attached to prevent air from entering. The film was then held at 80°C for 24 hours to obtain a thermosetting cured film. When polymer P or Q was used in the form of a solution, the film was dried at 80°C for 1 hour after application, and then a light-release PET film was attached and thermosetting was similarly carried out.

[0173] (Preparation of Hybrid Cured Film) Using a bar coater, Composition F or G was uniformly applied onto a 100 μm-thick PET film so that the thickness after drying would be 20 μm. After application, a light-release PET film was attached to prevent air contamination. The coated film was then subjected to one pass of UV irradiation under the same conditions as for preparing the UV-cured film, yielding a primary cured film. Subsequently, heat curing was carried out by holding at 80°C for 24 hours, yielding a cured film obtained by hybrid curing. When polymer P or Q was used in the form of a solution, the applied film was dried at 80°C for 1 hour, after which a light-release PET film was attached and similar UV and heat curing was carried out.

[0174] (Preparation of EB-cured film) Composition F was uniformly coated onto a 100 μm-thick PET film using a bar coater to achieve a dry thickness of 20 μm. Subsequently, under a nitrogen atmosphere, the film was irradiated with an electron beam (EB) at an acceleration voltage of 110 kV and an electron dose of 30 kGy (electron beam irradiator EC250 / 15 / 180L manufactured by Iwasaki Electric Co., Ltd.) to obtain an EB-cured film. When polymer P or Q was used in the form of a solution, the film was dried at 80°C for 1 hour after application, and then a light-release PET film was attached and EB irradiation was carried out under the same conditions.

[0175]

[0176] The polymerizable composition of the present disclosure contains structural units of N-substituted (meth)acrylamide E or E, and has high transparency and high curability against active energy rays such as UV or EB. In addition, a wide variety of curing methods, such as thermal curing and hybrid curing, can be suitably used, and it has been confirmed that, regardless of the curing method, polymerizable compositions containing the compounds and the like have high resistance to cure shrinkage, and the resulting cured films have excellent flex resistance.

[0177] Examples 24 to 33 and Comparative Examples 7 to 9 (Ink Preparation and Evaluation) N-substituted (meth)acrylamide E, polymerizable composition F, monofunctional monomer, polyfunctional compound, additive H, and initiator D were weighed out in the mass ratios shown in Table 4, and the mixture was stirred at 35°C for 1 hour to mix uniformly to prepare inks. The resulting inks were evaluated for viscosity, surface drying properties, water resistance, pigment dispersibility, transparency, ejection stability, and print clarity using the following methods. The evaluation results are shown in Table 4.

[0178] (Ink Viscosity Measurement) In accordance with JIS K 5600-2-3, the viscosity of the ink was measured at 25°C using a cone-plate viscometer (RE550 viscometer manufactured by Toki Sangyo Co., Ltd.), and the viscosity was evaluated according to the following criteria: ◎: 5 ​​to less than 100 mPa·s ○: 100 to less than 1,000 mPa·s ×: 1,000 mPa·s or more

[0179] (Evaluation of ink surface drying properties) Using a bar coater, a coating was created on a 100 μm thick PET film so that the thickness after curing would be 10 μm. Using a UV-LED lamp (wavelength 395 nm), the cumulative light intensity was 200 mJ / cm 2 The coating film was irradiated with UV light under the conditions of 1. The resulting print was left standing for 5 minutes in an environment of room temperature 23°C and relative humidity 50%, and then a sheet of wood-free paper was placed on the printed surface and the print was dried at 1 kg / cm 2 A load of 0.05 mm was applied for 1 minute, and the transfer of the ink to the high-quality paper was confirmed, and the surface dryness was evaluated according to the following criteria: ◎: The ink was dry and there was no transfer to the paper at all. ○: The ink was dry and there was a slight transfer to the paper. △: The ink was almost dry and there was some transfer to the paper. ×: The ink was barely dry and there was a lot of transfer to the paper.

[0180] (Evaluation of ink water resistance) A print was prepared in the same manner as for the surface drying evaluation, and in accordance with JIS L 0823, a Gakushin-type fastness tester (NR-100 manufactured by Daiei Scientific Instruments Manufacturing Co., Ltd.) was used to rub the surface of the print 50 times with a bleached cloth soaked in five drops of water while applying a load of 200 g. The degree of ink peeling from the PET film was then visually observed, and water resistance was evaluated according to the following criteria: ◎: No ink peeled off even after 50 rubs. ○: Almost no ink peeled off even after 40 to 49 rubs. △: Approximately half of the ink peeled off after 10 to 39 rubs. ×: Almost all of the ink peeled off after 1 to 9 rubs.

[0181] (Evaluation of pigment dispersibility in ink) After leaving the pigment-containing ink to stand at room temperature for two months, it was visually observed for pigment aggregation and precipitation, and the transparency was evaluated according to the following criteria: ⊚: No pigment aggregation or precipitation was observed at all. ◯: Slight pigment precipitation was observed. △: Pigment aggregation or precipitation was clearly observed. ×: Pigment aggregation or precipitation was clearly observed immediately after preparation.

[0182] (Evaluation of ink transparency) Pigment-free ink was left to stand in a dark place at room temperature for 24 hours, and then the transparency of the ink was visually observed and evaluated according to the following criteria: ◎: No layer separation or cloudiness of the liquid was observed. ○: Slight layer separation or cloudiness was observed. △: Layer separation or cloudiness was clearly observed. ×: Layer separation or cloudiness was clearly observed immediately after preparation.

[0183] (Evaluation of ink ejection stability) Ink was filled into a jig equipped with a temperature-adjustable inkjet head (Toshiba Tec Corporation CA4, 318 nozzles). The temperature of the head was adjusted so that the ink viscosity during ejection was 9 to 10 mPa·s, and the ink was ejected continuously for 60 minutes. The number of nozzles that became unable to eject (nozzle loss) was counted, and the ejection stability was evaluated according to the following criteria: ◎: The number of nozzle losses was 2 or less. ○: The number of nozzle losses was 3 to 5. △: The number of nozzle losses was 6 to 10. ×: The number of nozzle losses was 11 or more.

[0184] (Evaluation of print clarity of printed matter) The ink containing the pigment was filled into a commercially available inkjet printer (LuxelJet UV350GTW manufactured by Fujifilm Corporation) and printed on coated paper. The print clarity of the obtained print was visually observed and evaluated according to the following criteria. ⊚: No ink bleeding was observed at all and the image was clear. ◯: Almost no ink bleeding was observed and the image was good. Δ: Some ink bleeding was observed. ×: Significant ink bleeding was observed.

[0185]

[0186] As is clear from the results in Table 4, the inks of the examples contain structural units derived from N-substituted (meth)acrylamide (the compound itself, the polymerizable composition, and the portion carried over from the polymerized product). This structural unit is formed by a cyclic substituent and a (meth)acrylamide group being linked to a chain organic group (R 2), and the amphiphilicity of the compound provided excellent dispersibility of the pigment incorporated in the ink, and the transparency as a clear ink was also good. Furthermore, by containing this structural unit, the obtained printed matter also had excellent surface drying properties and water resistance. In addition, a uniform inkjet ink was obtained, and the ejection stability and print clarity during printing were also high. On the other hand, the ink of the comparative example showed poor evaluation results in any of viscosity, transparency, pigment dispersibility, curing properties, surface drying properties, water resistance, and ejection stability, and the print clarity of the obtained printed matter was not satisfactory.

[0187] Examples 34 to 41 and Comparative Examples 10 to 12 (Evaluation of Inks for Three-Dimensional Modeling) (Preparation of Inks for Three-Dimensional Modeling) N-substituted (meth)acrylamide E, polymerizable composition F or G, polymer P or Q, monofunctional monomer, polyfunctional compound, and initiator D were weighed out in the mass ratios shown in Table 5, and the mixture was stirred at 35°C for 1 hour to mix uniformly to prepare inks for three-dimensional modeling. The resulting inks for three-dimensional modeling were evaluated for curability, cure shrinkage resistance, strength, water resistance, impact resistance, and modeling accuracy using the following methods. The evaluation results are shown in Table 5.

[0188] (Evaluation of the curing properties of ink for 3D modeling) Light source wavelength 365 nm, illuminance 5 mW / cm 2 The curing property was evaluated in the same manner as in the above UV curing property evaluation, except that the UV-LED lamp used was changed to 1.

[0189] (Evaluation of cure shrinkage resistance of ink for three-dimensional modeling) In accordance with JIS K 5600-2-4, the cure shrinkage rate was calculated from the modeled object before and after curing, and the cure shrinkage resistance was evaluated according to the following criteria. The following formula was used to calculate the cure shrinkage rate: Cure shrinkage rate (%) = ((specific gravity after curing) - (specific gravity before curing)) / (specific gravity after curing) x 100% ◎: Less than 5% 〇: 5% or more but less than 6% △: 6% or more but less than 8% ×: 8% or more

[0190] (Strength Evaluation of Three-Dimensional Model) A No. 2 dumbbell-shaped spacer (1 mm thick) conforming to JIS K 6251 was placed on a 75 μm thick heavy-release PET film (Toyobo Co., Ltd., Polyester Film E7001), and the spacer was filled with ink for three-dimensional modeling. A 50 μm thick light-release PET film (Toyobo Co., Ltd., Polyester Film E7002) was placed on top of the spacer filled with the ink for three-dimensional modeling. Next, a UV irradiator (ITEC System Co., Ltd., Tabletop Batch-Type UV-LED Curing Device "MUVBA-0.3x0.3x0.5" was used to irradiate the three-dimensional model at 365 nm and an illuminance of 5 mW / cm. 2 , cumulative light intensity 5,000mJ / cm 2 UV irradiation was carried out on both sides under the above conditions to obtain a No. 2 dumbbell-shaped object. In accordance with JIS K 7161, a bench-top precision universal testing machine (Autograph AGS-X manufactured by Shimadzu Corporation) was used to measure the tensile strength at 25°C, with a tensile speed of 10 mm / min and a chuck distance of 50 mm, and the strength was evaluated according to the following criteria: ◎: 40 MPa or more ○: 30 MPa to less than 40 MPa △: 20 MPa to less than 30 MPa ×: Less than 20 MPa

[0191] (Evaluation of Water Resistance of Ink for Three-Dimensional Modeling) A 1g sample was cut from the model and placed in a thermo-hygrostat at a temperature of 85°C and a relative humidity of 95%. After leaving it for 48 hours, the weight was measured again and the water resistance was evaluated according to the following criteria. The water absorption rate was calculated using the following formula: Water absorption rate (%) = (weight after water absorption - weight before water absorption) / weight before water absorption x 100% ◎: Less than 1.0% ○: 1.0% to less than 2.0% △: 2.0% to less than 3.0% ×: 3.0% or more

[0192] (Evaluation of impact resistance of 3D objects) Objects were produced in the same manner as in the strength evaluation of 3D objects, except that spacers with a thickness of 4 mm and an internal dimension of 10 mm x 80 mm were used. The resulting objects were cured using a tabletop batch-type UV-LED curing device (MUVBA-0.3 x 0.3 x 0.5, wavelength 405 nm, manufactured by ITEC System Co., Ltd.) at a UV irradiance (UV-V) of 50 mW / cm. 2 , cumulative light intensity 5,000mJ / cm 2The specimens were post-cured under the conditions above to allow them to fully cure. Then, in accordance with JIS K 7110, the Izod impact strength (with notch) was measured using an Izod-Charpy impact tester (manufactured by Yasuda Seiki Seisakusho Co., Ltd., Model No. 195-R), and the impact resistance was evaluated according to the following criteria: ◎: 40 J / m or more ○: 30 J / m to less than 40 J / m △: 20 J / m to less than 30 J / m ×: Less than 20 J / m

[0193] (Evaluation of the modeling accuracy of three-dimensional objects) A spacer with a thickness of 10 mm and an internal dimension of 10 mm x 10 mm was filled with ink for three-dimensional modeling. The filled material was kept at 60°C for 30 seconds to smooth the surface, and then a UV irradiator (a tabletop batch-type UV-LED curing device "MUVBA-0.3x0.3x0.5" manufactured by Eye Graphics Co., Ltd.) was used to cure the ink at 365 nm with an illuminance of 5 mW / cm. 2 , cumulative light intensity 100mJ / cm 2 UV irradiation was performed on both sides under the above conditions to obtain a molded object. The same procedure was repeated 10 times to stack the molded objects, obtaining a three-dimensional molded object measuring 10 mm x 10 mm x 10 mm. The dimensions and appearance of the obtained three-dimensional molded object were observed, and the molding accuracy was evaluated according to the following criteria. The evaluation results are shown in Table 5. ◎: Height less than 10 mm ± 0.1 mm, and no unevenness on the side surface. ○: Height 10 mm ± 0.1 mm or more but less than ± 0.2 mm, or slight unevenness on the side surface. △: Height 10 mm ± 0.2 mm or more but less than ± 0.3 mm, or slight unevenness on the side surface. ×: Height 10 mm ± 0.3 mm or more, or obvious unevenness on the side surface.

[0194]

[0195] As is clear from the results in Table 5, the inks for three-dimensional modeling of the examples contained structural units derived from N-substituted (meth)acrylamide, and therefore exhibited high curing properties. Furthermore, the resulting models were excellent in water resistance, strength, flexibility, and impact resistance. Furthermore, due to their high resistance to curing shrinkage, they also exhibited excellent modeling precision. On the other hand, the inks of the comparative examples exhibited poor curing properties, strength, water resistance, impact resistance, and resistance to curing shrinkage, and the modeling precision of the resulting models was unsatisfactory.

[0196] Examples 42 to 50 and Comparative Examples 13 to 15 (Evaluation of Coating Ink Agents) N-substituted (meth)acrylamide E, polymerizable composition F or G, polymer P or Q, monofunctional monomer, polyfunctional compound, and initiator D were weighed out in the mass ratios shown in Table 6, and the mixture was stirred at 35°C for 1 hour to mix uniformly. The resulting coating agents were evaluated for wettability to the substrate, appearance of the coating film, surface hardness, and moldability (decorativeness) using the following methods. The results are shown in Table 6.

[0197] (Evaluation of Wetting Ability of Coating Agent to Substrate) Using a bar coater, the coating agent was applied to four types of substrate: PET, PVC, ABS, or aluminum plate. The degree of cissing of the coating agent during application was visually observed, and the wettability to the substrate was evaluated according to the following criteria: ◎: No cissing, uniform coating film. ○: Very little cissing, but a fairly uniform coating film. △: Some cissing, but a fairly uniform coating film overall. ×: Much cissing, non-uniform coating film.

[0198] (Appearance evaluation of coating film) Using a bar coater, the coating agent was applied to a 100 μm-thick PET film so that the film thickness after drying would be 5 μm. A UV irradiator (manufactured by Eye Graphics, product name "ECS-4011GX", equipped with Eye Graphics metal halide lamp M04-L41) was used, with the lamp height adjusted to 200 mm and the conveyor speed adjusted to 540 cm / min, and the UV irradiance was 700 mW / cm. 2 , cumulative light intensity 1,000mJ / cm 2 UV irradiation was carried out under the following conditions. When a solvent was used, the coating was dried at 80°C for 3 minutes after application before UV irradiation. The obtained coating film was visually inspected for transparency and surface smoothness. Next, the surface of the coating film was touched with a silicone rubber stopper, and the stickiness (tackiness) of the coating film surface was evaluated according to the following criteria: ◎: A smooth and transparent film was obtained, with no stickiness at all. ○: A smooth film with partial cloudiness was obtained, and there was some stickiness. △: A film with irregularities and partial cloudiness was obtained, and marks were left on the surface when touched. ×: An uneven and cloudy film was obtained, and the rubber stopper stuck to the surface.

[0199] (Evaluation of Surface Hardness of Coating Film) A coating film was prepared in the same manner as in the evaluation of the appearance of the coating film, and the surface hardness was evaluated according to the scratch hardness (pencil method) specified in JIS K 5600-5-4 using the following criteria: ◎: 2H or more ○: HB to H △: 3B to B ×: 4B or less

[0200] (Evaluation of coating film moldability) The coating agent was applied to a 100 μm thick polycarbonate film (FE-2000, manufactured by Mitsubishi Gas Chemical Company, Inc.) using a bar coater so that the film thickness after drying would be 5 μm. Next, a UV irradiator (manufactured by Eye Graphics, product name "ECS-4011GX," equipped with Eye Graphics' metal halide lamp "M04-L41") was used to apply the coating agent to the film at a UV irradiance of 200 mW / cm. 2 , cumulative light intensity 1,000mJ / cm 2 A decorative film was obtained by UV irradiation under the conditions. This decorative film was heated and molded at 130°C using a pressure molding machine SDF400 (Sodick Co., Ltd.) and allowed to cool to 25°C. After that, the state of the decorative layer of the molded product was visually inspected to evaluate moldability. ◎: No cracks were observed, and the surface had high transparency. ○: No cracks were observed, but the decorative layer had uneven thickness and partial reduction in transparency. △: Cracks and slight cracks were observed, and partial thickness unevenness and partial reduction in transparency were observed. ×: Numerous cracks were observed, and thickness unevenness and partial reduction in transparency were noted.

[0201]

[0202] As is clear from the results in Table 6, the coating agents of the examples contain structural units derived from N-substituted (meth)acrylamides, and therefore have excellent wettability with various substrates, and were able to form transparent and smooth coating films. Furthermore, it was confirmed that the tackiness disappeared quickly after curing, and the resulting coating films had high surface hardness and could be easily molded. On the other hand, the coating agents of the comparative examples had poor physical properties, and it was not possible to obtain coating films with good appearance.

[0203] Examples 51 to 59 and Comparative Examples 16 to 18 (Evaluation of Pressure-Sensitive Adhesives) (Preparation of Pressure-Sensitive Adhesives) N-substituted (meth)acrylamide E, polymerizable composition F or G, polymer P or Q, monofunctional monomer, polyfunctional compound, additive H, and initiator D were weighed out in the mass ratios shown in Table 7, and the mixture was stirred at 35°C for 1 hour to mix uniformly to prepare pressure-sensitive adhesives. The resulting pressure-sensitive adhesives were evaluated for curability, transparency, adhesion to substrates, step-following ability, and stain resistance using the following methods.

[0204] (Evaluation of adhesive curing properties) A ​​1 mm thick spacer with an internal dimension of 60 mm × 100 mm was placed on a 75 μm thick heavy-release PET film (Toyobo Co., Ltd., polyester film E7001), the spacer was filled with adhesive, and a 50 μm thick light-release PET film (Toyobo Co., Ltd., polyester film E7002) was placed on top of it. Next, a UV-LED lamp (wavelength 385 nm) was used to illuminate the film with an output of 100 mW / cm. 2 , cumulative light intensity 3,000mJ / cm 2 The adhesive was cured by UV irradiation under the conditions shown above to obtain an adhesive layer. The obtained adhesive layer was touched with a finger and the curability of the adhesive layer was evaluated according to the following criteria: ∘: A cured product that could maintain its shape was obtained, and no liquid uncured product adhered to the finger. Δ: A cured product that could maintain its shape was obtained, and liquid uncured product adhered to the finger. ×: Curing was insufficient, and no cured product that could maintain its shape was obtained.

[0205] (Transparency evaluation of adhesive layer) An adhesive layer was formed on a glass substrate under conditions of a temperature of 23°C and a relative humidity of 50% in the same manner as above to prepare an adhesive sheet. The total light transmittance of the adhesive sheet was measured using a haze meter (NDH-2000, manufactured by Nippon Denshoku Industries Co., Ltd.) in accordance with JIS K 7105, and the transparency was evaluated according to the following criteria: ◎: 90% or more ○: 85 to less than 90% △: 50 to less than 85% ×: less than 50%

[0206] (Adhesion evaluation of adhesive layer) The adhesive was applied to the substrate and laminated with a light-release PET separator (silicone coated) using a tabletop roll laminator (Royal Sovereign RSL-382S) to prevent air bubbles from forming, so that the adhesive layer was 5 μm thick. Next, ultraviolet light was irradiated (device: Eye Graphics inverter conveyor device ECS-4011GX, metal halide lamp: Eye Graphics M04-L41, ultraviolet irradiance: 700 mW / cm). 2 , Accumulated light intensity: 5,000mJ / cm 2 ) to obtain a pressure-sensitive adhesive sheet consisting of a pressure-sensitive adhesive layer and a substrate. Using the obtained pressure-sensitive adhesive sheet, a cross-cut method was carried out in accordance with JIS K 5600-5-6, and the number of squares remaining on the substrate was counted and the adhesion to the substrate was evaluated according to the following criteria: ◎: 100 squares 〇: 95-99 squares △: 70-94 squares ×: 0-69 squares

[0207] (Bump-Conforming Ability) A pressure-sensitive adhesive sheet was prepared under conditions of a temperature of 23°C and a relative humidity of 50% using the same procedure as for evaluating the adhesion of the pressure-sensitive adhesive layer, and an 8 cm x 8 cm test piece was cut out. A polyester (PEs) film piece (5 cm x 5 cm x 50 μm) was placed on a glass plate (10 cm x 10 cm x 2 mm), and the test piece was adhered to the top of the sheet while applying a load with a 2 kg roller. The resulting laminate was visually inspected for adhesion around the polyester, and the bump-conforming ability was evaluated according to the following criteria: ⊚: No lifting or bubbles around the PEs film piece. ◯: No lifting around the PEs film piece, but several bubbles were observed. △: Lifting of less than 2 cm was observed around the PEs film piece, and numerous or large bubbles were observed. ×: Lifting of 2 cm or more was observed around the PEs film piece.

[0208] (Evaluation of Stain Resistance of Pressure-Sensitive Adhesive Layer) Pressure-sensitive adhesive sheets were prepared using the same procedure as in the evaluation of adhesive layer adhesion under conditions of a temperature of 23°C and a relative humidity of 50%, and then left to stand at 80°C for 24 hours. The pressure-sensitive adhesive layer was then peeled off, and the surface of the substrate film was visually inspected for staining (adhesive residue), and the stain resistance was evaluated according to the following criteria: ◎: No adhesive residue was found. ○: A small amount of adhesive residue was found. △: Adhesive residue was found on about half of the surface. ×: Adhesive residue was found on most of the surface.

[0209]

[0210] As is clear from the results in Table 7, the adhesives of the examples contained structural units derived from N-substituted (meth)acrylamide, and therefore had high curability. Furthermore, the resulting adhesive layers were transparent and had excellent adhesion to various substrates, as well as high stain resistance and unevenness conformability. On the other hand, the adhesives of the comparative examples were poor in any of curability, transparency, adhesion, pressure-sensitive adhesiveness, unevenness conformability, and stain resistance, and did not satisfy the adhesive properties.

[0211] Examples 60 to 67 and Comparative Examples 19 and 20 (Evaluation of Adhesives) (Preparation of Adhesives) N-substituted (meth)acrylamide E, polymerizable composition F or G, polymer P or Q, monofunctional monomer, polyfunctional compound, and initiator D were weighed out in the mass ratios shown in Table 8, and the mixture was stirred at 35°C for 1 hour to mix uniformly to prepare adhesives. The resulting adhesives were evaluated for curability, adhesion, impact resistance, moist heat resistance, and water resistance using the following methods. The evaluation results are shown in Table 8.

[0212] (Evaluation of adhesive curing properties) Using a bar coater, the adhesive was applied to a PET film to a thickness of 20 μm, and a light-release film was placed on top of it. Then, using a UV-LED lamp (wavelength 405 nm), an output of 50 mW / cm was applied. 2 The adhesive was cured by UV irradiation under the conditions of , and an adhesive layer was obtained. The adhesive layer obtained was touched with a finger, and the cumulative amount of light required until the stickiness (tack) of the adhesive layer disappeared was calculated and evaluated according to the following criteria: ⊚: 500 mJ / cm 2 Tackiness disappeared at less than 500-1,000mJ / cm. 2 Tackiness was lost at less than 1,000 to 5,000 mJ / cm. 2 Tackiness disappeared at less than 5,000 mJ / cm. 2 But Tuck stayed.

[0213] (Evaluation of adhesive strength) Two substrates measuring 100 mm in length, 25 mm in width, and 1 mm in thickness were bonded together with an adhesive, with the two substrates overlapping over an area of ​​12.5 mm in length and 25 mm in width. The thickness of the adhesive layer was 100 μm, and when the adhesive contained a solvent, it was dried so that the thickness after drying was 100 μm. Next, ultraviolet light was irradiated from the transparent or translucent substrate side (device: Inverter type conveyor device ECS-4011GX manufactured by Eye Graphics, metal halide lamp: M04-L41 manufactured by Eye Graphics, ultraviolet light irradiance: 700 mW / cm 2 , Accumulated light intensity: 5,000mJ / cm 2 ) to prepare test specimens. The tensile shear strength of the test specimens obtained was measured in accordance with JIS K 6850 using a tensile tester (Tensilon RTA-100 (manufactured by ORIENTEC) at a tensile speed of 10 mm / min, and the adhesive strength was evaluated according to the following criteria: ◎: 20 MPa or more ○: 15 to less than 20 MPa △: 10 to less than 15 MPa ×: Less than 10 MPa

[0214] (Evaluation of Impact Resistance of Adhesive) Impact peel adhesive strength was measured using an impact tester No. 511 (manufactured by Mize Testing Instruments Co., Ltd.) in accordance with JIS K 6855, and impact resistance was evaluated according to the following criteria: ⊚: 20 KJ / m 2 More than ○:15~20KJ / m 2 Less than △: 10-15KJ / m 2 Less than ×:10KJ / m 2 less than

[0215] (Evaluation of moist heat resistance of adhesive layer) An adhesive layer was prepared using the same procedure as in the evaluation of adhesive curing properties and allowed to fully cure. The adhesive layer was left to stand for 100 hours in an environment at a temperature of 85°C and a relative humidity of 85%. The adhesive layer was visually inspected for peeling and cloudiness, and the moist heat resistance was evaluated according to the following criteria: ◎: The adhesive layer showed no peeling, was transparent, and no bubbles were observed. ○: Slight cloudiness was observed in the adhesive layer. △: The adhesive layer showed slight cloudiness and peeling was observed at the edges. ×: The adhesive layer became cloudy and most of the adhesive layer had peeled off.

[0216] (Evaluation of water resistance of adhesive) Test pieces were prepared using the same procedure as for evaluating the adhesive strength of adhesives, and after immersion in 60°C warm water for 48 hours, the adhesion state of the substrate was visually observed and water resistance was evaluated according to the following criteria: ◎: No peeling at the interface between the adhesive layer and the substrate ○: Peeling occurred in part of the interface between the adhesive layer and the substrate △: Peeling occurred over a wide area at the interface between the adhesive layer and the substrate, and the substrate peeled off when gently pulled ×: The substrates peeled off from each other.

[0217]

[0218] As is clear from the results in Table 8, the adhesives of the Examples contain structural units derived from N-substituted (meth)acrylamide, and therefore have high curing properties, enabling strong adhesion between substrates of the same or different types. It was also confirmed that the adhesives have excellent moist heat resistance and water resistance, as well as high impact resistance. On the other hand, the adhesives of the Comparative Examples had poor curing properties or adhesion properties, and did not satisfy the adhesive characteristics. Furthermore, durability such as impact resistance, moist heat resistance, and water resistance was poor.

[0219] Examples 68 to 73 and Comparative Examples 21 and 22 (Evaluation of Photosensitive Resins) (Preparation of Photosensitive Resins) N-substituted (meth)acrylamide E, polymerizable composition F or G, monofunctional monomer, polyfunctional compound, and initiator D were weighed out in the mass ratios shown in Table 9 and mixed uniformly by stirring at 35°C for 1 hour. The resulting photosensitive resins were evaluated for curability, pattern formability, storage stability of the cured product, chemical resistance, and heat resistance using the following methods. The evaluation results are shown in Table 9.

[0220] (Evaluation of curing property of photosensitive resin) Using a spin coater, a photosensitive resin was applied to a glass substrate to a film thickness of 15 μm, and dried in an oven at 80° C. for 3 minutes. After that, the resin was exposed to a wavelength of 405 nm and an illuminance of 0.5 mW / cm. 2 , cumulative light intensity 90mJ / cm 2 The coating was photocured by irradiating it with ultraviolet light for 3 minutes under the above conditions. The surface of the resulting cured film was touched with a finger and its curability was evaluated according to the following criteria: ◎: Not sticky at all. ○: Slightly sticky, but no finger marks were left on the surface. △: Sticky, and finger marks were left on the surface. ×: Severe stickiness, and fingers stuck to the surface.

[0221] (Storage stability of cured photosensitive resin) A photosensitive resin was applied to a glass substrate to a thickness of 15 μm using a spin coater. After application, the resin was dried in an oven at 80° C. for 3 minutes. Thereafter, the resin was dried at a wavelength of 405 nm and an illuminance of 0.5 mW / cm. 2 , cumulative light intensity 1000mJ / cm 2 The coating was photocured by irradiating it with ultraviolet light under the above conditions to obtain a cured film. The obtained cured film was left to stand in a thermo-humidistat chamber at a temperature of 40°C and a relative humidity of 50% for 168 hours. The condition of the film surface was visually observed, and the storage stability was evaluated according to the following criteria: ◎: No bleed-out was observed. ○: Slight bleed-out was observed. △: Bleed-out was observed. ×: Severe bleed-out was observed.

[0222] (Pattern Formability of Photosensitive Resin) A negative photomask (pattern mask) was used to prepare a cured product in the same manner as in the evaluation of storage stability of cured photosensitive resin products. After curing, the negative photomask was removed, and the unexposed portions were removed using cyclopentanone. The shape of the obtained patterned cured product was visually observed, and the pattern formability was evaluated according to the following criteria: ⊚: No pattern distortion or chipping at the edges was observed. ◯: No pattern distortion, and slight chipping at the edges was observed. Δ: There was slight pattern distortion and chipping at the edges was observed. ×: There was pattern distortion and chipping at the edges was observed.

[0223] (Chemical Resistance of Photosensitive Resin) Using a spin coater, a photosensitive resin was applied to a silicon substrate to a thickness of 20 μm. A g-ray exposure device (PPS-8200p1, manufactured by Oak Manufacturing Co., Ltd.) was used to apply the resin to a silicon substrate at an exposure dose of 1000 mJ / cm. 2The photosensitive resin was exposed to light under the conditions specified above to obtain a cured film. The thickness of the resulting cured film was precisely measured and designated as the film thickness before immersion (T1). The film was then immersed in acetone at 25°C for 5 minutes and dried at 80°C for 3 minutes, after which the film thickness was measured again and designated as the film thickness after immersion (T2). The film thickness variation rate was calculated using the following formula to evaluate the chemical resistance of the photosensitive resin: Film Thickness Variation Rate (%) = (T1 - T2) / T1 x 100 ◎: Film thickness variation rate was 1% or less. ○: Film thickness variation rate was greater than 1% and less than 3%. △: Film thickness variation rate was greater than 3% and less than 5%. ×: Film thickness variation rate was greater than 5%.

[0224] (Heat resistance of photosensitive resin) A cured film of photosensitive resin was prepared using the same method as used to evaluate the storage stability of the cured photosensitive resin. A cured product was cut out from the obtained cured film and dried at 120°C and a reduced pressure of 10 hPa for 30 minutes. After drying, the sample was heated in a thermogravimetric analyzer from 40°C to 300°C at a heating rate of 10°C / min, and the temperature at which a 5% weight loss occurred was measured. Based on the obtained results, the heat resistance was evaluated according to the following criteria: ◎: Over 280°C ○: Over 250°C to 280°C or less △: Over 200°C to 250°C or less ×: 200°C or less

[0225]

[0226] As is clear from the results in Table 9, the photosensitive resins of the examples contained structural units derived from N-substituted (meth)acrylamide, and therefore had high curability. Furthermore, the obtained cured products exhibited excellent storage stability as well as excellent chemical resistance and heat resistance. Furthermore, they had high curability with light sources over a wide wavelength range, and the exposed areas were completely cured, while the unexposed areas were completely removed by washing, demonstrating excellent pattern formability. On the other hand, the photosensitive resins of the comparative examples had poor curability and pattern formability, and their storage stability, chemical resistance, and heat resistance after curing were all insufficient.

[0227] Examples 74 to 79 and Comparative Examples 23 and 24 (Evaluation of Sealant) N-substituted (meth)acrylamide E, polymerizable composition F, monofunctional monomer, polyfunctional compound, and initiator D were weighed out in the mass ratios shown in Table 10, and the mixture was stirred at 35°C for 1 hour to mix uniformly. The resulting sealants were evaluated for outgassing resistance, thermal cycling resistance, moisture resistance, and corrosion resistance by the following methods. The evaluation results are shown in Table 10.

[0228] (Evaluation of outgassing resistance of cured encapsulant) 1 g of encapsulant was left standing in a thermostatic chamber (temperature 100°C) in a dry nitrogen gas stream for 24 hours, the weight of the encapsulant was measured before and after, and the outgassing resistance was evaluated according to the following criteria. The outgassing generation rate was calculated using the following formula: Outgassing generation rate (%) = (weight after test - weight before test) / weight before test x 100% ◎: Less than 0.1% ○: 0.1% to less than 0.3% △: 0.3% to less than 1.0% ×: 1.0% or more

[0229] (Evaluation of resistance to thermal cycles) 1 g of the encapsulant was left overnight in an environment at a temperature of 23°C and a relative humidity of 50%, and then a cycle of 30 minutes at -40°C and 30 minutes at 100°C (heating rate: 10°C / min) was repeated 100 times. The state of the encapsulant after each cycle was visually observed, and the resistance to thermal cycles was evaluated according to the following criteria: ◎: No change was observed. ○: Slight bubbles were observed. △: Bubbles and cracks were observed in some areas. ×: Bubbles and cracks were observed throughout the entire surface, resulting in a decrease in transparency.

[0230] (Evaluation of Moisture Resistance of Sealant) A silicon 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 5 mm wide x 80 μm thick) was placed in the center of the spacer, after which the sealant was poured in. Next, ultraviolet light was irradiated (apparatus: Eye Graphics inverter type conveyor device ECS-4011GX, metal halide lamp: Eye Graphics M04-L41, ultraviolet light intensity: 700 mW / cm 2 , Accumulated light intensity: 1,000mJ / cm 2) to obtain an encapsulant with copper foil enclosed inside. The encapsulant was left to stand in an environment at a temperature of 40°C and a relative humidity of 85% for 500 hours, after which discoloration was visually observed and the moisture resistance of the encapsulant was evaluated according to the following criteria: ◎: No change was observed. ○: Very slight clouding was observed. △: Partial clouding was observed. ×: Overall clouding was observed.

[0231] (Evaluation of Corrosion Resistance) After the moisture resistance test, the copper foil was removed from the encapsulant and visually observed, and the corrosion resistance was evaluated according to the following criteria: ⊚: no corrosion ◯: slight corrosion Δ: slight corrosion ×: significant corrosion

[0232]

[0233] As is clear from the results in Table 10, the sealants of the Examples contained structural units derived from N-substituted (meth)acrylamide, and therefore had high outgassing resistance, resistance to thermal cycling, moisture resistance, and corrosion resistance, and were suitable for use as sealants. On the other hand, the sealants of the Comparative Examples had poor properties in any of these areas, and were unable to satisfy the sealant properties.

[0234] Examples 80 to 85 and Comparative Examples 25 and 26 (Evaluation of Dental Materials) (Preparation of Dental Materials) N-substituted (meth)acrylamide E, polymerizable composition F or G, monofunctional monomer, polyfunctional compound, and initiator D were weighed out in the mass ratios shown in Table 9, and the mixture was stirred at 35°C for 1 hour to mix uniformly. The resulting dental materials were evaluated for curability, solubility, surface smoothness, hardness, adhesive strength, and storage stability by the following methods. The evaluation results are shown in Table 11.

[0235] (Evaluation of hardening properties of dental materials) Dental materials were filled into a polytetrafluoroethylene mold (20 mm × 20 mm × 10 mm) with a hole of 6 mm diameter in the center, and pressed with a polypropylene film. A UV-LED spotlight (365 nm) was used to illuminate the material at an illuminance of 700 mW / cm. 2 The cured product was irradiated with UV light for 30 seconds under the conditions. The polypropylene film was peeled off, and the cured product was touched with a finger to evaluate the curability of the cured product according to the following criteria: ◎: Not sticky at all. ○: Slightly sticky, but no marks left on the surface. △: Sticky, and marks left on the surface. ×: Severe stickiness, with a rubber stopper sticking to the surface.

[0236] (Evaluation of Dispersibility of Dental Material) The dispersed state of the dental material was visually observed, and the dispersibility of the dental material was evaluated according to the following criteria: ◎: Uniform and transparent. ○: Uniform and semi-transparent. △: Cloudy, making it difficult to judge the uniformity. ×: Not completely mixed.

[0237] (Surface Smoothness of Cured Dental Material) The surface of the cured dental material prepared in the same manner as in the evaluation of the hardenability of the dental material was visually observed, and the surface condition was evaluated according to the following criteria: ◎: The surface is smooth and glossy. ○: Slight irregularities are observed on the surface. △: Irregularities or granularities are observed on the surface. ×: The surface is rough.

[0238] (Hardness evaluation of cured dental materials) The surfaces of the cured dental materials prepared in the same manner as in the evaluation of the hardenability of the dental materials were polished by buffing, and the Knoop hardness was measured using a Matsuzawa Seiki microhardness tester at 23°C under a load of 10 g for 20 seconds, and the hardness was evaluated according to the following criteria: ◎: Knoop hardness of 200 KHN or more (equivalent to permanent tooth enamel). ○: Knoop hardness of 70 KHN or more but less than 200 KHN (equivalent to dentin). △: Knoop hardness less than 70 KHN. ×: Measurement was not possible because the material did not harden.

[0239] (Evaluation of Adhesion Strength of Dental Materials) A simulated cavity was prepared using the method described in JP 2010-208964 A, except for using #1000 waterproof abrasive paper. The simulated cavity was then filled with the dental material and cured by 60 seconds of irradiation with a dental light irradiator (TP). An 8 mm diameter stainless steel attachment was pressed against the adhesive surface onto which a drop of synthetic instant adhesive ("Aron Alpha" (registered trademark) manufactured by Toagosei Co., Ltd.) had been applied, to prepare an adhesion test specimen. After immersion in 37°C water for 24 hours, the tensile adhesion strength of the adhesion test specimen was measured using an Instron universal testing machine (crosshead speed: 2 mm / min). The adhesion strength between the dental material and dentin was evaluated according to the following criteria. The tensile adhesion strength values ​​are the average of five test specimens: ⊚: Adhesion strength of 20 MPa or more; ∘: Adhesion strength of 15 to less than 20 MPa; Δ: Adhesion strength of 7 to less than 15 MPa; ×: Adhesion strength of less than 7 MPa.

[0240] (Storage Stability of Dental Material) The dental material was placed in a light-shielding screw tube, the lid was closed, and stored at 40°C for one month. The dissolution or dispersion state of the dental material after storage was visually confirmed, and the storage stability was evaluated. ◎: No change in dispersion state. ○: Layer separation or slight floating matter was observed. △: Layer separation or floating matter was observed. ×: Complete layer separation occurred, or the material became cloudy.

[0241]

[0242] As is clear from the results in Table 11, the dental materials of the Examples, which contain structural units derived from N-substituted (meth)acrylamides, exhibited excellent curability and solubility (dispersibility) and also had high storage stability. Furthermore, the resulting cured products had high adhesive strength as well as high surface smoothness and hardness. On the other hand, the dental materials of the Comparative Examples were poor in any of curability, strength, solubility (dispersibility), surface smoothness, hardness, adhesive strength, and storage stability, and the resulting cured products were not satisfactory as dental materials.

[0243] The present disclosure includes the following: (1) An N-substituted (meth)acrylamide represented by general formula [1]. In the general formula [1], R 1 is a hydrogen atom or a methyl group, and L 1 is an organic group having a cyclic structure A ring represented by the general formula [2], and L 2 is a hydrogen atom, an organic group having a cyclic structure A ring represented by the general formula [2], or an organic group represented by the general formula [3], and R 2 is an alkylene group having 1 to 18 carbon atoms, an alkyleneoxyalkylene group having 2 to 36 carbon atoms, or a poly(alkyleneoxy)alkylene group having 2 to 36 carbon atoms; the carbon atom number A ring is a saturated or unsaturated aliphatic hydrocarbon group having 5 to 18 carbon atoms or a saturated or unsaturated heterocycle having 2 to 18 carbon atoms and 1 to 12 oxygen atoms; the carbon atom number R 3is an alkyl group having 1 to 18 carbon atoms, an alkyleneoxyalkyl group having 2 to 36 carbon atoms, or a poly(alkyleneoxy)alkyl group having 2 to 36 carbon atoms. (2) The N-substituted (meth)acrylamide according to (1) above, which contains at least one substituted atom or substituent in the structure of general formula [2]. (3) The N-substituted (meth)acrylamide according to (1) or (2) above, in which the substituted atom is one or more atoms selected from boron, silicon, nitrogen, phosphorus, oxygen, sulfur, fluorine, chlorine, bromine, and iodine. (4) The substituents are alkyl groups (having 1 to 18 carbon atoms), alkenyl groups (having 1 to 18 carbon atoms), hydroxyl groups, hydroxyalkyl groups (having 1 to 18 carbon atoms), hydroxyalkenyl groups (having 1 to 18 carbon atoms), amino groups, N-alkyl (having 1 to 18 carbon atoms) amino groups, N,N-dialkyl (having 1 to 18 carbon atoms) amino groups, N-alkenyl (having 1 to 18 carbon atoms) amino groups, N,N-dialkenyl (having 1 to 18 carbon atoms) amino groups, N,N-alkyl (having 1 to 18 carbon atoms) amino groups, (18) The N-substituted (meth)acrylamide according to any one of (1) to (3), wherein the N-substituted (meth)acrylamide is one or more substituents selected from the group consisting of an alkenyl (1 to 18 carbon atoms) amino group, a thiol group, an alkyl (1 to 18 carbon atoms) thiol group, an alkenyl (1 to 18 carbon atoms) thiol group, an alkyl (1 to 18 carbon atoms) halogen group, an alkenyl (1 to 18 carbon atoms) halogen group, an alkoxy group (1 to 18 carbon atoms), an ester group, an amide group, and a urethane group. (5) The N-substituted (meth)acrylamide according to any one of (1) to (4), wherein the heteroatom is at least one or more atoms selected from the group consisting of a nitrogen atom, an oxygen atom, and a sulfur atom. (6) The N-substituted (meth)acrylamide according to any one of (1) to (4), wherein L in the general formula [1] 1 (7) The N-substituted (meth)acrylamide according to any one of (1) to (5), wherein the ring A is a monovalent cyclic hydrocarbon group having 5 to 18 carbon atoms, or a cyclic hydrocarbon group in which at least one of any hydrogen atoms of the cyclic hydrocarbon group has been substituted with a substituent. 2 is a hydrogen atom or a methyl group, and L 1 The general formula [2] is R 2(8) The N-substituted (meth)acrylamide according to any one of (1) to (6), wherein L in the general formula [1] is an alkylene group having 1 to 3 carbon atoms, and the ring A is a ring consisting of 5 to 6 atoms. 2 is a hydrogen atom or a methyl group, and L 1 R 2(9) The N-substituted (meth)acrylamide according to any one of (1) to (7), wherein R is an alkylene group having 1 to 3 carbon atoms, and the ring A is a 5- or 6-membered ring in which the carbon atoms forming the ring are substituted with one or more selected from O, S, and NH. (10) The N-substituted (meth)acrylamide according to any one of (1) to (8), wherein the ring A further has one or more groups selected from a (meth)acrylate group, a (meth)acrylamide group, a vinyl group, and an allyl group. (11) A polymer obtained by polymerizing the N-substituted (meth)acrylamide according to any one of (1) to (9) with actinic energy rays and / or heat. (12) An ink containing the N-substituted (meth)acrylamide according to any one of (1) to (9) and / or the polymer according to (10). (13) An ink for three-dimensional modeling containing the N-substituted (meth)acrylamide according to any one of (1) to (9) and / or the polymer according to (10). (13) A coating agent containing the N-substituted (meth)acrylamide according to any one of (1) to (9) above and / or the polymer according to (10) above. (14) A pressure-sensitive adhesive containing the N-substituted (meth)acrylamide according to any one of (1) to (9) above and / or the polymer according to (10) above. (15) An adhesive containing the N-substituted (meth)acrylamide according to any one of (1) to (9) above and / or the polymer according to (10) above. (16) A photosensitive resin containing the N-substituted (meth)acrylamide according to any one of (1) to (9) above and / or the polymer according to (10). (17) A sealant containing the N-substituted (meth)acrylamide according to any one of (1) to (9) above and / or the polymer according to (10). (18) A dental material containing the N-substituted (meth)acrylamide according to any one of (1) to (9) above and / or the polymer according to (10). (19) A coating composition containing the N-substituted (meth)acrylamide according to any one of (1) to (9) above and / or the polymer according to (10). (20) A decorative coating agent containing the N-substituted (meth)acrylamide according to any one of (1) to (9) above and / or the polymer according to (10).

[0244] As described above, the polymerizable composition of the present invention has high transparency and excellent curability due to the inclusion of a specific N-substituted (meth)acrylamide (E) and / or a polymer thereof. Compound E has a low odor and excellent compatibility with a wide range of solvents, from polar to non-polar, as well as with monomers and oligomers. It also exhibits excellent polymerizability and curability in response to heat or actinic radiation. By including such E, the polymerizable composition combines high transparency, excellent curability, and resistance to cure shrinkage, and the resulting cured product exhibits good strength and flex resistance. The polymerizable composition of the present invention and / or its polymer can be used in a wide range of fields, including industrial applications, medical applications, and household products, as inks, pressure-sensitive adhesives, adhesives, coating agents, photosensitive resins, sealants, dental materials, and the like that can be polymerized and cured by heat or actinic radiation.

Claims

1. A polymerizable composition containing an N-substituted (meth)acrylamide represented by the general formula [1]. (In general formula [1], R 1 is a hydrogen atom or a methyl group, and L 1 is an organic group having a cyclic structure A ring represented by the general formula [2], and L 2 is a hydrogen atom, an organic group having a cyclic structure A ring represented by general formula [2], or an organic group represented by general formula [3], and L 1 and L 2 When both of R have ring A, they may be the same or different, 2 is an alkylene group having 1 to 18 carbon atoms, an alkyleneoxyalkylene group having 2 to 36 carbon atoms, or a poly(alkyleneoxy)alkylene group having 2 to 36 carbon atoms, ring A is a saturated or unsaturated aliphatic hydrocarbon group having 5 to 18 carbon atoms, or a saturated or unsaturated heterocycle containing 2 to 18 carbon atoms and 1 to 12 oxygen atoms, R 3 is an alkyl group having 1 to 18 carbon atoms, an alkyleneoxyalkyl group having 2 to 36 carbon atoms, or a poly(alkyleneoxy)alkyl group having 2 to 36 carbon atoms.

2. R 2 , R 3 or at least one of the A rings has a substituent, and the substituent is an alkyl group, an alkenyl group, an ethylenically unsaturated group, or a group in which a hydrogen atom of an alkyl or alkenyl group is substituted with one or more of a hydroxy group, an alkoxy group having 1 to 18 carbon atoms, a poly(alkyleneoxy)alkyl group having 2 to 36 carbon atoms, an alkenyl group, or the ethylenically unsaturated group.

3. The polymerizable composition according to claim 1 or 2, which contains a thermal polymerization initiator and / or a photopolymerization initiator.

4. A polymer comprising the composition according to claim 1 or 2 or the polymerizable composition according to claim 3.

5. The curable composition according to claim 1 or 2, which contains a crosslinking agent.

6. An ink containing any one or more of the polymerizable composition according to claims 1 to 3, the polymerized material according to claim 4, and the curable composition according to claim 5.

7. An inkjet ink containing at least one of the polymerizable composition according to claims 1 to 3, the polymerized material according to claim 4, and the curable composition according to claim 5.

8. An ink for three-dimensional modeling, comprising at least one of the polymerizable composition according to claims 1 to 3, the polymer according to claim 4, and the curable composition according to claim 5.

9. A coating agent comprising at least one of the polymerizable composition according to claims 1 to 3, the polymerized product according to claim 4, and the curable composition according to claim 5.

10. A pressure-sensitive adhesive comprising at least one of the polymerizable composition according to claims 1 to 3, the polymer according to claim 4, and the curable composition according to claim 5.

11. An adhesive comprising at least one of the polymerizable composition according to claims 1 to 3, the polymerized product according to claim 4, and the curable composition according to claim 5.

12. [Rule 26 Supplement 12.09.2025] A photosensitive resin comprising one or more of the polymerizable compositions according to claims 1 to 3, the polymerized product according to claim 4, and the curable composition according to claim 5.

13. [Rule 26 Supplement 12.09.2025] A sealant containing one or more of the polymerizable compositions according to claims 1 to 3, the polymerized product according to claim 4, and the curable composition according to claim 5.

14. [Rule 26 Supplement 12.09.2025] A dental material comprising one or more of the polymerizable compositions according to claims 1 to 3, the polymerized product according to claim 4, and the hardenable composition according to claim 5.

15. [Rule 26 Supplement 12.09.2025] N-substituted (meth)acrylamides represented by the general formula [5] (In general formula [5], R 4 is a hydrogen atom or a methyl group, and L 3 is an organic group having a cyclic structure A ring represented by the general formula [6], and L 4 is a hydrogen atom, an organic group having a cyclic structure A ring represented by general formula [6], or an organic group represented by general formula [7], and L 3 and L 4 When both of them have ring A, they may be the same or different, and R 5 is an alkylene group having 1 to 18 carbon atoms, an alkyleneoxyalkylene group having 2 to 36 carbon atoms, or a poly(alkyleneoxy)alkylene group having 2 to 36 carbon atoms; ring A is a saturated or unsaturated aliphatic hydrocarbon group having 5 to 18 carbon atoms, or a saturated or unsaturated heterocycle containing 2 to 18 carbon atoms and 1 to 12 oxygen atoms; R 6 is an alkyl group having 1 to 18 carbon atoms, an alkyleneoxyalkyl group having 2 to 36 carbon atoms, or a poly(alkyleneoxy)alkyl group having 2 to 36 carbon atoms.

16. [Amendment under Rule 91 12.09.2025 ][Rule 26 12.09.2025]L 3 is a hydrogen atom or an organic group represented by the general formula [6], and L 4 is an organic group represented by the general formula [7], and R 5 is an alkylene group having 1 to 6 carbon atoms, and ring A is a 5- or 6-membered ring containing 3 to 6 carbon atoms and 0 to 2 oxygen atoms.

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