Photopolymerization initiator

Abstract

[Problem] The present invention addresses the problem of providing a photopolymerization initiator which is unlikely to be affected by oxygen inhibition, exhibits good photoinitiation properties even in the air, has high sensitivity to long wavelength light rays, and can suppress odors and bleeding out in an obtained cured product. [Solution] Provided is a photopolymerization initiator which has, in the molecule, one or more benzopheno groups and one or more hetero atom-containing saturated or unsaturated cyclic substituent groups having 5 or more ring-forming atoms. One or more carbon atoms in an aryl group in one or more benzopheno groups is bonded to one or more hetero atom-containing saturated or unsaturated cyclic substituent groups having 5 or more ring-forming atoms via a carboxylic acid ester group or a carboxylic acid amide group.

Description

[Technical Field]

[0001] The present disclosure relates to photopolymerization initiators. [Background technology]

[0002] Photocuring reactions using active energy rays such as visible light or ultraviolet (UV) light generate active species such as radicals by irradiating a curable composition containing a photopolymerization initiator with UV light, polymerizing compounds with unsaturated groups, and solidifying (curing) the liquid composition in a short period of time. These reactions are used in a wide range of fields, including paints and coatings, pressure-sensitive adhesives and adhesives, elastomer materials, inkjet inks, sealing materials and encapsulants, dental hygiene materials, and photosensitive materials. In particular, because they can be cured in any location or shape, they are increasingly being used in nail cosmetics such as gel nails and as materials for three-dimensional photopolymerization.

[0003] Photopolymerization initiators can be classified into intramolecular cleavage and hydrogen abstraction types based on the radical generation mechanism after absorbing light. The former generates radicals by intramolecular cleavage, while the latter generates radicals by abstracting hydrogen from a hydrogen donor. In the case of intramolecular cleavage, decomposition products derived from the initiator remain in the cured product, causing problems such as reduced durability of the cured product, odor generation, and coloring over time, as well as low safety. In the case of hydrogen abstraction, there are no decomposition products of the initiator, so it has attracted attention in recent years, and active research is being conducted on improving the efficiency of photopolymerization initiation and using it in combination with additives such as hydrogen donors, photosensitizers, and curing accelerators. Summary of the Invention [Problem to be solved by the invention]

[0004] An object of the present disclosure is to provide a hydrogen abstraction photopolymerization initiator that has high radical generation ability and high reactivity of generated radicals, is resistant to oxygen inhibition, is compatible with long wavelength (360 nm to 420 nm) light, has good compatibility with general-purpose monomers and oligomers, and has excellent yellowing resistance. [Means for solving the problem]

[0005] As a result of extensive research, the present inventors have discovered a photopolymerization initiator which has one or more benzopheno groups and a saturated or unsaturated five- or larger-membered cyclic substituent having one or more heteroatoms in the molecule, and in which one or more saturated or unsaturated five- or larger-membered cyclic substituents having a heteroatom are bonded to one or more carbon atoms of the aryl groups of at least one or more benzopheno groups via a carboxylic acid ester group or a carboxylic acid amide group, thereby solving the problem. [Effects of the Invention]

[0006] The photopolymerization initiator of the present disclosure has high initiation efficiency for long-wavelength light beams with wavelengths of 360 nm to 420 nm and short-wavelength light beams output from UV-LED light sources, such as those with wavelengths of 365 nm, 385 nm, 395 nm, and 405 nm. It is resistant to curing inhibition by oxygen even in an air atmosphere, and does not generate decomposition products during the photoinitiation reaction and photopolymerization reaction (curing), making it highly safe. Furthermore, the photopolymerization initiator has good compatibility with general-purpose monomers and oligomers, resulting in excellent transparency of curable compositions containing the initiator. The cured products obtained upon curing exhibit minimal odor, bleed-out, yellowing, or deterioration over time, making them highly durable and safe. The photopolymerization initiator of the present disclosure is suitable for use in a variety of applications that use active energy ray-curable compositions, such as ink compositions, pressure-sensitive adhesive compositions, adhesive compositions, coating compositions, sealant compositions, inkjet inks, inks for three-dimensional modeling, nail cosmetic compositions, dental material compositions, and photosensitive compositions. DETAILED DESCRIPTION OF THE INVENTION

[0007] Hereinafter, embodiments of the present disclosure will be described in detail, but the scope of the present invention is not limited to the embodiments described herein, and various modifications can be made without departing from the spirit of the present invention. Furthermore, when multiple upper and lower limit values ​​are specified for a specific parameter, any upper and lower limit values ​​can be combined to form a suitable numerical range.

[0008] One embodiment of the present disclosure is a photopolymerization initiator (A) having one or more benzopheno groups and a saturated or unsaturated 5- or larger-membered cyclic substituent having one or more heteroatoms in the molecule, and one or more saturated or unsaturated 5- or larger-membered cyclic substituents having heteroatoms bonded to one or more carbon atoms of the aryl groups of at least one or more benzopheno groups via a carboxylic acid ester group or a carboxylic acid amide group.

[0009] The photopolymerization initiator (A) has a saturated or unsaturated five- or greater-membered cyclic substituent (hereinafter also referred to as a heterocycle) containing one or more benzopheno groups and one or more heteroatoms in the molecule, and at least one heterocycle is linked to a carbon atom of the aryl group of the benzopheno group via a carboxylic acid ester group or a carboxylic acid amide group. The benzopheno group is a hydrogen-abstraction-type photopolymerization initiation functional group, and the heterocycle is a hydrogen donor. The inclusion of the benzopheno group and the heterocycle allows efficient intramolecular and / or intermolecular hydrogen abstraction in the photopolymerization initiator (A) upon exposure to active energy rays, resulting in sufficient photoinitiation efficiency without the addition of general-purpose hydrogen donors such as alcohols or amines. The inventors speculate that the reasons for this are as follows: 1) The heteroatoms have high electron density, and the surrounding hydrogen atoms are highly active, making them more susceptible to abstraction. 2) The hydrogen atoms bonded to the heteroatoms and / or the hydrogen atoms bonded to the carbon atoms adjacent to the heteroatoms are all hydrogen donor sources, and the cyclic structure provides a large number of highly active hydrogen atoms around the heteroatoms. 3) The heteroatoms can easily absorb peroxide radicals generated from oxygen, suppressing the influence of oxygen due to the presence of the heterocycle. Furthermore, the presence of a carboxylic acid ester group or a carboxylic acid amide group between the benzopheno group and the heterocycle has been confirmed to improve the compatibility between the hydrophobic benzopheno group and the hydrophilic heterocycle, further enhancing the photoinitiation effect.

[0010] One embodiment of the present disclosure is a photopolymerization initiator (A) having one or more ethylenically unsaturated groups in its molecule selected from one or more (meth)acrylamide groups, (meth)acrylate groups, vinyl groups, vinyl ether groups, alkyl vinyl ether groups, allyl groups, (meth)allyl ether groups, styryl groups, and maleimide groups. By containing the ethylenically unsaturated groups, the photopolymerization initiator (A) is fixed as a structural unit in the cured product via a covalent bond after the photopolymerization reaction, preventing bleed-out over time and improving the durability, yellowing resistance, moisture resistance, and other properties of the resulting cured product. When the photopolymerization initiator (A) has two or more ethylenically unsaturated groups, they may be the same or different. Furthermore, (meth)acrylamide groups, (meth)acrylate groups, and allyl groups are preferred because they have high curability and can be cured quickly even with long-wavelength or short-wavelength light sources.

[0011] One embodiment of the present disclosure is a photopolymerization initiator (A) in which the heteroatom-containing 5- or larger-membered cyclic substituent (heterocycle) is one or more groups selected from piperidine, pyrrolidine, piperazine, pyridine, morpholine, tetrahydrofuran, hydrofuran, crown ether, and tetrahydrothiopyran groups. These substituents are highly effective in suppressing oxygen inhibition, and photopolymerization initiators (A) containing these substituents are preferred because they can initiate polymerization initiation reactions efficiently even in air. Furthermore, it is more preferred to have a morpholine, tetrahydrofuran, or piperidine group, which are highly effective as hydrogen donor groups. These heterocycles can be used alone or in combination of two or more.

[0012] One embodiment of the present disclosure is a photopolymerization initiator (A) that further contains one or more groups selected from a urethane group, a urea group, an ester group, a thioester group, an amide group, and an imide group in the molecule. These groups contain a heteroatom, and the hydrogen atoms bonded to the heteroatom and / or the hydrogen atoms bonded to the carbon atom adjacent to the heteroatom are all hydrogen donors, improving the initiation efficiency of the photopolymerization initiator (A). At the same time, these groups have the effect of suppressing oxygen inhibition, improving curability even in air. Furthermore, from the perspective of ease of industrial introduction, the inclusion of a urethane group, a urea group, an ester group, an amide group, and an imide group is preferred. These groups can be used alone or in combination of two or more.

[0013] The photopolymerization initiator (A) of the present disclosure can be obtained by reacting a carboxylic acid and / or carboxylic anhydride having a benzophenone group (hereinafter also referred to as a benzophenone-based compound (a1)) with a compound having a heterocycle and a functional group reactive with the carboxylic acid and / or carboxylic anhydride (hereinafter also referred to as a heterocyclic compound (a2)). Examples of functional groups reactive with the carboxylic acid and / or carboxylic anhydride include hydroxyl, amine, epoxy, oxazoline, carbodiimide, isocyanate, thiol, phenol, and halogen groups. Hydroxyl, amine, epoxy, oxazoline, isocyanate, thiol, and halogen groups are preferred because they can be easily reacted at room temperature (0°C to 150°C) and atmospheric pressure (0.8 to 1.2 atm). From the perspective of adaptability of both direct and indirect reaction of (a1) and (a2), as described below, it is more preferable that the heterocyclic compound (a2) have at least one hydroxyl, amine, or epoxy group. (a2) may use one of these groups alone or two or more of them in combination.

[0014] Specific examples of the method for producing the photopolymerization initiator (A) include a method of directly reacting the benzophenone compound (a1) with the heterocyclic compound (a2), in which (a1) and (a2) are mixed together and reacted, and a method of adding dropwise one of (a1) and (a2) to the other and reacting them sequentially. Examples of methods for indirectly reacting (a1) and (a2) include a method in which (a1) reacts with a compound (a5) capable of reacting with it to obtain a compound (a3) ​​having a benzophenone group into which a reactive functional group (hereinafter also referred to as a reactive group), such as a hydroxyl group, a carboxylic acid group, an amine group, an epoxy group, an oxazoline group, an isocyanate group, a thiol group, or a halogen group, has been introduced, and (a3) ​​is then reacted with a heterocyclic compound (a2); and a method in which (a2) reacts with a compound (a5) capable of reacting with it to obtain a compound (a4) having a heterocycle into which a reactive group, such as a hydroxyl group, a carboxylic acid group, an amine group, an epoxy group, an oxazoline group, an isocyanate group, a thiol group, or a halogen group, has been introduced, and (a4) is then reacted with a benzophenone compound (a1).

[0015] The reaction for producing the photopolymerization initiator (A) can proceed appropriately within a temperature range of 0°C to 150°C, and a solvent, catalyst, and other additives may be used as needed. To suppress the generation of radicals during the production, the reaction is preferably carried out in an environment that blocks active energy rays, and more preferably in a dark room or under a yellow room or red safelight that blocks active energy rays with wavelengths of 500 nm or less.

[0016] Examples of the benzophenone compound (a1) include benzophenone-2-carboxylic acid, 4-methylbenzophenone-3'-carboxylic acid, 4-phenylbenzophenone-2'-carboxylic acid, 4-methoxybenzophenone-4'-carboxylic acid, 4,4'-benzophenonedicarboxylic acid, 3,4-benzophenonedicarboxylic acid, 2,3'-dimethyl-4,4'-benzophenonedicarboxylic acid, 2,5,4'-benzophenonetricarboxylic acid, 3,3',4,4'-benzophenonetetracarboxylic acid, 2,2'-dimethyl-3,3',4,4'-benzophenonetetracarboxylic acid, 3,3',4,4'-benzophenonetetracarboxylic acid dianhydride, 2,2'-dimethyl-3,3',4,4'-benzophenonetetracarboxylic acid dianhydride, 5-methyl-3,3',4,4'-benzophenonetetracarboxylic acid dianhydride, etc. (a1) can be used alone or in combination of two or more of these. Among these, (a1) is preferably 3',4,4'-benzophenonetetracarboxylic acid dianhydride, 2,2'-dimethyl-3,3',4,4'-benzophenonetetracarboxylic acid dianhydride, or 5-methyl-3,3',4,4'-benzophenonetetracarboxylic acid dianhydride because of the high reactivity of the acid anhydride with the heterocyclic compound (a2), and more preferably 3,3',4,4'-benzophenonetetracarboxylic acid dianhydride from the viewpoint of easy availability of industrial products.

[0017] Examples of the heterocyclic compound (a2) include tetrahydrofurfuryl alcohol, 3-hydroxytetrahydrofuran, (S)-(+)-2,2-dimethyl-1,3-dioxolane-4-methanol, glycerol 1,2-carbonate, tetrahydro-4-pyranol, 2-(hydroxymethyl)-12-crown 4-ether, N-hydroxysuccinimide, 1-(2-hydroxyethyl)-2-pyrrolidone, 2-(2-hydroxyethyl)-1-methylpyridine, 1-piperidineethanol, 4-methylpiperazine-1-ethanol, tetrahydro-2H-thiopyran-4-ol, 4-(2-hydroxyethyl)-morpholine, 4-(3-hydroxyethyl)-2H-pyrrolidone ... Examples of suitable amines include N-(2-hydroxyethyl)-morpholine, N-(2-hydroxypropyl)-morpholine, N-(2-hydroxyethyl)maleimide, tetrahydrofurfurylamine, 3-(aminomethyl)tetrahydrofuran, 2-(aminomethyl)-1,3-dioxolane, 5-aminopyrimidine, 4-(1-pyrrolidinyl)piperidine, 1-aminopiperidine, 1-(3-aminopropyl)-2-methylpiperidine, 1-(2-methoxyethyl)piperazine, 1-(2-pyrimidyl)piperazine, 2-(furfurylthio)ethylamine, morpholine, thiomorpholine, 4-aminomorpholine, 4-(2-aminoethyl)morpholine, and 4-morpholinoaniline. Among these, from the viewpoint of high stability of the cyclic substituent, 4-hydroxy-1-methylpiperidine, 1-piperidineethanol, 4-methylpiperazine-1-ethanol, 4-(2-hydroxyethyl)-morpholine, 4-(3-hydroxyethyl)-morpholine, N-(2-hydroxypropyl)-morpholine, 1-aminopiperidine, 1-(3-aminopropyl)-2-methylpiperidine, 1-(2-methoxyethyl)piperazine, 4-(4-methyl-1-piperazinyl)aniline, morpholine, 4-aminomorpholine, 4-(2-aminoethyl)morpholine, and 4-morpholinoaniline are more preferred. As (a2), one of these can be used alone, or two or more can be used in combination.

[0018] The compound (a5) capable of reacting with (a1) or (a2) is not particularly limited as long as it contains a reactive group such as a hydroxyl group, a carboxylic acid group, an amine group, an epoxy group, an oxazoline group, an isocyanate group, a thiol group, a halogen group, or an ethylenically unsaturated group. Examples of such an alkylene glycol include water, a linear alcohol having 1 to 24 carbon atoms or a branched or alicyclic alcohol having 3 to 24 carbon atoms and having a hydroxyl group, a linear alcohol having 2 to 24 carbon atoms or a branched or alicyclic alkylene glycol having 2 to 24 carbon atoms, a hydroxyl group-containing (meth)acrylate, a hydroxyl group-containing (meth)acrylamide, a linear alkylene diamine having 2 to 24 carbon atoms or a branched or alicyclic alkylene diamine having 3 to 24 carbon atoms and having an amino group, a phenylenediamine, 1,2-butylene oxide having an epoxy group, 1,2-epoxydodecane, 1,2-epoxytetradecane, butyl glycidyl ether, glycidyl phenyl ether, 2-ethylhexyl glycidyl ether, dodecyl glycidyl ether, glycidyl (meth)acrylate, 4-hydroxybutyl acrylate glycidyl ether, 1,2-epoxycyclohexane, and 1,2-epoxy-4-butyl-4-octanol. Furthermore, since the epoxy group reacts with the carboxylic acid to generate a hydroxyl group, which can be used for urethane formation or esterification, (a5) is preferably a compound having an epoxy group. Furthermore, from the viewpoint of high reactivity, butyl glycidyl ether, glycidyl phenyl ether, 2-ethylhexyl glycidyl ether, dodecyl glycidyl ether, 2-[(butoxymethoxy)methyl]oxirane, 1,2-epoxydodecane, 1,2-epoxytetradecane, glycidyl (meth)acrylate, and 4-hydroxybutyl acrylate glycidyl ether are more preferred. Compound (a5) can be used alone or in combination of two or more.

[0019] Examples of solvents that can be used in producing the photopolymerization initiator (A) of the present disclosure include hydrocarbon solvents such as toluene, xylene, n-hexane, and cyclohexanone; ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; ester solvents such as ethyl acetate and butyl acetate; halogenated hydrocarbon solvents such as methylene chloride and chlorobenzene; and high-boiling polar solvents such as N,N'-dimethylformamide, 3-methoxy-N,N'-dimethylpropionamide, 3-butoxy-N,N'-dimethylpropionamide, dimethylacetamide, dimethyl sulfoxide, 2-pyrrolidone, N-methyl-2-pyrrolidone, and 1,3-dimethyl-2-imidazolidinone. Furthermore, monofunctional or polyfunctional monomers and / or oligomers reactive with the photopolymerization initiator (A) and its raw materials (a1) and (a2) can also be used as reaction solvents. Examples of such monomers and / or oligomers include various (meth)acrylic acid esters having a chain and / or cyclic hydrocarbon group (having 1 to 22 carbon atoms) or an alkoxy group (having 1 to 22 carbon atoms), N-substituted (meth)acrylamides, and N,N-disubstituted (meth)acrylamides, and also (meth)acryloylmorpholine (meth)acryloyl, N-vinylpyrrolidone, etc. can also be used.

[0020] In the production of the photopolymerization initiator (A) of the present disclosure, the above-mentioned direct reaction and various indirect reactions can proceed without the use of a catalyst. Furthermore, the use of a catalyst is preferable because it allows both the direct and indirect reactions to proceed at lower temperatures and faster rates. Examples of catalysts used in the production of (A) include thionyl chloride, quaternary ammonium salts, tertiary phosphine derivatives, tertiary amine derivatives, and organometallic compounds. Examples of quaternary ammonium salts include tetrabutylammonium bromide, triethylbenzylammonium chloride, tetrabutylphosphonium bromide, and tetraphenylphosphonium bromide. Examples of tertiary phosphines include triarylphosphines such as triphenylphosphine and tritolylphosphine, tricycloalkylphosphines such as tricyclohexylphosphine, and trialkylphosphines such as triethylphosphine. Examples of tertiary amines include trialkyl (C1-8) amines such as triethylamine, tributylamine, and dimethylethylamine, and dialkyl (C1-8) arylamines such as dimethylbenzylamine and diethylbenzylamine. Examples of organometallic compounds include metal salts of metals such as zinc, tin, lead, zirconium, bismuth, cobalt, manganese, and iron with organic acids such as octenic acid and naphthenic acid; metal chelate compounds such as dibutyltin dilaurate, dioctyltin dilaurate, tin 2-ethylhexanoate, dibutyltin diacetylacetonate, zirconium tetraacetylacetonate, titanium acetylacetonate, aluminum acetylacetonate, cobalt acetylacetonate, iron acetylacetonate, copper acetylacetonate, and zinc acetylacetonate; potassium or sodium salts of alkyl (C1-C8)phosphonic acid; and sodium or potassium salts of fatty acids having C8-C20. Among these, quaternary ammonium salts, tertiary amine derivatives, tertiary phosphine derivatives, and tin-, zirconium-, or iron-based organometallic compounds, which have high catalytic effects, are more preferred. These catalysts can be used alone or in combination of two or more.

[0021] The amount of catalyst used in producing the photopolymerization initiator (A) is not particularly limited, but is preferably 0.001 to 5.0% by mass relative to the total mass of the raw materials. A mass ratio of 0.001% or more allows the reaction to proceed quickly, and a mass ratio of 5.0% or less is preferred because coloration caused by the catalyst can be suppressed. A mass ratio of 0.01 to 1.0% is even more preferred.

[0022] The method for introducing an ethylenically unsaturated group into the photopolymerization initiator (A) molecule is not particularly limited, but examples include using an ethylenically unsaturated group-containing benzophenone compound (a1) and / or an ethylenically unsaturated group-containing heterocyclic compound (a2), or using an ethylenically unsaturated group-containing compound (a5) that can react with (a1) and / or (a2). The ethylenically unsaturated group-containing compound (a5) has a structure formed by any combination of one or more reactive groups selected from the group consisting of hydroxyl groups, carboxylic acid groups, amine groups, epoxy groups, oxazoline groups, isocyanate groups, thiol groups, and halogen groups, and one or more ethylenically unsaturated groups selected from the group consisting of (meth)acrylamide groups, (meth)acrylate groups, vinyl groups, vinyl ether groups, alkyl vinyl ether groups, allyl groups, (meth)allyl ether groups, styryl groups, and maleimide groups. Examples of compound (a5) include compounds having a hydroxyl group and a (meth)acrylate group, compounds having a hydroxyl group and a (meth)acrylamide group, compounds having a hydroxyl group and a vinyl group, compounds having a hydroxyl group and an allyl group, compounds having a hydroxyl group and a maleimide group, compounds having an amino group and a (meth)acrylate group, compounds having an amino group and a (meth)acrylamide group, compounds having an amino group and a vinyl group, compounds having an amino group and an allyl group, compounds having an amino group and a maleimide group, compounds having a carboxyl group and a (meth)acrylate group, compounds having a carboxyl group and a (meth)acrylamide group, compounds having a carboxyl group and a vinyl group, compounds having a carboxyl group and an allyl group, compounds having a carboxyl group and a maleimide group, etc. These (a1), (a2) and (a5) can each be used independently, either alone or in combination of two or more.

[0023] Specific examples of the compound (a5) include hydroxyalkyl (C1-22) (meth)acrylates such as hydroxyethyl (meth)acrylate, hydroxyisopropyl (meth)acrylate, and hydroxypropyl (meth)acrylate; N-hydroxyalkyl (C1-22) (meth)acrylamides such as N-hydroxymethyl (meth)acrylamide, N-hydroxyisopropyl (meth)acrylamide, and N,N-dihydroxyethyl (meth)acrylamide; N-alkyl (C1-22) hydroxyalkyl (C1-22) (meth)acrylamides such as N-methylhydroxyethyl (meth)acrylamide and N-ethylhydroxypropyl (meth)acrylamide; and N,N-dihydroxymethyl (meth)acrylamide and N,N-dihydroxyethyl (meth)acrylamide. Examples include N-dihydroxyalkyl (C1-22) (meth)acrylamide, hydroxyalkyl (C1-22) vinyls such as 3-buten-1-ol, 4-penten-1-ol, and 5-hexen-1-ol, hydroxyalkyl (C1-22) allyls, N-hydroxyalkyl (C1-22) maleimides such as N-hydroxymethylmaleimide and N-hydroxyethylmaleimide, hydroxyalkyl (C1-22) vinyl ethers such as ethylene glycol monovinyl ether and tetramethylene glycol monovinyl ether, N-aminoalkyl (C1-22) (meth)acrylamide, N-aminoalkyl (C1-22)-N-alkyl (C1-22) (meth)acrylamide, and N,N-diaminoalkyl (C1-22) (meth)acrylamide.

[0024] The method for introducing a urethane group, urea group, ester group, amide group, or imide group into the molecule of the photopolymerization initiator (A) is not particularly limited, and examples thereof include (1) a method in which a compound having one or more groups selected from a hydroxyl group, an amine group, a carboxylic acid group, and an isocyanate group (hereinafter also referred to as a urethane group-introducing compound) is used and further reacted with a reaction product of a benzophenone compound (a1) and a heterocyclic compound (a2); (2) a method in which the compound is reacted with (a1), and then further reacted with (a2); (3) a method in which the compound is reacted with (a2), and then further reacted with (a1); and (4) a method in which the compound is reacted with (a1) and (a2) simultaneously. Examples of urethane group-introducing compounds include monourethane group-introducing compounds having one group selected from a hydroxyl group, an amine group, a carboxylic acid group, or an isocyanate group in the molecule, and polyurethane group-introducing compounds having two or more groups selected from a hydroxyl group, an amine group, a carboxylic acid group, or an isocyanate group in the molecule. Examples of polyurethane group-introducing compounds include polyols, polyamines, polycarboxylic acids, polyisocyanates, polyamino acids, amino group-containing polyols, hydroxyl group-containing polyamines, and hydroxyl group-containing polycarboxylic acids. They may also have a polyester skeleton, a polyether skeleton, a polycarbonate skeleton, a polyolefin skeleton (a polyalkadiene skeleton and / or a hydrogenated polyalkadiene skeleton), a polyacrylic skeleton, or a silicone skeleton (various modified polydimethylsiloxanes). These urethane group-introducing compounds may be used alone or in combination of two or more.

[0025] The molecular weight of the photopolymerization initiator (A) can be adjusted arbitrarily by combining various raw materials, but a number average of 500 to 100,000 is preferred. A number average molecular weight of 500 or higher reduces the content of low-molecular-weight components (molecular weights less than 500) in the cured product obtained after the photopolymerization reaction, resulting in high safety, durability, and heat resistance of the cured product. Furthermore, a number average molecular weight of 100,000 or less facilitates adjustment of the polarity (balance between hydrophilicity and hydrophobicity) of (A), enhances solubility in commonly used monomers and oligomers used in active energy ray-curable compositions, and allows the viscosity of the curable composition containing (A) to be easily adjusted within a range suitable for various processing methods, such as coating, spraying, and extrusion, resulting in high transparency of the resulting curable composition and cured product. Furthermore, based on the molecular weight of (A), photopolymerization initiators can be classified into low-molecular-weight types (number average molecular weights of 500 to less than 1,000), medium-molecular-weight types (number average molecular weights of 1,000 to less than 10,000), and high-molecular-weight types (number average molecular weights of 10,000 to 100,000). The low molecular weight type (A) is a compound in which a heterocycle is directly or indirectly bonded to a carboxylic acid ester group and / or a carboxylic acid amide group that is directly bonded to a benzophenone group represented by general formula (1). The medium molecular weight type (A) is a compound in which a heterocycle is directly or indirectly bonded to a carboxylic acid ester group and / or a carboxylic acid amide group that is directly bonded to a benzophenone group represented by general formula (1), and at the same time, a structural unit derived from an introduced compound such as a urethane group and a urethane group having one or more skeletons selected from a polyester skeleton, a polyether skeleton, a polycarbonate skeleton, a polyolefin skeleton, and a polyacrylic skeleton are bonded. The order and position in which the heterocycle and the structural unit derived from an introduced compound such as a urethane group and the urethane group are bonded are not limited.The high molecular weight type (A) is primarily a compound having a structure formed by repeating structural units derived from a compound incorporating a urethane group or the like and bonds of urethane groups, etc., having one or more skeletons selected from a polyester skeleton, a polyether skeleton, a polycarbonate skeleton, a polyolefin skeleton, and a polyacrylic skeleton, in which a heterocycle is bonded directly or indirectly to a carboxylic acid ester group and / or a carboxylic acid amide group directly bonded to a benzophenone group represented by general formula (1). The order and position of the bonds between the heterocycle and the repeating structural units derived from the compound incorporating a urethane group or the like and the urethane groups, etc., are not limited. Among these, medium molecular weight type photopolymerization initiators are particularly preferred because they have good solubility in various common organic solvents, monomers, or oligomers used in curable compositions, allow the viscosity of the resulting curable resin composition to be appropriately adjusted, have excellent workability, and exhibit high sensitivity to polymerization initiation with active energy rays, particularly to long-wavelength light rays with wavelengths of 360 nm to 420 nm.

[0026] JPEG0007811041000001.jpg38127 (in the formula, Q 1 , Q 3 are each independently a hydrogen atom or a monovalent organic group represented by general formula (2) or general formula (3), and Q 1 , Q 3 at least one of the following is a monovalent organic group having one or more saturated or unsaturated 5- or greater-membered cyclic substituents having a heteroatom; Q 2 , Q 4 are each independently a divalent organic group represented by general formula (4) or general formula (5), L 1 , L 2 are each independently a direct bond or a divalent organic group containing at least one of a urethane group, a urea group, an ester group, an amide group, and an imide group. 2 -L 1 -R 5 and Q 4 -L 2 -R 6 may be hydrogen atoms, but these are 1 , Q 3Except when both are hydrogen atoms, JPEG0007811041000002.jpg1351JPEG0007811041000003.jpg1851JPEG0007811041000004.jpg1351JPEG0007811041000005.jpg1851R 1 ~R 9 , R 12 each independently represents a hydrogen atom or a linear or cyclic, saturated or unsaturated monovalent hydrocarbon group having 1 to 36 carbon atoms, in which one or more hydrogen atoms may be substituted with a hydroxyl group, an amine group, a thiol group, or a halogen group, and one or more carbon atoms may be substituted with an ether group, an amino group, a thioether group, or a thioester group; R 10 , R 11 each independently represents a direct bond or a linear or cyclic, saturated or unsaturated divalent hydrocarbon group having 1 to 36 carbon atoms in which one or more hydrogen atoms may be substituted with a hydroxyl group, an amine group, a thiol group, or a halogen group, and one or more carbon atoms may be substituted with an ether group, an amino group, a thioether group, or a thioester group; R 8 and R 9 may combine with the nitrogen atom carrying them to form a 5- to 7-membered ring cyclic substituent structure, and, except for being a hydrogen atom at the same time, R 10 , R 11 may combine with the nitrogen atom carrying them to form a 5- to 7-membered cyclic substituent structure, R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 At least one of the above has a saturated or unsaturated 5- or greater ring substituent having a heteroatom, n is an integer from 1 to 100.

[0027] Photopolymerization initiator (A) can be used in combination with a photocationic polymerization initiator, a photoanionic polymerization initiator, or a thermal polymerization initiator, and can also be used for hybrid or dual polymerization, curing, etc. Photopolymerization and thermal polymerization can be carried out simultaneously or in any order. However, while photopolymerization is fast, it can leave unreacted monomers or oligomers. Therefore, it is preferable to complete the remaining polymerization reactions and crosslinking reactions by thermal polymerization after photopolymerization. Furthermore, by using photoradical polymerization initiators of different types or structures in combination and irradiating them stepwise with light of different wavelengths, the curable material can be completely cured.

[0028] Examples of light rays that can be applied to the photopolymerization initiator (A) include active energy rays such as visible light, electron beams, ultraviolet rays, infrared rays, X-rays, α-rays, β-rays, and γ-rays. Among these, ultraviolet rays are preferred in terms of the balance between the active energy ray generator, the photopolymerization initiation rate, and safety. 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. UV-LED lamps are more preferred because they have a high energy-to-light conversion efficiency, can easily be increased in output, and do not use harmful mercury.

[0029] In the photopolymerization initiator (A), the light irradiation energy required to generate radical active species is 5 to 50,000 mJ / cm when converted into irradiation energy (cumulative light amount). 2 The range is preferably 10 to 20,000 mJ / cm 2 If the irradiation energy is within this range, radicals with sufficient activity can be generated from (A), which is preferable.

[0030] The content of the photopolymerization initiator (A) in the curable composition varies depending on the type and content of the monomers and oligomers in the curable composition. However, a content of 0.1% by mass or more based on the total curable composition is preferred because it allows photopolymerization to initiate immediately and allows the curable composition to cure rapidly and sufficiently. Furthermore, when (A) has an ethylenically unsaturated group, even if it contains 100% by mass, it can cure rapidly and sufficiently, similar to conventional curable compositions. Furthermore, to optimally adjust the physical properties of the resulting cured product, it is preferable to use (A) in combination with other monomers or oligomers. In this case, the content of (A) is preferably 0.5 to 70% by mass, more preferably 1 to 50% by mass, and most preferably 2 to 30% by mass based on the total curable composition.

[0031] The monomers and oligomers used in combination with (A) can be classified as monofunctional monomers, polyfunctional monomers, or oligomers. The content of the combined monomers and oligomers is 0 to 99.9% by mass of the entire curable composition, and from the viewpoint of suitably adjusting the physical properties of the cured product, it is preferably 10 to 99.5% by mass, more preferably 30 to 99% by mass, and most preferably 50 to 90% by mass.

[0032] Examples of monofunctional monomers include compounds containing a (meth)acrylate group, a (meth)acrylamide group, a vinyl group, an allyl group, a styryl group, an acetylene group, etc., and these can be used alone or in combination of two or more. The content of the monofunctional monomer is preferably 0 to 90 mass% of the entire curable composition, more preferably 5 to 70 mass%, and most preferably 10 to 50 mass%. Monofunctional monomers usually have low viscosity, and by adding an appropriate amount of monofunctional monomer, effects such as lowering the viscosity of the curable composition and improving workability can be expected.

[0033] Specific examples of monofunctional monomers containing a (meth)acrylate group (excluding photopolymerization initiators) include (meth)acrylates into which a linear, branched, or cyclic alkyl group or hydroxyalkyl group having 1 to 18 carbon atoms, a branched group having 3 to 18 carbon atoms, an alkylcarboxylic acid, an alkylsulfonic acid, or an alkylphosphate group has been introduced; phenoxyalkylene glycol (meth)acrylates into which a functional group consisting of a phenoxy group and an alkylene glycol group having 1 to 4 carbon atoms has been introduced; dialkylaminoethyl (meth)acrylates, dialkylaminopropyl (meth)acrylates into which an alkyl group having 1 to 6 carbon atoms has been introduced; Examples of the methacrylate include (meth)acrylates containing an amino group such as meth)acrylamide, (meth)acrylates into which a cyclic structure has been introduced such as benzyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, isobornyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, and 2-methyl-2-adamantyl (meth)acrylate, and (meth)acrylates into which an epoxy group has been introduced such as glycidyl (meth)acrylate and 4-hydroxybutyl (meth)acrylate glycidyl ether.

[0034] Specific examples of monofunctional monomers containing a (meth)acrylamide group (excluding photopolymerization initiators) include (meth)acrylamide, mono- or di-substituted (meth)acrylamides, (meth)acroylmorpholine, and diacetone (meth)acrylamide. Examples of mono- or di-substituted (meth)acrylamides include N-alkyl(meth)acrylamides having a linear alkyl group with 1 to 18 carbon atoms, or a branched or cyclic alkyl group with 3 to 18 carbon atoms, N,N-dialkyl(meth)acrylamides, N-hydroxyalkyl(meth)acrylamides having a hydroxyalkyl group with 1 to 6 carbon atoms, and N,N-dialkylaminopropyl(meth)acrylamides having an alkyl group with 1 to 6 carbon atoms.

[0035] Specific examples of the monofunctional monomer (excluding photopolymerization initiators) containing a vinyl group, an allyl group, or a styryl group include vinyl carboxylic acid esters and allyl carboxylic acid esters into which a linear, branched, or cyclic carboxylic acid having 1 to 18 carbon atoms has been introduced, alkyl vinyl ethers and alkyl allyl ethers into which a linear, branched, or cyclic alkyl group having 1 to 18 carbon atoms has been introduced, vinyl chloride, N-vinylpyrrolidone, N-vinylcaprolactam, N-vinyloxazoline, maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, unsaturated dicarboxylic acids mono- or di-esterified with a linear, branched, or cyclic alkyl group having 1 to 18 carbon atoms, vinyl carboxylic acid, vinyl sulfonic acid, vinyl phosphoric acid, allylamine, diallylamine, styrene, α-methylstyrene, α-methylstyrene dimer, and p-styrenesulfonic acid.

[0036] Examples of polyfunctional monomers or oligomers include compounds containing two or more unsaturated groups, such as (meth)acrylate groups, (meth)acrylamide groups, vinyl groups, allyl groups, styrene groups, and acetylene groups. These unsaturated groups may be compounds containing one type alone or two or more types in combination. Furthermore, to obtain good curability, it is more preferable to use at least one (meth)acrylate group or (meth)acrylamide group as the unsaturated group. The content of the polyfunctional monomer (excluding the photopolymerization initiator) is preferably 0 to 95% by mass, more preferably 1 to 70% by mass, and most preferably 5 to 50% by mass, based on the total curable composition. By appropriately adjusting the content of the polyfunctional monomer, the resulting cured product can be expected to have high strength and hardness and excellent durability.

[0037] Examples of the polyfunctional monomer or oligomer include allyl (meth)acrylate, allyl (meth)acrylamide, diallylamine, alkyl diallylamine having an alkyl group having 1 to 18 carbon atoms introduced therein, alkylene glycol di(meth)acrylates, polyalkylene glycol di(meth)acrylates, bisphenol A diglycidyl ether acrylic acid adducts, alkoxylated bisphenol A diacrylates, polyester di(meth)acrylates, polycarbonate di(meth)acrylates, polyurethane di(meth)acrylates, and polyurethane di(meth)acrylamides. Examples of the polyfunctional monomer having three or more functional groups include pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, trimethylolpropane tri(meth)acrylate, dipentaerythritol tri(meth)acrylate, and the like. acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tri(meth)acryloyloxyethoxytrimethylolpropane, glycerin polyglycidyl ether poly(meth)acrylate, ethylene oxide-modified isocyanuric acid tri(meth)acrylate, 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. These polyfunctional monomers or oligomers can be used alone or in combination of two or more.

[0038] The photopolymerization initiator (A) of the present disclosure has high photoinitiating properties even without the use of a sensitizer, but the use of a general-purpose sensitizer in combination can be expected to further improve polymerization initiation and the physical properties of the cured product after curing. Sensitizers that can be used in combination with (A) are not particularly limited, but examples include unsaturated ketones such as benzophenones and anthracene derivatives, 1,2-diketone derivatives such as benzil and camphorquinone, benzoin derivatives, anthraquinone derivatives, thioxanthone derivatives, coumarin derivatives, tertiary amines, thiols, and disulfides. These can be used in any ratio as needed, and one type can be used alone or two or more types can be used in combination.

[0039] Specific examples of sensitizers that can be used in combination include anthracene-based sensitizers such as 9,10-dibutoxyanthracene, 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, and 9,10-bis(2-ethylhexyloxy)anthracene, and thioxanthone-based sensitizers such as 2,4-diethylthioxanthone, 2-isopropylthioxanthone, and 4-isopropylthioxanthone. Representative examples of commercially available anthracene-based sensitizers include DBA and DEA (manufactured by Kawasaki Chemical Industries, Ltd.), and thioxanthone-based sensitizers include DETX and ITX (manufactured by Lambson Chemical Industries, Ltd.). The content of the sensitizer is not particularly limited, but is preferably 0.5 to 5.0 mass% and more preferably 0.8 to 3.0 mass% based on the total mass of the curable composition. When the content of the sensitizer is within this range, the curability of the curable composition is improved, and the resulting cured product has good durability and yellowing resistance.

[0040] Other polymerization initiators that can be used in combination with the photopolymerization initiator (A) of the present disclosure include benzoins such as benzoin and benzoin alkyl ethers, acetophenones such as acetophenone and 2-hydroxy-2-methyl-1-phenylpropan-1-one, anthraquinones, thioxanthones, ketals, benzophenones, aminobenzophenones, aminoacetophenones, xanthones, etc. These can be used in any ratio as needed, and can be used either alone or in combination of two or more.

[0041] The active energy ray-curable composition can be used without containing an organic solvent. Furthermore, to improve workability such as coatability, an organic solvent can be added as needed to adjust the liquid viscosity. The added organic solvent may be removed before photocuring, or the composition may be cured while still containing the organic solvent. Furthermore, the organic solvent may be removed after curing, and this can be appropriately selected depending on the intended use and purpose of the curable composition and the resulting cured product. The amount of organic solvent added is not particularly limited, but is preferably 80% by mass or less, and more preferably 50% by mass or less, of the total active energy ray-curable composition, in order to reduce the energy and time required for removing the organic solvent.

[0042] An organic solvent can be used in the curable composition. Examples of the solvent that can be used include alcohols such as methanol and isopropanol, ketones such as acetone, methyl ethyl ketone and cyclohexanone, esters such as ethyl acetate, propyl acetate, methyl lactate and ethyl lactate, alkylene glycols such as ethylene glycol and propylene glycol, polyalkylene glycols such as polyethylene glycol and polypropylene glycol, glycol ethers such as ethoxydiethylene glycol and methoxypropylene glycol, glycol esters such as propylene glycol acetate, tetrahydrofuran, methyltetrahydrofuran, cyclopentyl methyl ether, methyltetrahydropyran, methyl methyl ether ... Examples of suitable organic solvents include ethers such as ethyl tert-butyl ether toluene, aromatic hydrocarbons such as xylene, aliphatic hydrocarbons such as hexane and cyclohexane, amides such as N,N'-dimethylformamide and dimethylacetamide, amide ethers such as β-methoxy-N,N-dimethylpropionamide and β-butoxy-N,N-dimethylpropionamide, pyrrolidones such as 2-pyrrolidone and N-methylpyrrolidone, piperidines such as N-methylpiperidine, halogenated hydrocarbons such as methylene chloride, chloroform and dichloroethane, sulfoxides such as dimethyl sulfoxide, and imidazolidinones such as 1,3-dimethyl-2-imidazolidinone. These organic solvents may be used alone or in combination of two or more.

[0043] The photopolymerization initiator of the present disclosure can be used in active energy ray-curable inks such as active energy ray-curable flexographic inks, active energy ray-curable offset inks, active energy ray-curable screen inks, and active energy ray-curable inkjet inks; active energy ray-curable nail cosmetic compositions used for gel nails and the like; active energy ray-curable pressure-sensitive adhesive compositions; active energy ray-curable adhesive compositions; active energy ray-curable sealant compositions used for sealing materials, sealants, and the like; active energy ray-curable coating agent compositions used for paints and coating agents for automobiles, electrical appliances, furniture, and the like; active energy ray-curable decorative sheet compositions used for decorative sheets used for surface coatings of automobiles, electrical appliances, and the like; The active energy ray-curable self-repairing material compositions used in coating compositions, three-dimensional objects, nail decoration materials, dental materials, automobile exterior protection, functional components such as decorative films, devices, etc., active energy ray-curable elastomer compositions used in materials for elastomers used in transparent adhesive sheets, buffer materials, packing, vibration-proofing materials, sound-absorbing materials, printing plates, sealants, abrasives, etc., active energy ray-curable three-dimensional modeling inks used for 3D printer model materials, support materials, or three-dimensional shapes with unevenness, active energy ray-curable dental material compositions, active energy ray-curable photosensitive compositions, active energy ray-curable hydrogel compositions, active energy ray-curable material compositions for intraocular implants, etc. Furthermore, the obtained hydrogel composition can be suitably used as a material in a wide variety of fields, such as in the hygiene field (e.g., superabsorbent resins, disposable diapers, soft contact lenses, etc.), in the coating field (e.g., ship bottom paints, anti-fogging materials, antifouling paints, etc.), in the medical field (e.g., medical device surface coatings, artificial organs, etc.), in the civil engineering and construction field (e.g., soil conditioners, etc.), in the agricultural field (e.g., water-retaining materials, etc.), and in the shock-absorbing material field. [Example]

[0044] 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 these examples. In the following, "parts" and "%" are all by mass unless otherwise specified.

[0045] (1-1) Infrared absorption spectroscopy (IR analysis) IR analysis was carried out using the following equipment. Nicolet iS50 (Thermo Fisher Scientific) (1-2) Liquid chromatography mass spectrometry (LC-MS analysis) LC-MS analysis was carried out using the following equipment and conditions. Column: XBridge C18, 6 mm x 150 mm, 3.5 μm (Nihon Waters Co., Ltd.) Eluent conditions: water / methanol / 1% formic acid aqueous solution = 60 / 30 / 10 Measurement wavelength: 258 nm; column oven temperature: 40°C (1-3) Nuclear magnetic resonance spectroscopy (NMR analysis) 1 H-NMR analysis was carried out using a 400 MHz instrument manufactured by JEOL Ltd. (1-4) Gas Chromatography Analysis (GC Analysis) The GC analysis was carried out under the following conditions using the following equipment. Equipment: GC-2025 (Shimadzu Corporation) Column: DB-1 (Agilent Technologies, Inc.) (1-5) Gel Permeation Chromatography Analysis (GPC Analysis) GPC analysis was carried out using the following equipment and conditions. Equipment: Prominence-I LC-2030C (Shimadzu Corporation) Guard column: Shodex KF-G (Showa Denko K.K.) Column: Shodex KF-803 (Showa Denko K.K.) Column temperature: 40°C; Mobile phase: tetrahydrofuran (THF) Flow rate: 0.5 mL / min; Standard sample: polystyrene

[0046] The benzophenone compound (a1), heterocyclic compound (a2), and compound (a5) capable of reacting with (a1) or (a2) used in the examples are shown below. (2-1) Benzophenone-based compounds (a1) a1-1: 4-benzoylbenzoic acid methyl ester a1-2: 3,4-benzophenonedicarboxylic acid anhydride a1-3: 2-(4-biphenylylcarbonyl)benzoic acid a1-4: 4-(4-carboxybenzoyl) 2,3-diethylbenzoic acid a1-5: 4-(4-methoxybenzoyl)benzoic acid a1-6: 3,3',4,4'-benzophenonetetracarboxylic dianhydride (2-2) Heterocyclic compound (a2) a2-1: Piperazine a2-2: Morpholine a2-3: Hydroxyethylmaleimide a2-4: tetrahydrofurfuryl alcohol a2-5: Tetrahydrofuran-2-acetic acid chloride a2-6: tetrahydrofurfurylamine a2-7: 2-(hydroxymethyl)-15-crown-5 ether a2-8: 1-piperidineethanol a2-9: 4-(2-hydroxyethyl)morpholine a2-10: tetrahydro-2H-thiopyran-4-ol (2-3) Compound (a5) capable of reacting with (a1) or (a2) a5-1: acrylic acid chloride A5-2: 4-hydroxybutyl acrylate glycidyl ether A5-3: Glycidyl methacrylate A5-4: Ethylene glycol A5-5: Butylene oxide A5-6: Methanol A5-7: Octadecyl glycidyl ether a5-8: Ion-exchanged water A5-9: 1,2-epoxyoctane A5-10: 4-hydroxybutyl acrylate a5-11: Allyl alcohol a5-12: N-(2-hydroxyethyl)acrylamide

[0047] The polyol (B1), amine compound (B2), monoalcohol compound (B3), isocyanate compound (C1), and carboxylic acid compound (C2) used in the examples are shown below. (2-4) Polyol (B1) B1-1: UH-100 (Ube Industries, 1,6-HD polycarbonate diol, number average molecular weight 1,000) B1-2: Kuraray Polyol P-1010 (Kuraray, polyester polyol, number average molecular weight 1,000) B1-3: KF-6000 (Shin-Etsu Chemical Co., Ltd., reactive silicone oil, carbinol-modified (both terminals), hydroxyl value 120 mg KOH / g, number average molecular weight 900) B1-4: Uniol D-1000 (NOF, polypropylene glycol, number average molecular weight 1,000) B1-5: GI-2000 (Nippon Soda, polybutadiene diol, number average molecular weight 2,000) B1-6: Kuraray Polyol P-5010 (Kuraray, polyester polyol, number average molecular weight 5,000) B1-7: PEG-300 (polyethylene glycol, number average molecular weight 300) B1-8: PTMG650 (polytetramethylene ether glycol, number average molecular weight 650) (2-5) Amine compound (B2) B2-1: D-400 (Mitsui Chemicals Fine Chemicals, polyetheramine, number average molecular weight 400) (2-6) Monoalcohol compound (B3) B3-1: Hydroxyethyl acrylate B3-2: N-(2-hydroxyethyl)acrylamide (KJ Chemicals Co., Ltd., registered trademarks "Kohshylmer" and "HEAA") B3-3: 4-hydroxybutyl acrylate B3-4: 3-hydroxypropyl methacrylamide B3-5: Hydroxyethylmaleimide B3-6: Methanol B3-7: 4-Hydroxybutyl vinyl ether B3-8: Ethylene glycol monoallyl ether B3-9: (6-hydroxyhexyl) methacrylamide (2-7) Isocyanate compound (C1) C1-1: 2-Acryloyloxyethyl isocyanate C1-2: Isophorone diisocyanate C1-3: Toluene diisocyanate C1-4: 1,5-pentamethylene diisocyanate C1-5: 1,3-bis(isocyanatomethyl)cyclohexane C1-6: Isophorone diisocyanate trimer (nurate) (Evonik, VESTANAT T1890 / 100) (2-8) Carboxylic acid compound (C2) C2-1: Adipic acid C2-2: Sebacic acid

[0048] The photopolymerization initiator (D), monofunctional monomer (E), polyfunctional monomer or oligomer (F), and other components (G) used in the examples and comparative examples are shown below. (3-1) Photopolymerization initiator (D) D-1: 1-hydroxycyclohexyl phenyl ketone D-2: Benzophenone D-3: Isopropylthioxanthone D-4: Diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide D-5:Escacure KIP-150 (manufactured by IGM Rseins BV) D-6: Camphorquinone (3-2) Monofunctional Monomer (E) E-1: Diethylacrylamide (manufactured by KJ Chemicals Co., Ltd., registered trademarks "Kohshylmer" and "DEAA") E-2: Isobornyl acrylate E-3: Acryloylmorpholine (manufactured by KJ Chemicals Co., Ltd., registered trademarks "Kohshylmer" and "ACMO") E-4: Tetrahydrofurfuryl acrylate E-5: 4-t-butylcyclohexyl acrylate (manufactured by KJ Chemicals Co., Ltd., registered trademark "Kohshylmer") E-6: Phenoxyethyl acrylate E-7: 4-hydroxybutyl acrylate E-8: Dimethylacrylamide (manufactured by KJ Chemicals Co., Ltd., registered trademarks "Kohshylmer" and "DMAA") E-9: N-vinylpyrrolidone E-10: N-octylacrylamide (KJ Chemicals Co., Ltd., registered trademark "Kohshylmer") E-11: N-(2-hydroxyethyl)acrylamide (manufactured by KJ Chemicals Co., Ltd., registered trademarks "Kohshylmer" and "HEAA") E-12: n-dodecyl acrylate E-13: Isobornyl methacrylate E-14: Hydroxyethyl methacrylate E-15: 2-Methacryloyloxyethyl acid phosphate (3-3) Polyfunctional Monomer or Oligomer (F) F-1: A-400 (Shinnakamura Chemical Co., Ltd., polyethylene glycol No. 400 diacrylate) F-2: EBECRYL8807 (manufactured by Daicel-Allnex Corporation, aliphatic bifunctional urethane acrylate, average molecular weight 1000) F-3: Urethane diacrylate (Shiko UV6630, manufactured by Mitsubishi Chemical Corporation) F-4: Polyethylene glycol (20)-incorporated bisphenol A diacrylate (NK Ester A-BPE-20, manufactured by Shin-Nakamura Chemical Co., Ltd.) F-5: Hexanediol diacrylate F-6: Polyether-based urethane acrylamide (manufactured by KJ Chemicals Co., Ltd., registered trademark "Quick Cure") F-7: Dipentaerythritol hexaacrylate ( F-8: Urethane diacrylate (UV3000, manufactured by Mitsubishi Chemical Corporation) F-9: Dimethylol-tricyclodecane diacrylate F-10: Polyethylene glycol (10)-incorporated bisphenol A diacrylate (NK Ester A-BPE-10, manufactured by Shin-Nakamura Chemical Co., Ltd.) F-11: Pentaerythritol triacrylate F-12: Polyethylene glycol (10) dimethacrylate F-13: Ethylenebisacrylamide F-14: Polyester-based urethane acrylamide (KJ Chemicals Co., Ltd., registered trademark "Quik Cure") F-15: Trimethylolpropane triacrylate F-16: Polycarbonate-based urethane acrylamide (KJ Chemicals Co., Ltd., registered trademark "Quick Cure") F-17: Bisphenol A epoxy acrylate oligomer (Miramer PE-210, manufactured by MIWON Co., Ltd.) (3-4) Other ingredients (G) G-1: TEGO Rad2100 (manufactured by Evonik, a silicone acrylate with a polydimethylsiloxane structure) G-2: Pentaerythritol tetrakis(3-mercaptobutyrate) G-3: MEK-ST-40 (Nissan Chemical Co., Ltd., colloidal silica dispersion) G-4: Omnipol ASA (manufactured by IGM Resins BV) G-5: Carbon black dispersion (manufactured by Mitsubishi Chemical Corporation) / BYK-JET9151 (pigment dispersant, maleimide-styrene copolymer with ammonium salt structure, manufactured by BYK Chemie) = 1 / 2 (weight ratio) mixed liquid G-6: VALIFAST BLUE 1613 (manufactured by Orient Chemical Industry Co., Ltd.) G-7: Petrotack 100V (Tosoh Corporation) G-8: Reoloseal QS-30 (Tokuyama Corporation) G-9: Methacrylic acid / methyl methacrylate / styrene copolymer binder G-10: Azobisisobutyronitrile (3-5) Organic solvent (H) H-1: Ethyl acetate H-2: 3-Methoxy-N,N-dimethylpropanamide (manufactured by KJ Chemicals Co., Ltd., registered trademarks "Kohshylvent" and "KJCMPA") H-3: Methyl ethyl ketone H-4: Dimethylformamide H-5: N-methylpyrrolidone

[0049] Example 1 Synthesis of Photopolymerization Initiator (A-1) A 500 mL flask equipped with a reflux condenser, stirrer, thermometer, and dropping funnel was charged with 35.9 g of piperazine (a2-1) and 50 g of N,N-dimethylformamide (DMF). 37.7 g of acrylic acid chloride (a5-1) was added dropwise with stirring at 0°C, and the mixture was allowed to react for 1 hour to obtain 1-acroylpiperazine. Subsequently, 100 g of methyl 4-benzoylbenzoate (a1-1) and 3.1 g of triethylamine (TEA) were added, and the mixture was allowed to react for 2 hours with stirring at 65°C. After the reaction was complete, the mixture was purified to obtain the desired pale yellow viscous liquid (purity 95%). IR analysis of the resulting viscous liquid revealed the C=O specific absorption of the amide group (1650 cm). -1 ) was detected, and the C=O specific absorption of the ester group (1725 cm -1 ) was not detected, confirming the formation of amide groups and the disappearance of ester groups. 1H-NMR analysis detected the following peaks: 8.60-7.90 ppm (9H, aromatic ring); 6.34 ppm (H, -CH= of acrylamide group); 6.22 ppm and 5.74 ppm (2H, =CH2 of acrylamide group); and 3.80 ppm and 3.60 ppm (4H, -N-CH2- of piperazine ring), confirming the presence of benzophenone, piacryloyl, and piperazine groups. Furthermore, the molecular ion peak in the LC-MS mass spectrum gave a molecular weight of 348, which matched the molecular weight of the target compound (Table 2), confirming the production of the photopolymerization initiator (A-1) with the structure shown in Table 2.

[0050] Example 2 Synthesis of Photopolymerization Initiator (A-2) Using a similar apparatus, 100 g of (a1-2), 34.5 g of (a2-2), 1.5 g of TEA, and 50 g of DMF were added and reacted at 65°C for 2 hours, after which 79.3 g of (a5-2) and 0.4 g of triphenylphosphine (TPP) were added and reacted at 70°C for 3 hours. After the reaction was completed, the mixture was purified to obtain a pale yellow viscous liquid (purity 97%). Similarly, IR analysis confirmed the formation of ester groups and amide groups (1725 cm of the C=O of the ester group). -1 and amide group C=O at 1650cm -1 was detected.) and the disappearance of the acid anhydride group (the C=O specific absorption of the acid anhydride group 1770 cm -1 and 1851cm -1 was not detected.) Also, 1 H-NMR analysis detected 8.60-7.95 ppm (8H, aromatic ring); 6.56 ppm (H, -CH= of acrylate group); 4.28 ppm and 4.32 ppm (2H, =CH of acrylate group); 3.63 ppm (8H, -CH-O- in morpholine group); and 3.41 ppm (8H, -N-CH- in morpholine group). The molecular weight (540) obtained by LC-MS analysis matched the molecular weight of the target compound (Table 2). Based on these results, the production of photopolymerization initiator (A-2) with the structure shown in Table 2 was confirmed.

[0051] Example 3 Synthesis of Photopolymerization Initiator (A-3) Using a similar apparatus, 100 g of (a1-3), 47.2 g of (a2-3), and 39.4 g of thionyl chloride were stirred at 0°C for 10 minutes, then heated to 70°C and reacted for 3 hours. After the reaction was completed, the mixture was purified to obtain a pale yellow viscous liquid (purity 93%). IR analysis of the viscous liquid similarly revealed the formation of ester groups (1725 cm). -1 ) and 1 H-NMR analysis detected 8.50-7.80 ppm (13H, aromatic ring); 7.05 ppm (2H, -HC=CH- of maleimide group); 4.65 ppm (2H, -O-CH2-); and 3.78 ppm (2H, -N-CH2-). The molecular weight (425) obtained by LC-MS analysis matched the molecular weight of the target compound (Table 2). Based on these results, the production of photopolymerization initiator (A-3) with the structure shown in Table 2 was confirmed.

[0052] Example 4 Synthesis of Photopolymerization Initiator (A-4) The reaction was carried out in the same manner as in Example 3, except that (a1-3) was changed to (a1-4), to obtain a pale yellow viscous liquid (purity 97%). 1 From the results of H-NMR analysis (described below) and LC-MS analysis (molecular weight 495), the production of photopolymerization initiator (A-4) with the structure shown in Table 2 was confirmed. 1 H-NMR: 8.62-7.97 ppm (6H, aromatic ring); 4.52 ppm (4H, -COO-CH2-); 4.02 ppm (2H, -CH-O- in two tetrahydrofuran groups); 3.82 ppm (4H, -CH2-O- in two tetrahydrofuran groups); 1.63-2.02 ppm (8H, -CH2-CH2- in two tetrahydrofuran groups).

[0053] Example 5 Synthesis of Photopolymerization Initiator (A-5) Using a similar apparatus, 100 g of (a1-5), 55.5 g of (a5-3), and 50 g of DMF were mixed and reacted at 65°C for 2 hours. The reaction mixture was then cooled to 0°C, and 58.0 g of (a2-5) was added. After stirring for 10 minutes, the mixture was heated to 70°C and reacted for 3 hours. After the reaction was completed, the mixture was purified to obtain a pale yellow viscous liquid (purity 87%). IR analysis of the resulting viscous liquid revealed the presence of an ester group (1725 cm). -1 ) was confirmed to be produced.1 H-NMR analysis confirmed the presence of benzophenone groups (8.50-7.85 ppm, 6H, aromatic ring), tetrahydrofuran groups (as in Example 4), and methacrylate groups (5.97 ppm and 5.48 ppm, 2H, =CH2; 1.96 ppm, 3H, -CH3). LC-MS analysis revealed a molecular weight (511) consistent with the molecular weight of the target compound (Table 2). Based on these results, the production of photopolymerization initiator (A-5) with the structure shown in Table 2 was confirmed.

[0054] Example 6 Synthesis of Photopolymerization Initiator (A-6) Using a similar apparatus, 100 g of (a1-6), 63.4 g of (a2-4), 3.1 g of TEA, and 50 g of DMF were mixed and reacted at 65°C for 2 hours. The reaction mixture was cooled to 0°C, and 38.5 g of (a5-4) and 73.8 g of thionyl chloride were added. After stirring for 10 minutes, the mixture was reacted at 70°C for 3 hours and purified to obtain a pale yellow viscous liquid (purity 91%). IR analysis of the resulting viscous liquid revealed the presence of an ester group (1725 cm). -1 The formation of ) and the disappearance of the acid anhydride group were confirmed. 1 H-NMR analysis confirmed the presence of a benzophenone group (8.62-7.95 ppm, 6H, aromatic ring) and a tetrahydrofuran group (as in Example 4). The molecular weight (615) determined by LC-MS analysis matched the molecular weight of the target compound (Table 2). Based on these results, the production of photopolymerization initiator (A-6) with the structure shown in Table 2 was confirmed.

[0055] Example 7 Synthesis of Photopolymerization Initiator (A-7) Using a similar apparatus, 100 g of (a1-6), 54.1 g of (a2-2), 3.1 g of TEA, and 50 g of DMF were mixed and reacted at 65°C for 2 hours. The reaction solution was cooled to 0°C, and 44.8 g of (a5-5) and 0.8 g of TPP were added. After stirring for 10 minutes, the reaction was continued at 70°C for 3 hours. After purification, a pale yellow viscous liquid (purity 84%) was obtained. Similarly, IR analysis of the resulting viscous liquid confirmed the formation of ester groups and amide groups and the disappearance of acid anhydride groups. 1H-NMR analysis confirmed the presence of benzophenone and morpholine groups, and LC-MS analysis confirmed that the molecular weight (641) matched that of the target compound (Table 2). These results confirmed the production of photopolymerization initiator (A-7) with the structure shown in Table 2.

[0056] Example 8 Synthesis of Photopolymerization Initiator (A-8) Using a similar apparatus, 100 g of (a1-6), 63.7 g of (a2-4), and 50 g of DMF were mixed and reacted at 70°C for 4 hours. The reaction solution was cooled to 0°C, and 19.9 g of (a5-6) and 73.8 g of thionyl chloride were added. After stirring for 10 minutes, the reaction was continued at 70°C for 3 hours. After the reaction was completed, the mixture was purified to obtain a pale yellow viscous liquid (purity 96%). Similarly, IR analysis of the obtained viscous liquid confirmed the formation of ester groups and the disappearance of acid anhydride groups. 1 H-NMR analysis confirmed the presence of benzophenone and tetrahydrofuran groups, and LC-MS analysis confirmed that the molecular weight (555) matched that of the target compound (Table 2). These results confirmed the production of photopolymerization initiator (A-8) with the structure shown in Table 2.

[0057] Example 9 Synthesis of Photopolymerization Initiator (A-9) Using a similar apparatus, 100 g of (a1-6), 54.1 g of (a2-2), 3.1 g of TEA, and 50 g of DMF were mixed and reacted at 65°C for 2 hours, after which 202.7 g of (a5-7) was added and reacted at 85°C for 5 hours. After the reaction was completed, the mixture was purified to obtain a pale yellow viscous liquid (purity 81%). Similarly, IR analysis of the obtained viscous liquid confirmed the formation of ester groups and amide groups and the disappearance of acid anhydride groups. 1 H-NMR analysis confirmed the presence of benzophenone and morpholine groups, and LC-MS analysis confirmed that the molecular weight (1150) matched that of the target compound (Table 2). These results confirmed the production of photopolymerization initiator (A-9) with the structure shown in Table 2.

[0058] Example 10 Synthesis of Photopolymerization Initiator (A-10) Using a similar apparatus, 100 g of (a1-6), 27.0 g of (a2-2), 1.5 g of TEA, and 50 g of DMF were mixed and reacted at 65°C for 2 hours, after which 11.2 g of ion-exchanged water was added and the reaction was continued at 65°C for 3 hours. After the reaction was completed, the mixture was purified to obtain a pale yellow viscous liquid (purity 97%). Similarly, IR analysis of the obtained viscous liquid confirmed the formation of amide groups and the disappearance of acid anhydride groups. 1 H-NMR analysis confirmed the presence of benzophenone and morpholine groups, and LC-MS analysis confirmed that the molecular weight (427) matched that of the target compound (Table 2). These results confirmed the production of photopolymerization initiator (A-10) with the structure shown in Table 2.

[0059] Examples 11, 14, and 15 Synthesis of photopolymerization initiators (A-11), (A-14), and (A-15) The reactions of Examples 11, 14 and 15 were carried out in the same manner as in Example 7 using the raw material compounds shown in Table 1, and pale yellow viscous liquids were obtained. 1 The formation of photopolymerization initiators (A-11), (A-14), and (A-15), whose structures are shown in Table 2, was confirmed by H-NMR analysis and LC-MS analysis.

[0060] Examples 12, 17, 19, and 20 Synthesis of photopolymerization initiators (A-12), (A-17), (A-19), and (A-20) The reactions of Examples 12, 17, 19, and 20 were carried out in the same manner as in Example 6 using the raw material compounds shown in Table 1, and pale yellow viscous liquids were obtained. 1 The formation of photopolymerization initiators (A-12), (A-17), (A-19), and (A-20), whose structures are shown in Table 2, was confirmed by H-NMR analysis and LC-MS analysis.

[0061] Example 13 Synthesis of Photopolymerization Initiator (A-13) Using a similar apparatus, 100 g of (a1-7), 135.6 g of 2-(hydroxymethyl)-15-crown-5-ether, 1.5 g of TEA, and 50 g of DMF were mixed and reacted at 65°C for 2 hours. After the reaction was completed, the mixture was purified to obtain a pale yellow viscous liquid (purity 84%). 1The production of the photopolymerization initiator (A-13) with the structure shown in Table 2 was confirmed by H-NMR analysis (described below) and LC-MS analysis. 1 H-NMR: 8.61-7.78 ppm (6H, aromatic ring); 5.02 ppm (2H, -COO-CH-); 3.68-4.01 ppm (28H, -CH2-O- in crown ether).

[0062] Example 16 Synthesis of Photopolymerization Initiator (A-16) Using a similar apparatus, 100 g of (a1-6), 88.2 g of (a5-3), 10.0 g of tetrabutylammonium bromide, and 50 g of DMF were mixed and reacted at 70°C for 4 hours. The reaction solution was cooled to 0°C, and 54.1 g of (a2-4) and 73.8 g of thionyl chloride were added. After stirring for 10 minutes, the mixture was reacted at 70°C for 3 hours. After the reaction was completed, the mixture was purified to obtain a pale yellow viscous liquid (83% purity). Similarly, IR analysis of the resulting viscous liquid confirmed the formation of ester groups and the disappearance of acid anhydride groups. 1 H-NMR analysis confirmed the presence of benzophenone, tetrahydrofuran, and methacrylate groups, and LC-MS analysis confirmed that the molecular weight (811) matched that of the target compound (Table 2). These results confirmed the production of photopolymerization initiator (A-16) with the structure shown in Table 2.

[0063] Example 18 Synthesis of Photopolymerization Initiator (A-18) The reaction of Example 18 was carried out in the same manner as in Example 16 using the raw material compounds shown in Table 1, and a pale yellow viscous liquid was obtained. 1 The production of the photopolymerization initiator (A-18) with the structure shown in Table 2 was confirmed by H-NMR analysis (described below) and LC-MS analysis. 1 H-NMR: 4.91ppm (2H, -O-CH-), 2.71ppm (4H, -CH2-N-), 2.22ppm (8H, -N-CH2- in the thiopyran group); 1.53-1.41ppm (10H, -CH2-CH2- in the thiopyran group).

[0064] [Table 1]

[0065] [Table 2-1]

[0066] [Table 2-2]

[0067] Example 21 Synthesis of Photopolymerization Initiator (A-21) 79.27 g of (A-2) and 0.05 g of dibutylhydroxytoluene (BHT) as a polymerization inhibitor were added to a 300 mL flask equipped with a reflux condenser, stirrer, thermometer, and dropping funnel, and the temperature was raised to 70°C while stirring. 20.73 g of (C1-1) and 0.02 g of dibutyltin dilaurate were then added to the mixture, and the reaction was continued at 70°C for 5 hours. IR analysis confirmed that the absorption peak of the isocyanate group had disappeared, and the reaction was terminated. A pale yellow liquid was obtained by purification. IR analysis of the resulting liquid revealed the NH specific absorption of the urethane bond (1532 cm). -1 ), the C=O specific absorption of the ketone group of benzophenone (1650cm -1 ) was confirmed, and the molecular weight obtained by LC-MS analysis was 681, which matched the molecular weight of the target compound shown in Table 3, confirming the production of photopolymerization initiator (A-21).

[0068] Example 22 Synthesis of Photopolymerization Initiator (A-22) Using the same apparatus as in Example 21, 34.42 g of (C1-2) and 0.02 g of dibutyltin dilaurate were added to a mixed solution of 47.59 g of (A-6) and 0.05 g of BHT at 70°C, and the mixture was allowed to react at 70°C for 5 hours. After confirming that the decrease in isocyanate groups had stopped by IR analysis, 17.99 g of (B3-1) and 0.01 g of dibutyltin dilaurate were added, and the mixture was allowed to react for an additional 3 hours at 70°C. After completion of the reaction, the disappearance of the isocyanate groups was confirmed by IR analysis, and the mixture was purified to obtain a pale yellow solid. Similarly, IR analysis of the solid revealed that the urethane groups (1532 cm) -1 ), benzophenone group (1650cm -1The presence of (A-22) was confirmed, and the production of photopolymerization initiator (A-22) was confirmed. Furthermore, the number average molecular weight of (A-22) was calculated to be 1,900 by GPC analysis. The results are shown in Table 3.

[0069] Example 23 Synthesis of Photopolymerization Initiator (A-23) Using the same apparatus as in Example 21, 20.47 g of (A-7), 31.95 g of (B1-1), 30 g of (H-1), and 0.05 g of BHT were mixed at 70°C, followed by the addition of 13.90 g of (C1-3) and 0.02 g of dibutyltin dilaurate. The mixture was allowed to react at 70°C for 4 hours, and IR analysis confirmed the cessation of isocyanate group reduction. Subsequently, 3.68 g of (B3-2) and 0.01 g of dibutyltin dilaurate were added to the reaction solution, and the mixture was allowed to react at 70°C for 4 hours. The disappearance of isocyanate groups was confirmed by IR analysis, and the mixture was purified to obtain a pale yellow viscous liquid. Similarly, IR analysis confirmed the formation of photopolymerization initiator (A-23). ​​Furthermore, the number average molecular weight of (A-23) was calculated to be 6,600 by GPC analysis, and the results are shown in Table 3.

[0070] Examples 24 to 27, 29, and 30 Synthesis of photopolymerization initiators (A-24) to (A-27), (A-29), and (A-30) In the same manner as in Example 23, synthesis, purification, and analysis were carried out with the compositions shown in Table 3, and the production of photopolymerization initiators (A-24) to (A-27), (A-29), and (A-30) was confirmed. The number average molecular weights calculated by GPC analysis are also shown in Table 3.

[0071] Example 28 Synthesis of Photopolymerization Initiator (A-28) Synthesis, purification, analysis, etc. were carried out in the same manner as in Example 23 with the composition shown in Table 3, and the production of photopolymerization initiator (A-28) was confirmed. Furthermore, the number average molecular weight of (A-28) was calculated to be 10,500 by GPC analysis, and the results are shown in Table 3.

[0072] Example 31 Synthesis of Photopolymerization Initiator (A-31) In an apparatus similar to that used in Example 21, equipped with a nitrogen inlet tube, 53.04 g of (A-11), 9.37 g of (B1-9), 28.97 g of (C2-1), and 0.05 g of BHT were mixed, and the mixture was heated to 190°C under atmospheric pressure while blowing nitrogen into it. 0.01 g of zinc oxide was added to the mixture, and the reaction was carried out while distilling off water at 195°C. After the distillation of water stopped, the acid value of the reaction mixture (in accordance with JIS K0070:1992) was measured and found to be 48 mgKOH / g. Thereafter, the reflux condenser was replaced with a Dean-Stark azeotropic fractional distillation apparatus, and 4.57 g of (B3-2), 4.05 g of (B3-8), and 0.01 g of concentrated sulfuric acid were added to the reaction solution, and water and toluene (both azeotropic) were distilled out of the reaction system at 125°C. After completion of the reaction, purification was carried out, and a pale yellow viscous liquid was obtained. Similarly, IR analysis confirmed the production of photopolymerization initiator (A-31), and GPC analysis calculated the number average molecular weight to be 3,800 (Table 3).

[0073] Example 32 Synthesis of Photopolymerization Initiator (A-32) Using the same apparatus as in Example 21, 40.23 g of (A-7), 12.56 g of (B2-1), 15 g of (H-5), and 0.05 g of BHT were mixed at 70°C. 21.86 g of (C1-3) was added to the mixture, and the mixture was allowed to react at 70°C for 2 hours. After confirming that the decrease in isocyanate groups had stopped by IR analysis, 4.53 g of (B3-3), 5.82 g of (B3-9), and 0.01 g of dibutyltin dilaurate were added, and the mixture was allowed to react at 70°C for 3 hours. After confirming the disappearance of isocyanate groups by IR analysis, the mixture was purified to obtain a pale yellow viscous liquid. Similarly, IR analysis confirmed the formation of photopolymerization initiator (A-32), and GPC analysis calculated the number average molecular weight to be 4,100 (Table 3).

[0074] Example 33 Synthesis of Photopolymerization Initiator (A-33) Using the same apparatus as in Example 31, 19.44 g of (A-10), 18.40 g of (C2-2), 15 g of (H-5), and 0.05 g of BHT were mixed. 40.42 g of (C1-2) and 0.02 g of dibutyltin dilaurate were added to the mixture, which was then heated to 120°C over 2 hours and reacted at 120°C for an additional 10 hours. The reaction mixture was then cooled to 60°C, and 5.28 g of (B3-1), 1.46 g of (B3-6), and 0.01 g of dibutyltin dilaurate were added. The mixture was then reacted at 60°C for 2 hours. After completion of the reaction, the disappearance of the isocyanate groups was confirmed by IR analysis, and further purification was performed to obtain a pale yellow viscous liquid. Similarly, IR analysis confirmed the formation of photopolymerization initiator (A-33), and GPC analysis calculated the number average molecular weight to be 2,800 (Table 3).

[0075] [Table 3]

[0076] Examples 34 to 72 and Comparative Examples 1 to 4 Using the photopolymerization initiators (A-1) to (A-33) obtained in the examples and a known photopolymerization initiator (D), the monofunctional monomer (E), the polyfunctional monomer or oligomer (F), and other components (G) were weighed in the proportions shown in Table 4 and mixed for 30 minutes at 25°C to prepare active energy ray-curable compositions. The transparency of the obtained active energy ray-curable compositions, the compatibility of the photopolymerization initiator (A) or (D) with the monofunctional monomer (E) and the polyfunctional monomer or oligomer (F), and the curability of the curable compositions under different curing conditions (with or without oxygen inhibition, different wavelengths of active energy rays) were evaluated by the following methods, and the results are shown in Tables 4-1 and 4-2. (5-1) Transparency and compatibility The state of the obtained active energy ray-curable composition was visually observed, and the transparency was evaluated according to the following criteria. Also, 20 g each of the obtained photopolymerization initiators (A-1) to (A-33) and known photopolymerization initiators (D-1) to (D-4) and 80 g each of monofunctional monomers (E-2), (E-3), or polyfunctional monomers or oligomers (F-15) were weighed and mixed at 25°C for 30 minutes to prepare evaluation liquids. The state of the mixed liquid was visually observed, and the compatibility of the photopolymerization initiator with the monofunctional monomer or polyfunctional monomer or oligomer was evaluated according to the following criteria. The transparency evaluation and compatibility evaluation were performed using the same criteria. ◯: High transparency or compatibility, with no turbidity or separation observed. △: No phase separation, but turbidity. ×: Turbidity or phase separation is observed. (5-2) Curability without oxygen inhibition The obtained active energy ray-curable composition was applied to the adhesively treated surface of a 100 μm-thick polyethylene terephthalate (PET) film (Cosmoshine A-4100, manufactured by Toyobo Co., Ltd.) using a bar coater to a film thickness of 20 μm. The release surface of a biaxially oriented PET film (Diafoil MRF38, manufactured by Mitsubishi Plastics, Inc.) having a release surface on one side was then bonded to the coated surface. The coating was then cured by irradiating with ultraviolet light. The cumulative light dose required to remove tackiness when the release surface was peeled off and the cured product was touched was determined, and the curability was evaluated on a four-point scale. The following two types of ultraviolet irradiating lamps, 1) and 2), were used. The lower the cumulative light dose required to remove tackiness, the higher the curability. 1) UV-LED lamp: wavelength 365 nm, output 100 mW / cm 2 2) UV-LED lamp: wavelength 405 nm, output 100 mW / cm 2 ◎: Accumulated light intensity 1000mJ / cm 2 If it is less than this, the tack will disappear. ○: Accumulated light intensity 1000mJ / cm 2 More than 3000mJ / cm 2 If it is less than this, the tack will disappear. △: Accumulated light intensity 3000mJ / cm 2 More than 20000mJ / cm2 If it is less than this, the tack will disappear. ×: Accumulated light intensity 20,000 mJ / cm 2 But the tack remains. (5-3) Hardening under oxygen inhibition conditions In the same manner as in the evaluation of curability under conditions without oxygen inhibition, a coating film was prepared before curing, and without laminating a film on its surface, the coating film was cured by irradiating it with ultraviolet light. Similarly, the integrated amount of light required for the cured product to lose its tackiness when touched was determined, and the curability was similarly evaluated into four levels. (5-4) Bleed-out resistance Test specimens were prepared after curing in the same manner as for the evaluation of curing properties under conditions without oxygen inhibition (UV-LED lamp: wavelength 395 nm, illuminance 100 mW / cm 2 , cumulative light intensity 10,000mJ / cm 2 The test pieces were then left to stand in a thermo-hygrostat set at a temperature of 40°C and a relative humidity of 50% for 168 hours, and the surfaces of the test pieces were visually observed to evaluate the bleed-out resistance according to the following criteria. ⊚: No bleeding out was observed. ○: Very little bleeding was observed. △: Slight bleeding out was observed. ×: Severe bleeding out was observed.

[0077] [Table 4-1]

[0078] [Table 4-2]

[0079] Examples 73 to 79 and Comparative Examples 5 to 7 Using the obtained photopolymerization initiator (A) and a known photopolymerization initiator (D), a monofunctional monomer (E), a polyfunctional monomer or oligomer (F), other components (G), and an organic solvent (H) were weighed in the proportions shown in Table 5, and mixed at 25°C for 30 minutes to prepare an active energy ray-curable coating composition. The adhesion, pencil hardness, and durability of the coating composition were evaluated by the following methods, and the results are shown in Table 5.

[0080] (5-5) Adhesion The obtained coating composition was applied to test pieces of a PET plate (PET-1060, manufactured by C.I. Takiron Co., Ltd.), a polycarbonate (PC) plate (PC1600, manufactured by C.I. Takiron Co., Ltd.), a glass (GL) plate (Eagle XG, manufactured by Corning Japan Co., Ltd.), and a SUS304 plate using a bar coater so that the dry film thickness was 10 μm, and then dried in a thermostatic oven at 80°C for 2 minutes. The wavelength was 395 nm and the output was 100 mW / cm. 2 The UV-LED lamp provides an integrated light output of 3000mJ / cm 2 Using the obtained cured film, 100 1 mm square grids were made with a cutter knife in accordance with JIS K 5600-5-6, and a commercially available adhesive tape was attached to the test piece, and then peeled off. The number of grids remaining on the test piece was evaluated into four levels. The more grids remaining on the test piece, the higher the adhesion. ◎: The number of remaining squares is 100. ○: The number of remaining grids is 90 to 99. △: The number of remaining grids is 60 to 89. ×: The number of remaining squares is less than 60. (5-6) Pencil hardness As in the evaluation of adhesion, a cured film was prepared on a PC test piece, and the surface of the cured film was scratched with a pencil (at a 45° angle, approximately 10 mm) in accordance with JIS K 5600-5-4. The pencil hardness was then determined by the hardest pencil that did not scratch the surface of the cured film, and the hardness was evaluated into four levels. ◎: Pencil hardness is 2H or more. ◯: Pencil hardness is HB to H. △: Pencil hardness is 3B to B. ×: Pencil hardness is 4B or less. (5-7)Durability As in the evaluation of adhesion, a cured film was prepared on a PC test piece and held at a temperature of 85°C and a relative humidity of 85% for 100 hours. The cured film was then visually inspected for any lifting, peeling, bubbles, or cloudiness, and durability was evaluated according to the following criteria. ◎: Transparent, no floating, peeling or bubbles. ○: There is a slight cloudiness, but no lifting, peeling, or bubbles. △: Slight lifting, peeling or bubbles occurred. ×: Cloudy, floating, peeling, or bubbles are present.

[0081] [Table 5]

[0082] Examples 80 to 85 and Comparative Examples 8 and 9 Using the obtained photopolymerization initiator (A) and a known photopolymerization initiator (D), a monofunctional monomer (E), a polyfunctional monomer or oligomer (F), and other components (G) were weighed in the proportions shown in Table 6, and mixed at 25°C for 30 minutes to prepare an actinic ray-curable ink composition. The obtained ink composition was applied to a 100 μm-thick PET film using a bar coater (RDS12) (film thickness after drying: 20 μm), and then irradiated with ultraviolet light (UV-LED lamp: wavelength 395 nm, illuminance 1000 mW / cm). 2 The curability of the ink composition was evaluated in the same manner as in (5-3) above, in which curability was evaluated under oxygen-inhibited conditions, and the viscosity of the ink composition, pigment dispersibility, and ejection stability, as well as the print clarity of the printed matter, were evaluated by the following methods. The results are shown in Table 6. (5-8) Viscosity The viscosity of the ink composition was measured at 25°C using a cone-plate viscometer (RE550 viscometer manufactured by Toki Sangyo Co., Ltd.) in accordance with JIS K 5600-2-3, and the ink composition was evaluated as an ink jet printing ink composition into the following four levels. ◎: Less than 5 to 50 mPa·s ○: Less than 50 to 500 mPa·s △: 500 to less than 2000 mPa·s ×:2000mPa·s or more (5-9) Pigment dispersibility Using a pigment-containing ink composition, the state of aggregation or precipitation of the pigment was visually observed immediately after preparation and after standing at room temperature for 2 months, and the pigment dispersibility was evaluated according to the following criteria. ⊚: No aggregation or precipitation of the pigment was observed immediately after preparation or after leaving it to stand for 2 months. ◯: No aggregation or precipitation was observed immediately after preparation, but slight aggregation or precipitation of the pigment was observed after standing for 2 months. △: Slight aggregation or precipitation was observed immediately after preparation, and aggregation or precipitation of the pigment was clearly observed after standing for 2 months. ×: Pigment aggregation and precipitation were clearly observed even immediately after preparation. (5-10) Discharge stability The obtained ink composition was filled into an inkjet printer (LuxelJet UV350GTW, manufactured by Fujifilm Corporation), and a solid image was printed on coated paper. The printing condition of the obtained print was visually observed, and the ejection stability was evaluated according to the following criteria. ⊚: No nozzles were missing and printing was good. ○: There was slight nozzle missing. ×: Missing nozzles were observed over a wide area. (5-11) Print clarity The image clarity of the prints obtained in the above-mentioned ejection stability evaluation was visually observed and evaluated according to the following criteria. ⊚: No ink bleeding was observed and the image was clear. ◯: There was almost no ink bleeding and the image was good. ×: Ink bleeding was observed.

[0083] [Table 6]

[0084] Examples 86 to 90 and Comparative Examples 10 and 11 Using the photopolymerization initiator (A) thus obtained and a known photopolymerization initiator (D), a monofunctional monomer (E), a polyfunctional monomer or oligomer (F), and other components (G) were weighed in the proportions shown in Table 7, and mixed for 30 minutes at 25°C to prepare active energy ray-curable pressure-sensitive adhesive compositions. A 75 μm-thick heavy-release PET film (E7001, manufactured by Toyobo Co., Ltd.) was adhered to a horizontally placed glass plate, a 1 mm-thick spacer with an internal dimension of 60 mm × 100 mm was placed, and the pressure-sensitive adhesive compositions prepared in the Examples and Comparative Examples were filled inside the spacer, and a 50 μm-thick light-release PET film (E7002, manufactured by Toyobo Co., Ltd.) was placed on top of it. The resulting mixture was mixed at a wavelength of 395 nm and an illuminance of 100 mW / cm. 2 The UV-LED lamp provides an integrated light output of 1000mJ / cm 2 The pressure-sensitive adhesive composition was cured by irradiating the specimen so that the light release PET film was irradiated to a temperature of 100°C. The pressure-sensitive adhesive composition was then ...

[0085] (5-12) Transparency Under conditions of a temperature of 23°C and a relative humidity of 50%, the adhesive layer was transferred from the adhesive sheet to a glass plate, and the transmittance of the glass plate and adhesive layer was measured using a haze meter (NDH-2000, manufactured by Nippon Denshoku Industries Co., Ltd.) in accordance with JIS K 7105. The transmittance of the glass plate was then measured in the same manner, and subtracted from the total light transmittance of the glass plate and adhesive layer to calculate the transmittance of the adhesive layer, and the transparency was evaluated according to the following criteria. ◎: Transmittance is 90% or more ○: Transmittance is 85% or more and less than 90% △: Transmittance is 50% or more and less than 85% ×: Transmittance is less than 50% (5-13) Yellowing resistance An adhesive sheet was prepared in the same manner as above, and set in a xenon fade meter (SC-700-WA, manufactured by Suga Test Instruments Co., Ltd.) and measured at 70 mW / cm 2 After 120 hours of irradiation with ultraviolet light of an intensity of 1000 ppm, the discoloration of the adhesive layer on the adhesive sheet was visually observed and evaluated according to the following criteria. ⊚: No yellowing was observed visually. ○: Yellowing is very slight and visible. △: Yellowing can be visually confirmed. ×: Obvious yellowing is visible. (5-14) Adhesive strength The adhesive layer of the adhesive sheet was transferred to the following substrate (film or plate) under conditions of 23°C temperature and 50% relative humidity, and then pressure-attached by two reciprocating motions using a 2 kg pressure roller, and left in the same atmosphere for 30 minutes. The 180° peel strength (N / 25 mm) was then measured at a peel rate of 300 mm / min in accordance with JIS Z 0237 using a tensile tester (Tensilon RTA-100, manufactured by ORIENTEC Corporation), and the adhesive strength of the adhesive sheet on each substrate was evaluated according to the following criteria. PET: Cosmoshine A4160 (corona treated surface, manufactured by Toyobo Co., Ltd.) PC: PC1600 (manufactured by Takiron C.I. Co., Ltd.) GL (glass): Eagle XG (manufactured by Corning Inc.) ◎:20(N / 25mm) or more ○: 10 (N / 25mm) or more, less than 20 (N / 25mm) △: 5 (N / 25mm) or more, less than 10 (N / 25mm) ×: Less than 5 (N / 25mm) (5-15) Reworkability As in the adhesive strength evaluation, the adhesive layer was transferred from the adhesive sheet to the substrate, and then left to stand in a thermostatic chamber at 80°C for 24 hours. After the adhesive sheet was peeled off, the state of the adhesive layer (glue) remaining on the surface of the substrate was visually observed, and the reworkability of the adhesive sheet was evaluated according to the following criteria. ◎: No adhesive residue was left. ○: There was a very small amount of adhesive residue. △: A small amount of adhesive remained. ×: There was adhesive residue.

[0086] [Table 7]

[0087] Examples 91 to 96 and Comparative Examples 12 and 13 Using the photopolymerization initiator (A) thus obtained and a known photopolymerization initiator (D), a monofunctional monomer (E), a polyfunctional monomer or oligomer (F), and other components (G) were weighed in the proportions shown in Table 8, and mixed for 30 minutes at 25°C to prepare active energy ray-curable adhesive compositions. The adhesive composition was applied to various horizontally placed plate- or film-shaped substrates, and the PET film described below was laminated to the coated surface. After that, the adhesive layers were laminated to a thickness of 20 μm using a desktop roll laminator (RSL-382S), taking care not to trap air bubbles. The lamination was performed at a wavelength of 405 nm and an illuminance of 50 mW / cm. 2 The UV-LED lamp provides an integrated light output of 2000mJ / cm 2 The adhesive strength and water resistance of the obtained laminate were evaluated by the following methods, and the results are shown in Table 8. The following substrates were used. PET: Film (E5100, corona treated surface, manufactured by Toyobo Co., Ltd.) PMMA: Plate (Comoglass P, manufactured by Kuraray Co., Ltd.) PC: Plate (PC1600, manufactured by Takiron C.I. Co., Ltd.) (5-16)Water resistance The produced laminate was immersed in warm water at 60°C for 48 hours, and the presence or absence of peeling at the interface was checked, and the water resistance was evaluated according to the following criteria. ◎: No peeling at the interface (less than 1 mm) ○: Partial peeling at the interface (1mm or more, less than 3mm) △: Partial peeling at the interface (3mm or more, less than 5mm) ×: Peeling at the interface (5 mm or more) (5-17) Adhesive strength The 180° peel strength (N / 25 mm) of the produced laminate was measured at a peel rate of 300 mm / min in accordance with JIS Z0237 using a tensile tester (Tensilon RTA-100), and the adhesive strength was evaluated according to the following criteria. ◎:20(N / 25mm) or more ○: 10 (N / 25mm) or more, less than 20 (N / 25mm) △: 5 (N / 25mm) or more, less than 10 (N / 25mm) ×: Less than 5 (N / 25mm)

[0088] [Table 8]

[0089] Examples 97 to 101 and Comparative Examples 14 and 15 Using the obtained photopolymerization initiator (A) and a known photopolymerization initiator (D), a monofunctional monomer (E), a polyfunctional monomer or oligomer (F), and other components (G) were weighed in the proportions shown in Table 9 and mixed at 25°C for 30 minutes to prepare an active energy ray-curable ink composition for three-dimensional modeling. The obtained ink composition for three-dimensional modeling was used to evaluate three-dimensional modeling curability and cure shrinkage resistance. The obtained modeled objects were also evaluated for modeling accuracy, strength, heat resistance, and water resistance using the methods described below, and the results are shown in Table 9. (5-18) Three-dimensional modeling hardenability An ARM-10 (manufactured by Roland DG Corporation) was used as a hanging-type DLP-type liquid tank photopolymerization device. The liquid tanks were filled with the ink compositions for three-dimensional modeling obtained in each Example and Comparative Example, and ultraviolet light was irradiated (wavelength 405 nm, illuminance 0.2 mW / cm) so that the thickness of one layer was 0.15 mm. 2 , cumulative light intensity 5mJ / cm 2 ) and a rectangular parallelepiped of 25 × 20 × 1 mm was modeled. After modeling, the object was immersed in isopropanol for 1 minute (twice) to wash and remove any uncured ink composition for three-dimensional modeling. The state of the modeled object was then observed and its curability was evaluated according to the following criteria. ◎: The object is formed and can be washed with isopropanol while retaining its shape. ○: A printed object is formed, but some deformation is observed in the printed object due to washing with isopropanol. △: The printed object was not formed properly, and was damaged when washed with isopropanol. ×: No object is formed. (5-19) Resistance to curing shrinkage A 75 μm thick heavy-release PET film (E7001) was placed on a horizontally placed glass plate, and a 1 mm thick spacer with an internal dimension of 60 mm x 100 mm was placed. The ink composition for three-dimensional modeling obtained in each example and comparative example was filled inside the spacer, and then a light-release PET film (E7002) was placed on top of it, and ultraviolet light was irradiated from both sides (wavelength 405 nm, illuminance 10 mW / cm). 2 , cumulative light intensity 5,000mJ / cm 2 ), cured, and the release PET films on both sides were removed to obtain a test specimen. According to JIS K5600 2-4, the cure shrinkage rate was calculated from the density change of the ink composition for three-dimensional modeling and the test specimen using the following formula. The density was measured according to JIS K7112 using an electronic hydrometer (MDS-300, manufactured by Alpha Mirage Co., Ltd.). The cure shrinkage resistance of the ink composition for three-dimensional modeling was evaluated from the obtained cure shrinkage rate according to the following criteria. Curing shrinkage rate (%)=(Ds-Dl) / Dl×100% (In the formula, Ds is the density of the ink composition for three-dimensional modeling after curing, and Dl is the density of the ink composition for three-dimensional modeling before curing.) ◎: Curing shrinkage rate less than 6% ○: Cure shrinkage rate 6% or more and less than 7% △: Curing shrinkage rate 7% or more and less than 8% ×: Cure shrinkage rate 8% or more (5-20) Strength Test pieces were prepared in the same manner as for the cure shrinkage resistance, and six pieces were stacked together to measure the Shore D hardness in accordance with JIS K 6253 (rubber hardness testing method), and the strength of the three-dimensionally shaped object was evaluated according to the following criteria. ◎: Shore D hardness 60 or more ○: Shore D hardness 40 or more and less than 60 ×: Shore D hardness less than 40 (5-21) Heat resistance Test pieces were prepared in the same manner as for the curing shrinkage resistance test, and measured using a differential scanning calorimeter (DSC-60plus, The glass transition temperature (Tg) of the three-dimensionally shaped object was measured using a glass transition temperature (Tg) tester (manufactured by Shimadzu Corporation), and the heat resistance of the three-dimensionally shaped object was evaluated according to the following criteria. ◎: Cured product Tg 50℃ or higher ○: Tg of cured product is 40℃ or higher and lower than 50℃ ×: Tg of cured product less than 40°C (5-22) Modeling accuracy A heavy-release PET film (E7001) was placed on a horizontally placed glass plate, and a spacer 10 mm thick with an internal dimension of 10 mm x 10 mm was placed thereon. The ink composition for three-dimensional modeling obtained in each of the Examples and Comparative Examples was filled to a thickness of 1 mm inside the spacer. The surface was then smoothed by heating at 60°C for 30 seconds, and then irradiated with ultraviolet light (UV-LED lamp, wavelength 405 nm, illuminance 10 mW / cm). 2 , cumulative light intensity 1,000mJ / cm 2 ) and the ink composition for three-dimensional modeling was cured. The ink composition for three-dimensional modeling was then filled to a thickness of 1 mm, and the curing process was repeated a total of 10 times to obtain a three-dimensional object measuring 10 x 10 x 10 mm. The height of the obtained object was measured, and the side surface of the object was visually observed. These results were combined and the modeling accuracy of the object was evaluated according to the following criteria. ◎: Height is less than 10mm ± 0.1mm and there are no irregularities on the side. ○: Height is 10mm ±0.1mm or more but less than ±0.2mm, or there are slight irregularities on the side. △: Height is 10mm ±0.2mm or more but less than ±0.3mm, or there are slight irregularities on the side. ×: Height is 10 mm ± 0.3 mm or more, or there are obvious irregularities on the side. (5-23)Water resistance Test pieces were prepared in the same manner as for the cure shrinkage resistance, and immersed in ion-exchanged water at 25° C. for 24 hours, and the water resistance of the three-dimensional model was evaluated according to the following criteria. Water absorption rate (%)=(Wb-Wa) / Wa×100 (In the formula, Wa is the weight of the test piece before immersion in ion-exchanged water, and Wb is the weight of the test piece after immersion in ion-exchanged water.) ◎: Water absorption rate is less than 0.5%. ○: Water absorption rate is 0.5% or more and less than 1%. △: Water absorption rate is 1% or more but less than 2%. ×: Water absorption rate is 2% or more.

[0090] [Table 9]

[0091] Examples 102 to 106 and Comparative Examples 16 and 17 Using the obtained photopolymerization initiator (A) and a known photopolymerization initiator (D), a monofunctional monomer (E), a polyfunctional monomer or oligomer (F), and other components (G) were weighed in the proportions shown in Table 10 and mixed at 25°C for 30 minutes to prepare an active energy ray-curable nail cosmetic composition. The curability of the obtained nail cosmetic composition was evaluated (LED 405 nm) in the same manner as in the evaluation of curability under conditions without oxygen inhibition described in (5-2) above. The adhesion, surface hardness, surface gloss, and removability of the nail cosmetic composition were also evaluated using the following methods, and the results are shown in Table 10. (5-24) Adhesion The curable nail cosmetic composition was applied to a nylon 6 test piece and irradiated for 3 minutes using a UV-LED lamp (manufactured by Beauty Nailer, wavelength 405 nm, output 48 W) designed specifically for gel nails to form a cured film. Using the resulting cured film, the adhesion of the nail cosmetic composition was evaluated according to the following criteria, in accordance with JIS K 5600, in the same manner as for evaluating the adhesion of coating compositions. The greater the number of cross-cut marks remaining on the test piece, the higher the adhesion. ◎: The number of remaining squares is 100. ○: The number of remaining grids is 90 to 99. △: The number of remaining grids is 60 to 89. ×: The number of remaining squares is less than 60. (5-25)Surface hardness A cured film was prepared in the same manner as in the adhesion evaluation, and a 750 g load of an HB hardness pencil was pressed against the surface of the film at a 45° angle and pulled, and the presence or absence of peeling and scratches was visually confirmed, and the surface hardness was evaluated according to the following criteria. The fewer scratches and peeling occurred, the higher the surface hardness. ◯: No scratches or peeling occurred. The surface hardness was pencil hardness HB or higher. △: No peeling occurred, but scratches occurred. ×: Peeling occurred. (5-26) Surface gloss A cured film was prepared in the same manner as in the adhesion evaluation, and left to stand for 24 hours in a thermo-hygrostat chamber at a temperature of 40°C and a relative humidity of 50%. The gloss of the surface of the film was then visually observed, and the surface gloss of the cured film was evaluated according to the following criteria. ○: Shiny. △: Light reflection can be seen, but there is some cloudiness. ×: No light reflection was observed and there was no gloss. (5-27)Removability As in the adhesion evaluation, a cured film measuring 10 mm x 10 mm was prepared on a test piece, and absorbent cotton soaked in acetone was covered for 5 minutes. After that, the absorbent cotton was removed, and the cured film was rubbed 10 times with a cotton swab. The state of peeling of the cured film from the test piece was observed, and the removability of the cured film was evaluated according to the following criteria. ◯: The cured film peeled off without any residue. Δ: The cured film peeled off, but a portion of the cured film remained. ×: Most of the cured film remained.

[0092] [Table 10]

[0093] Examples 107 to 112 and Comparative Examples 18 and 19 Using the obtained photopolymerization initiator (A) and a known photopolymerization initiator (D), a monofunctional monomer (E), a polyfunctional monomer or oligomer (F), and other components (G) were weighed in the proportions shown in Table 11 and mixed at 25°C for 30 minutes to prepare an active energy ray-curable dental material composition. Using the obtained dental material composition, the solubility (dispersibility), storage stability, and curability (using a 405 nm LED as a method similar to the evaluation of curability under conditions without oxygen inhibition in (5-2) above) were evaluated. The hardness, surface smoothness, and adhesive strength of the obtained cured product were evaluated according to the following criteria. The results are shown in Table 11. (5-28) Solubility (dispersibility) The state of the hardenable dental material composition was visually observed, and the solubility or dispersibility was evaluated according to the following criteria. ◯: The composition was in a homogeneous state. △: The composition was slightly non-uniform. ×: The composition was in a non-uniform state. (5-29) Storage stability The hardenable dental material composition was placed in a light-shielding screw tube, the lid was closed, and the composition was stored under two conditions: at 40°C for 1 month and at 80°C for 2 weeks. The state of dissolution or dispersion of the composition after storage was confirmed, and the storage stability of the composition was evaluated according to the following criteria. ○: No change in state was observed after storage under both conditions of 40°C for one month and 80°C for two weeks. △: A change in state was observed after storage under either one of the conditions of 40°C for one month or 80°C for two weeks. ×: Changes in state were observed after storage under both conditions: 1 month at 40°C and 2 weeks at 80°C. (5-30)Hardness The surface of the cured product obtained in the curability evaluation was buffed, and the Knoop hardness was measured at 23°C using a Matsuzawa Seiki microhardness tester with a load of 10 g for 20 seconds, and the hardness of the cured product was evaluated according to the following criteria. ◎: Knoop hardness is 200KHN or more (equivalent to permanent tooth enamel). ○: Knoop hardness is 70KHN or more and less than 200KHN (equivalent to dentin). △: Knoop hardness is less than 70KHN. ×: Not cured, so measurement was not possible. (5-31)Surface smoothness The surface smoothness and gloss of the cured product obtained in the curability evaluation were visually observed and evaluated according to the following criteria. ◎: The surface is smooth and glossy. ○: The surface is almost smooth, with slight cloudiness or slight irregularities. △: The surface is cloudy overall, and some irregularities and granularity are observed. ×: The surface is entirely cloudy and covered with granular particles. (5-32) Adhesive strength A bovine mandibular anterior tooth was polished with No. 1000 waterproof abrasive paper under running water to remove a flat dentin surface for bonding. The surface was then dried with a 10-second blast of compressed air. Tape with a 3 mm diameter hole was then attached to the surface to set the adhesion surface. Adhesion test specimens were then prepared using a known method (see the method described in JP 2010-208964 A). The adhesion test specimens were immersed in 37°C water for 24 hours, and the tensile bond strength was measured using an Instron universal testing machine (crosshead speed: 2 mm / min) to determine the adhesion strength to the enamel and dentin. The bond strength was evaluated according to the following criteria. ◎: The bond strength between enamel and dentin is 20 MPa or more. ○: The bond strength between enamel and dentin is 20 MPa or more in only one case. △: The bond strength between enamel and dentin is 7 MPa or more. ×: The bond strength between enamel and dentin is less than 7 MPa.

[0094] [Table 11]

[0095] Examples 113 to 118 and Comparative Examples 20 and 21 Using the obtained photopolymerization initiator (A) and a known photopolymerization initiator (D), a polyfunctional monomer or oligomer (F), other components (G), and an organic solvent (H) were weighed in the proportions shown in Table 12 and mixed at 25°C for 30 minutes to prepare active energy ray-curable photosensitive compositions. Using the obtained photosensitive compositions, photosensitive resins for evaluation were produced in Examples 113 to 115 and Comparative Example 20 according to the following (5-33) Photosensitive Resin Production 1, and in Examples 116 to 118 and Comparative Example 21 according to the following (5-34) Photosensitive Resin Production 2. The sensitivity, pattern formability, and storage stability of the photosensitive compositions were evaluated, and the results are shown in Table 12. (5-33) Production of photosensitive resin 1 The active energy ray-curable photosensitive compositions of Examples 113 to 115 and Comparative Example 20 were applied to a PET film (E5100, corona-treated surface) using a rotary coater to a film thickness of 15 μm, and then dried in an oven at 80°C for 3 minutes. Thereafter, the coating was irradiated with ultraviolet light (wavelength 405 nm, illuminance 0.5 mW / cm) using a negative photomask for 3 minutes. 2 , cumulative light intensity 90mJ / cm 2 Next, the negative photomask was removed, and the unexposed areas were removed using cyclopentanone to obtain a cured photosensitive resin for evaluation. (5-34) Production of photosensitive resin 2 The active energy ray-curable photosensitive compositions of Examples 116 to 118 and Comparative Example 21 were applied to a PET film (E5100, corona-treated surface) using a rotary coater to a film thickness of 15 μm, and then dried in an oven at 40°C for 30 minutes. Thereafter, the coating was irradiated with ultraviolet light (wavelength 405 nm, illuminance 0.5 mW / cm) for 3 minutes using a negative photomask. 2 , cumulative light intensity 90mJ / cm 2 After the exposure, the negative photomask was removed and the unexposed areas were removed using cyclopentanone. The resulting film was then heat-treated in an oven at 130°C for 30 minutes to obtain a photosensitive resin for evaluation. (5-35) Sensitivity The obtained photosensitive resin for evaluation was touched with hands to check for stickiness and the presence of uncured components, and the curability of the photosensitive composition was evaluated according to the following criteria. ◎: No stickiness at all. ○: There is some stickiness, but no finger marks remain on the surface. △: Sticky and leaves finger marks on the surface. ×: Extremely sticky, fingers stick to the surface. (5-36)Pattern Formation The pattern formability of the photosensitive resin for evaluation was evaluated according to the following criteria. ⊚: The pattern is free of distortion and no chipping is observed at the edges. ◯: There is no distortion in the pattern, and slight chipping at the edges is observed. △: There is no distortion in the pattern, but chipping is observed at the edge. ×: The pattern is distorted. (5-37) Storage stability The obtained photosensitive resin for evaluation was left to stand in a thermo-hygrostat chamber at a temperature of 40°C and a relative humidity of 50% for 168 hours, and the presence or absence of bleed-out on the surface of the test piece was visually observed, and the storage stability was evaluated according to the following criteria. The less bleed-out, the higher the storage stability. ⊚: No bleeding out was observed. ○: Slight bleeding out is observed. ×: Severe bleeding out is observed.

[0096] [Table 12]

[0097] As is clear from the results in Tables 4 to 12, the photopolymerization initiator (A) (Examples 1 to 33) of the present disclosure has good compatibility with general-purpose monofunctional monomers and polyfunctional monomers or oligomers, has high photoinitiating ability with various active energy rays from short to long wavelengths, and exhibits high curability of active energy ray-curable compositions containing it. Both the resulting curable compositions and cured products had excellent transparency. Furthermore, the photopolymerization initiator (A) is not easily inhibited by oxygen, and both the initiation reaction and the photopolymerization reaction with long-wavelength light in air proceed at a sufficient rate. The curable compositions containing the photopolymerization initiator (A) (Examples 34 to 72) exhibited high curability even when irradiated with long-wavelength light in the air or under oxygen-shielded conditions. Furthermore, the active energy ray-curable compositions (Examples 73 to 118) prepared for various applications exhibited good adhesion, tackiness, and adhesiveness, and the cured products in various forms after curing also possessed high physical properties such as hardness and strength. Furthermore, the cured products obtained by curing exhibited very little odor, bleed-out, outgassing, yellowing over time, or deterioration, and the cured products exhibited high resistance to yellowing, water resistance, durability, heat resistance, and sealing properties. In contrast, compositions containing known photopolymerization initiators (Comparative Examples 1 to 21) exhibited poor curability with long-wavelength light, and the cured products exhibited poor physical properties such as adhesion, tackiness, adhesiveness, hardness, and strength, as well as poor resistance to yellowing, water resistance, durability, and heat resistance. Therefore, the photopolymerization initiators of the present disclosure and active energy ray-curable compositions containing them can be suitably used in a variety of applications.

[0098] This disclosure includes the following content: (1) A photopolymerization initiator having one or more benzopheno groups and saturated or unsaturated 5- or larger-membered cyclic substituents having one or more heteroatoms in the molecule, and having one or more saturated or unsaturated 5- or larger-membered cyclic substituents having heteroatoms bonded to one or more carbon atoms of the aryl groups of at least one or more benzopheno groups via a carboxylic acid ester group or a carboxylic acid amide group. (2) The photopolymerization initiator according to (1) above, which has in its molecule one or more ethylenically unsaturated groups selected from one or more of a (meth)acrylamide group, a (meth)acrylate group, a vinyl group, a vinyl ether group, an alkyl vinyl ether group, an allyl group, a (meth)allyl ether group, a styryl group, and a maleimide group. (3) The photopolymerization initiator according to (1) or (2), wherein the cyclic substituent is one or more groups selected from a piperidine group, a pyrrolidine group, a piperazine group, a pyridine group, a morpholine group, a tetrahydrofuran group, a hydrofuran group, a crown ether group, and a tetrahydrothiopyran group. (4) The photopolymerization initiator according to claim 1 or 2, wherein the cyclic substituent is one or more groups selected from the group consisting of a piperidine group, a pyrrolidine group, a piperazine group, a pyridine group, a morpholine group, a tetrahydrofuran group, a hydrofuran group, a crown ether group, and a tetrahydrothiopyran group. 4. The photopolymerization initiator according to claim 1, which has one or more groups selected from the group consisting of urethane groups, urea groups, ester groups, thioester groups, amide groups, and imide groups in the molecule. (5) The photopolymerization initiator according to any one of (1) to (4) above, which has a structure represented by general formula (1). JPEG0007811041000020.jpg38127 (in the formula, Q 1 , Q 3 are each independently a hydrogen atom or a monovalent organic group represented by general formula (2) or general formula (3), and Q 1 , Q 3 at least one of the following is a monovalent organic group having one or more saturated or unsaturated 5- or greater-membered cyclic substituents having a heteroatom; Q 2 , Q 4 are each independently a divalent organic group represented by general formula (4) or general formula (5), L 1 , L 2 are each independently a direct bond or a divalent organic group containing at least one of a urethane group, a urea group, an ester group, an amide group, and an imide group. 2 -L 1 -R5 and Q 4 -L 2 -R 6 may be hydrogen atoms, but these are 1 , Q 3 Except when both are hydrogen atoms, JPEG0007811041000021.jpg1351JPEG0007811041000022.jpg1851JPEG0007811041000023.jpg1351JPEG0007811041000024.jpg1851R 1 ~R 9 , R 12 each independently represents a hydrogen atom or a linear or cyclic, saturated or unsaturated monovalent hydrocarbon group having 1 to 36 carbon atoms, in which one or more hydrogen atoms may be substituted with a hydroxyl group, an amine group, a thiol group, or a halogen group, and one or more carbon atoms may be substituted with an ether group, an amino group, a thioether group, or a thioester group; R 10 , R 11 each independently represents a direct bond or a linear or cyclic, saturated or unsaturated divalent hydrocarbon group having 1 to 36 carbon atoms in which one or more hydrogen atoms may be substituted with a hydroxyl group, an amine group, a thiol group, or a halogen group, and one or more carbon atoms may be substituted with an ether group, an amino group, a thioether group, or a thioester group; R 8 and R 9 may combine with the nitrogen atom carrying them to form a 5- to 7-membered ring cyclic substituent structure, and, except for being a hydrogen atom at the same time, R 10 , R 11 may combine with the nitrogen atom carrying them to form a 5- to 7-membered cyclic substituent structure, R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 At least one of the above has a saturated or unsaturated 5- or greater ring substituent having a heteroatom, n is an integer from 1 to 100. (6) An active energy ray-curable composition containing the photopolymerization initiator according to any one of (1) to (5) above. (7) An actinic ray-curable ink composition containing the photopolymerization initiator according to any one of (1) to (5) above. (8) An active energy ray-curable pressure-sensitive adhesive composition containing the photopolymerization initiator according to any one of (1) to (5). (9) An active energy ray-curable adhesive composition containing the photopolymerization initiator according to any one of (1) to (5) above. (10) An active energy ray-curable coating composition containing the photopolymerization initiator according to any one of claims 1 to 5. (11) An active energy ray-curable sealing material composition containing the photopolymerization initiator according to any one of (1) to (5) above. (12) An actinic ray-curable inkjet ink containing the photopolymerization initiator according to any one of (1) to (5) above. (13) An actinic ray-curable ink for three-dimensional modeling, containing the photopolymerization initiator according to any one of (1) to (5) above. (14) An active energy ray-curable nail cosmetic composition containing the photopolymerization initiator according to any one of (1) to (5) above. (15) An active energy ray-curable dental material composition containing the photopolymerization initiator according to any one of (1) to (5) above. (16) An active energy ray-curable photosensitive composition containing the photopolymerization initiator according to any one of (1) to (5) above. (17) An active energy ray-curable hydrogel composition containing the photopolymerization initiator according to any one of (1) to (5) above. (18) An active energy ray-curable intraocular implant material composition containing the photopolymerization initiator according to any one of (1) to (5). (19) An active energy ray-curable adhesive composition for skin containing the photopolymerization initiator according to any one of (1) to (5). (20) An active energy ray-curable adhesive composition for living organisms, containing the photopolymerization initiator according to any one of (1) to (5). (21) An active energy ray-curable automotive paint repair composition containing the photopolymerization initiator according to any one of (1) to (5) above. Industrial Applicability

[0099] As explained above, the photopolymerization initiator (A) of the present disclosure has high photoinitiating properties and can be used with light sources of a wide variety of wavelengths, such as UV-LED lamps with wavelengths of 360 nm to 420 nm, and can initiate photopolymerization and initiate curing reactions with active energy rays in the presence of oxygen. Furthermore, it does not generate decomposition products during the photoinitiation reaction and photopolymerization reaction (curing), making it highly safe and resulting cured products with very little odor, bleed-out, yellowing over time, or deterioration. In particular, when the photopolymerization initiator contains an ethylenically unsaturated group, the photopolymerization initiator becomes a structural unit of the cured product after curing, resulting in a cured product with good physical properties and durability. The photopolymerization initiator of the present invention can be combined with various unsaturated group-containing compounds to produce active energy ray-curable compositions suitable for a variety of applications, and can impart various physical properties such as high adhesion, surface hardness, yellowing resistance, and water resistance. The photopolymerization initiator of the present invention can be suitably used as an active energy ray-curable composition, an active energy ray-curable ink composition, an active energy ray-curable pressure-sensitive adhesive composition, an active energy ray-curable adhesive composition, an active energy ray-curable coating composition, an active energy ray-curable sealant composition, an active energy ray-curable inkjet ink composition, an active energy ray-curable ink composition for three-dimensional modeling, an active energy ray-curable nail cosmetic composition, an active energy ray-curable dental composition, an active energy ray-curable photosensitive composition, an active energy ray-curable hydrogel composition, an active energy ray-curable intraocular implant material composition, an active energy ray-curable pressure-sensitive adhesive composition for skin, an active energy ray-curable adhesive composition for living organisms, an active energy ray-curable automobile paint repair composition, and the like.

Claims

1. A photopolymerization initiator having, in the molecule, one or more ethylenically unsaturated bonds, one or more benzophenone groups, and a saturated or unsaturated 5- or larger-membered cyclic substituent having one or more heteroatoms, and in which one or more saturated or unsaturated 5- or larger-membered cyclic substituents having heteroatoms are bonded to one or more carbon atoms of the aryl groups of at least one or more benzophenone groups via a carboxylic acid ester group or a carboxylic acid amide group.

2. One or more ethylenically unsaturated groups selected from the group consisting of (meth)acrylamide groups, (meth)acrylate groups, vinyl groups, vinyl ether groups, alkyl vinyl ether groups, allyl groups, (meth)allyl ether groups, styryl groups and maleimide groups in the molecule; and / or one or more groups selected from a urethane group, a urea group, an ester group, a thioester group, an amide group and an imide group; and / or 2. The photopolymerization initiator according to claim 1, which has, as a cyclic substituent, one or more groups selected from a piperidine group, a pyrrolidine group, a piperazine group, a pyridine group, a morpholine group, a tetrahydrofuran group, a hydrofuran group, a crown ether group, and a tetrahydrothiopyran group.

3. The photopolymerization initiator according to claim 1 or 2, which has a structure represented by general formula (1): (In the formula, Q １ , Q ３ are each independently a hydrogen atom or a monovalent organic group represented by general formula (2) or general formula (3), and Q １ , Q ３ at least one of the following is a monovalent organic group having one or more saturated or unsaturated 5- or greater-membered cyclic substituents having a heteroatom; Q ２ , Q ４ are each independently a divalent organic group represented by general formula (4) or general formula (5), L １ , L ２ are each independently a direct bond or a divalent organic group containing at least one of a urethane group, a urea group, an ester group, an amide group, and an imide group. ２ -L １ -R ５ and Q ４ -L ２ -R ６ may be a hydrogen atom, but these are １ , Q ３ Except when both are hydrogen atoms, R １ ~R ９ , R １２ each independently represents a hydrogen atom or a linear or cyclic, saturated or unsaturated monovalent hydrocarbon group having 1 to 36 carbon atoms, in which one or more hydrogen atoms may be substituted with a hydroxyl group, an amine group, a thiol group, or a halogen group, and one or more carbon atoms may be substituted with an ether group, an amino group, a thioether group, or a thioester group; R １０ , R １１ each independently represents a direct bond or a linear or cyclic, saturated or unsaturated divalent hydrocarbon group having 1 to 36 carbon atoms in which one or more hydrogen atoms may be substituted with a hydroxyl group, an amine group, a thiol group, or a halogen group, and one or more carbon atoms may be substituted with an ether group, an amino group, a thioether group, or a thioester group; R ８ and R ９ may form a 5- to 7-membered cyclic substituent structure together with the nitrogen atom directly bonded thereto, and, unless they are simultaneously hydrogen atoms, R １１ , R １２ may form a 5- to 7-membered cyclic substituent structure together with the nitrogen atom directly bonded thereto, R ５ , R ６ , R ７ , R ８ , R ９ , R １０ , R １１ , R １２ at least one of the above has a saturated or unsaturated 5- or greater ring substituent having a heteroatom, n is an integer from 1 to 100.

4. An active energy ray-curable composition containing the photopolymerization initiator according to claim 1 or 2.

5. An actinic ray-curable ink composition containing the photopolymerization initiator according to claim 1 or 2.

6. An active energy ray-curable pressure-sensitive adhesive composition containing the photopolymerization initiator according to claim 1 or 2.

7. An active energy ray-curable adhesive composition containing the photopolymerization initiator according to claim 1 or 2.

8. An active energy ray-curable coating composition containing the photopolymerization initiator according to claim 1 or 2.

9. An active energy ray-curable sealing material composition containing the photopolymerization initiator according to claim 1 or 2.

10. An actinic ray-curable inkjet ink containing the photopolymerization initiator according to claim 1 or 2.

11. An actinic ray-curable ink for three-dimensional modeling, comprising the photopolymerization initiator according to claim 1 or 2.

12. An active energy ray-curable nail cosmetic composition containing the photopolymerization initiator according to claim 1 or 2.

13. An active energy ray-curable dental material composition containing the photopolymerization initiator according to claim 1 or 2.

14. An active energy ray-curable photosensitive composition containing the photopolymerization initiator according to claim 1 or 2.

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