Photopolymerization initiator

Abstract

[Problem] The technical problem of the present invention is to provide a photopolymerization initiator which is less susceptible to hindrance by oxygen, has good photoinitiation in the air, has high sensitivity to long-wavelength light rays, and is capable of suppressing odor and bleeding of the resulting cured product. [Solution] A photopolymerization initiator having, in the molecule, one or more benzophenone groups and one or more saturated or unsaturated cyclic substituents having a heteroatom and having a five-membered ring or more, and having at least one carbon atom in the aryl group of the at least one benzophenone group, at least one carbon atom in the aryl group of the at least one benzophenone group, at least one carbon atom in the aryl group of the at least one benzophenone group, at least one carbon atom in the aryl group of the at least one benzophenone group; and at least one saturated or unsaturated cyclic substituent having a five-membered or more ring and having a heteroatom is bonded via a carboxylic acid ester group or a carboxylic acid amide group.

Description

Technical Field

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

[0002] The photocuring reaction using active energy rays such as visible light and ultraviolet (UV) rays generates active species such as free radicals from a curable composition containing a photopolymerization initiator by UV irradiation, polymerizes compounds having unsaturated groups, and solidifies (cures) the liquid composition in a short time. It is used in a wide range of fields such as coatings, coating agents, adhesives, bonding agents, elastomer materials, inkjet inks, sealing materials, filling materials, dental hygiene materials, photosensitive materials, etc. In particular, from the viewpoint of being able to cure in any location and shape, it is widely used as a nail cosmetic material such as gel nails, and is widely used as a material for three-dimensional light shaping.

[0003] Photopolymerization initiators can be classified into intramolecular cleavage type and hydrogen abstraction type according to the mechanism of free radical generation after absorbing light. The former is a type that generates free radicals by cleavage within the molecule, and the latter is a type that generates free radicals by abstracting hydrogen from a hydrogen donor. In the intramolecular cleavage type, since the decomposition products from the initiator remain in the cured product, problems such as reduced durability of the cured product, generation of odor, and coloration over time will occur, and there is also a problem of low safety. In the hydrogen abstraction type, since there are no decomposition products of the initiator, attention has increased in recent years, and research has been actively conducted to improve the efficiency of photopolymerization initiation and use additives such as hydrogen donors, photosensitizers, and curing accelerators. Summary of the invention

[0004] Technical problem to be solved by the invention

[0005] The technical problem of the present disclosure is to provide a hydrogen abstraction type photopolymerization initiator, which has high free radical generation ability and reactivity of generated free radicals, is not easily hindered by oxygen, can cope with long wavelength (360nm to 420nm) light, has good compatibility with general monomers and oligomers, and has excellent yellowing resistance.

[0006] Technical solutions for solving technical problems

[0007] The present inventors have repeatedly conducted in-depth studies and found a photopolymerization initiator having one or more benzophenone groups and one or more saturated or unsaturated five-membered ring or more cyclic substituents having heteroatoms in the molecule, and one or more saturated or unsaturated five-membered ring or more cyclic substituents having heteroatoms are bonded to one or more carbon atoms of the aromatic group of at least one benzophenone group via a carboxylate group or a carboxylic acid amide group, thereby solving the technical problem.

[0008] Effects of the Invention

[0009] The photopolymerization initiator disclosed in the present invention has high initiation efficiency for long-wavelength light with a wavelength of 360nm to 420nm and single-wavelength light output from UV-LED light sources such as 365nm, 385nm, 395nm and 405nm, and is not easily hindered by curing due to oxygen in an air environment, and does not produce decomposition products in the photoinitiation reaction and photopolymerization reaction (curing), and has high safety. In addition, the photopolymerization initiator has good compatibility with general monomers and oligomers, and the curable composition containing the photopolymerization initiator has excellent transparency, and the cured product obtained by curing has very little odor, exudation, yellowing and deterioration over time, and has high durability and safety. The photopolymerization initiator disclosed in the present invention can be suitable for various uses using active energy ray curable compositions such as ink compositions, adhesive compositions, adhesive compositions, coating compositions, sealing material compositions, inkjet inks, three-dimensional modeling inks, nail cosmetic material compositions, dental material compositions, and photosensitive compositions. DETAILED DESCRIPTION

[0010] Hereinafter, the 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 changes can be made within the scope of the gist of the present invention. In addition, with respect to a specific parameter, when a plurality of upper limits and lower limits are recorded, any upper limit and lower limit among these upper limits and lower limits can be combined to set a preferred numerical range.

[0011] One embodiment of the present disclosure is a photopolymerization initiator (A), which has one or more benzophenone groups and one or more saturated or unsaturated five-membered ring or more cyclic substituents having heteroatoms in the molecule, and one or more saturated or unsaturated five-membered ring or more cyclic substituents having heteroatoms are bonded to one or more carbon atoms of the aromatic group of at least one benzophenone group via a carboxylate group or a carboxylic acid amide group.

[0012] The photopolymerization initiator (A) has one or more benzophenone groups and one or more saturated or unsaturated five-membered ring or more cyclic substituents (hereinafter also referred to as heterocycles) having heteroatoms in the molecule, and at least one heterocycle is linked to the carbon atom of the aromatic group of the benzophenone group via a carboxylate group or a carboxylic acid amide group. The benzophenone group is a photopolymerization initiation functional group of the hydrogen abstraction type, and the heterocycle is a hydrogen donor. By containing the benzophenone group and the heterocycle, the photopolymerization initiator (A) effectively generates intramolecular and / or intermolecular hydrogen abstraction caused by active energy ray irradiation, and has a sufficient photoinitiation effect even without adding alcohols or amines as universal hydrogen donors. The inventors speculate the reasons as follows. 1) Since the electron density of heteroatoms is high, the activity of the hydrogen atoms around them is high, so they are easily abstracted. 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 supply sources. In addition, since it has a cyclic structure, the number of highly active hydrogen atoms around the heteroatoms is large. 3) The heteroatom can easily absorb the peroxide radical generated by oxygen, thus suppressing the influence of oxygen due to the presence of the heterocycle. In addition, it was confirmed that the presence of a carboxylate group or a carboxylic acid amide group between the benzophenone group and the heterocycle improves the compatibility of the hydrophobic benzophenone group and the hydrophilic heterocycle, thereby further improving the above-mentioned photoinitiation effect.

[0013] One embodiment of the present disclosure is a photopolymerization initiator (A) having one or more ethylenically unsaturated groups 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, styrene groups and maleimide groups in the molecule. By containing ethylenically unsaturated groups, the photopolymerization initiator (A) is fixed in the cured product as a constituent unit by means of covalent bonds after the photopolymerization reaction, and will not ooze out over time, and the durability, yellowing resistance, moisture resistance, etc. of the obtained cured product are improved. In the case where the photopolymerization initiator (A) has two or more ethylenically unsaturated groups, these ethylenically unsaturated groups may be the same or different. In addition, the curability of the (meth)acrylamide group, the (meth)acrylate group and the allyl group is high, and even a light source of long wavelength light or single wavelength light can be cured at a high speed, so it is preferred.

[0014] One embodiment of the present disclosure is that the cyclic substituent (heterocycle) containing more than the five-membered ring of heteroatoms has a photopolymerization initiator (A) selected from one or more groups of piperidinyl, pyrrolidinyl, piperazinyl, pyridinyl, morpholinyl, tetrahydrofuranyl, hydrogen furanyl, crown ether group, tetrahydrothiopyranyl. These substituents have a high inhibitory effect on oxygen hindrance, and the photopolymerization initiator (A) containing them can efficiently cause polymerization initiation reaction even in air, so it is preferred. In addition, it is more preferred to have a morpholinyl, tetrahydrofuranyl, piperidinyl with high effect as a hydrogen-donating group. These heterocycles can be used alone or in combination of two or more.

[0015] One embodiment of the present disclosure is a photopolymerization initiator (A) having one or more groups selected from carbamate, urea, ester, thioester, amide, and imide groups in the molecule. These groups have heteroatoms, and the hydrogen atoms bonded to the heteroatoms and / or the hydrogen atoms bonded to the carbon atoms adjacent to the heteroatoms are all hydrogen supply sources, and the initiation efficiency of the photopolymerization initiator (A) is improved. At the same time, these groups have the inhibitory effect of oxygen hindrance, and can also improve curability in the air. In addition, from the viewpoint of easy industrial introduction, it is preferred to contain carbamate, urea, ester, amide, and imide groups. These groups can be used alone or in combination of two or more.

[0016] The photopolymerization initiator (A) of the present invention can be obtained by reacting a carboxylic acid and / or carboxylic anhydride having a benzophenone group (hereinafter also referred to as a benzophenone compound (a1)) and a compound having a functional group capable of reacting with a carboxylic acid and / or a carboxylic anhydride and a heterocyclic compound (hereinafter also referred to as a heterocyclic compound (a2)). The functional group capable of reacting with a carboxylic acid and / or a carboxylic anhydride can be exemplified by a hydroxyl group, an amine group, an epoxy group, an oxazoline group, a carbodiimide group, an isocyanate group, a thiol group, a phenol group, a halogen group, etc. In addition, from the viewpoint of being able to react easily at room temperature (0°C to 150°C) and normal pressure (0.8 to 1.2 atmospheres), a hydroxyl group, an amine group, an epoxy group, an oxazoline group, an isocyanate group, a thiol group, and a halogen group are preferred. From the viewpoint that both the method of direct reaction of (a1) and (a2) described later and the method of indirect reaction can be applied, the heterocyclic compound (a2) more preferably has at least one hydroxyl group, an amine group or an epoxy group. In (a2), these groups can be used alone or in combination of two or more.

[0017] The method for producing the photopolymerization initiator (A) includes, specifically, a method for directly reacting a benzophenone compound (a1) with a heterocyclic compound (a2), a method of mixing (a1) and (a2) together and reacting them, and a method of dropping one of (a1) and (a2) into the other and gradually reacting them. Examples of methods for indirectly reacting (a1) with (a2) include: (a1) reacting with a compound (a5) capable of reacting therewith 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 is introduced; (a3) ​​a method for reacting a heterocyclic compound (a2); (a2) reacting with a compound (a5) capable of reacting therewith to obtain a compound (a4) having a heterocyclic ring 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 is introduced; (a4) a method for reacting a benzophenone compound (a1).

[0018] The reaction for producing the photopolymerization initiator (A) can be appropriately carried out in a temperature range of 0° C. to 150° C., and a solvent, a catalyst, and other additives may be used as needed. In order to suppress the generation of free radicals during the production, the reaction is preferably carried out in an environment that blocks active energy rays, more preferably in a dark room, a yellow room that blocks active energy rays with a wavelength of 500 nm or less, or under a red safe light.

[0019] 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′-benzophenone dicarboxylic acid, 3,4-benzophenone dicarboxylic acid, 2,3′-dimethyl-4,4′-benzophenone dicarboxylic acid, 2,5,4′-benzophenone tricarboxylic acid, 3,3′,4,4′-benzophenone tetracarboxylic acid, 2,2′-dimethyl-3,3′,4,4′-benzophenone tetracarboxylic acid, 3,3′,4,4′-benzophenone tetracarboxylic acid dianhydride, 2,2′-dimethyl-3,3′,4,4′-benzophenone tetracarboxylic acid dianhydride, and 5-methyl-3,3′,4,4′-benzophenone tetracarboxylic acid dianhydride. (a1) can be used alone or in combination of two or more thereof. Among them, since the reactivity of the acid anhydride and the heterocyclic compound (a2) is high, (a1) is preferably 3', 4, 4'-benzophenone tetracarboxylic dianhydride, 2, 2'-dimethyl-3, 3', 4, 4'-benzophenone tetracarboxylic dianhydride, 5-methyl-3, 3', 4, 4'-benzophenone tetracarboxylic dianhydride, and from the viewpoint of easy acquisition of industrial products, 3, 3', 4, 4'-benzophenone tetracarboxylic dianhydride is more preferred.

[0020] 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-pyran, 2-(hydroxymethyl)-12-crown 4-ether, N-hydroxysuccinimide, 1-(2-hydroxyethyl)-2-pyrrolidone, 2-(2-hydroxyethyl)-1-methylpyridine, 1-piperidinol, 4-methylpiperazine-1-ethanol, tetrahydro-2H-thiopyran-4-ol, 4-(2-hydroxyethyl)-morpholine, 4-(3-hydroxyethyl)-morpholine, ethyl)-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-pyrimidinyl)piperazine, 2-(furfurylthio)ethylamine, morpholine, thiomorpholine, 4-aminomorpholine, 4-(2-aminoethyl)morpholine, 4-(4-morpholinyl)aniline, and the like. Among them, 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-(4-morpholinyl)aniline are more preferred from the viewpoint of high stability of the cyclic substituent. (a2) These can be used alone or in combination of two or more.

[0021] The compound (a5) that can react with (a1) or (a2) is not particularly limited as long as it is a compound containing 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. For example, linear alcohols having 1 to 24 carbon atoms or branched or alicyclic alcohols having 3 to 24 carbon atoms, linear alcohols having 2 to 24 carbon atoms or branched or alicyclic alcohols having 3 to 24 carbon atoms, alkylene glycols having 2 to 24 carbon atoms, (meth)acrylates containing a hydroxyl group, (meth)acrylamides containing a hydroxyl group, linear alcohols having 2 to 24 carbon atoms or branched or alicyclic alcohols having 3 to 24 carbon atoms, alkylene diamines having 2 to 24 carbon atoms, branched or alicyclic alcohols having 3 to 24 carbon atoms, phenylenediamines, 1,2-butylene oxide, 1,2-epoxydodecane, 1,2-epoxytetradecane, butyl glycidyl ether, phenyl glycidyl ether, 2-ethylhexyl glycidyl ether, dodecyl glycidyl ether, glycidyl (meth)acrylate, 4-hydroxybutyl acrylate glycidyl ether, 1,2-epoxycyclohexane, 1,2-epoxy-4-butyl-4-octanol, etc. having an epoxy group can be mentioned. In addition, the epoxy group reacts with the carboxylic acid to generate a hydroxyl group, which can be used for carbamateization and esterification, so (a5) is preferably a compound having an epoxy group. Further, from the viewpoint of high reactivity, butyl glycidyl ether, phenyl glycidyl ether, 2-ethylhexyl glycidyl ether, dodecyl glycidyl ether, 2-[(butoxymethoxy)methyl] oxirane, 1,2-epoxydodecane, 1,2-epoxytetradecane, (meth) glycidyl acrylate, 4-hydroxybutyl acrylate glycidyl ether are more preferred. Compound (a5) can be used alone or in combination of two or more.

[0022] The solvent used in the production of the photopolymerization initiator (A) of the present invention includes, for example, 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 dichloromethane and chlorobenzene; and high-boiling-point 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. In addition, 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 solvents for the reaction, and examples thereof include various (meth)acrylates, N-substituted (meth)acrylamides and N,N-disubstituted (meth)acrylamides having chain and / or cyclic hydrocarbon groups (1 to 22 carbon atoms) or alkoxy groups (1 to 22 carbon atoms). (Meth)acryloylmorpholine (meth)acryloyl, N-vinylpyrrolidone, etc. can also be used.

[0023] The manufacture of the photopolymerization initiator (A) disclosed in the present invention can carry out the above-mentioned direct reaction and various indirect reactions even without using a catalyst. In addition, by using a catalyst, both direct reaction and indirect reaction can be carried out at a lower temperature and high speed, so it is preferred. The catalyst used in the manufacture of (A) can be listed, for example, thionyl chloride, quaternary ammonium salts, tertiary phosphine derivatives, tertiary amine derivatives, organic metal compounds, etc. As quaternary ammonium salts, tetrabutylammonium bromide, triethylbenzylammonium chloride, tetrabutylphosphonium bromide, tetraphenylphosphonium bromide, etc. can be listed. As tertiary phosphines, triphenylphosphine, triarylphosphines such as tritolylphosphine, tricycloalkylphosphines such as tricyclohexylphosphine, trialkylphosphines such as triethylphosphine, etc. can be listed. As tertiary amines, trialkyl (carbon number 1 to 8) amines such as triethylamine, tributylamine, dimethylethylamine, dialkyl (carbon number 1 to 8) arylamines such as diethylbenzylamine, etc. such as dimethylbenzylamine, etc. As the organometallic compound, there can be listed: metal salts of metals such as zinc, tin, lead, zirconium, bismuth, cobalt, manganese, and iron with organic acids such as octenic acid and cyclohexane acid; metal chelate compounds such as dibutyltin dilaurate, dioctyltin dilaurate, 2-ethylhexanoate tin, dibutyltin diacetylacetonate, tetraacetylacetonazinium, acetylacetonato titanium, acetylacetonato aluminum, acetylacetonato cobalt, acetylacetonato iron, acetylacetonato copper, and acetylacetonato zinc; potassium or sodium salts of alkyl (carbon number 1 to 8) phosphonic acid, sodium or potassium salts of fatty acids having carbon numbers 8 to 20, etc. Among them, quaternary ammonium salts, tertiary amine derivatives, tertiary phosphine derivatives, tin, zirconium, or iron organic metal compounds having high catalyst effects are more preferred. These catalysts can be used alone or in combination of two or more.

[0024] The amount of the catalyst used in the manufacture of 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. If it is 0.001% or more, the reaction can proceed rapidly, and if it is 5.0% or less, the coloring caused by the catalyst can be suppressed, so it is preferred. It is more preferably 0.01% to 1.0%.

[0025] The method of introducing an ethylenically unsaturated group into the molecule of the photopolymerization initiator (A) is not particularly limited, and examples thereof include: using a benzophenone compound (a1) containing an ethylenically unsaturated group and / or a heterocyclic compound (a2) containing an ethylenically unsaturated group; using a compound (a5) containing an ethylenically unsaturated group that can react with (a1) and / or (a2). The compound (a5) containing an ethylenically unsaturated group has a structure formed by any combination of one or more reactive groups selected from the group consisting of a hydroxyl group, a carboxylic acid group, an amine group, an epoxy group, an oxazoline group, an isocyanate group, a thiol group, and a halogen group, and one or more ethylenically unsaturated groups selected from the group consisting 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. Examples of the 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 be used alone or in combination of two or more.

[0026] Specifically, the compound (a5) includes: hydroxyalkyl (meth)acrylates (having 1 to 22 carbon atoms) such as hydroxyethyl (meth)acrylate, hydroxyisopropyl (meth)acrylate, and hydroxypropyl (meth)acrylate; N-hydroxyalkyl (having 1 to 22 carbon atoms) (meth)acrylamides such as N-hydroxymethyl (meth)acrylamide, N-hydroxyisopropyl (meth)acrylamide, and N,N-dihydroxyethyl (meth)acrylamide; N-alkyl (having 1 to 22 carbon atoms) hydroxyalkyl (having 1 to 22 carbon atoms) (meth)acrylamides such as N-methylhydroxyethyl (meth)acrylamide and N-ethylhydroxypropyl (meth)acrylamide; N,N-dihydroxymethyl (meth)acrylamide, N,N-dihydroxyethyl (meth)acrylamide, and N,N-dihydroxyethyl (meth)acrylamide. Hydroxyalkyl (carbon number 1 to 22) (meth) acrylamide; hydroxyalkyl (carbon number 1 to 22) ethylene such as 3-butene-1-ol, 4-pentene-1-ol, 5-hexene-1-ol; N-hydroxyalkyl (carbon number 1 to 22) maleimide such as hydroxyalkyl (carbon number 1 to 22) allyl, N-hydroxymethylmaleimide, N-hydroxyethylmaleimide; hydroxyalkyl (carbon number 1 to 22) vinyl ether such as ethylene glycol monovinyl ether and tetramethylene glycol monovinyl ether; N-aminoalkyl (carbon number 1 to 22) (meth) acrylamide, N-aminoalkyl (carbon number 1 to 22)-N-alkyl (carbon number 1 to 22) (meth) acrylamide, N,N-diaminoalkyl (carbon number 1 to 22) (meth) acrylamide, etc.

[0027] The method for introducing a carbamate group, a urea group, an ester group, an amide group and an imide group into the molecule of the photopolymerization initiator (A) is not particularly limited, and examples thereof include: using 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 carbamate group etc. introducing compound); (1) a method of further reacting a reactive product of a benzophenone compound (a1) and a heterocyclic compound (a2); (2) a method of further reacting with (a2) after reacting with (a1); (3) a method of further reacting with (a1) after reacting with (a2); (4) a method of reacting with (a1) and (a2) simultaneously. In addition, the compounds introduced with carbamate groups etc. include: compounds introduced with monocarbamate groups etc. having one group selected from hydroxyl, amine, carboxylic acid and isocyanate groups in the molecule; and compounds introduced with polycarbamate groups etc. having two or more groups selected from hydroxyl, amine, carboxylic acid and isocyanate groups in the molecule. As compounds introduced with polycarbamate groups etc., polyols, polyamines, polycarboxylic acids, polyisocyanates, polyamino acids, amino-containing polyols, hydroxyl-containing polyamines, hydroxyl-containing polycarboxylic acids etc. can be listed. In addition, compounds may also have polyester skeletons, polyether skeletons, polycarbonate skeletons, polyolefin skeletons (polydiene skeletons and / or hydrogenated polydiene skeletons), polyacrylic acid skeletons, and silicon skeletons (various modified polydimethylsiloxanes). These compounds introduced with carbamate groups etc. can be used alone or in combination of two or more.

[0028] The molecular weight of the photopolymerization initiator (A) can be arbitrarily adjusted by combining various raw materials, but it is preferably 500 to 100,000 in number average. If the number average molecular weight is 500 or more, the content of low molecular weight components with a molecular weight of less than 500 in the cured product obtained after the photopolymerization reaction is low, so the safety, durability, heat resistance, etc. of the cured product are high. In addition, if the number average molecular weight is 100,000 or less, it is easy to adjust the polarity (balance between hydrophilicity and hydrophobicity) of (A), the solubility is high relative to the general monomers and oligomers used in the active energy ray curable composition, the viscosity of the curable composition containing (A) can be easily adjusted to a range suitable for various processing forms such as coating, spraying, extrusion, etc., and the obtained curable composition and cured product have high transparency. Furthermore, according to the molecular weight of (A), it can be classified into a low molecular weight type having a number average molecular weight of 500 to less than 1,000, a medium molecular weight type having a number average molecular weight of 1,000 to less than 10,000, and a high molecular weight type having a number average molecular weight of 10,000 to 100,000. The low molecular weight type (A) is mainly a compound in which a heterocyclic ring is directly or indirectly bonded to a carboxylic acid ester group and / or a carboxylic acid amide group directly bonded to a benzophenone group represented by the general formula (1). The medium molecular weight type (A) is a compound in which a heterocyclic ring is directly or indirectly bonded to a carboxylic acid ester group and / or a carboxylic acid amide group directly bonded to a benzophenone group represented by the general formula (1), and a structural unit derived from an introduced compound such as a carbamate group having one or more skeletons selected from a polyester skeleton, a polyether skeleton, a polycarbonate skeleton, a polyolefin skeleton, and a polyacrylic acid skeleton, and a carbamate group, etc. are bonded, and the order and position of bonding the heterocyclic ring and the structural unit derived from an introduced compound such as a carbamate group and the carbamate group, etc. are not limited. The high molecular weight type (A) is mainly a compound having a structure formed by directly or indirectly bonding a heterocycle to a carboxylate group and / or a carboxylic acid amide group directly bonded to a benzophenone group represented by the general formula (1), and repeatedly bonding structural units derived from a carbamate group or the like introduced compound having one or more skeletons selected from a polyester skeleton, a polyether skeleton, a polycarbonate skeleton, a polyolefin skeleton, and a polyacrylic acid skeleton, and a carbamate group, etc., and the sequence and position of bonding the heterocycle and the repeated structural units derived from a carbamate group or the like introduced compound, and the carbamate group, etc. are not limited. Among them, the medium molecular weight type photopolymerization initiator has good solubility in various general organic solvents, monomers or oligomers used in the curable composition, can appropriately adjust the viscosity of the obtained curable resin composition, has excellent workability, and has high sensitivity to polymerization initiation of active energy rays, especially to long-wavelength light rays with a wavelength of 360nm to 420nm, and is therefore particularly preferred.

[0029]

[0030] (Where Q 1 , Q3 are independently a hydrogen atom, or a monovalent organic group represented by the general formula (2) or the general formula (3), Q 1 , Q 3 Any one or more of them is a monovalent organic group containing one or more saturated or unsaturated five-membered or more cyclic substituents having a heteroatom;

[0031] Q 2 , Q 4 are each independently a divalent organic group represented by the general formula (4) or the general formula (5);

[0032] L 1 , L 2 are independently directly bonded, or are divalent organic groups containing at least one of a carbamate group, a urea group, an ester group, an amide group, and an imide group. 2 -L 1 -R 5 With Q 4 -L 2 -R 6 Can be a hydrogen atom, but excludes the 1 , Q 3 The case where they are both hydrogen atoms;

[0033]

[0034] R 1 To R 9 , R 12 Each independently represents a hydrogen atom, or a chain or cyclic saturated or unsaturated monovalent hydrocarbon group having 1 to 36 carbon atoms, wherein one or more hydrogen atoms of the chain or cyclic saturated or unsaturated monovalent hydrocarbon group having 1 to 36 carbon atoms may be substituted by a hydroxyl group, an amine group, a thiol group or a halogen group, and one or more carbon atoms may be substituted by an ether group, an amino group, a thioether group or a thioester group;

[0035] R 10 , R 11 Each independently represents a direct bond, or a chain or cyclic saturated or unsaturated divalent hydrocarbon group having 1 to 36 carbon atoms, wherein one or more hydrogen atoms of the chain or cyclic saturated or unsaturated divalent hydrocarbon group having 1 to 36 carbon atoms may be substituted by a hydroxyl group, an amine group, a thiol group or a halogen group, and one or more carbon atoms may be substituted by an ether group, an amino group, a thioether group or a thioester group;

[0036] R 8 and R 9 structures of cyclic substituents that can form a five-membered ring to a seven-membered ring together with the nitrogen atom to which they are attached, excluding the case where they are simultaneously hydrogen atoms;

[0037] R10 , R 11 structures of cyclic substituents that can form a five-membered to seven-membered ring together with the nitrogen atom to which they are attached;

[0038] R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 Any one or more of the cyclic substituents contain a saturated or unsaturated five-membered ring or more containing a heteroatom;

[0039] n is an integer from 1 to 100. ).

[0040] The 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 mixed or dual polymerization, curing, etc. Photopolymerization and thermal polymerization can be performed simultaneously or in any order. However, although photopolymerization is fast, unreacted monomers and oligomers sometimes remain. It is preferred that after photopolymerization, thermal polymerization is performed to complete the residual polymerization reaction and crosslinking reaction. In addition, by using a photoradical polymerization initiator of different species or different structures and irradiating with light of different wavelengths in stages, the curable material can be completely cured.

[0041] As light suitable for the photopolymerization initiator (A), active energy rays such as visible light, electron beam, ultraviolet light, infrared light, X-ray, α-ray, β-ray, and γ-ray can be listed. Among them, from the balance of the generating device of the active energy ray, the photopolymerization initiation speed, and the safety, ultraviolet light is preferably used. In addition, as ultraviolet light sources, xenon lamps, low-pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, UV-LED lamps, microwave excimer lamps, etc. can be listed. From the viewpoint of high conversion efficiency of energy to light, easy high output, and no use of harmful mercury, UV-LED lamps are more preferred.

[0042] In the photopolymerization initiator (A), the light irradiation energy required to generate radical active species is preferably 5 to 50,000 mJ / cm 2 The range of is preferably 10 to 20,000 mJ / cm 2 When the irradiation energy is within this range, sufficiently active free radicals can be generated from (A), which is preferred.

[0043] The content of the photopolymerization initiator (A) in the curable composition varies according to the type, content, etc. of the monomers and oligomers in the curable composition, but when it is 0.1% by mass or more relative to the whole curable composition, photopolymerization can start immediately, and the curable composition can also be cured at high speed and fully, so it is preferred. In addition, in the case where (A) has an ethylenically unsaturated group, even if it contains 100% by mass, it can be cured at high speed and fully in the same manner as a conventional curable composition. In addition, in order to appropriately adjust the physical properties of the obtained cured product, (A) is preferably used in combination with other monomers and oligomers. In this case, the content of (A) is preferably 0.5 to 70% by mass relative to the whole curable composition, more preferably 1 to 50% by mass, and most preferably 2 to 30% by mass.

[0044] The monomers and oligomers used in combination with (A) can be classified as monofunctional monomers, multifunctional monomers or oligomers. The content of the monomers and oligomers used in combination is 0 to 99.9% by mass relative to the whole curable composition, and from the viewpoint of being able to appropriately adjust 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.

[0045] As monofunctional monomers, compounds containing (meth) acrylate groups, (meth) acrylamide groups, vinyl groups, allyl groups, styryl groups, ethynyl groups, etc. can be listed, and they can be used alone or in combination of two or more. The content of monofunctional monomers is preferably 0 to 90 mass %, more preferably 5 to 70 mass %, and most preferably 10 to 50 mass % relative to the whole curable composition. Monofunctional monomers are generally low viscosity, and by appropriately containing monofunctional monomers, effects such as low viscosity and improved operability of curable compositions can be expected.

[0046] Specific examples of the monofunctional monomer containing a (meth)acrylate group (excluding the photopolymerization initiator) include: (meth)acrylates into which a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, a hydroxyalkyl group, an alkyl carboxylic acid, an alkyl sulfonic acid or an alkyl phosphoric acid is 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 is introduced; dialkylaminoethyl (meth)acrylates into which an alkyl group having 1 to 6 carbon atoms is introduced; (Meth)acrylates containing amino groups, such as (meth)acrylate, dialkylaminopropyl (meth)acrylamide, etc.; (meth)acrylates having a cyclic structure, such as benzyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, isobornyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate, etc.; (meth)acrylates having an epoxy group, such as glycidyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, etc.

[0047] Specific examples of the monofunctional monomer containing a (meth)acrylamide group (excluding the photopolymerization initiator) include (meth)acrylamide, monosubstituted or disubstituted (meth)acrylamide, (meth)acryloylmorpholine, diacetone (meth)acrylamide, and the like. In addition, examples of the monosubstituted or disubstituted (meth)acrylamide include: N-alkyl (meth)acrylamide and N,N-dialkyl (meth)acrylamide introduced with a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms; N-hydroxyalkyl (meth)acrylamide introduced with a hydroxyalkyl group having 1 to 6 carbon atoms; and N,N-dialkylaminopropyl (meth)acrylamide introduced with an alkyl group having 1 to 6 carbon atoms.

[0048] Specific examples of the monofunctional monomer containing a vinyl group, an allyl group, or a styrene group (excluding the photopolymerization initiator) include: carboxylic acid vinyl esters and carboxylic acid allyl esters into which a straight-chain, branched-chain, or cyclic carboxylic acid having 1 to 18 carbon atoms is introduced; alkyl vinyl ethers and alkyl allyl ethers into which a straight-chain, branched-chain, or cyclic alkyl having 1 to 18 carbon atoms is introduced; vinyl chloride, N-vinylpyrrolidone, N-vinylcaprolactam, N-vinyloxazoline, maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride; unsaturated dicarboxylic acids monoesterified or diesterified with a straight-chain, branched-chain, or cyclic alkyl having 1 to 18 carbon atoms, vinyl carboxylic acid, vinyl sulfonic acid, vinyl phosphoric acid, allylamine, diallylamine, styrene, α-methylstyrene, α-methylstyrene dimer, p-styrenesulfonic acid, and the like.

[0049] As a multifunctional monomer or oligomer, compounds containing unsaturated groups such as two or more (meth) acrylate groups, (meth) acrylamide groups, vinyl, allyl, styryl and ethynyl groups can be listed, and these unsaturated groups can be compounds containing one alone, or compounds containing two or more. In addition, in order to obtain good curability, it is more preferred to use at least one (meth) acrylate group or (meth) acrylamide group as an unsaturated group. The content of the multifunctional monomer (except the photopolymerization initiator) is preferably 0 to 95% by mass relative to the entire curable composition, more preferably 1 to 70% by mass, and most preferably 5 to 50% by mass. The strength and hardness of the cured product obtained by appropriately adjusting the content of the multifunctional monomer are high, and excellent durability can be expected.

[0050] Examples of the polyfunctional monomer or oligomer include allyl (meth)acrylate, allyl (meth)acrylamide, diallylamine, alkyldiallylamine introduced with an alkyl group having 1 to 18 carbon atoms, alkanediol 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 functions include pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and trimethylolpropane tri(meth)acrylate. The polyfunctional monomers or oligomers may be used alone or in combination of two or more.

[0051] The photopolymerization initiator (A) disclosed in the present invention has high photoinitiability even without using a sensitizer, but by using a general sensitizer in combination, it is expected that the polymerization initiability and the physical properties of the cured product after curing can be further improved. The sensitizer that can be used in combination with (A) is not particularly limited, and examples thereof include unsaturated ketones represented by benzophenones and anthracene derivatives, 1,2-diketone derivatives represented by benzyl and camphorquinone, benzoin derivatives, anthraquinone derivatives, thioxanthone derivatives, coumarin derivatives, tertiary amines, thiols, disulfides, etc. These sensitizers can be used in any ratio as needed, and can be used alone or in combination of two or more.

[0052] As sensitizers that can be used together, specifically, anthracene sensitizers such as 9,10-dibutoxyanthracene, 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, and 9,10-bis(2-ethylhexyloxy)anthracene can be listed; thioxanthone sensitizers such as 2,4-diethylthioxanthone, 2-isopropylthioxanthone, and 4-isopropylthioxanthone can be listed. In addition, in representative examples of commercial products, anthracene sensitizers include DBA and DEA (manufactured by Kawasaki Chemicals Co., Ltd.), and thioxanthone sensitizers include DETX and ITX (manufactured by Lambson Co., Ltd.). The content of the sensitizer is not particularly limited, but is preferably 0.5 to 5.0% by mass, more preferably 0.8 to 3.0% by mass, relative to the entire curable composition. If the content of the sensitizer is within this range, the curability of the curable composition is improved, and the durability and yellowing resistance of the obtained cured product are good.

[0053] Examples of other polymerization initiators that can be used together with the photopolymerization initiator (A) of the present disclosure include benzoin, benzoin alkyl ethers and other benzoins, acetophenones such as acetophenone and 2-hydroxy-2-methyl-1-phenylpropane-1-one, anthraquinones, thioxanthones, ketals, benzophenones, aminobenzophenones, aminoacetophenones, xanthones, etc. These polymerization initiators can be used in any ratio as required, and can be used alone or in combination of two or more.

[0054] The active energy ray curable composition can be used without containing an organic solvent. In addition, in order to improve the operability such as coating, an organic solvent can be added as needed to adjust the liquid viscosity. The added organic solvent can be removed in advance during photocuring and cured, or it can be cured while containing an organic solvent. The organic solvent can also be further removed after curing, and can be appropriately selected according to the method of use and purpose of the curable composition and the obtained cured product. The amount of organic solvent added is not particularly limited, but from the viewpoint of being able to reduce the energy and time required to remove the organic solvent, it is preferably 80% by mass or less, and more preferably 50% by mass or less relative to the entire active energy ray curable composition.

[0055] 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; ethers such as tetrahydrofuran, methyltetrahydrofuran, cyclopentyl methyl ether, methyltetrahydropyran, and methyl tert-butyl ether toluene; dimethyl Aromatic hydrocarbons such as benzene; 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 dichloromethane, chloroform and dichloroethane; sulfoxides such as dimethyl sulfoxide; imidazolidinones such as 1,3-dimethyl-2-imidazolidinone, etc. These organic solvents can be used alone or in combination of two or more.

[0056] The photopolymerization initiator of the present invention can be suitably used for: active energy ray-curable inks such as active energy ray-curable flexographic inks, active energy ray-curable lithographic inks, active energy ray-curable screen inks, and active energy ray-curable inkjet inks; active energy ray-curable nail cosmetic material compositions used in gel nail art, etc.; active energy ray-curable adhesive compositions; active energy ray-curable adhesive compositions; active energy ray-curable sealing material compositions used in sealing materials, sealing materials, etc.; active energy ray-curable coating agent compositions used in coatings or coating agents for automobiles, electrical products, furniture, etc.; active energy ray-curable decorative sheet compositions used in decorative sheets used in surface coatings for automobiles and electrical products, etc.; and compositions having self-healing properties. Coating composition; active energy ray-curable self-healing material composition used in functional parts and equipment such as three-dimensional shapes, nail decoration materials, dental materials, automobile exterior protection, decorative films, etc.; active energy ray-curable elastomeric composition used in materials facing elastomers used in transparent adhesive sheets, cushioning materials, pads, vibration-proof materials, sound-absorbing materials, printing plates, sealing materials, abrasives, etc.; active energy ray-curable three-dimensional shaping ink for decorating the film in a three-dimensional manner on model materials, support materials or three-dimensional shapes with concave and convex shapes for 3D printers; active energy ray-curable dental material composition; active energy ray-curable photosensitive composition; active energy ray-curable hydrogel composition; active energy ray-curable material composition for intraocular implants, etc. In addition, the obtained hydrogel composition can be suitably used as a material in a variety of fields, such as super absorbent resins, disposable diapers, soft contact lenses and other sanitary fields, various coating fields such as ship bottom coatings, anti-fogging materials, anti-fouling coatings, medical fields such as medical device surface coatings and artificial organs, civil engineering fields such as soil improvers, agricultural fields such as water-retaining materials, and impact absorbing materials.

[0057] Example

[0058] 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 addition, "parts" and "%" hereinafter are all based on mass unless otherwise specified.

[0059] (1-1) Infrared absorption spectroscopy analysis (IR analysis)

[0060] IR analysis was performed by the following apparatus.

[0061] Nicolet iS50 (manufactured by THERMO FISHER SCIENTIFIC CO., LTD.)

[0062] (1-2) Liquid chromatography mass spectrometry analysis (LC-MS analysis)

[0063] LC-MS analysis was performed using the following apparatus and conditions.

[0064] Column: XBridge C18, 6mm×150mm, 3.5μm (manufactured by Japan WATERS Co., Ltd.)

[0065] Elution conditions: water / methanol / 1% formic acid aqueous solution = 60 / 30 / 10

[0066] Measurement wavelength: 258nm; column oven: 40℃

[0067] (1-3) Nuclear Magnetic Resonance Spectroscopy Analysis (NMR Analysis)

[0068] 1 H-NMR analysis was performed using a 400 MHz device manufactured by JEOL Ltd.

[0069] (1-4) Gas chromatography analysis (GC analysis)

[0070] The GC analysis was performed using the following equipment.

[0071] Device: GC-2025 (manufactured by Shimadzu Corporation)

[0072] Column: DB-1 (manufactured by Agilent Technologies, Inc.)

[0073] (1-5) Gel Permeation Chromatography Analysis (GPC Analysis)

[0074] GPC analysis was performed using the following apparatus and conditions.

[0075] Device: Prominence-I LC-2030C (manufactured by Shimadzu Corporation)

[0076] Protection column: One Shodex KF-G (manufactured by Showa Denko K.K.)

[0077] Column: Shodex KF-803 (manufactured by Showa Denko K.K.)

[0078] Column temperature: 40°C; Mobile phase: tetrahydrofuran (THF)

[0079] Liquid delivery speed: 0.5mL / min; Standard sample: polystyrene

[0080] The benzophenone compound (a1), the heterocyclic compound (a2), and the compound (a5) capable of reacting with (a1) or (a2) used in the Examples are shown below.

[0081] (2-1) Benzophenone compounds (a1)

[0082] a1-1: 4-Benzophenonecarboxylic acid methyl ester

[0083] a1-2: 3,4-Benzophenone dicarboxylic anhydride

[0084] a1-3: 2-(4-biphenylcarbonyl)benzoic acid

[0085] a1-4: 4-(4-carboxybenzoyl)2,3-diethylbenzoic acid

[0086] a1-5: 4-(4-methoxybenzoyl)benzoic acid

[0087] a1-6: 3,3',4,4'-Benzophenonetetracarboxylic dianhydride

[0088] (2-2) Heterocyclic compound (a2)

[0089] a2-1: Piperazine

[0090] a2-2: Morpholine

[0091] a2-3: Hydroxyethyl maleimide

[0092] a2-4: Tetrahydrofurfuryl alcohol

[0093] a2-5: Tetrahydrofuran-2-acetyl chloride

[0094] a2-6: Tetrahydrofurfurylamine

[0095] a2-7: 2-(Hydroxymethyl)-15-crown 5-ether

[0096] a2-8: 1-piperidineethanol

[0097] a2-9: 4-(2-Hydroxyethyl)morpholine

[0098] a2-10: Tetrahydro-2H-thiopyran-4-ol

[0099] (2-3) Compound (a5) capable of reacting with (a1) or (a2)

[0100] a5-1: Acryloyl chloride

[0101] a5-2: 4-Hydroxybutyl acrylate glycidyl ether

[0102] a5-3: Glycidyl methacrylate

[0103] a5-4: Ethylene glycol

[0104] a5-5: Butylene oxide

[0105] a5-6: Methanol

[0106] a5-7: Octadecyl glycidyl ether

[0107] a5-8: Ion exchange water

[0108] a5-9: 1,2-octyl oxide

[0109] a5-10: 4-Hydroxybutyl acrylate

[0110] a5-11: Allyl alcohol

[0111] a5-12: N-(2-hydroxyethyl) acrylamide

[0112] The polyol (B1), amine compound (B2), monool compound (B3), isocyanate compound (C1), and carboxylic acid compound (C2) used in the examples are shown below.

[0113] (2-4) Polyol (B1)

[0114] B1-1: UH-100 (manufactured by Ube Industries, 1,6-HD polycarbonate diol, number average molecular weight 1,000)

[0115] B1-2: Kuraray Polyol P-1010 (manufactured by Kuraray, polyester polyol, number average molecular weight 1,000)

[0116] B1-3: KF-6000 (manufactured by Shin-Etsu Chemical Co., Ltd., reactive silicone oil methanol-modified (both end type), hydroxyl value 120 mgKOH / g, number average molecular weight 900)

[0117] B1-4: UNIOL D-1000 (manufactured by NOF Corporation, polypropylene glycol, number average molecular weight 1,000)

[0118] B1-5: GI-2000 (manufactured by Nippon Soda, polybutadiene glycol, number average molecular weight 2,000)

[0119] B1-6: Kuraray Polyol P-5010 (manufactured by Kuraray, polyester polyol, number average molecular weight 5,000)

[0120] B1-7: PEG-300 (polyethylene glycol, number average molecular weight 300)

[0121] B1-8: PTMG650 (polytetramethylene ether glycol, number average molecular weight 650)

[0122] (2-5) Amine compound (B2)

[0123] B2-1: D-400 (Mitsui Chemicals FINE, polyetheramine, number average molecular weight 400)

[0124] (2-6) Monohydric alcohol compound (B3)

[0125] B3-1: Hydroxyethyl acrylate

[0126] B3-2: N-(2-Hydroxyethyl)acrylamide (manufactured by Kohshylmer Chemical Co., Ltd., registered trademarks "Kohshylmer" and "HEAA")

[0127] B3-3: 4-Hydroxybutyl acrylate

[0128] B3-4: 3-Hydroxypropyl Methacrylamide

[0129] B3-5: Hydroxyethyl maleimide

[0130] B3-6: Methanol

[0131] B3-7: 4-Hydroxybutyl vinyl ether

[0132] B3-8: Ethylene glycol monoallyl ether

[0133] B3-9: (6-Hydroxyhexyl)methacrylamide

[0134] (2-7) Isocyanate compound (C1)

[0135] C1-1: 2-Acryloyloxyethyl isocyanate

[0136] C1-2: Isophorone diisocyanate

[0137] C1-3: Toluene diisocyanate

[0138] C1-4: 1,5-pentamethylene diisocyanate

[0139] C1-5: 1,3-bis(isocyanatomethyl)cyclohexane

[0140] C1-6: trimer of isophorone diisocyanate (urate) (manufactured by EVONIK, VESTANATT1890 / 100)

[0141] (2-8) Carboxylic acid compound (C2)

[0142] C2-1: Adipic acid

[0143] C2-2: Sebacic acid

[0144] The photopolymerization initiator (D), the monofunctional monomer (E), the polyfunctional monomer or oligomer (F), and other components (G) used in Examples and Comparative Examples are shown below.

[0145] (3-1) Photopolymerization initiator (D)

[0146] D-1: 1-Hydroxycyclohexyl phenyl ketone

[0147] D-2: Benzophenone

[0148] D-3: Isopropylthioxanthone

[0149] D-4: Diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide

[0150] D-5: Escacure KIP-150 (manufactured by IGM Resins BV)

[0151] D-6: Camphorquinone

[0152] (3-2) Monofunctional monomer (E)

[0153] E-1: Diethylacrylamide (manufactured by Kohshylmer Chemical Co., Ltd., registered trademarks "Kohshylmer" and "DEAA")

[0154] E-2: Isobornyl acrylate

[0155] E-3: Acryloylmorpholine (manufactured by Kohshylmer Chemical Co., Ltd., registered trademarks "Kohshylmer" and "ACMO")

[0156] E-4: Tetrahydrofurfuryl acrylate

[0157] E-5: 4-tert-butyl cyclohexyl acrylate (manufactured by Kohshylmer Chemical Co., Ltd., registered trademark "Kohshylmer")

[0158] E-6: Phenoxyethyl acrylate

[0159] E-7: 4-Hydroxybutyl acrylate

[0160] E-8: Dimethylacrylamide (manufactured by Kohshylmer Chemical Co., Ltd., registered trademarks "Kohshylmer" and "DMAA")

[0161] E-9: N-vinyl pyrrolidone

[0162] E-10: N-octylacrylamide (manufactured by Kohshylmer Chemical Co., Ltd., registered trademark "Kohshylmer")

[0163] E-11: N-(2-Hydroxyethyl)acrylamide (manufactured by Kohshylmer Chemical Co., Ltd., registered trademarks "Kohshylmer" and "HEAA")

[0164] E-12: n-Dodecyl acrylate

[0165] E-13: Isobornyl methacrylate

[0166] E-14: Hydroxyethyl Methacrylate

[0167] E-15: 2-Methacryloyloxyethyl acid phosphate

[0168] (3-3) Multifunctional monomer or oligomer (F)

[0169] F-1: A-400 (manufactured by Shin-Nakamura Chemical Industry, polyethylene glycol No. 400 diacrylate)

[0170] F-2: EBECRYL 8807 (manufactured by DAICEL-ALLNEX CO., LTD., aliphatic bifunctional urethane acrylate, average molecular weight 1000)

[0171] F-3: Urethane diacrylate (Ultraviolet UV6630, manufactured by Mitsubishi Chemical Corporation)

[0172] F-4: Polyethylene glycol (20) introduced bisphenol A diacrylate (NK ester A-BPE-20, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)

[0173] F-5: Hexanediol diacrylate

[0174] F-6: Polyether urethane acrylamide (manufactured by Cosmic Chemical Co., Ltd., registered trademark "Quick Cure")

[0175] F-7: Dipentaerythritol hexaacrylate

[0176] F-8: Urethane diacrylate (Ultraviolet UV3000, manufactured by Mitsubishi Chemical Corporation)

[0177] F-9: Dimethylol-tricyclodecane diacrylate

[0178] F-10: Polyethylene glycol (10) introduced bisphenol A diacrylate (NK ester A-BPE-10, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)

[0179] F-11: Pentaerythritol triacrylate

[0180] F-12: Polyethylene glycol (10) dimethacrylate

[0181] F-13: Vinyl Bisacrylamide

[0182] F-14: Polyester urethane acrylamide (manufactured by Cosmic Chemical Co., Ltd., registered trademark "Quick Cure")

[0183] F-15: Trimethylolpropane triacrylate

[0184] F-16: Polycarbonate urethane acrylamide (manufactured by Cosmic Chemical Co., Ltd., registered trademark "Quick Cure")

[0185] F-17: Bisphenol A epoxy acrylate oligomer (Miramer PE-210, manufactured by MIWON Co., Ltd.)

[0186] (3-4) Other ingredients (G)

[0187] G-1: TEGO Rad2100 (manufactured by EVONIK, silicone acrylate with a polydimethylsiloxane structure)

[0188] G-2: Pentaerythritol tetrakis (3-mercaptobutyl ester)

[0189] G-3: MEK-ST-40 (manufactured by Nissan Chemical Co., Ltd., colloidal silica dispersion)

[0190] G-4: Omnipol ASA (manufactured by IGM Resins BV)

[0191] G-5: Carbon black dispersion (manufactured by Mitsubishi Chemical Corporation) / BYK-JET9151 (pigment dispersant, maleimide-styrene copolymer having an ammonium salt structure, manufactured by BYK Chemie) = 1 / 2 (weight ratio) mixed solution

[0192] G-6: VALIFAST BLUE1613 (manufactured by ORIENT CHEMICAL INDUSTRY CO., LTD.)

[0193] G-7: PETROTACK 100V (manufactured by Tosoh Corporation)

[0194] G-8: REOLOSIL QS-30 (manufactured by TOKUYAMA Co., Ltd.)

[0195] G-9: Methacrylic acid / methyl methacrylate / styrene copolymer adhesive

[0196] G-10: Azobisisobutyronitrile

[0197] (3-5) Organic solvent (H)

[0198] H-1: Ethyl acetate

[0199] H-2: 3-methoxy-N,N-dimethylpropionamide (manufactured by Kohshylvent Chemical Co., Ltd., registered trademarks "Kohshylvent" and "KJCMPA")

[0200] H-3: Methyl ethyl ketone

[0201] H-4: Dimethylformamide

[0202] H-5: N-methylpyrrolidone

[0203] Example 1 Synthesis of Photopolymerization Initiator (A-1)

[0204] In a 500 ml flask equipped with a reflux cooling tube, a stirrer, a thermometer and a dropping funnel, add 35.9 g of piperazine (a2-1) and 50 g of N,N-dimethylformamide (DMF), and add 37.7 g of acryloyl chloride (a5-1) dropwise while stirring at 0°C. The mixture is reacted for 1 hour to obtain 1-acryloylpiperazine. Then, 100 g of methyl 4-benzophenonecarboxylate (a1-1) and 3.1 g of triethylamine (TEA) are added, and the mixture is reacted for 2 hours while stirring at 65°C. After the reaction is completed, purification is performed to obtain the target light yellow viscous liquid (purity 95%). IR analysis of the obtained viscous liquid revealed that the C=O specific absorption of the amide group (1650 cm-1) was detected, while the C=O specific absorption of the ester group (1725 cm-1) was not detected, thereby confirming the formation of the amide group and the disappearance of the ester group. 1 H-NMR analysis detected 8.60 to 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); 3.80 ppm and 3.60 ppm (4H, -N-CH2- of piperazine ring), which confirmed the presence of benzophenone group, acryloyl group and piperazine group. In addition, the molecular weight indicated by the molecular ion peak of the mass spectrum of LC-MS was 348, which was consistent with the molecular weight of the target compound (Table 2), confirming the generation of the photopolymerization initiator (A-1) with the structure shown in Table 2.

[0205] Example 2 Synthesis of Photopolymerization Initiator (A-2)

[0206] Using the same 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 the mixture was reacted at 65°C for 2 hours. Then, 79.3 g of (a5-2) and 0.4 g of triphenylphosphine (TPP) were added, and the mixture was reacted at 70°C for 3 hours. After the reaction was completed, the mixture was purified to obtain a light yellow viscous liquid (purity 97%). Similarly, IR analysis confirmed the formation of ester and amide groups (1725 cm-1 of C=O of ester group and 1650 cm-1 of C=O of amide group were detected) and the disappearance of anhydride group (the absorption of 1770 cm-1 specific to C=O of anhydride group was not detected). -1 and 1851cm -1 ). In addition, through 1H-NMR analysis detected 8.60 to 7.95 ppm (8H, aromatic ring); 6.56 ppm (H, -CH= of acrylate group); 4.28 ppm and 4.32 ppm (2H, =CH2 of acrylate group); 3.63 ppm (8H, -CH2-O- in morpholine group); 3.41 ppm (8H, -N-CH2- in morpholine group). The molecular weight (540) obtained by LC-MS analysis was consistent with the molecular weight of the target compound (Table 2). Based on these results, the generation of the photopolymerization initiator (A-2) with the structure shown in Table 2 was confirmed.

[0207] Example 3 Synthesis of Photopolymerization Initiator (A-3)

[0208] Using the same 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, it was purified to obtain a light yellow viscous liquid (purity 93%). Similarly, the formation of ester groups was confirmed by IR analysis of the obtained viscous liquid (1725 cm -1 ),pass 1 H-NMR analysis detected 8.50 to 7.80 ppm (13H, aromatic ring); 7.05 ppm (2H, -HC=CH- of maleimide group); 4.65 ppm (2H, -O-CH2-); 3.78 ppm (2H, -N-CH2-), and the molecular weight (425) obtained by LC-MS analysis was consistent with the molecular weight of the target compound (Table 2). Based on these results, the generation of the photopolymerization initiator (A-3) with the structure shown in Table 2 was confirmed.

[0209] Example 4 Synthesis of Photopolymerization Initiator (A-4)

[0210] (a1-3) was replaced by (a1-4), and the reaction was carried out in the same manner as in Example 3 to obtain a pale yellow viscous liquid (purity 97%). 1 As a result of H-NMR analysis (described below) and LC-MS analysis (molecular weight: 495), the formation of the photopolymerization initiator (A-4) having the structure shown in Table 2 was confirmed. 1 H-NMR: 8.62 to 7.97 ppm (6H, aromatic ring); 4.52 ppm (4H, -COO-CH2-); 4.02 ppm (2H, -CH-O- within 2 tetrahydrofuranyl groups); 3.82 ppm (4H, -CH2-O- within 2 tetrahydrofuranyl groups); 1.63-2.02 ppm (8H, -CH2-CH2- within 2 tetrahydrofuranyl groups).

[0211] Example 5 Synthesis of Photopolymerization Initiator (A-5)

[0212] Using the same 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. Then, the reaction solution was cooled to 0°C, 58.0 g of (a2-5) was added, stirred for 10 minutes, and then heated to 70°C and reacted for 3 hours. After the reaction was completed, it was purified to obtain a light yellow viscous liquid (purity 87%). The ester group (1725 cm -1 ). 1 H-NMR analysis confirmed the presence of benzophenone groups (8.50 to 7.85 ppm, 6H, aromatic ring), tetrahydrofuran groups (same as Example 4) and methacrylate groups (5.97 ppm and 5.48 ppm, 2H, =CH2; 1.96 ppm, 3H, -CH3). The molecular weight (511) of the LC-MS analysis value was consistent with the molecular weight of the target compound (Table 2). Based on these results, the generation of the photopolymerization initiator (A-5) having the structure shown in Table 2 was confirmed.

[0213] Example 6 Synthesis of Photopolymerization Initiator (A-6)

[0214] Using the same 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 solution was cooled to 0°C, 38.5 g of (a5-4) and 73.8 g of thionyl chloride were added, stirred for 10 minutes, and reacted at 70°C for 3 hours. Purification was performed to obtain a light yellow viscous liquid (purity 91%). The ester group (1725 cm -1 ) and the disappearance of the anhydride group. 1 H-NMR analysis confirmed the presence of benzophenone group (8.62 to 7.95 ppm, 6H, aromatic ring) and tetrahydrofuran group (same as Example 4). The molecular weight (615) of LC-MS analysis value was consistent with the molecular weight of the target compound (Table 2). Based on these results, the generation of the photopolymerization initiator (A-6) having the structure shown in Table 2 was confirmed.

[0215] Example 7 Synthesis of Photopolymerization Initiator (A-7)

[0216] Using the same 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, 44.8 g of (a5-5) and 0.8 g of TPP were added, stirred for 10 minutes, and reacted at 70°C for 3 hours. Purification was performed to obtain a light yellow viscous liquid (purity 84%). Similarly, the generation of ester groups and amide groups and the disappearance of anhydride groups were confirmed by IR analysis of the obtained viscous liquid. 1 H-NMR analysis confirmed the presence of benzophenone groups and morpholine groups, and LC-MS analysis confirmed that the molecular weight (641) was consistent with the target compound (Table 2). These results confirmed the formation of the photopolymerization initiator (A-7) having the structure shown in Table 2.

[0217] Example 8 Synthesis of Photopolymerization Initiator (A-8)

[0218] Using the same 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, 19.9 g of (a5-6) and 73.8 g of thionyl chloride were added, stirred for 10 minutes, and reacted at 70°C for 3 hours. After the reaction was completed, purification was performed to obtain a light yellow viscous liquid (purity 96%). Similarly, the formation of ester groups and the disappearance of anhydride groups were confirmed by IR analysis of the obtained viscous liquid. 1 H-NMR analysis confirmed the presence of benzophenone groups and tetrahydrofuran groups, and LC-MS analysis confirmed that the molecular weight (555) was consistent with the target compound (Table 2). These results confirmed the formation of the photopolymerization initiator (A-8) having the structure shown in Table 2.

[0219] Example 9 Synthesis of Photopolymerization Initiator (A-9)

[0220] Using the same 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, and then 202.7 g of (a5-7) was added and reacted at 85°C for 5 hours. After the reaction was completed, purification was performed to obtain a light yellow viscous liquid (purity 81%). Similarly, the IR analysis of the obtained viscous liquid confirmed the generation of ester groups and amide groups and the disappearance of anhydride groups. 1 H-NMR analysis confirmed the presence of benzophenone groups and morpholine groups, and LC-MS analysis confirmed that the molecular weight (1150) was consistent with the target compound (Table 2). These results confirmed the formation of the photopolymerization initiator (A-9) having the structure shown in Table 2.

[0221] Example 10 Synthesis of Photopolymerization Initiator (A-10)

[0222] Using the same 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. Then, 11.2 g of ion exchange water was added and reacted at 65°C for 3 hours. After the reaction was completed, purification was performed to obtain a light yellow viscous liquid (purity 97%). Similarly, the generation of amide groups and the disappearance of anhydride groups were confirmed by IR analysis of the obtained viscous liquid. 1 H-NMR analysis confirmed the presence of benzophenone groups and morpholine groups, and LC-MS analysis confirmed that the molecular weight (427) was consistent with the target compound (Table 2). These results confirmed the formation of the photopolymerization initiator (A-10) having the structure shown in Table 2.

[0223] Examples 11, 14, 15 Synthesis of Photopolymerization Initiators (A-11), (A-14), (A-15)

[0224] Using the raw material compounds shown in Table 1, the reactions of Examples 11, 14 and 15 were carried out in the same manner as in Example 7 to obtain a pale yellow viscous liquid. 1 H-NMR analysis and LC-MS analysis confirmed the production of photopolymerization initiators (A-11), (A-14), and (A-15) having the structures shown in Table 2.

[0225] Examples 12, 17, 19, 20 Synthesis of Photopolymerization Initiators (A-12), (A-17), (A-19), (A-20)

[0226] Using the raw material compounds shown in Table 1, the reactions of Examples 12, 17, 19, and 20 were carried out in the same manner as in Example 6 to obtain a pale yellow viscous liquid. 1 H-NMR analysis and LC-MS analysis confirmed the production of photopolymerization initiators (A-12), (A-17), (A-19), and (A-20) having the structures shown in Table 2.

[0227] Example 13 Synthesis of Photopolymerization Initiator (A-13)

[0228] Using the same 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, purification was performed to obtain a light yellow viscous liquid (purity 84%). Similarly, IR analysis, 1 H-NMR analysis (described below) and LC-MS analysis confirmed the formation of the photopolymerization initiator (A-13) having the structure shown in Table 2.

[0229] 1 H-NMR: 8.61 to 7.78 ppm (6H, aromatic ring); 5.02 ppm (2H, -COO-CH-); 3.68 to 4.01 ppm (28H, -CH2-O- in crown ether).

[0230] Example 16 Synthesis of Photopolymerization Initiator (A-16)

[0231] Use the same apparatus to mix (a1-6) 100g, (a5-3) 88.2g, tetrabutylammonium bromide 10.0g and DMF 50g, and react at 70°C for 4 hours. Cool the reaction solution to 0°C, add (a2-4) 54.1g, thionyl chloride 73.8g, stir for 10 minutes, and react at 70°C for 3 hours. After the reaction is completed, purification is carried out to obtain a light yellow viscous liquid (purity 83%). Similarly, the formation of ester groups and the disappearance of anhydride groups were confirmed by IR analysis of the obtained viscous liquid. 1 H-NMR analysis confirmed the presence of benzophenone groups, tetrahydrofuran groups, and methacrylate groups, and LC-MS analysis confirmed that the molecular weight (811) was consistent with the target compound (Table 2). Based on these results, the formation of the photopolymerization initiator (A-16) having the structure shown in Table 2 was confirmed.

[0232] Example 18 Synthesis of Photopolymerization Initiator (A-18)

[0233] 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 to obtain a pale yellow viscous liquid. 1 H-NMR analysis (described below) and LC-MS analysis confirmed the formation of the photopolymerization initiator (A-18) having the structure shown in Table 2.

[0234] 1 H-NMR: 4.91 ppm (2H, -O-CH-), 2.71 ppm (4H, -CH2-N-), 2.22 ppm (8H, thiopyranyl-N-CH2-); 1.53 to 1.41 ppm (10H, thiopyranyl-CH2-CH2-).

[0235] [Table 1]

[0236]

[0237] [Table 2-1]

[0238]

[0239] [Table 2-2]

[0240]

[0241] Example 21 Synthesis of Photopolymerization Initiator (A-21)

[0242] In a 300 ml flask equipped with a reflux cooling tube, a stirrer, a thermometer and a dropping funnel, 79.27 g of (A-2) and 0.05 g of butylated hydroxytoluene (BHT) as a polymerization inhibitor were added, and the mixture was heated to 70°C while stirring. Then, 20.73 g of (C1-1) and 0.02 g of dibutyltin dilaurate were added to the mixture, and the mixture was reacted at 70°C for 5 hours. The absorption peak of the isocyanate group disappeared by IR analysis, and the reaction was terminated. A light yellow liquid was obtained by purification. The NH-specific absorption of the carbamate bond (1532 cm- 1 ), the C=O specific absorption of the ketone group of benzophenone (1650 cm- 1 ), and the molecular weight obtained by LC-MS analysis was 681, which was consistent with the molecular weight of the target compound shown in Table 3, confirming the generation of the photopolymerization initiator (A-21).

[0243] Example 22 Synthesis of Photopolymerization Initiator (A-22)

[0244] 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 mixture of 47.59 g of (A-6) and 0.05 g of BHT at 70°C, and the mixture was reacted at 70°C for 5 hours. After confirming that the isocyanate group had stopped decreasing by IR analysis, 17.99 g of (B3-1) and 0.01 g of dibutyltin dilaurate were added, and the mixture was further reacted at 70°C for 3 hours. After the reaction was completed, the disappearance of the isocyanate group was confirmed by IR analysis, and the mixture was purified to obtain a light yellow solid. Similarly, the presence of carbamate groups (1532 cm- 1 ), benzophenone group (1650cm- 1 ) was present, confirming the generation of the photopolymerization initiator (A-22). In addition, the number average molecular weight of (A-22) was calculated by GPC analysis and was 1,900. The results are shown in Table 3.

[0245] Example 23 Synthesis of Photopolymerization Initiator (A-23)

[0246] Using the same apparatus as in Example 21, after mixing (A-7) 20.47g, (B1-1) 31.95g, (H-1) 30g, and BHT 0.05g at 70°C, 13.90g (C1-3) and 0.02g dibutyltin dilaurate were added, and the mixture was reacted at 70°C for 4 hours. It was confirmed by IR analysis that the isocyanate group stopped decreasing. Then, 3.68g (B3-2) and 0.01g dibutyltin dilaurate were added to the reaction solution, and the mixture was reacted at 70°C for 4 hours. The disappearance of the isocyanate group was confirmed by IR analysis, and the mixture was purified to obtain a light yellow viscous liquid. Similarly, the generation of the photopolymerization initiator (A-23) was confirmed by IR analysis. In addition, 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.

[0247] Examples 24 to 27, 29, 30 Synthesis of Photopolymerization Initiators (A-24) to (A-27), (A-29), (A-30)

[0248] In the same manner as in Example 23, synthesis, purification and analysis were performed with the composition shown in Table 3, and the generation of photopolymerization initiators (A-24) to (A-27), (A-29) and (A-30) was confirmed. In addition, the number average molecular weight calculated by GPC analysis is shown in Table 3.

[0249] Example 28 Synthesis of Photopolymerization Initiator (A-28)

[0250] The formation of the photopolymerization initiator (A-28) was confirmed by synthesis, purification, analysis, etc. with the composition shown in Table 3 in the same manner as in Example 23. The number average molecular weight of (A-28) was calculated by GPC analysis and was 10,500. The results are shown in Table 3.

[0251] Example 31 Synthesis of Photopolymerization Initiator (A-31)

[0252] A nitrogen inlet pipe was installed on the same apparatus as in Example 21, and 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. The mixture was heated to 190° C. while nitrogen was blown into the mixture under normal pressure. 0.01 g of zinc oxide was added to the mixture, and the reaction was carried out while water was distilled off at 195° C. After the distillation of water stopped, the acid value of the reaction liquid was measured (according to JIS K0070:1992), and it was confirmed to be 48 mgKOH / g. Then, the reflux cooler was replaced with a Dean-Stark type azeotropic 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 liquid, and water and toluene (azeotropic) were both distilled off to the outside of the reaction system at 125° C. After the reaction was completed, purification was carried out to obtain a light yellow viscous liquid. Similarly, the generation of the photopolymerization initiator (A-31) was confirmed by IR analysis, and the number average molecular weight was calculated by GPC analysis to be 3,800 (Table 3).

[0253] Example 32 Synthesis of Photopolymerization Initiator (A-32)

[0254] 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 mixed solution, and the mixture was reacted at 70°C for 2 hours. After confirming that the isocyanate group stopped decreasing 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 reacted at 70°C for 3 hours. The disappearance of the isocyanate group was confirmed by IR analysis, and the mixture was purified to obtain a light yellow viscous liquid. Similarly, the generation of the photopolymerization initiator (A-32) was confirmed by IR analysis, and the number average molecular weight was calculated by GPC analysis to be 4,100 (Table 3).

[0255] Example 33 Synthesis of Photopolymerization Initiator (A-33)

[0256] 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 added and mixed. 40.42 g of (C1-2) and 0.02 g of dibutyltin dilaurate were added to the mixed solution, and the temperature was raised to 120°C over 2 hours, and the mixture was further reacted at 120°C for 10 hours. Then, the reaction solution was cooled to 60°C, 5.28 g of (B3-1), 1.46 g of (B3-6), and 0.01 g of dibutyltin dilaurate were added, and the mixture was reacted at 60°C for 2 hours. After the reaction was completed, the disappearance of the isocyanate group was confirmed by IR analysis, and further purification was performed to obtain a light yellow viscous liquid. Similarly, the generation of the photopolymerization initiator (A-33) was confirmed by IR analysis, and the number average molecular weight was calculated to be 2,800 by GPC analysis (Table 3).

[0257] [Table 3]

[0258]

[0259] Examples 34 to 72 and Comparative Examples 1 to 4

[0260] 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 the other components (G) were weighed in the ratio shown in Table 4, and mixed at 25°C for 30 minutes to prepare an active energy ray-curable composition. The transparency of the obtained active energy ray-curable composition, the compatibility of the photopolymerization initiator (A) or (D) with the monofunctional monomer (E), the polyfunctional monomer or oligomer (F), and the curability of the curable composition under different curing conditions (with or without oxygen hindrance, active energy rays of different wavelengths) were evaluated by the following method, and the results are shown in Tables 4-1 and 4-2.

[0261] (5-1) Transparency and compatibility

[0262] The state of the active energy ray-curable composition obtained by visual observation was evaluated for transparency according to the following criteria. In addition, 20 g of each of the photopolymerization initiator (A-1) to (A-33) and the known photopolymerization initiator (D-1) to (D-4), and 80 g of each of the monofunctional monomer (E-2), (E-3), or the multifunctional monomer or oligomer (F-15) were measured and mixed at 25°C for 30 minutes to prepare an evaluation solution. The state of the mixed solution was visually observed, and the compatibility of the photopolymerization initiator with the monofunctional monomer, the multifunctional monomer or the oligomer was evaluated according to the following criteria. In addition, the transparency evaluation and the compatibility evaluation were performed according to the same criteria.

[0263] ○: Transparency and compatibility are high, and turbidity and separation are not observed at all.

[0264] Δ: No phase separation, but turbidity.

[0265] ×: Turbidity and phase separation.

[0266] (5-2) Curing properties under oxygen-free conditions

[0267] Using a rod coater, the obtained active energy ray curable composition was coated on the easy-adhesion treated surface of a polyethylene terephthalate (PET) film (COSMOSHINEA-4100, manufactured by Toyobo Co., Ltd.) with a thickness of 100 μm. After the release surface of a biaxially stretched PET film (DIAFOIL MRF38, manufactured by Mitsubishi Resins Co., Ltd.) having a release surface on one side was attached to the above-mentioned coating surface, the coating was cured by irradiating ultraviolet light, and the cumulative light amount at which the viscosity disappears when the roll-up release surface contacts the cured product was calculated, and the curability was divided into 4 levels for evaluation. In addition, the following two types of ultraviolet irradiation lamps 1) and 2) were used. In addition, the lower the cumulative light amount required until the viscosity disappears, the higher the curability.

[0268] 1) UV-LED lamp: wavelength 365nm, output power 100mW / cm 2

[0269] 2) UV-LED lamp: wavelength 405nm, output power 100mW / cm 2

[0270] ◎: Cumulative light intensity is less than 1000mJ / cm 2 The viscosity disappears.

[0271] ○: Cumulative light intensity is 1000mJ / cm 2 Above and less than 3000mJ / cm 2 The viscosity disappears.

[0272] Δ: Cumulative light intensity is 3000mJ / cm 2 Above and less than 20000mJ / cm 2 The viscosity disappears.

[0273] ×: Even if the cumulative light intensity is 20000mJ / cm 2 , the stickiness still remains.

[0274] (5-3) Curing under oxygen-hindered conditions

[0275] A coating film before curing was prepared in the same manner as the evaluation of curability under oxygen-free conditions, and the coating film was cured by irradiating ultraviolet light without laminating a film on the surface. The accumulated light intensity at which tack disappears when in contact with the cured product was determined in the same manner, and the curability was evaluated in the same manner using four levels.

[0276] (5-4) Leakage resistance

[0277] The test piece after curing was prepared in the same manner as the curing evaluation under oxygen-free conditions (UV-LED lamp: wavelength 395 nm, illumination 100 mW / cm 2 , cumulative light intensity 10000mJ / cm 2 ), and placed in a constant temperature and humidity chamber set at a temperature of 40°C and a relative humidity of 50% for 168 hours. The surface of the test piece was visually observed and the anti-bleeding property was evaluated according to the following criteria.

[0278] ◎: No bleeding was observed at all.

[0279] ○: Very little bleeding was observed. Δ: A little bleeding was observed. ×: Severe bleeding was observed.

[0280] [Table 4-1]

[0281]

[0282] [Table 4-2]

[0283]

[0284] Examples 73 to 79 and Comparative Examples 5 to 7

[0285] 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 ratio 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 method, and the results are shown in Table 5.

[0286] (5-5)Tightness

[0287] The obtained coating composition was applied to a PET plate (PET-1060, manufactured by CITAKIRON Co., Ltd.), a polycarbonate (PC) plate (PC1600, manufactured by CITAKIRON Co., Ltd.), a glass (GL) plate (EAGLE XG, manufactured by CORNING JAPAN Co., Ltd.), and a SUS304 plate using a bar coater to a dry film thickness of 10 μm, and dried in a constant temperature bath at 80° C. for 2 minutes. The wavelength was 395 nm, the output power was 100 mW / cm 2 UV-LED lamp with a cumulative light intensity of 3000mJ / cm 2 The cured film was irradiated in a manner to prepare a cured film. Using the obtained cured film, 100 1 mm square grids were made with a cutter according to JIS K5600-5-6, and the number of grids remaining on the test piece when the commercially available tape was attached and peeled off was divided into 4 levels for evaluation. The more the number of grids remaining on the test piece, the higher the adhesion.

[0288] ◎: The number of remaining chessboard squares is 100.

[0289] ○: The number of remaining checkerboard squares is between 90 and 99.

[0290] Δ: The number of remaining checkerboard squares ranges from 60 to 89.

[0291] ×: The number of remaining checkerboard squares is less than 60.

[0292] (5-6) Pencil hardness

[0293] In the same manner as in the evaluation of adhesion, a cured film prepared on a PC test piece was used, and the surface of the cured film was scratched with a pencil (at an angle of 45°, about 10 mm) in accordance with JIS K5600-5-4. The hardest pencil that did not scratch the surface of the cured film was used as the pencil hardness, and the hardness was evaluated in four grades.

[0294] ◎: Pencil hardness is 2H or more.

[0295] ○: Pencil hardness is HB to H.

[0296] △: Pencil hardness is 3B to B.

[0297] ×: Pencil hardness is 4B or less.

[0298] (5-7) Durability

[0299] In the same manner as in the evaluation of adhesion, a cured film produced on a PC test piece was kept at a temperature of 85° C. and a relative humidity of 85% for 100 hours, and the presence or absence of floating, peeling, bubbles, and white turbidity of the cured film was visually observed to evaluate durability based on the following criteria.

[0300] ◎: Transparent, with no floating, peeling, or bubbles.

[0301] ○: Although there was slight blurring, floating, peeling, and bubbles did not occur.

[0302] △: Floating, peeling, or bubbles occurred although the amount was small.

[0303] ×: Blurring, floating, peeling, or bubbles are present.

[0304] [Table 5]

[0305]

[0306] Examples 80 to 85 and Comparative Examples 8 and 9

[0307] 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 ratio shown in Table 6, and mixed at 25°C for 30 minutes to prepare an active energy ray-curable ink composition. The obtained ink composition was applied to a 100 μm thick PET film (film thickness after drying: 20 μm) using a bar coater (RDS12) and irradiated with ultraviolet light (UV-LED lamp: wavelength 395 nm, illumination 1000 mW / cm 2 ) to cure the ink composition to produce a printed product. The curability of the ink composition was evaluated in the same manner as the curability evaluation under the conditions of oxygen hindrance in (5-3) above. The viscosity, pigment dispersibility, ejection stability of the ink composition and the print clarity of the printed product were evaluated according to the following methods. The results are shown in Table 6.

[0308] (5-8) Viscosity

[0309] The viscosity of the ink composition was measured at 25° C. using a cone and plate viscometer (RE550 viscometer manufactured by Toki Sangyo Co., Ltd.) in accordance with JIS K 5600-2-3, and the ink composition for inkjet printing was evaluated in four grades as follows.

[0310] ◎: 5mPa·s to less than 50mPa·s

[0311] ○: 50mPa·s to less than 500mPa·s

[0312] Δ: 500mPa·s to less than 2000mPa·s

[0313] ×: 2000mPa·s or more

[0314] (5-9) Pigment dispersibility

[0315] Using the ink composition containing the pigment, the aggregation and precipitation state of the pigment immediately after preparation and after being left to stand at room temperature for 2 months were visually observed, and the pigment dispersibility was evaluated according to the following criteria.

[0316] ◎: No aggregation or precipitation of the pigment was observed immediately after preparation and after standing for 2 months.

[0317] ○: No aggregation or precipitation was observed immediately after preparation, but after standing for 2 months, some aggregation or precipitation of the pigment was observed.

[0318] Δ: Slight aggregation or precipitation was observed immediately after preparation, but aggregation and precipitation of the pigment were clearly observed after standing for 2 months.

[0319] ×: Aggregation and precipitation of the pigment were clearly observed immediately after preparation.

[0320] (5-10) Ejection stability

[0321] The obtained ink composition was filled in an inkjet printer (LuxelJet UV350GTW, manufactured by Fuji Film Co., Ltd.), and a solid image was printed using coated paper. The printing state of the obtained printed matter was visually observed, and the ejection stability was evaluated according to the following criteria.

[0322] ◎: No leakage, good printing.

[0323] ○: There is a little leakage.

[0324] ×: There are spray leaks in a large area.

[0325] (5-11) Printing clarity

[0326] The image clarity of the printed matter obtained in the above-mentioned discharge stability evaluation was visually observed and evaluated according to the following criteria.

[0327] ◎: No ink bleeding was observed and the image was clear.

[0328] ○: There is almost no ink bleeding and the image is good.

[0329] ×: Ink bleeding was observed.

[0330] [Table 6]

[0331]

[0332] Examples 86 to 90 and Comparative Examples 10 and 11

[0333] Using the obtained photopolymerization initiator (A) and a known photopolymerization initiator (D), a monofunctional monomer (E), a multifunctional monomer or oligomer (F) and other components (G) were weighed in the ratio shown in Table 7, and mixed at 25°C for 30 minutes to prepare an active energy ray-curable adhesive composition. A heavy release PET film (E7001, manufactured by Toyobo Co., Ltd.) with a thickness of 75 μm was placed in close contact with a horizontally arranged glass plate, and a spacer with a thickness of 1 mm and an inner area of ​​60 mm×100 mm was set. The adhesive composition of the prepared embodiment and comparative example was filled inside the spacer, and a light release PET film (E7002, manufactured by Toyobo Co., Ltd.) with a thickness of 50 μm was overlapped thereon. The light release PET film was illuminated by a wavelength of 395 nm and an illumination of 100 mW / cm 2 The UV-LED lamp has a cumulative light intensity of 1000mJ / cm 2 The adhesive composition was cured by irradiation in a manner of 100°. Then, the light-peel PET film was peeled off to obtain an adhesive sheet consisting of a cured product (adhesive layer) of the adhesive composition and a heavy-peel PET film. The transparency, adhesive strength, reworkability and yellowing resistance of the test piece were evaluated according to the following method, and the results are shown in Table 7.

[0334] (5-12) Transparency

[0335] The adhesive layer was transferred from the adhesive sheet to a glass plate under the conditions of a temperature of 23°C and a relative humidity of 50%, and the transmittance of the glass plate and the adhesive layer was measured using a haze meter (NDH-2000, manufactured by Nippon Denshoku Industries Co., Ltd.) in accordance with JIS K 7105. Then, the transmittance of the glass plate was measured in the same manner, and the transmittance of the adhesive layer was calculated by deducting it from the total light transmittance of the glass plate and the adhesive layer, and the transparency was evaluated according to the following criteria.

[0336] ◎: Transmittance is more than 90%

[0337] ○: Transmittance is 85% or more and less than 90%

[0338] △: Transmittance is 50% or more and less than 85%

[0339] ×: Transmittance is less than 50%

[0340] (5-13) Yellowing resistance

[0341] The adhesive sheet was prepared in the same manner as above, and was mounted on a xenon fade meter (SC-700-WA, manufactured by SUGA Testing Instruments Co., Ltd.) and irradiated with 70 mW / cm 2 After being exposed to ultraviolet rays of a certain intensity for 120 hours, the discoloration of the adhesive layer on the adhesive sheet was visually observed and evaluated based on the following criteria.

[0342] ◎: No yellowing was observed visually.

[0343] ○: Yellowing is very slightly observed by visual inspection.

[0344] Δ: Yellowing was observed visually.

[0345] ×: Clear yellowing was observed visually.

[0346] (5-14) Adhesion

[0347] Under the conditions of temperature 23°C and relative humidity 50%, the adhesive layer was transferred from the adhesive sheet to the following substrate (film or plate), and a 2kg pressure roller was used to reciprocate twice for pressure bonding, and placed in the same environment for 30 minutes. Then, a tensile tester (Tensilon RTA-100, manufactured by ORIENTEC Co., Ltd.) was used to measure the 180° peel strength (N / 25mm) at a peeling speed of 300mm / min according to JISZ0237, and the adhesive strength of the adhesive sheet in each substrate was evaluated according to the following criteria.

[0348] PET℃OSMOSHINE A4160 (corona treated surface, manufactured by Toyobo Co., Ltd.)

[0349] PC: PC1600 (manufactured by CITAKIRON Co., Ltd.)

[0350] GL (Glass): EAGLEXG (manufactured by CORNING Co., Ltd.)

[0351] ◎: 20 (N / 25mm) or more

[0352] ○: 10 (N / 25mm) or more, less than 20 (N / 25mm)

[0353] Δ: 5 (N / 25mm) or more, less than 10 (N / 25mm)

[0354] ×: less than 5 (N / 25mm)

[0355] (5-15) Reprocessability

[0356] The adhesive layer was transferred from the adhesive sheet to the substrate in the same manner as in the adhesive strength evaluation. Then, after standing in a thermostatic chamber at 80°C for 24 hours, the residual state of the adhesive layer (glue) on the substrate surface after peeling off the adhesive sheet was visually observed, and the reprocessability of the adhesive sheet was evaluated according to the following criteria.

[0357] ◎: No residual glue.

[0358] ○: There is very little residual adhesive.

[0359] △: There is a small amount of residual glue.

[0360] ×: There is residual glue.

[0361] [Table 7]

[0362]

[0363] Examples 91 to 96 and Comparative Examples 12 and 13

[0364] Using the obtained photopolymerization initiator (A) and a known photopolymerization initiator (D), a monofunctional monomer (E), a multifunctional monomer or oligomer (F) and other components (G) were weighed in the ratio shown in Table 8, and mixed at 25°C for 30 minutes to prepare an active energy ray-curable adhesive composition. The adhesive composition was applied to various plate-shaped or film-shaped substrates arranged horizontally, and the following PET film was attached to the coated surface. Then, the adhesive layer was attached using a tabletop roll laminator (RSL-382S) in a manner that did not generate bubbles so that the thickness of the adhesive layer became 20 μm. The adhesive composition was subjected to a 405 nm wavelength and an illumination of 50 mW / cm 2 The UV-LED lamp has a cumulative light intensity of 2000mJ / cm 2 The laminate was irradiated in the manner of , and the laminate was produced. The adhesive force and water resistance of the obtained laminate were evaluated by the following methods, and the results are shown in Table 8. In addition, the following substrate was used.

[0365] PET: Film (E5100, corona-treated surface, manufactured by Toyobo Co., Ltd.)

[0366] PMMA: Plate-shaped (COMOGLAS P, manufactured by Kuraray Co., Ltd.)

[0367] PC: Plate (PC1600, manufactured by CITAKIRON Co., Ltd.)

[0368] (5-16) Water resistance

[0369] 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 confirmed. The water resistance was evaluated according to the following criteria.

[0370] ◎: No peeling on the interface (less than 1mm)

[0371] ○: Part of the interface is peeled off (more than 1 mm and less than 3 mm)

[0372] Δ: Part of the interface is peeled off (3mm or more, less than 5mm)

[0373] ×: There is peeling at the interface (more than 5 mm)

[0374] (5-17) Adhesion

[0375] The produced laminate was measured for 180° peel strength (N / 25 mm) at a peeling speed of 300 mm / min using a tensile tester (Tensilon RTA-100) in accordance with JIS Z0237, and the adhesive strength was evaluated based on the following criteria.

[0376] ◎: 20 (N / 25mm) or more

[0377] ○: 10 (N / 25mm) or more, less than 20 (N / 25mm)

[0378] Δ: 5 (N / 25mm) or more, less than 10 (N / 25mm)

[0379] ×: less than 5 (N / 25mm)

[0380] [Table 8]

[0381]

[0382] Examples 97 to 101 and Comparative Examples 14 and 15

[0383] 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 ratio shown in Table 9, and mixed at 25°C for 30 minutes to prepare an active energy ray-curable three-dimensional modeling ink composition. Using the obtained three-dimensional modeling ink composition, the three-dimensional modeling curability and curing shrinkage resistance were evaluated. In addition, the obtained shapes were also used to evaluate the shape accuracy, the strength of the shapes, the heat resistance and the water resistance of the shapes according to the following methods, and the results are shown in Table 9.

[0384] (5-18) Three-dimensional shaping solidification

[0385] As a suspended DLP method liquid tank photopolymerization device, ARM-10 (manufactured by ROLAND DG Co., Ltd.) was used. The three-dimensional modeling ink composition obtained in each example and comparative example was filled in the liquid tank, and ultraviolet rays (wavelength 405 nm, illumination 0.2 mW / cm) were irradiated so that the thickness of one layer was 0.15 mm. 2 , cumulative light intensity 5mJ / cm 2 ), a rectangular parallelepiped of 25×20×1 mm was formed. After forming, the three-dimensional ink composition was removed by immersion in isopropyl alcohol for one minute (twice) to remove the uncured three-dimensional forming ink composition. Then, the curability was evaluated according to the following criteria by observing the state of the formed object.

[0386] ◎: A shaped object was formed and could be washed with isopropyl alcohol while maintaining its shape.

[0387] ○: A shape was formed, but a part of the shape was deformed due to washing with isopropyl alcohol.

[0388] △: The formation of the shape is insufficient, and the shape is damaged by washing with isopropyl alcohol.

[0389] ×: A state where no object is formed.

[0390] (5-19) Resistance to curing shrinkage

[0391] A heavy-peel PET film (E7001) with a thickness of 75 μm was placed in close contact with a horizontally arranged glass plate, and a spacer with a thickness of 1 mm and an inner size of 60 mm×100 mm was set. The inside of the spacer was filled with the ink composition for three-dimensional modeling obtained in each example and comparative example, and then a light-peel PET film (E7002) was stacked thereon, and ultraviolet rays (wavelength 405 nm, illumination 10 mW / cm 2 , cumulative light intensity 5,000mJ / cm 2 ), cured, and the peeling PET films on both sides were removed to prepare test pieces. According to JIS K5600 2-4, the curing shrinkage was calculated from the density change of the ink composition for three-dimensional modeling and the test piece by the following formula. The density was measured using an electronic densitometer (MDS-300, manufactured by ALFA MIRAGE Co., Ltd.) according to JIS K7112. Based on the obtained curing shrinkage, the curing shrinkage resistance of the ink composition for three-dimensional modeling was evaluated according to the following criteria.

[0392] Curing shrinkage (%) = (Ds-Dl) / Dl×100%

[0393] (Wherein, Ds is the density of the three-dimensional modeling ink composition after curing, and D1 is the density of the three-dimensional modeling ink composition before curing.)

[0394] ◎: Curing shrinkage is less than 6%

[0395] ○: Curing shrinkage is 6% or more and less than 7%

[0396] △: Curing shrinkage is 7% or more and less than 8%

[0397] ×: Curing shrinkage is 8% or more

[0398] (5-20) Strength

[0399] Test pieces were prepared in the same manner as for the curing shrinkage resistance, 6 pieces were stacked, and the Shore D hardness was measured according to JIS K6253 (rubber hardness test method), and the strength of the three-dimensional shape was evaluated according to the following criteria.

[0400] ◎: Shore D hardness is 60 or above

[0401] ○: Shore D hardness is 40 or more and less than 60

[0402] ×: Shore D hardness less than 40

[0403] (5-21) Heat resistance

[0404] Test pieces were prepared in the same manner as for the cure shrinkage resistance, and the glass transition temperature (Tg) of the three-dimensional object was measured using a differential scanning calorimeter (DSC-60plus, manufactured by Shimadzu Corporation). The heat resistance of the three-dimensional object was evaluated based on the following criteria.

[0405] ◎: Cured product Tg is 50°C or higher

[0406] ○: Cured product Tg is 40°C or higher and less than 50°C

[0407] ×: Cured product Tg is less than 40°C

[0408] (5-22) Forming accuracy

[0409] A heavy peelable PET film (E7001) was placed in close contact with a horizontally placed glass plate, and a spacer with a thickness of 10 mm and an inner size of 10 mm×10 mm was set. The inner side of the spacer was filled with a 1 mm thick ink composition for three-dimensional shaping obtained in each example and comparative example. After keeping the temperature at 60° C. for 30 seconds to smooth the surface, ultraviolet rays (UV-LED lamp, wavelength 405 nm, illumination 10 mW / cm 2 , cumulative light intensity 1,000mJ / cm 2 ), and the ink composition for three-dimensional modeling was cured. Then, the ink composition for three-dimensional modeling was filled and cured at a thickness of 1 mm, and the process was repeated 10 times to obtain a three-dimensional model of 10×10×10 mm. The height of the obtained model was measured, and the side of the model was visually observed. Combining these results, the modeling accuracy of the model was evaluated according to the following criteria.

[0410] ◎: The height is less than 10mm±0.1mm, and there are no bumps on the side.

[0411] ○: The height is 10 mm±0.1 mm or more and less than ±0.2 mm, or there are slight irregularities on the side surface.

[0412] △: The height is 10 mm ± 0.2 mm or more and less than ± 0.3 mm, or there are some irregularities on the side surface.

[0413] ×: The height is 10 mm ± 0.3 mm or more, or there are obvious irregularities on the side.

[0414] (5-23) Water resistance

[0415] A test piece was 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 shape was evaluated based on the following criteria.

[0416] Water absorption (%) = (Wb-Wa) / Wa×100

[0417] (Wa is the weight of the test piece before immersion in ion-exchange water, and Wb is the weight of the test piece after immersion in ion-exchange water.)

[0418] ◎: Water absorption rate is less than 0.5%.

[0419] ○: The water absorption rate is 0.5% or more and less than 1%.

[0420] △: The water absorption rate is 1% or more and less than 2%.

[0421] ×: The water absorption rate is 2% or more.

[0422] [Table 9]

[0423]

[0424] Examples 102 to 106 and Comparative Examples 16 and 17

[0425] 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 ratio shown in Table 10, and mixed at 25°C for 30 minutes to prepare an active energy ray-curable nail cosmetic composition. Using the obtained nail cosmetic composition, the curability of the nail cosmetic composition was evaluated in the same manner as the curability evaluation under the oxygen-free hindrance condition described in (5-2) above (LED 405nm). In addition, the adhesion, surface hardness, surface glossiness and removability of the nail cosmetic composition were evaluated according to the following method, and the results are shown in Table 10.

[0426] (5-24)Tightness

[0427] The curable nail cosmetic composition was applied to a nylon 6 test piece and irradiated for 3 minutes using a UV-LED lamp for gel nail art (manufactured by BEAUTY NAILER, wavelength 405nm, output power 48W) to prepare a cured film. The obtained cured film was used to evaluate the adhesion of the nail cosmetic composition according to the following criteria in accordance with JIS K 5600, in the same manner as the adhesion evaluation of the coating composition. The more the number of checkerboards remaining on the test piece, the higher the adhesion.

[0428] ◎: The number of remaining chessboard squares is 100.

[0429] ○: The number of remaining checkerboard squares is between 90 and 99.

[0430] Δ: The number of remaining checkerboard squares ranges from 60 to 89.

[0431] ×: The number of remaining checkerboard squares is less than 60.

[0432] (5-25) Surface hardness

[0433] A cured film was prepared in the same manner as in the adhesion evaluation, and a pencil with a hardness of HB was pressed at an angle of 45° with a load of 750 g on the surface of the film to visually confirm the presence or absence of peeling and scratches, and the surface hardness was evaluated according to the following criteria. The fewer scratches and peeling occurred, the higher the surface hardness.

[0434] ○: Neither scratches nor peeling occurs. The surface hardness is a pencil hardness HB or higher.

[0435] Δ: No peeling occurred, but scratches occurred.

[0436] ×: Peeling occurred.

[0437] (5-26) Surface gloss

[0438] Cured films were prepared in the same manner as in the adhesion evaluation and allowed to stand in a constant temperature and humidity chamber at 40° C. and 50% relative humidity for 24 hours. The surface gloss of the films was visually observed and the surface gloss of the cured films was evaluated based on the following criteria.

[0439] ○: Glossy.

[0440] Δ: Reflection of light was confirmed, but blurriness was observed.

[0441] ×: No light reflection can be confirmed, no gloss.

[0442] (5-27) Removal

[0443] A 10 mm × 10 mm cured film was prepared on the test piece in the same manner as in the adhesion evaluation. After covering it with absorbent cotton soaked in acetone for 5 minutes, the absorbent cotton was removed and the cured film was rubbed 10 times with a cotton swab. The state of the cured film peeling off from the test piece was observed and the removability of the cured film was evaluated according to the following criteria.

[0444] ○: The cured film was peeled off without remaining.

[0445] Δ: The cured film peeled off, but a part of the cured film remained.

[0446] ×: Most of the cured film remained.

[0447] [Table 10]

[0448]

[0449] Examples 107 to 112 and Comparative Examples 18 and 19

[0450] Using the obtained photopolymerization initiator (A) and a known photopolymerization initiator (CD), the monofunctional monomer (E), the polyfunctional monomer or oligomer (F) and the other components (G) were weighed in the ratio shown in Table 11, and mixed at 25°C for 30 minutes to prepare an active energy ray-curable dental material composition. The obtained dental material composition was used to evaluate solubility (dispersibility), storage stability, and curability (the same method as the curability evaluation under the oxygen-free conditions of (5-2) above, LED405nm). In addition, the hardness, surface smoothness, and bonding strength of the obtained cured product were evaluated according to the following criteria, and the results are shown in Table 11.

[0451] (5-28) Solubility (dispersibility)

[0452] The state of the curable dental material composition was visually observed, and the solubility or dispersibility was evaluated according to the following criteria.

[0453] ○: The composition is in a uniform state.

[0454] Δ: The composition was observed to be slightly non-uniform.

[0455] ×: The composition is in a non-uniform state.

[0456] (5-29) Storage stability

[0457] The curable dental material composition was placed in a light-shielding spiral tube, the lid was closed, and the tube was stored at 40° C. for one month and at 80° C. for two weeks. The dissolved or dispersed state of the composition after storage was confirmed, and the storage stability of the composition was evaluated according to the following criteria.

[0458] ○: There is no change in state after storage at 40°C for one month and at 80°C for two weeks.

[0459] Δ: A change in state after storage was observed under either the storage conditions of 40°C for one month or 80°C for two weeks.

[0460] ×: Changes in state after storage were observed in both conditions of one month at 40°C and two weeks at 80°C.

[0461] (5-30) Hardness

[0462] The surface of the cured product obtained in the evaluation of curability was buffed and the Knoop hardness was measured at 23° C. under a load of 10 g and 20 seconds using a microhardness tester manufactured by Matsuzawa Seiki Co., Ltd. The hardness of the cured product was evaluated according to the following criteria.

[0463] ◎: Knoop hardness is above 200KHN (equivalent to permanent tooth enamel).

[0464] ○: Knoop hardness is 70 KHN or more and less than 200 KHN (equivalent to dentin).

[0465] Δ: Knoop hardness is less than 70KHN.

[0466] ×: Uncured, so measurement was impossible.

[0467] (5-31) Surface smoothness

[0468] The surface smoothness and gloss of the cured product obtained in the curability evaluation were visually observed and evaluated based on the following criteria.

[0469] ◎: The surface is smooth and glossy.

[0470] ○: The surface is generally smooth, but slight blurring or slight irregularities are observed.

[0471] Δ: The entire surface is blurred, and irregularities and granular materials are slightly observed.

[0472] ×: The entire surface is blurred and covered with granular matter.

[0473] (5-32) Adhesion strength

[0474] Under water injection, the bovine mandibular front teeth were ground with No. 1000 water-resistant abrasive paper to cut out a flat dentin surface for bonding, and compressed air was blown for 10 seconds to dry it. A tape with a hole of 3 mm in diameter was pasted to set the bonded surface. Then, a bonding test piece was made by a known method (refer to the method described in Japanese Patent Application Laid-Open No. 2010-208964). After the bonding test piece was immersed in 37°C water for 24 hours, the tensile bonding strength was measured by an Instron universal testing machine (crosshead speed 2 mm / min), and the bonding strength was evaluated according to the following criteria as the bonding force to enamel and dentin.

[0475] ◎: The bonding strength between enamel and dentin is 20 MPa or more.

[0476] ○: Only one of the bonding strengths of enamel and dentin is 20 MPa or more.

[0477] Δ: The bonding strength between enamel and dentin is above 7Mpa.

[0478] ×: The bonding strength between enamel and dentin is less than 7Mpa.

[0479] [Table 11]

[0480]

[0481] Examples 113 to 118 and Comparative Examples 20 and 21

[0482] Using the obtained photopolymerization initiator (A) and a known photopolymerization initiator (D), a multifunctional monomer or oligomer (F), other components (G) and an organic solvent (H) were weighed in the ratio shown in Table 12, and mixed at 25° C. for 30 minutes to prepare an active energy ray-curable photosensitive composition. Using the obtained photosensitive composition, photosensitive resins for evaluation of Examples 113 to 115 and Comparative Example 20 were prepared by the following (5-33) Preparation of Photosensitive Resin 1, and photosensitive resins for evaluation of Examples 116 to 118 and Comparative Example 21 were prepared by the following (5-34) Preparation of Photosensitive Resin 2, and the sensitivity, pattern forming properties and storage stability of the photosensitive compositions were evaluated. The results are shown in Table 12.

[0483] (5-33) Production of photosensitive resin 1

[0484] 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) by a spin coater to a film thickness of 15 μm, and dried in an oven at 80° C. for 3 minutes. Then, ultraviolet rays (wavelength 405 nm, illuminance 0.5 mW / cm 2 , cumulative light intensity 90mJ / cm 2 ). Next, the negative photomask was removed, and the unexposed portion was removed using cyclopentanone to obtain a photosensitive resin cured product for evaluation.

[0485] (5-34) Production of photosensitive resin 2

[0486] 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) by a spin coater to a film thickness of 15 μm, and dried in an oven at 40° C. for 30 minutes. Then, ultraviolet rays (wavelength 405 nm, illumination 0.5 mW / cm 2 , cumulative light intensity 90mJ / cm 2 ), the negative photomask was removed, and the unexposed portion was removed using cyclopentanone. Then, a heat treatment was performed in an oven at 130° C. for 30 minutes to obtain a photosensitive resin for evaluation.

[0487] (5-35) Sensitivity

[0488] The obtained photosensitive resin for evaluation was touched by hand to confirm the presence of stickiness and uncured components, and the curability of the photosensitive composition was evaluated based on the following criteria.

[0489] ◎: No stickiness at all.

[0490] ○: Slightly sticky, but no traces of fingers remain on the surface.

[0491] Δ: It is sticky, and traces of fingers remain on the surface.

[0492] ×: Very sticky, fingers stick to the surface.

[0493] (5-36) Pattern forming properties

[0494] The pattern forming properties of the evaluation photosensitive resin were evaluated based on the following criteria.

[0495] ◎: The pattern was not deformed and no loss of the edge portion was observed.

[0496] ○: The pattern is not deformed, but a slight loss of the edge portion is observed.

[0497] Δ: The pattern is not deformed, but a defect is observed at the edge.

[0498] ×: The pattern is deformed.

[0499] (5-37) Storage stability

[0500] The obtained photosensitive resin for evaluation was left to stand in a constant temperature and humidity chamber at 40°C and 50% relative humidity for 168 hours, and the surface of the test piece was visually observed for oozing out, and the storage stability was evaluated according to the following criteria. The less oozing out, the higher the storage stability.

[0501] ◎: No bleeding was observed at all.

[0502] ○: Bleeding was slightly observed.

[0503] ×: Bleeding was clearly observed.

[0504] [Table 12]

[0505]

[0506] As can be seen from the results of Tables 4 to 12, the photopolymerization initiator (A) (Examples 1 to 33) disclosed in the present invention has good compatibility with general monofunctional monomers, multifunctional monomers or oligomers, and has high photoinitiability to various active energy rays from short wavelengths to long wavelengths, and the active energy ray curable composition containing the photopolymerization initiator (A) has high curability. The obtained curable composition and the cured product have excellent transparency. In addition, the photopolymerization initiator (A) is not easily affected by the obstruction caused by oxygen, and the initiation reaction and photopolymerization reaction based on the long-wavelength light in the air can be carried out at a sufficient speed. The curable composition (Examples 34 to 72) containing the photopolymerization initiator (A) has high curability even under oxygen blocking or in the air under long-wavelength light irradiation. In addition, the various forms of cured products after curing of the active energy ray curable composition (Examples 73 to 118) adjusted for various uses show good adhesion, adhesion, and cohesion, and have high physical properties such as hardness and strength. Furthermore, the cured product obtained by curing has very little odor, exudation, exhaust, yellowing over time, deterioration, etc., and the obtained cured product has high yellowing resistance, water resistance, durability, heat resistance, and sealing. In contrast, the composition containing the known photopolymerization initiator (Comparative Examples 1 to 21) has low curability with respect to long-wavelength light, and the obtained cured product has low physical properties such as adhesion, adhesion, tackiness, hardness, and strength, and low yellowing resistance, water resistance, durability, and heat resistance. Therefore, the photopolymerization initiator disclosed in the present invention and the active energy ray curable composition containing it can be suitable for various uses.

[0507] The present disclosure includes the following contents.

[0508] (1) A photopolymerization initiator having one or more benzophenone groups and one or more saturated or unsaturated 5-membered or higher cyclic substituents having heteroatoms in the molecule, wherein one or more saturated or unsaturated 5-membered or higher cyclic substituents having heteroatoms are bonded to one or more carbon atoms of the aromatic group of at least one benzophenone group via a carboxylate group or a carboxylic acid amide group.

[0509] (2) A photopolymerization initiator as described in (1) above, wherein the molecule has one or more ethylenically unsaturated groups selected from the group consisting of (meth)acrylamide, (meth)acrylate, vinyl, vinyl ether, alkyl vinyl ether, allyl, (meth)allyl ether, styrene and maleimide.

[0510] (3) The photopolymerization initiator according to (1) or (2) above, wherein the cyclic substituent is one or more groups selected from piperidinyl, pyrrolidinyl, piperazinyl, pyridyl, morpholinyl, tetrahydrofuranyl, hydrofuranyl, crown ether, and tetrahydrothiopyranyl.

[0511] (4) The photopolymerization initiator according to (1) or (2) above, wherein the cyclic substituent is one or more groups selected from piperidinyl, pyrrolidinyl, piperazinyl, pyridyl, morpholinyl, tetrahydrofuranyl, hydrofuranyl, crown ether, and tetrahydrothiopyranyl.

[0512] The photopolymerization initiator as described in any one of (1) to (3) above, which has one or more groups selected from a carbamate group, a urea group, an ester group, a thioester group, an amide group and an imide group in the molecule.

[0513] (5) The photopolymerization initiator according to any one of (1) to (4) above, which has a structure represented by the general formula (1).

[0514]

[0515] (Where Q 1 , Q 3 are independently a hydrogen atom, or a monovalent organic group represented by the general formula (2) or the general formula (3), Q 1 , Q 3 Any one or more of them is a monovalent organic group containing one or more saturated or unsaturated five-membered or more cyclic substituents having a heteroatom;

[0516] Q 2 , Q 4 are each independently a divalent organic group represented by the general formula (4) or the general formula (5);

[0517] L 1 , L 2 are independently directly bonded, or are divalent organic groups containing at least one of a carbamate group, a urea group, an ester group, an amide group, and an imide group. 2 -L 1 -R 5 With Q 4 -L 2 -R 6 Can be a hydrogen atom, but excludes the 1 , Q 3 The case where they are both hydrogen atoms;

[0518]

[0519] R 1 To R 9 , R 12Each independently represents a hydrogen atom, or a chain or cyclic saturated or unsaturated monovalent hydrocarbon group having 1 to 36 carbon atoms, wherein one or more hydrogen atoms of the chain or cyclic saturated or unsaturated monovalent hydrocarbon group having 1 to 36 carbon atoms may be substituted by a hydroxyl group, an amine group, a thiol group or a halogen group, and one or more carbon atoms may be substituted by an ether group, an amino group, a thioether group or a thioester group;

[0520] R 10 , R 11 Each independently represents a direct bond, or a chain or cyclic saturated or unsaturated divalent hydrocarbon group having 1 to 36 carbon atoms, wherein one or more hydrogen atoms of the chain or cyclic saturated or unsaturated divalent hydrocarbon group having 1 to 36 carbon atoms may be substituted by a hydroxyl group, an amine group, a thiol group or a halogen group, and one or more carbon atoms may be substituted by an ether group, an amino group, a thioether group or a thioester group;

[0521] R 8 and R 9 structures of cyclic substituents that can form a five-membered ring to a seven-membered ring together with the nitrogen atom to which they are attached, excluding the case where they are simultaneously hydrogen atoms;

[0522] R 10 , R 11 structures of cyclic substituents that can form a five-membered to seven-membered ring together with the nitrogen atom to which they are attached;

[0523] R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 Any one or more of the cyclic substituents contain a saturated or unsaturated five-membered ring or more containing a heteroatom;

[0524] n is an integer from 1 to 100. ).

[0525] (6) An active energy ray-curable composition comprising the photopolymerization initiator according to any one of (1) to (5) above.

[0526] (7) An active energy ray-curable ink composition comprising the photopolymerization initiator according to any one of (1) to (5) above.

[0527] (8) An active energy ray-curable adhesive composition comprising the photopolymerization initiator according to any one of (1) to (5) above.

[0528] (9) An active energy ray-curable adhesive composition comprising the photopolymerization initiator according to any one of (1) to (5) above.

[0529] (10) An active energy ray-curable coating composition comprising the photopolymerization initiator according to any one of (1) to (5) above.

[0530] (11) An active energy ray-curable encapsulating material composition comprising the photopolymerization initiator according to any one of (1) to (5) above.

[0531] (12) An active energy ray-curable inkjet ink comprising the photopolymerization initiator according to any one of (1) to (5) above.

[0532] (13) An active energy ray-curable three-dimensional modeling ink comprising the photopolymerization initiator described in any one of (1) to (5) above.

[0533] (14) An active energy ray-curable nail cosmetic composition comprising the photopolymerization initiator according to any one of (1) to (5) above.

[0534] (15) An active energy ray-curable dental material composition comprising the photopolymerization initiator according to any one of (1) to (5) above.

[0535] (16) An active energy ray-curable photosensitive composition comprising the photopolymerization initiator according to any one of (1) to (5) above.

[0536] (17) An active energy ray-curable hydrogel composition comprising the photopolymerization initiator according to any one of (1) to (5) above.

[0537] (18) An active energy ray-curable intraocular implant material composition comprising the photopolymerization initiator according to any one of (1) to (5) above.

[0538] (19) An active energy ray-curable pressure-sensitive adhesive composition for skin use, comprising the photopolymerization initiator according to any one of (1) to (5) above.

[0539] (20) An active energy ray-curable adhesive composition for use in a living body, comprising the photopolymerization initiator described in any one of (1) to (5) above.

[0540] (21) An active energy ray-curable automobile paint repair composition comprising the photopolymerization initiator according to any one of (1) to (5) above.

[0541] Industrial Applicability

[0542] As described above, the photopolymerization initiator (A) of the present disclosure has high photoinitiability, and can use a variety of light sources with wavelengths such as UV-LED lamps with wavelengths of 360nm to 420nm, and can initiate photopolymerization in the presence of oxygen and perform curing reactions with active energy rays. In addition, no decomposition products are generated during the photoinitiation reaction and photopolymerization reaction (curing), and the safety is high. The obtained cured product has very little odor, exudation, yellowing over time, and deterioration. In particular, when it has an ethylenically unsaturated group, the photopolymerization initiator becomes a constituent unit of the cured product after curing, and a cured product with good physical properties and durability can be obtained. A photopolymerization initiator of the present invention can be combined with various unsaturated group-containing compounds to produce active energy ray-curable compositions corresponding to various uses, and can impart various physical properties such as high adhesion, surface hardness, yellowing resistance, and water resistance. It can be suitably used as an active energy ray-curable composition, an active energy ray-curable ink composition, an active energy ray-curable adhesive composition, an active energy ray-curable adhesive composition, an active energy ray-curable coating composition, an active energy ray-curable sealing material composition, an active energy ray-curable inkjet ink composition, an active energy ray-curable three-dimensional modeling ink composition, an active energy ray-curable nail cosmetic material 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 skin adhesive composition, an active energy ray-curable living body adhesive composition, an active energy ray-curable automobile paint repair composition, and the like.

Claims

1. A photopolymerization initiator having one or more benzophenone groups and one or more saturated or unsaturated 5-membered or more cyclic substituents having heteroatoms in the molecule, wherein one or more saturated or unsaturated 5-membered or more cyclic substituents having heteroatoms are bonded to one or more carbon atoms of the aromatic group of at least one benzophenone group via a carboxylate group or a carboxylic acid amide group.

2. The photopolymerization initiator according to claim 1, wherein The molecule contains one or more ethylenically unsaturated groups selected from the group consisting 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 styrene group and a maleimide group.

3. The photopolymerization initiator according to claim 1 or 2, wherein The cyclic substituent is one or more groups selected from piperidinyl, pyrrolidinyl, piperazinyl, pyridyl, morpholinyl, tetrahydrofuranyl, hydrofuranyl, crown ether group, and tetrahydrothiopyranyl.

4. The photopolymerization initiator according to any one of claims 1 to 3, wherein The molecule has one or more groups selected from the group consisting of a carbamate group, a urea group, an ester group, a thioester group, an amide group, and an imide group.

5. The photopolymerization initiator according to any one of claims 1 to 4, wherein has a structure represented by the general formula (1), In the formula, Q 1 , Q 3 are independently a hydrogen atom, or a monovalent organic group represented by the general formula (2) or the general formula (3), Q 1 , Q 3 Any one or more of them is a monovalent organic group containing one or more saturated or unsaturated five-membered or more cyclic substituents having a heteroatom; Q 2 , Q 4 are each independently a divalent organic group represented by the general formula (4) or the general formula (5); L 1 , L 2 are independently directly bonded, or are divalent organic groups containing any one or more of a carbamate group, a urea group, an ester group, an amide group, and an imide group; and Q 2 -L 1 -R 5 With Q 4 -L 2 -R 6 Can be a hydrogen atom, but excludes the 1 , Q 3 The case where they are both hydrogen atoms; R 1 To R 9 , R 12 Each independently represents a hydrogen atom, or a chain or cyclic saturated or unsaturated monovalent hydrocarbon group having 1 to 36 carbon atoms, wherein one or more hydrogen atoms of the chain or cyclic saturated or unsaturated monovalent hydrocarbon group having 1 to 36 carbon atoms may be substituted by a hydroxyl group, an amine group, a thiol group or a halogen group, and one or more carbon atoms may be substituted by an ether group, an amino group, a thioether group or a thioester group; R 阳 , R 11 Each independently represents a direct bond, or a chain or cyclic saturated or unsaturated divalent hydrocarbon group having 1 to 36 carbon atoms, wherein one or more hydrogen atoms of the chain or cyclic saturated or unsaturated divalent hydrocarbon group having 1 to 36 carbon atoms may be substituted by a hydroxyl group, an amine group, a thiol group or a halogen group, and one or more carbon atoms may be substituted by an ether group, an amino group, a thioether group or a thioester group; R 8 and R 9 structures of cyclic substituents that can form a five-membered ring to a seven-membered ring together with the nitrogen atom to which they are attached, excluding the case where they are simultaneously hydrogen atoms; R 阳 , R 11 structures of cyclic substituents that can form a five-membered to seven-membered ring together with the nitrogen atom to which they are attached; R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 Any one or more of the cyclic substituents contain a saturated or unsaturated five-membered ring or more containing a heteroatom; n is an integer from 1 to 100. 6 . An active energy ray-curable composition comprising the photopolymerization initiator according to claim 1 . 7 . An active energy ray-curable ink composition comprising the photopolymerization initiator according to claim 1 . 8 . An active energy ray-curable adhesive composition comprising the photopolymerization initiator according to claim 1 . 9 . An active energy ray-curable adhesive composition comprising the photopolymerization initiator according to claim 1 . 10 . An active energy ray-curable coating composition comprising the photopolymerization initiator according to claim 1 . 11 . An active energy ray-curable sealing material composition comprising the photopolymerization initiator according to claim 1 . 12 . An active energy ray-curable inkjet ink comprising the photopolymerization initiator according to claim 1 . 13 . An active energy ray-curable ink for three-dimensional modeling, comprising the photopolymerization initiator according to claim 1 . 14 . An active energy ray-curable nail cosmetic composition comprising the photopolymerization initiator according to claim 1 . 15 . An active energy ray-curable dental material composition comprising the photopolymerization initiator according to claim 1 . 16 . An active energy ray-curable photosensitive composition comprising the photopolymerization initiator according to claim 1 .

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