WO2024085227A1 - 光重合開始剤 - Google Patents

光重合開始剤 Download PDF

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Publication number
WO2024085227A1
WO2024085227A1 PCT/JP2023/037865 JP2023037865W WO2024085227A1 WO 2024085227 A1 WO2024085227 A1 WO 2024085227A1 JP 2023037865 W JP2023037865 W JP 2023037865W WO 2024085227 A1 WO2024085227 A1 WO 2024085227A1
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Prior art keywords
group
groups
photopolymerization initiator
active energy
curable
Prior art date
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Ceased
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PCT/JP2023/037865
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English (en)
French (fr)
Japanese (ja)
Inventor
賀美 竹田
俊次 清貞
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
KJ Chemicals Corp
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KJ Chemicals Corp
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Filing date
Publication date
Application filed by KJ Chemicals Corp filed Critical KJ Chemicals Corp
Priority to KR1020257012929A priority Critical patent/KR20250091213A/ko
Priority to JP2024551857A priority patent/JP7811041B2/ja
Priority to EP23879870.6A priority patent/EP4606824A1/en
Priority to US19/121,271 priority patent/US20260027035A1/en
Priority to CN202380070743.3A priority patent/CN120019084A/zh
Publication of WO2024085227A1 publication Critical patent/WO2024085227A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • A61K6/60—Preparations for dentistry comprising organic or organo-metallic additives
    • A61K6/62—Photochemical radical initiators
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
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    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
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    • G—PHYSICS
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    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
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    • C09J2301/302—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C
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    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
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    • C09K2200/0435—Aldehydes, ketones

Definitions

  • This disclosure relates to photopolymerization initiators.
  • Photocuring reactions using active energy rays such as visible light or ultraviolet (UV) light generate active species such as radicals by irradiating a curable composition containing a photopolymerization initiator with UV light, polymerizing compounds with unsaturated groups, and solidifying (curing) the liquid composition in a short time. They are used in a wide range of fields, including paints and coatings, pressure sensitive adhesives and adhesives, elastomer materials, inkjet inks, sealing materials and sealants, dental hygiene materials, and photosensitive materials. In particular, because they can be cured in any location or shape, they are being used widely as nail cosmetics such as gel nails and as materials for three-dimensional photo-modeling.
  • active energy rays such as visible light or ultraviolet (UV) light
  • UV light ultraviolet
  • Photopolymerization initiators can be classified into intramolecular cleavage type and hydrogen abstraction type based on the radical generation mechanism after absorbing light.
  • the former is a type that generates radicals by cleaving intramolecularly, while the latter is a type that generates radicals by abstracting hydrogen from a hydrogen donor.
  • the intramolecular cleavage type decomposition products derived from the initiator remain in the cured product, causing problems such as reduced durability of the cured product, odor generation, and coloring over time, as well as low safety.
  • the hydrogen abstraction type does not produce decomposition products from the initiator, so it has attracted attention in recent years, and active research is being conducted on improving the efficiency of photopolymerization initiation and using it in combination with additives such as hydrogen donors, photosensitizers, and curing accelerators.
  • the objective of this disclosure is to provide a hydrogen abstraction type photopolymerization initiator that has high radical generation capability and high reactivity of the generated radicals, is resistant to oxygen inhibition, can handle long wavelength (360 nm to 420 nm) light, has good compatibility with general-purpose monomers and oligomers, and has excellent resistance to yellowing.
  • a photopolymerization initiator that has one or more benzopheno groups and a saturated or unsaturated cyclic substituent of five or more members having one or more heteroatoms in the molecule, and in which one or more saturated or unsaturated cyclic substituent of five or more members having a heteroatom is bonded to one or more carbon atoms of the aryl group of at least one or more benzopheno groups via a carboxylic acid ester group or a carboxylic acid amide group, thereby solving the problem.
  • the photopolymerization initiator disclosed herein has high initiation efficiency for long-wavelength light beams with wavelengths of 360 nm to 420 nm and short-wavelength light beams output from UV-LED light sources such as 365 nm, 385 nm, 395 nm, and 405 nm, is not easily inhibited by oxygen even in an air atmosphere, and does not generate decomposition products during photoinitiation and photopolymerization reactions (curing), making it highly safe.
  • the photopolymerization initiator has good compatibility with general-purpose monomers and oligomers, and the curable composition containing it has excellent transparency, and the cured product obtained by curing has very little odor, bleed-out, yellowing over time, deterioration, etc., and is highly durable and safe.
  • the photopolymerization initiator disclosed herein can be suitably used in various applications using active energy ray curable compositions such as ink compositions, pressure-sensitive adhesive compositions, adhesive compositions, coating compositions, sealant compositions, inkjet inks, inks for three-dimensional modeling, nail cosmetic compositions, dental material compositions, and photosensitive compositions.
  • One embodiment of the present disclosure is a photopolymerization initiator (A) having one or more benzopheno groups and one or more heteroatoms in the molecule, and one or more saturated or unsaturated 5-membered or larger ring substituents having heteroatoms bonded to one or more carbon atoms of the aryl groups of at least one or more benzopheno groups via a carboxylic acid ester group or a carboxylic acid amide group.
  • A photopolymerization initiator having one or more benzopheno groups and one or more heteroatoms in the molecule, and one or more saturated or unsaturated 5-membered or larger ring substituents having heteroatoms bonded to one or more carbon atoms of the aryl groups of at least one or more benzopheno groups via a carboxylic acid ester group or a carboxylic acid amide group.
  • Photopolymerization initiator (A) has one or more benzopheno groups and one or more heteroatoms in the molecule, and a saturated or unsaturated cyclic substituent having a 5-membered ring or more (hereinafter also referred to as a heterocycle), and at least one or more heterocycles are linked to a carbon atom of an aryl group of the benzopheno group via a carboxylic acid ester group or a carboxylic acid amide group.
  • the benzopheno group is a photopolymerization initiation functional group of hydrogen abstraction type
  • the heterocycle is a hydrogen donor.
  • photopolymerization initiator (A) By containing a benzopheno group and a heterocycle, photopolymerization initiator (A) efficiently abstracts hydrogen within and/or between molecules by irradiation with active energy rays, and has a sufficient photoinitiation effect without adding alcohol, amine, or the like as a general-purpose hydrogen donor.
  • the inventors speculate that the reason for this is as follows. 1) The electron density of the heteroatom is high, and the activity of the hydrogen atoms around it is high, so they are easily abstracted. 2) The hydrogen atoms bonded to the heteroatom and/or the hydrogen atoms bonded to the carbon atom adjacent to the heteroatom are all hydrogen donor sources, and since it has a cyclic structure, the number of highly active hydrogen atoms around the heteroatom is large.
  • the heteroatom can easily absorb the peroxide radicals generated from oxygen, so the influence of oxygen due to the presence of the heterocycle is suppressed.
  • the presence of a carboxylic acid ester group or a carboxylic acid amide group between the benzopheno group and the heterocycle improves the compatibility between the hydrophobic benzopheno group and the hydrophilic heterocycle, and it has been confirmed that the photoinitiation effect tends to be further enhanced.
  • 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, styryl groups, and maleimide groups in the molecule.
  • the photopolymerization initiator (A) is fixed as a structural unit in the cured product via a covalent bond after the photopolymerization reaction, does not bleed out over time, and improves the durability, yellowing resistance, moisture resistance, etc. of the obtained cured product.
  • the photopolymerization initiator (A) When the photopolymerization initiator (A) has two or more ethylenically unsaturated groups, they may be the same or different.
  • (meth)acrylamide groups, (meth)acrylate groups, and allyl groups are preferred because they have high curability and can be cured quickly even with a light source of long wavelength light or single wavelength light.
  • the photopolymerization initiator (A) has a heteroatom-containing 5- or larger-membered cyclic substituent (heterocycle) selected from one or more groups selected from a piperidine group, a pyrrolidine group, a piperazine group, a pyridine group, a morpholine group, a tetrahydrofuran group, a hydrofuran group, a crown ether group, and a tetrahydrothiopyran group.
  • substituents have a high effect of suppressing oxygen inhibition, and the photopolymerization initiator (A) containing these is capable of initiating a polymerization reaction with high efficiency even in air, and is therefore preferred.
  • the photopolymerization initiator (A) has a morpholine group, a tetrahydrofuran group, or a piperidine group, which are highly effective as hydrogen donor groups. These heterocycles can be used alone or in combination of two or more types.
  • One embodiment of the present disclosure is a photopolymerization initiator (A) further having one or more groups selected from a urethane group, a urea group, an ester group, a thioester group, an amide group, and an imide group in the molecule.
  • These groups 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 donors, improving the initiation efficiency of the photopolymerization initiator (A).
  • these groups have an effect of suppressing oxygen inhibition, improving the curing properties even in air.
  • the photopolymerization initiator (A) it is preferable for the photopolymerization initiator (A) to contain a urethane group, a urea group, an ester group, an amide group, and an imide group. These groups can be used alone or in combination of two or more.
  • the photopolymerization initiator (A) of the present disclosure can be obtained by reacting a carboxylic acid and/or a carboxylic anhydride having a benzophenone group (hereinafter also referred to as a benzophenone-based compound (a1)) with a compound having a functional group and a heterocycle that can react with a carboxylic acid and/or a carboxylic anhydride (hereinafter also referred to as a heterocyclic compound (a2)).
  • Examples of functional groups that can react with a carboxylic acid and/or a carboxylic anhydride include a hydroxyl group, an amine group, an epoxy group, an oxazoline group, a carbodiimide group, an isocyanate group, a thiol group, a phenol, a halogen group, etc., and from the viewpoint of being easily reactive at room temperature (0°C to 150°C) and normal pressure (0.8 to 1.2 atm), a hydroxyl group, an amine group, an epoxy group, an oxazoline group, an isocyanate group, a thiol group, and a halogen group are preferable.
  • the heterocyclic compound (a2) has at least one hydroxyl group, an amine group, or an epoxy group. (a2) can use one of these groups alone or two or more of them in combination.
  • Specific examples of the method for producing the photopolymerization initiator (A) include a method for directly reacting a benzophenone compound (a1) with a heterocyclic compound (a2), in which (a1) and (a2) are mixed together and reacted, and a method for dropping one of (a1) or (a2) onto the other and reacting them sequentially.
  • Examples of methods for indirectly reacting (a1) and (a2) include a method in which (a1) reacts with a compound (a5) capable of reacting with it to obtain a compound (a3) having a benzophenone group into which a reactive functional group (hereinafter also referred to as a reactive group) such as a hydroxyl group, a carboxylic acid group, an amine group, an epoxy group, an oxazoline group, an isocyanate group, a thiol group, or a halogen group has been introduced, and (a3) is reacted with a heterocyclic compound (a2); and a method in which (a2) reacts with a compound (a5) capable of reacting with it to obtain a compound (a4) having a 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 hal
  • the reaction for producing the photopolymerization initiator (A) can proceed appropriately within the temperature range of 0°C to 150°C, and solvents, catalysts, and other additives may be used as necessary.
  • the reaction is preferably carried out in an environment that blocks active energy rays, and more preferably in a dark room or under a yellow room or red safe light that blocks active energy rays with wavelengths of 500 nm or less.
  • benzophenone-based compound (a1) examples 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,
  • (a1) can be used alone or in combination of two or more of these.
  • (a1) is preferably 3',4,4'-benzophenonetetracarboxylic acid dianhydride, 2,2'-dimethyl-3,3',4,4'-benzophenonetetracarboxylic acid dianhydride, or 5-methyl-3,3',4,4'-benzophenonetetracarboxylic acid dianhydride, due to the high reactivity of the acid anhydride with the heterocyclic compound (a2), and more preferably 3,3',4,4'-benzophenonetetracarboxylic acid dianhydride, due to the ease of obtaining industrial products.
  • Heterocyclic compounds (a2) include tetrahydrofurfuryl alcohol, 3-hydroxytetrahydrofuran, (S)-(+)-2,2-dimethyl-1,3-dioxolane-4-methanol, glycerol 1,2-carbonate, tetrahydro-4-pyranol, 2-(hydroxymethyl)-12-crown-4-ether, N-hydroxysuccinimide, 1-(2-hydroxyethyl)-2-pyrrolidone, 2-(2-hydroxyethyl)-1-methylpyridine, 1-piperidineethanol, 4-methylpiperazine-1-ethanol, tetrahydro-2H-thiopyran-4-ol, 4-(2-hydroxyethyl)-morpholine, 4-(3-hydroxy ethyl)-morpholine, N-(2-hydroxypropyl)-morpholine, N-(2-hydroxyethyl)maleimide, tetrahydrofurfurylamine, 3-(aminomethyl)tetrahydrofur
  • 4-hydroxy-1-methylpiperidine, 1-piperidineethanol, 4-methylpiperazine-1-ethanol, 4-(2-hydroxyethyl)-morpholine, 4-(3-hydroxyethyl)-morpholine, N-(2-hydroxypropyl)-morpholine, 1-aminopiperidine, 1-(3-aminopropyl)-2-methylpiperidine, 1-(2-methoxyethyl)piperazine, 4-(4-methyl-1-piperazinyl)aniline, morpholine, 4-aminomorpholine, 4-(2-aminoethyl)morpholine, and 4-morpholinoaniline are more preferred.
  • (a2) one of these can be used alone, or two or more can be used in combination.
  • the compound (a5) capable of reacting with (a1) or (a2) is not particularly limited as long as it contains a reactive group such as a hydroxyl group, a carboxylic acid group, an amine group, an epoxy group, an oxazoline group, an isocyanate group, a thiol group, a halogen group, or an ethylenically unsaturated group.
  • 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.
  • alkylene glycol examples include water, linear alcohols having 1 to 24 carbon atoms or branched or alicyclic alcohols having 3 to 24 carbon atoms and having a hydroxyl group, linear alkylene glycols having 2 to 24 carbon atoms or branched or alicyclic alkylene glycols having 2 to 24 carbon atoms or having 3 to 24 carbon atoms, hydroxyl group-containing (meth)acrylates, hydroxyl group-containing (meth)acrylamides, linear alkylene diamines having 2 to 24 carbon atoms or branched or alicyclic alkylene diamines having 3 to 24 carbon atoms and having an amino group, phenylenediamines, 1,2-butylene oxide having an epoxy group, 1,2-epoxydodecane, 1,2-epoxytetradecane, butyl glycidyl ether, glycidyl phenyl ether, 2-ethylhexyl glycidyl ether, do
  • (a5) is a compound having an epoxy group.
  • Compound (a5) can be used alone or in combination of two or more kinds.
  • Solvents used in the production of the photopolymerization initiator (A) of the present disclosure include, for example, hydrocarbon solvents such as toluene, xylene, n-hexane, cyclohexanone, etc.; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.; ester solvents such as ethyl acetate, butyl acetate, etc.; halogenated hydrocarbon solvents such as methylene chloride, chlorobenzene, etc.; and high-boiling polar solvents such as N,N'-dimethylformamide, 3-methoxy-N,N'-dimethylpropionamide, 3-butoxy-N,N'-dimethylpropionamide, dimethylacetamide, dimethylsulfoxide, 2-pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, etc
  • monofunctional or polyfunctional monomers and/or oligomers that are reactive with the photopolymerization initiator (A) and its raw materials (a1) and (a2) can also be used as reaction solvents.
  • monomers include various (meth)acrylic acid esters having linear and/or cyclic hydrocarbon groups (1 to 22 carbon atoms) or alkoxy groups (1 to 22 carbon atoms), N-substituted (meth)acrylamides, and N,N-disubstituted (meth)acrylamides.
  • (meth)acryloylmorpholine (meth)acryloyl, N-vinylpyrrolidone, etc. can also be used.
  • the above-mentioned direct reaction and various indirect reactions can proceed without using a catalyst.
  • both the direct reaction and the indirect reaction can proceed at a lower temperature and at a higher speed, which is preferable.
  • catalysts used in the production of (A) include thionyl chloride, quaternary ammonium salts, tertiary phosphine derivatives, tertiary amine derivatives, and organometallic compounds.
  • Examples of quaternary ammonium salts include tetrabutylammonium bromide, triethylbenzylammonium chloride, tetrabutylphosphonium bromide, and tetraphenylphosphonium bromide.
  • Examples of tertiary phosphines include triarylphosphines such as triphenylphosphine and tritolylphosphine, tricycloalkylphosphines such as tricyclohexylphosphine, and trialkylphosphines such as triethylphosphine.
  • tertiary amines examples include trialkyl (carbon number 1 to 8) amines such as triethylamine, tributylamine, and dimethylethylamine, and dialkyl (carbon number 1 to 8) arylamines such as dimethylbenzylamine and diethylbenzylamine.
  • organometallic compounds include metal salts of metals such as zinc, tin, lead, zirconium, bismuth, cobalt, manganese, and iron with organic acids such as octenic acid and naphthenic acid, metal chelate compounds such as dibutyltin dilaurate, dioctyltin dilaurate, tin 2-ethylhexanoate, dibutyltin diacetylacetonate, zirconium tetraacetylacetonate, titanium acetylacetonate, acetylacetone aluminum, acetylacetone cobalt, acetylacetone iron, acetylacetone copper, and acetylacetone zinc, potassium or sodium salts of alkyl (C1-8) phosphonic acid, and sodium or potassium salts of fatty acids having C8-20.
  • metal salts of metals such as zinc, tin, lead, zirconium, bismuth, cobalt
  • quaternary ammonium salts tertiary amine derivatives, tertiary phosphine derivatives, and tin, zirconium, or iron-based organometallic compounds having high catalytic effects are more preferable.
  • These catalysts can be used alone or in combination of two or more.
  • the amount of catalyst used in the production of photopolymerization initiator (A) is not particularly limited, but is preferably 0.001 to 5.0% by mass relative to the total mass of each raw material. If it is 0.001% or more, the reaction can proceed quickly, and if it is 5.0% or less, coloring caused by the catalyst can be suppressed, which is preferable. Furthermore, it is more preferable that it is 0.01 to 1.0%.
  • the method of introducing an ethylenically unsaturated group into the molecule of the photopolymerization initiator (A) is not particularly limited, but examples thereof include using an ethylenically unsaturated group-containing benzophenone compound (a1) and/or an ethylenically unsaturated group-containing heterocyclic compound (a2), and using an ethylenically unsaturated group-containing compound (a5) capable of reacting with (a1) and/or (a2).
  • the ethylenically unsaturated group-containing compound (a5) has a structure formed by any combination of one or more reactive groups selected from the group consisting of hydroxyl groups, carboxylic acid groups, amine groups, epoxy groups, oxazoline groups, isocyanate groups, thiol groups, and halogen groups, and one or more ethylenically unsaturated groups selected from the group consisting of (meth)acrylamide groups, (meth)acrylate groups, vinyl groups, vinyl ether groups, alkyl vinyl ether groups, allyl groups, (meth)allyl ether groups, styryl groups, and maleimide groups.
  • Examples of 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.
  • compound (a5) include hydroxyalkyl (C1-22) (meth)acrylates such as hydroxyethyl (meth)acrylate, hydroxyisopropyl (meth)acrylate, and hydroxypropyl (meth)acrylate; N-hydroxyalkyl (C1-22) (meth)acrylamides such as N-hydroxymethyl (meth)acrylamide, N-hydroxyisopropyl (meth)acrylamide, and N,N-dihydroxyethyl (meth)acrylamide; N-alkyl (C1-22) hydroxyalkyl (C1-22) (meth)acrylamides such as N-methylhydroxyethyl (meth)acrylamide and N-ethylhydroxypropyl (meth)acrylamide; and N-alkyl (C1-22) hydroxyalkyl (C1-22) (meth)acrylamides such as N,N-dihydroxymethyl (meth)acrylamide and N,N-dihydroxyethyl (meth)acrylamide.
  • N-dihydroxyalkyl (1 to 22 carbon atoms) (meth)acrylamide N-dihydroxyalkyl (1 to 22 carbon atoms) (meth)acrylamide
  • hydroxyalkyl (1 to 22 carbon atoms) vinyl such as 3-buten-1-ol, 4-penten-1-ol, 5-hexen-1-ol, hydroxyalkyl (1 to 22 carbon atoms) allyl
  • N-hydroxyalkyl (1 to 22 carbon atoms) maleimide such as N-hydroxymethylmaleimide and N-hydroxyethylmaleimide
  • hydroxyalkyl (1 to 22 carbon atoms) vinyl ether such as ethylene glycol monovinyl ether and tetramethylene glycol monovinyl ether
  • N-aminoalkyl (1 to 22 carbon atoms) (meth)acrylamide N-aminoalkyl (1 to 22 carbon atoms)-N-alkyl (1 to 22 carbon atoms) (meth)acrylamide
  • the method for introducing a urethane group, urea group, ester group, amide group, or imide group into the molecule of the photopolymerization initiator (A) is not particularly limited, but examples thereof include a method of 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 urethane group-introducing compound) to further react with the reactive product of a benzophenone compound (a1) and a heterocyclic compound (a2), (2) a method of reacting with (a1) and then further reacting with (a2), (3) a method of reacting with (a2) and then further reacting with (a1), and (4) a method of reacting with (a1) and (a2) simultaneously.
  • 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
  • urethane group-introducing compound examples include monourethane group-introducing compounds having one group selected from hydroxyl group, amine group, carboxylic acid group, or isocyanate group in the molecule, and polyurethane group-introducing compounds having two or more groups selected from hydroxyl group, amine group, carboxylic acid group, or isocyanate group in the molecule.
  • polyurethane group-introducing compound examples include polyol, polyamine, polycarboxylic acid, polyisocyanate, polyamino acid, amino group-containing polyol, hydroxyl group-containing polyamine, hydroxyl group-containing polycarboxylic acid, etc., and may also have a polyester skeleton, a polyether skeleton, a polycarbonate skeleton, a polyolefin skeleton (polyalkadiene skeleton and/or hydrogenated polyalkadiene skeleton), a polyacrylic skeleton, or a silicone skeleton (various modified polydimethylsiloxanes). These urethane group-introducing compounds may be used alone or in combination of two or more.
  • the molecular weight of the photopolymerization initiator (A) can be adjusted arbitrarily by combining various raw materials, but a number average of 500 to 100,000 is preferable. 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.
  • the polarity of (A) (balance between hydrophilicity and hydrophobicity) can be easily adjusted, solubility in general-purpose monomers and oligomers used in active energy ray curable compositions is high, the viscosity of the curable composition containing (A) can be easily adjusted within a range suitable for various processing formats such as coating, spraying, and extrusion, and the obtained curable composition and cured product have high transparency.
  • the low molecular weight type (A) is a compound in which a heterocycle is directly or indirectly bonded to a carboxylic acid ester group and/or a carboxylic acid amide group that is directly bonded to a benzophenone group represented mainly by the general formula (1).
  • the medium molecular weight type (A) is a compound in which a heterocycle is directly or indirectly bonded to a carboxylic acid ester group and/or a carboxylic acid amide group that is directly bonded to a benzophenone group represented mainly by the general formula (1), and at the same time, a structural unit derived from an introduced compound such as a urethane group and a urethane group having one or more skeletons selected from a polyester skeleton, a polyether skeleton, a polycarbonate skeleton, a polyolefin skeleton, and a polyacrylic skeleton, and the order and position in which the heterocycle and the structural unit derived from an introduced compound such as a urethane group and the urethane group are bonded are not limited.
  • the high molecular weight type (A) is mainly a compound having a structure formed by directly or indirectly bonding a heterocycle to a carboxylic acid ester group and/or a carboxylic acid amide group that is directly bonded to a benzophenone group represented by the general formula (1), and at the same time repeating structural units derived from a compound that introduces a urethane group, etc., and bonds of a urethane group, etc., having one or more skeletons selected from a polyester skeleton, a polyether skeleton, a polycarbonate skeleton, a polyolefin skeleton, and a polyacrylic skeleton, and the order and position of bonding the heterocycle and the repeating structural units derived from a compound that introduces a urethane group, etc., and the urethane group, etc., are not limited.
  • a medium molecular weight type photopolymerization initiator is particularly preferred because it has good solubility in various general-purpose organic solvents, monomers, or oligomers used in curable compositions, can appropriately adjust the viscosity of the obtained curable resin composition, has excellent workability, and has high polymerization initiation to active energy rays, especially high sensitivity to long-wavelength light rays with a wavelength of 360 nm to 420 nm.
  • Q 1 and Q 3 are each independently a hydrogen atom or a monovalent organic group represented by general formula (2) or general formula (3), and at least one of Q 1 and Q 3 is a monovalent organic group having at least one saturated or unsaturated 5- or larger-membered cyclic substituent having a heteroatom;
  • Q 2 and Q 4 each independently represent a divalent organic group represented by general formula (4) or general formula (5);
  • L 1 and L 2 are each independently a direct bond or a divalent organic group containing at least one of a urethane group, a urea group, an ester group, an amide group, and an imide group.
  • Q 2 -L 1 -R 5 and Q 4 -L 2 -R 6 may be hydrogen atoms, except when Q 1 and Q 3 are both hydrogen atoms.
  • R 1 to R 9 and R 12 each independently represent a hydrogen atom or a linear or cyclic, saturated or unsaturated monovalent hydrocarbon group having 1 to 36 carbon atoms in which one or more hydrogen atoms may be substituted with a hydroxyl group, an amine group, a thiol group, or a halogen group and one or more carbon atoms may be substituted with an ether group, an amino group, a thioether group, or a thioester group;
  • R 10 and R 11 each independently represent a direct bond or a linear or cyclic, saturated or unsaturated divalent hydrocarbon group having 1 to 36 carbon atoms in which one or more hydrogen atoms may be substituted with a hydroxyl group, an amine group, a thiol group, or a halogen group, and one or
  • 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 hybrid or dual polymerization, curing, etc.
  • Photopolymerization and thermal polymerization can be carried out simultaneously or in any order, but while photopolymerization is fast, it can leave unreacted monomers or oligomers, so it is preferable to complete the remaining polymerization reactions and crosslinking reactions by thermal polymerization after photopolymerization.
  • a photoradical polymerization initiator of a different type or structure and irradiating it stepwise with light of different wavelengths it is possible to completely cure a curable material.
  • the light beams applied to the photopolymerization initiator (A) include active energy beams such as visible light, electron beams, ultraviolet rays, infrared rays, X-rays, alpha rays, beta rays, and gamma rays.
  • active energy beams such as visible light, electron beams, ultraviolet rays, infrared rays, X-rays, alpha rays, beta rays, and gamma rays.
  • ultraviolet rays are preferred in terms of the balance between the active energy beam generator, the photopolymerization initiation speed, and safety.
  • Examples of light sources for ultraviolet rays include xenon lamps, low-pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, UV-LED lamps, and microwave excimer lamps. UV-LED lamps are more preferred because they have a high energy-to-light conversion efficiency, are easy to increase output, and do not use harmful mercury.
  • the light irradiation energy required for generating radical active species is preferably in the range of 5 to 50,000 mJ/cm 2 , and more preferably 10 to 20,000 mJ/cm 2 , converted into irradiation energy (integral light amount). If the irradiation energy is within this range, it is preferable because radicals with sufficient activity can be generated from (A).
  • the content of the photopolymerization initiator (A) in the curable composition varies depending on the type and content of the monomer or oligomer in the curable composition, but it is preferable to have 0.1 mass% or more based on the entire curable composition, because photopolymerization can be initiated immediately and the curable composition can be cured quickly and sufficiently. Furthermore, when (A) has an ethylenically unsaturated group, even if it contains 100 mass%, it can be cured quickly and sufficiently like a normal curable composition. Furthermore, in order to suitably adjust the physical properties of the resulting cured product, it is preferable to use (A) in combination with other monomers or oligomers. In that case, the content of (A) is preferably 0.5 to 70 mass% based on the entire curable composition, more preferably 1 to 50 mass%, and most preferably 2 to 30 mass%.
  • the monomers and oligomers used in combination with (A) can be classified as monofunctional monomers, polyfunctional monomers, or oligomers.
  • the content of the monomers and oligomers used in combination is 0 to 99.9% by mass based on the total curable composition, and from the viewpoint of being able to suitably 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.
  • Monofunctional monomers include compounds containing a (meth)acrylate group, a (meth)acrylamide group, a vinyl group, an allyl group, a styryl group, an acetylene group, etc., and these can be used alone or in combination of two or more.
  • the content of the monofunctional monomer is preferably 0 to 90 mass% of the entire curable composition, more preferably 5 to 70 mass%, and most preferably 10 to 50 mass%.
  • Monofunctional monomers usually have a low viscosity, and by adding an appropriate amount of this, it is possible to expect effects such as lowering the viscosity of the curable composition and improving workability.
  • monofunctional monomers (excluding photopolymerization initiators) containing a (meth)acrylate group include (meth)acrylates having linear, branched, or cyclic alkyl or hydroxyalkyl groups with 1 to 18 carbon atoms, alkyl carboxylic acids, alkyl sulfonic acids, and alkyl phosphates, phenoxyalkylene glycol (meth)acrylates having functional groups consisting of a phenoxy group and an alkylene glycol group with 1 to 4 carbon atoms, and dialkylaminoethyl (meth)acrylates and dialkylaminopropyl (meth)acrylates having alkyl groups with 1 to 6 carbon atoms.
  • acrylates examples include (meth)acrylates containing amino groups such as (meth)acrylamide, (meth)acrylates having a cyclic structure such as benzyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, isobornyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, and 2-methyl-2-adamantyl (meth)acrylate, and (meth)acrylates having an epoxy group such as glycidyl (meth)acrylate and 4-hydroxybutyl (meth)acrylate glycidyl ether.
  • amino groups such as (meth)acrylamide
  • (meth)acrylates having a cyclic structure such as benzyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, isobornyl (meth)acrylate, tetrahydrofurfur
  • monofunctional monomers (excluding photopolymerization initiators) containing a (meth)acrylamide group include (meth)acrylamide, mono- or di-substituted (meth)acrylamides, (meth)acroylmorpholine, and diacetone (meth)acrylamide.
  • Examples of mono- or di-substituted (meth)acrylamides include N-alkyl (meth)acrylamides with a linear alkyl group having 1 to 18 carbon atoms, or a branched or cyclic alkyl group having 3 to 18 carbon atoms, N,N-dialkyl (meth)acrylamides, N-hydroxyalkyl (meth)acrylamides with a hydroxyalkyl group having 1 to 6 carbon atoms, and N,N-dialkylaminopropyl (meth)acrylamides with an alkyl group having 1 to 6 carbon atoms.
  • monofunctional monomers excluding photopolymerization initiators
  • vinyl carboxylates and allyl carboxylates with linear, branched, or cyclic carboxylic acids having 1 to 18 carbon atoms alkyl vinyl ethers and alkyl allyl ethers with linear, branched, or cyclic alkyl groups having 1 to 18 carbon atoms, vinyl chloride, N-vinylpyrrolidone, N-vinylcaprolactam, N-vinyloxazoline, maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, unsaturated dicarboxylic acids mono- or di-esterified with linear, branched, or cyclic alkyl groups having 1 to 18 carbon atoms, vinyl carboxylic acid, vinyl sulfonic acid, vinyl phosphoric acid, allylamine, diallylamine, styrene, ⁇ -methyl
  • the polyfunctional monomer or oligomer may be a compound containing two or more unsaturated groups such as (meth)acrylate, (meth)acrylamide, vinyl, allyl, styrene, and acetylene groups.
  • the unsaturated groups may be one type or two or more types. In order to obtain good curability, it is more preferable to use at least one (meth)acrylate or (meth)acrylamide group as the unsaturated group.
  • the content of the polyfunctional monomer (excluding the photopolymerization initiator) is preferably 0 to 95% by mass, more preferably 1 to 70% by mass, and most preferably 5 to 50% by mass, based on the total curable composition. By appropriately adjusting the content of the polyfunctional monomer, the cured product obtained has high strength and hardness, and excellent durability can be expected.
  • polyfunctional monomers or oligomers examples include allyl (meth)acrylate, allyl (meth)acrylamide, diallylamine, alkyl diallylamine with an alkyl group having 1 to 18 carbon atoms, alkylene glycol di(meth)acrylates, polyalkylene glycol di(meth)acrylates, bisphenol A diglycidyl ether acrylic acid adducts, alkoxylated bisphenol A diacrylates, polyester di(meth)acrylates, polycarbonate di(meth)acrylates, polyurethane di(meth)acrylates, and polyurethane di(meth)acrylamides.
  • polyfunctional monomers having three or more functional groups examples include pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, trimethylolpropane tri(meth)acrylate, dipentaerythritol ...
  • acrylate ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tri(meth)acryloyloxyethoxytrimethylolpropane, glycerin polyglycidyl ether poly(meth)acrylate, isocyanuric acid ethylene oxide modified tri(meth)acrylate, ethylene oxide modified dipentaerythritol penta(meth)acrylate, ethylene oxide modified dipentaerythritol hexa(meth)acrylate, ethylene oxide modified pentaerythritol tri(meth)acrylate, ethylene oxide modified pentaerythritol tetra(meth)acrylate, succinic acid modified pentaerythritol tri(meth)acrylate
  • the photopolymerization initiator (A) disclosed herein has high photoinitiation properties even without the use of a sensitizer, but the use of a general-purpose sensitizer in combination is expected to further improve polymerization initiation and the physical properties of the cured product after curing.
  • Sensitizers that can be used in combination with (A) are not particularly limited, but examples include unsaturated ketones such as benzophenones and anthracene derivatives, 1,2-diketone derivatives such as benzil and camphorquinone, benzoin derivatives, anthraquinone derivatives, thioxanthone derivatives, coumarin derivatives, tertiary amines, thiols, disulfides, etc. These can be used in any ratio as needed, and one type can be used alone, or two or more types can be used in combination.
  • sensitizers that can be used in combination include anthracene sensitizers such as 9,10-dibutoxyanthracene, 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, and 9,10-bis(2-ethylhexyloxy)anthracene, and thioxanthone sensitizers such as 2,4-diethylthioxanthone, 2-isopropylthioxanthone, and 4-isopropylthioxanthone.
  • anthracene sensitizers such as 9,10-dibutoxyanthracene, 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, and 9,10-bis(2-ethylhexyloxy)anthracene
  • thioxanthone sensitizers such as 2,4-diethylthioxanthone, 2-isopropylthioxanthone, and
  • anthracene sensitizers include DBA and DEA (manufactured by Kawasaki Chemical Industries, Ltd.), and thioxanthone sensitizers include DETX and ITX (manufactured by Lambson Corporation).
  • the content of the sensitizer is not particularly limited, but is preferably 0.5 to 5.0 mass% and more preferably 0.8 to 3.0 mass% based on the total curable composition. If the content of the sensitizer is within this range, the curability of the curable composition is improved, and the resulting cured product has good durability and yellowing resistance.
  • polymerization initiators that can be used in combination with the photopolymerization initiator (A) of the present disclosure include benzoins such as benzoin and benzoin alkyl ethers, acetophenones such as acetophenone and 2-hydroxy-2-methyl-1-phenylpropan-1-one, anthraquinones, thioxanthones, ketals, benzophenones, aminobenzophenones, aminoacetophenones, xanthones, etc. These can be used in any ratio as needed, and one type can be used alone, or two or more types can be used in combination.
  • the active energy ray curable composition can be used without containing organic solvent.
  • an organic solvent can be added as necessary to adjust the liquid viscosity.
  • the added organic solvent may be removed before curing at the time of photocuring, or the composition may be cured while still containing the organic solvent.
  • the organic solvent may be removed after curing, and can be appropriately selected depending on the method of use and purpose of the curable composition and the resulting cured product.
  • the amount of organic solvent added is preferably 80 mass% or less, and more preferably 50 mass% or less, of the entire active energy ray curable composition in order to reduce the energy and time required for removing the organic solvent.
  • Organic solvents can be used in the curable composition.
  • Usable solvents include alcohols such as methanol and isopropanol, ketones such as acetone, methyl ethyl ketone and cyclohexanone, esters such as ethyl acetate, propyl acetate, methyl lactate and ethyl lactate, alkylene glycols such as ethylene glycol and propylene glycol, polyalkylene glycols such as polyethylene glycol and polypropylene glycol, glycol ethers such as ethoxydiethylene glycol and methoxypropylene glycol, glycol esters such as propylene glycol acetate, tetrahydrofuran, methyltetrahydrofuran, cyclopentyl methyl ether, methyltetrahydropyran, methyltetrahydropyran, methyltetrahydrofu ...
  • organic solvent examples include ethers such as ethyl tert-butyl ether and toluene, aromatic hydrocarbons such as xylene, aliphatic hydrocarbons such as hexane and cyclohexane, amides such as N,N'-dimethylformamide and dimethylacetamide, amide ethers such as ⁇ -methoxy-N,N-dimethylpropionamide and ⁇ -butoxy-N,N-dimethylpropionamide, pyrrolidones such as 2-pyrrolidone and N-methylpyrrolidone, piperidines such as N-methylpiperidine, halogenated hydrocarbons such as methylene chloride, chloroform, and dichloroethane, sulfoxides such as dimethyl sulfoxide, and imidazolidinones such as 1,3-dimethyl-2-imidazolidinone. These organic solvents can be used alone or in combination of two or more.
  • aromatic hydrocarbons
  • the photopolymerization initiator disclosed herein is useful in active energy ray curable inks such as active energy ray curable flexographic inks, active energy ray curable offset inks, active energy ray curable screen inks, and active energy ray curable inkjet inks; active energy ray curable nail cosmetic compositions used in gel nails and the like; active energy ray curable pressure sensitive adhesive compositions; active energy ray curable adhesive compositions; active energy ray curable sealant compositions used in sealing materials and sealants; active energy ray curable coating agent compositions used in paints and coating agents for automobiles, electrical appliances, furniture, and the like; active energy ray curable decorative sheet compositions used in decorative sheets used in surface coatings for automobiles and electrical appliances;
  • the active energy ray curable self-repairing material composition used in functional parts such as coating compositions, three-dimensional objects, nail decoration materials, dental materials, automobile exterior protection, decorative films, devices, etc., active energy ray curable elastomer compositions used in materials for
  • the obtained hydrogel composition can also be suitably used in a wide variety of fields, including in the hygiene field, such as superabsorbent resins, paper diapers, and soft contact lenses; in the coating field, such as ship bottom paints, anti-fogging materials, and antifouling paints; in the medical field, such as medical device surface coatings and artificial organs; in the civil engineering and construction field, such as soil conditioners; in the agricultural field, such as water-retaining materials; and as shock-absorbing materials.
  • the hygiene field such as superabsorbent resins, paper diapers, and soft contact lenses
  • the coating field such as ship bottom paints, anti-fogging materials, and antifouling paints
  • in the medical field such as medical device surface coatings and artificial organs
  • in the civil engineering and construction field such as soil conditioners
  • the agricultural field such as water-retaining materials
  • shock-absorbing materials such as water-retaining materials.
  • the benzophenone compound (a1), heterocyclic compound (a2), and compound (a5) capable of reacting with (a1) or (a2) used in the examples are shown below.
  • polyol (B1), amine compound (B2), monoalcohol compound (B3), isocyanate compound (C1), and carboxylic acid compound (C2) used in the examples are shown below.
  • F-2 EBECRYL8807 (manufactured by Daicel Allnex Corporation, aliphatic bifunctional urethane acrylate, average molecular weight 1000)
  • F-3 Urethane diacrylate (Shiko UV6630, manufactured by Mitsubishi Chemical Corporation)
  • F-4 Polyethylene glycol (20)-introduced bisphenol A diacrylate (NK Ester A-BPE-20, manufactured by Shin-Nakamura Chemical Co., Ltd.)
  • F-5 Hexanediol diacrylate
  • F-6 Polyether-based urethane acrylamide (manufactured by KJ Chemicals Co., Ltd., registered trademark "Quick Cure")
  • F-7 Dipentaerythritol hexaacrylate
  • F-8 Urethane diacrylate (UV3000, manufactured by Mitsubishi Chemical Corporation)
  • F-9 Dimethylol-tricyclodecane diacrylate
  • F-10 Polyethylene glycol (10)-introduced bisphenol A diacrylate (NK Ester
  • Example 1 Synthesis of photopolymerization initiator (A-1) 35.9 g of piperazine (a2-1) and 50 g of N,N-dimethylformamide (DMF) were added to a 500 mL flask equipped with a reflux condenser, a stirrer, a thermometer and a dropping funnel, and 37.7 g of acrylic acid chloride (a5-1) was added dropwise while stirring at 0°C and reacted for 1 hour to obtain 1-acroylpiperazine. Then, 100 g of 4-benzoyl methyl benzoate (a1-1) and 3.1 g of triethylamine (TEA) were added and reacted for 2 hours while stirring at 65°C.
  • A-1 photopolymerization initiator
  • the mixture was purified to obtain the desired pale yellow viscous liquid (purity 95%).
  • Example 2 Synthesis of photopolymerization initiator (A-2) Using a similar apparatus, 100 g of (a1-2), 34.5 g of (a2-2), 1.5 g of TEA, and 50 g of DMF were added and reacted at 65°C for 2 hours, and then 79.3 g of (a5-2) and 0.4 g of triphenylphosphine (TPP) were added and reacted at 70°C for 3 hours. After the reaction was completed, the mixture was purified to obtain a pale yellow viscous liquid (purity 97%).
  • TPP triphenylphosphine
  • Example 3 Synthesis of photopolymerization initiator (A-3) Using a similar apparatus, 100 g of (a1-3), 47.2 g of (a2-3), and 39.4 g of thionyl chloride were stirred at 0°C for 10 minutes, then heated to 70°C and reacted for 3 hours. After the reaction was completed, the mixture was purified to obtain a pale yellow viscous liquid (purity 93%).
  • Example 4 Synthesis of Photopolymerization Initiator (A-4) A reaction was carried out in the same manner as in Example 3, except that (a1-3) was replaced with (a1-4), to obtain a pale yellow viscous liquid (purity 97%). From the results of IR analysis, 1 H-NMR analysis (see below) and LC-MS analysis (molecular weight 495) of the obtained viscous liquid, the production of photopolymerization initiator (A-4) having the structure shown in Table 2 was confirmed.
  • Example 5 Synthesis of photopolymerization initiator (A-5) Using a similar device, 100 g of (a1-5), 55.5 g of (a5-3) and 50 g of DMF were mixed and reacted at 65°C for 2 hours. The reaction solution was then cooled to 0°C, 58.0 g of (a2-5) was added, and the mixture was stirred for 10 minutes, then heated to 70°C and reacted for 3 hours. After the reaction was completed, the mixture was purified to obtain a pale yellow viscous liquid (purity 87%). The IR analysis of the obtained viscous liquid confirmed the generation of an ester group (1725 cm -1 ).
  • the molecular weight (511) determined by LC-MS analysis was consistent with the molecular weight of the target compound (Table 2). Based on these results, the production of the photopolymerization initiator (A-5) having the structure shown in Table 2 was confirmed.
  • Example 6 Synthesis of Photopolymerization Initiator (A-6) Using a similar apparatus, 100 g of (a1-6), 63.4 g of (a2-4), 3.1 g of TEA, and 50 g of DMF were mixed and reacted at 65°C for 2 hours. The reaction solution was cooled to 0°C, and 38.5 g of (a5-4) and 73.8 g of thionyl chloride were added, stirred for 10 minutes, and then reacted at 70°C for 3 hours. The mixture was purified to obtain a pale yellow viscous liquid (purity 91%). The IR analysis of the obtained viscous liquid confirmed the generation of an ester group (1725 cm -1 ) and the disappearance of an acid anhydride group.
  • the 1 H-NMR analysis confirmed the presence of a benzophenone group (8.62-7.95 ppm, 6H, aromatic ring) and a tetrahydrofuran group (same as in Example 4).
  • the molecular weight (615) of the LC-MS analysis value was consistent with the molecular weight of the target compound (Table 2). Based on these results, the production of the photopolymerization initiator (A-6) having the structure shown in Table 2 was confirmed.
  • Example 7 Synthesis of photopolymerization initiator (A-7) Using a similar device, 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, and the mixture was stirred for 10 minutes, and then reacted at 70 ° C. for 3 hours. The mixture was purified to obtain a pale yellow viscous liquid (purity 84%).
  • Example 8 Synthesis of photopolymerization initiator (A-8) Using a similar device, 100 g of (a1-6), 63.7 g of (a2-4), and 50 g of DMF were mixed and reacted at 70°C for 4 hours. The reaction solution was cooled to 0°C, and 19.9 g of (a5-6) and 73.8 g of thionyl chloride were added, stirred for 10 minutes, and then reacted at 70°C for 3 hours. After the reaction was completed, the mixture was purified to obtain a pale yellow viscous liquid (purity 96%).
  • Example 9 Synthesis of Photopolymerization Initiator (A-9) Using a similar device, 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, the mixture was purified to obtain a pale yellow viscous liquid (purity 81%).
  • Example 10 Synthesis of Photopolymerization Initiator (A-10) Using a similar device, 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, and then 11.2 g of ion-exchanged water was added and reacted at 65° C. for 3 hours. After the reaction was completed, the mixture was purified to obtain a pale yellow viscous liquid (purity 97%).
  • Examples 11, 14, and 15 Synthesis of photopolymerization initiators (A-11), (A-14), and (A-15)
  • the reactions of Examples 11, 14, and 15 were carried out in the same manner as in Example 7 using the raw material compounds shown in Table 1 , and pale yellow viscous liquids were obtained.
  • the production of photopolymerization initiators (A-11), (A-14), and (A-15) having structures shown in Table 2 was confirmed by IR analysis, 1 H-NMR analysis, and LC-MS analysis.
  • Examples 12, 17, 19, and 20 Synthesis of photopolymerization initiators (A-12), (A-17), (A-19), and (A-20)
  • the reactions of Examples 12, 17, 19, and 20 were carried out in the same manner as in Example 6 using the raw material compounds shown in Table 1, and pale yellow viscous liquids were obtained.
  • the production of photopolymerization initiators (A-12), (A-17), (A-19), and (A-20) having structures shown in Table 2 was confirmed by IR analysis, 1 H-NMR analysis, and LC-MS analysis.
  • Example 13 Synthesis of photopolymerization initiator (A-13) Using a similar device, 100 g of (a1-7), 135.6 g of 2-(hydroxymethyl)-15-crown-5-ether, 1.5 g of TEA, and 50 g of DMF were mixed and reacted at 65°C for 2 hours. After the reaction was completed, the mixture was purified to obtain a pale yellow viscous liquid (purity 84%). Similarly, the production of photopolymerization initiator (A-13) having the structure shown in Table 2 was confirmed by IR analysis, 1 H-NMR analysis (see below), and LC-MS analysis. 1H -NMR: 8.61-7.78 ppm (6H, aromatic ring); 5.02 ppm (2H, -COO-CH-); 3.68-4.01 ppm (28H, -CH2-O- in crown ether).
  • Example 16 Synthesis of photopolymerization initiator (A-16) Using a similar device, 100 g of (a1-6), 88.2 g of (a5-3), 10.0 g of tetrabutylammonium bromide and 50 g of DMF were mixed and reacted at 70°C for 4 hours. The reaction solution was cooled to 0°C, 54.1 g of (a2-4) 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, the mixture was purified to obtain a pale yellow viscous liquid (purity 83%).
  • Example 18 Synthesis of Photopolymerization Initiator (A-18)
  • the reaction of Example 18 was carried out in the same manner as in Example 16 using the raw material compounds shown in Table 1 to obtain a pale yellow viscous liquid.
  • the production of photopolymerization initiator (A-18) having the structure shown in Table 2 was confirmed by IR analysis, 1H -NMR analysis (described below) and LC-MS analysis.
  • Example 21 Synthesis of photopolymerization initiator (A-21) 79.27 g of (A-2) and 0.05 g of dibutylhydroxytoluene (BHT) as a polymerization inhibitor were added to a 300 mL flask equipped with a reflux condenser, a stirrer, a thermometer and a dropping funnel, and the temperature was raised 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.
  • A-21 photopolymerization initiator
  • Example 22 Synthesis of photopolymerization initiator (A-22) Using the same apparatus as in Example 21, 34.42 g of (C1-2) and 0.02 g of dibutyltin dilaurate were added to a 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 the end of the decrease in isocyanate groups by IR analysis, 17.99 g of (B3-1) and 0.01 g of dibutyltin dilaurate were added, and the mixture was reacted at 70°C for another 3 hours.
  • Example 23 Synthesis of photopolymerization initiator (A-23) Using the same apparatus as in Example 21, 20.47 g of (A-7), 31.95 g of (B1-1), 30 g of (H-1), and 0.05 g of BHT were mixed at 70 ° C., and then 13.90 g of (C1-3) and 0.02 g of dibutyltin dilaurate were added, and the mixture was reacted at 70 ° C. for 4 hours, and the cessation of the decrease in isocyanate groups was confirmed by IR analysis. Thereafter, 3.68 g of (B3-2) and 0.01 g of dibutyltin dilaurate were added to the reaction solution, and the mixture was reacted at 70 ° C.
  • the number average molecular weights calculated by GPC analysis are shown in Table 3.
  • Example 28 Synthesis of photopolymerization initiator (A-28) Synthesis, purification, analysis, etc. were performed in the same manner as in Example 23 with the composition shown in Table 3, and the production of photopolymerization initiator (A-28) was confirmed. In addition, the number average molecular weight of (A-28) was calculated to be 10,500 by GPC analysis, and the results are shown in Table 3.
  • Example 31 Synthesis of Photopolymerization Initiator (A-31) 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 in the same apparatus as in Example 21, but with a nitrogen inlet tube attached, and the mixture was heated to 190° C. while blowing nitrogen into the mixture under normal pressure. 0.01 g of zinc oxide was added to the mixture, and the reaction was carried out while distilling off water at 195° C. After the distillation of water stopped, the acid value (in accordance with JIS K0070:1992) of the reaction solution was measured, and it was confirmed to be 48 mgKOH/g.
  • Example 32 Synthesis of photopolymerization initiator (A-32) Using the same apparatus as in Example 21, 40.23 g of (A-7), 12.56 g of (B2-1), 15 g of (H-5) and 0.05 g of BHT were mixed at 70 ° C. 21.86 g of (C1-3) was added to the mixed solution, reacted at 70 ° C. for 2 hours, and after confirming the end of the decrease in isocyanate groups by IR analysis, 4.53 g of (B3-3), 5.82 g of (B3-9) and 0.01 g of dibutyltin dilaurate were added, reacted at 70 ° C.
  • Example 33 Synthesis of photopolymerization initiator (A-33) Using the same apparatus as in Example 31, 19.44 g of (A-10), 18.40 g of (C2-2), 15 g of (H-5), and 0.05 g of BHT were added and mixed. 40.42 g of (C1-2) and 0.02 g of dibutyltin dilaurate were added to the mixed liquid, and the temperature was raised to 120°C over 2 hours, and the reaction was continued for 10 hours at 120°C. Thereafter, the reaction liquid was cooled to 60°C, and 5.28 g of (B3-1), 1.46 g of (B3-6), and 0.01 g of dibutyltin dilaurate were added, and the reaction was continued for 2 hours at 60°C.
  • Examples 34 to 72 and Comparative Examples 1 to 4 Using the photopolymerization initiators (A-1) to (A-33) obtained in the examples and a known photopolymerization initiator (D), the monofunctional monomer (E), the polyfunctional monomer or oligomer (F) and other components (G) were weighed in the proportions shown in Table 4, and mixed for 30 minutes at 25° C. to prepare active energy ray-curable compositions.
  • each of the obtained photopolymerization initiators (A-1) to (A-33) and known photopolymerization initiators (D-1) to (D-4) and 80 g each of the monofunctional monomers (E-2), (E-3), or polyfunctional monomers or oligomers (F-15) were weighed and mixed at 25° C. for 30 minutes to prepare an evaluation liquid. The state of the mixed liquid was visually observed, and the compatibility of the photopolymerization initiator with the monofunctional monomer or polyfunctional monomer or oligomer was evaluated according to the following criteria. The transparency evaluation and compatibility evaluation were performed according to the same criteria. ⁇ : High transparency or compatibility, with no turbidity or separation observed. ⁇ : No phase separation, but turbidity.
  • UV-LED lamp wavelength 365 nm, output 100 mW/ cm2
  • UV-LED lamp wavelength 405 nm, output 100 mW/ cm2
  • No tack is observed with an integrated light amount of less than 1000 mJ/ cm2 .
  • ⁇ Tack disappears when the integrated light amount is 1000 mJ/ cm2 or more and less than 3000 mJ/ cm2 .
  • Tack disappears when the integrated light amount is 3000 mJ/ cm2 or more and less than 20000 mJ/ cm2 .
  • ⁇ Tack remains even with an integrated light quantity of 20,000 mJ/ cm2 .
  • Examples 73 to 79 and Comparative Examples 5 to 7 Using the obtained photopolymerization initiator (A) and a known photopolymerization initiator (D), a monofunctional monomer (E), a polyfunctional monomer or oligomer (F), other components (G) and an organic solvent (H) were weighed in the proportions shown in Table 5, and mixed at 25° C. for 30 minutes to prepare an active energy ray-curable coating composition. The adhesion, pencil hardness and durability of the coating composition were evaluated by the following methods, and the results are shown in Table 5.
  • a cured film was produced by irradiating with a UV-LED lamp having a wavelength of 395 nm and an output of 100 mW/cm 2 so that the accumulated light amount was 3000 mJ/cm 2.
  • 100 1 mm square checkerboards were produced with a cutter knife in accordance with JIS K 5600-5-6, and the number of checkerboards remaining on the test piece when a commercially available adhesive tape was attached and then peeled off was evaluated in four stages. The more checkerboards remaining on the test piece, the higher the adhesion.
  • the number of remaining grids is 100.
  • the number of remaining grids is 90 to 99.
  • ⁇ The number of remaining squares is 60 to 89.
  • Pencil Hardness 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 K 5600-5-4. The pencil hardness of the hardest pencil that did not scratch the surface of the cured film was determined as the pencil hardness and was evaluated into 4 levels.
  • Pencil hardness is 2H or more.
  • Pencil hardness is 3B to B.
  • Pencil hardness is 4B or less.
  • Examples 80 to 85 and Comparative Examples 8 and 9 Using the obtained photopolymerization initiator (A) and a known photopolymerization initiator (D), a monofunctional monomer (E), a polyfunctional monomer or oligomer (F) and other components (G) were weighed in the proportions shown in Table 6, and mixed at 25°C for 30 minutes to prepare an active energy ray curable ink composition.
  • the obtained ink composition was applied to a PET film having a thickness of 100 ⁇ m using a bar coater (RDS12) (film thickness after drying: 20 ⁇ m), and cured by ultraviolet irradiation (UV-LED lamp: wavelength 395 nm, illuminance 1000 mW/cm 2 ) to prepare a printed matter.
  • RDS12 bar coater
  • the curability of the ink composition was evaluated in the same manner as in the evaluation of curability under oxygen inhibition conditions in (5-3) above, and the viscosity, pigment dispersibility, ejection stability and print clarity of the ink composition were evaluated by the following methods, and the results are shown in Table 6.
  • Viscosity The viscosity of the ink composition was measured at 25° C. in accordance with JIS K 5600-2-3 using a cone-plate viscometer (RE550 viscometer manufactured by Toki Sangyo Co., Ltd.), and the ink composition for ink-jet printing was evaluated into the following four levels.
  • Pigment dispersibility Using a pigment-containing ink composition, the state of pigment aggregation and precipitation was visually observed immediately after preparation and after being allowed to stand at room temperature for 2 months, and the pigment dispersibility was evaluated according to the following criteria. ⁇ : No aggregation or precipitation of the pigment was observed either immediately after preparation or after standing for two months. ⁇ : No aggregation or precipitation was observed immediately after preparation, but slight aggregation or precipitation of the pigment was observed after standing for 2 months.
  • Examples 86 to 90 and Comparative Examples 10 and 11 Using the obtained photopolymerization initiator (A) and a known photopolymerization initiator (D), the monofunctional monomer (E), the polyfunctional monomer or oligomer (F) and other components (G) were weighed in the proportions shown in Table 7, and mixed at 25 ° C. for 30 minutes to prepare an active energy ray-curable adhesive composition.
  • the light release PET film was then peeled off to obtain an adhesive sheet consisting of the cured product (adhesive layer) of the adhesive composition and the heavy release PET film.
  • the transparency, adhesive strength, reworkability, and yellowing resistance of the test piece were evaluated by the following methods, and the results are shown in Table 7.
  • An adhesive sheet was prepared in the same manner as above, set in a xenon fade meter (SC-700-WA, manufactured by Suga Test Instruments Co., Ltd.), and irradiated with ultraviolet light at an intensity of 70 mW/ cm2 for 120 hours. Then, the discoloration of the adhesive layer on the adhesive sheet was visually observed and evaluated according to the following criteria. ⁇ : No yellowing was observed with the naked eye. ⁇ : Yellowing is very slight and visible. ⁇ : Yellowing is visually confirmed.
  • Adhesive Strength The adhesive layer of the adhesive sheet was transferred to the following substrate (film or plate) under conditions of a temperature of 23°C and a relative humidity of 50%, and pressure-applied by two reciprocating motions using a pressure roller weighing 2 kg, and left for 30 minutes in the same atmosphere. Thereafter, the 180° peel strength (N/25 mm) was measured at a peel speed of 300 mm/min in accordance with JIS Z0237 using a tensile tester (Tensilon RTA-100, manufactured by ORIENTEC Co., Ltd.), and the adhesive strength of the adhesive sheet on each substrate was evaluated according to the following criteria.
  • PET Cosmoshine A4160 (corona treated surface, manufactured by Toyobo Co., Ltd.)
  • PC PC1600 (manufactured by Takiron C.I. Co., Ltd.)
  • GL glass
  • Eagle XG manufactured by Corning Inc.
  • Examples 91 to 96 and Comparative Examples 12 and 13 Using the obtained photopolymerization initiator (A) and a known photopolymerization initiator (D), the monofunctional monomer (E), the polyfunctional monomer or oligomer (F) and other components (G) were weighed in the proportions shown in Table 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 horizontally placed plate-like or film-like substrates, and the following PET film was laminated to the coated surface, and then the adhesive layer was laminated to a thickness of 20 ⁇ m using a tabletop roll-type laminator machine (RSL-382S) so as not to trap air bubbles, and irradiation was performed with a UV-LED lamp with a wavelength of 405 nm and an illuminance of 50 mW / cm 2 so that the accumulated light amount was 2000 mJ / cm 2 to prepare a laminate.
  • the adhesive strength and water resistance of the obtained laminate were evaluated by the following method, and the results are shown in Table 8. The following substrates were used.
  • PET film (E5100, corona treated surface, manufactured by Toyobo Co., Ltd.)
  • PMMA Plate-shaped (COMOGLAS P, manufactured by Kuraray Co., Ltd.)
  • PC Plate-shaped (PC1600, manufactured by Takiron C.I. Co., Ltd.)
  • Adhesive Strength No peeling at the interface (less than 1 mm) ⁇ : Peeling occurred in part of the interface (1 mm or more, less than 3 mm) ⁇ : Peeling occurred in part of the interface (3 mm or more, less than 5 mm) ⁇ : Peeling occurred at the interface (5 mm or more) (5-17) Adhesive Strength The 180° peel strength (N/25 mm) of the prepared laminate was measured at a peel rate of 300 mm/min in accordance with JIS Z0237 using a tensile tester (Tensilon RTA-100), and the adhesive strength was evaluated according to the following criteria.
  • Examples 97 to 101 and Comparative Examples 14 and 15 Using the obtained photopolymerization initiator (A) and a known photopolymerization initiator (D), the monofunctional monomer (E), the polyfunctional monomer or oligomer (F) and other components (G) were weighed in the proportions shown in Table 9, and mixed at 25 ° C. for 30 minutes to prepare an active energy ray curable ink composition for three-dimensional modeling.
  • the obtained ink composition for three-dimensional modeling was used to evaluate three-dimensional modeling curability and cure shrinkage resistance.
  • the obtained modeled object was also used to evaluate the modeling accuracy, strength, heat resistance and water resistance of the modeled object by the following methods, and the results are shown in Table 9.
  • a 75 ⁇ m thick heavy release PET film (E7001) was attached to a horizontally placed glass plate, a 1 mm thick spacer with an internal dimension of 60 mm ⁇ 100 mm was placed, and the ink composition for three-dimensional modeling obtained in each Example and Comparative Example was filled inside the spacer, and then a light release PET film (E7002) was placed on top of it, and ultraviolet light was irradiated from both sides (wavelength 405 nm, illuminance 10 mW/cm 2 , cumulative light amount 5,000 mJ/cm 2 ) to cure, and the release PET films on both sides were removed to obtain a test piece.
  • the cure shrinkage rate was calculated from the density change of the ink composition for three-dimensional modeling and the test piece according to the following formula.
  • the density was measured according to JIS K7112 using an electronic specific gravity meter (MDS-300, manufactured by Alpha Mirage Co., Ltd.).
  • the resistance to curing shrinkage of the ink composition for three-dimensional modeling was evaluated based on the obtained curing shrinkage rate according to the following criteria.
  • Cure shrinkage rate (%) (Ds - Dl) / Dl x 100% (In the formula, Ds is the density of the ink composition for three-dimensional modeling after curing, and Dl is the density of the ink composition for three-dimensional modeling before curing.)
  • ⁇ Cure shrinkage rate less than 6%
  • ⁇ Cure shrinkage rate 6% or more and less than 7%
  • ⁇ Cure shrinkage rate 7% or more and less than 8%
  • Cure shrinkage rate 8% or more 5-20)
  • Strength Test pieces were prepared in the same manner as for the cure shrinkage resistance, and six pieces were stacked together.
  • the Shore D hardness was measured in accordance with JIS K 6253 (rubber hardness testing method), and the strength of the three-dimensional object was evaluated according to the following criteria.
  • ⁇ Shore D hardness 60 or more
  • ⁇ Shore D hardness less than 40 (5-21)
  • Heat resistance Test pieces were prepared in the same manner as for the curing shrinkage resistance, and measured using a differential scanning calorimeter (DSC-60plus, The glass transition temperature (Tg) of the three-dimensional object was measured using a glass sintering machine (manufactured by Shimadzu Corporation), and the heat resistance of the three-dimensional object was evaluated according to the following criteria.
  • the ink composition for three-dimensional modeling was filled with a thickness of 1 mm each, and the curing was repeated a total of 10 times to obtain a three-dimensional model of 10 x 10 x 10 mm.
  • the height of the obtained model was measured, and the side of the model was visually observed.
  • ⁇ Height is 10 mm ⁇ 0.3 mm or more, or there are obvious irregularities on the side surface.
  • (5-23) Water Resistance Test pieces were prepared in the same manner as in the case of the cure shrinkage resistance and immersed in ion-exchanged water at 25° C. for 24 hours. The water resistance of the three-dimensional model was evaluated according to the following criteria.
  • Water absorption rate (%) (Wb - Wa) / Wa x 100 (In the formula, Wa is the weight of the test piece before immersion in ion-exchanged water, and Wb is the weight of the test piece after immersion in ion-exchanged water.)
  • ⁇ Water absorption rate is less than 0.5%.
  • ⁇ Water absorption rate is 0.5% or more and less than 1%.
  • ⁇ Water absorption rate is 1% or more and less than 2%.
  • Water absorption rate is 2% or more.
  • Examples 102 to 106 and Comparative Examples 16 and 17 Using the obtained photopolymerization initiator (A) and a known photopolymerization initiator (D), a monofunctional monomer (E), a polyfunctional monomer or oligomer (F) and other components (G) were weighed in the proportions shown in Table 10, and mixed at 25°C for 30 minutes to prepare an active energy ray-curable nail cosmetic composition. Using the obtained nail cosmetic composition, the curability of the nail cosmetic composition was evaluated in the same manner as in the evaluation of curability under conditions without oxygen inhibition described in (5-2) above (LED 405 nm). The adhesion, surface hardness, surface gloss and removability of the nail cosmetic composition were also evaluated by the following methods, and the results are shown in Table 10.
  • x The number of remaining squares is less than 60.
  • 5-25 Surface hardness A cured film was prepared in the same manner as in the adhesion evaluation, and a 750 g load was applied to the surface of the film with a pencil having a hardness of HB at an angle of 45° and pulled, and the presence or absence of peeling and scratches was visually confirmed, and the surface hardness was evaluated according to the following criteria. The fewer scratches and peeling, the higher the surface hardness. A: No scratches or peeling occurred. The surface hardness was pencil hardness HB or higher. ⁇ : No peeling occurred, but scratches occurred. ⁇ : Peeling occurred.
  • Examples 107 to 112 and Comparative Examples 18 and 19 Using the obtained photopolymerization initiator (A) and a known photopolymerization initiator (D), a monofunctional monomer (E), a polyfunctional monomer or oligomer (F) and other components (G) were weighed in the proportions shown in Table 11, and mixed for 30 minutes at 25° C. to prepare an active energy ray-curable dental material composition. Using the obtained dental material composition, the solubility (dispersibility), storage stability and curability (method similar to the evaluation of curability under conditions without oxygen inhibition in (5-2) above, LED 405 nm) were evaluated, and the hardness, surface smoothness and adhesive strength of the obtained cured product were evaluated according to the following criteria. The results are shown in Table 11.
  • Knoop hardness is 70 KHN or more and less than 200 KHN (equivalent to dentin).
  • ⁇ Knoop hardness is less than 70 KHN.
  • (5-31) Surface Smoothness The surface smoothness and gloss of the cured product obtained in the curability evaluation were visually observed and evaluated according to the following criteria. A: The surface is smooth and glossy. ⁇ : The surface is almost smooth, with slight cloudiness or slight irregularities observed. ⁇ : The surface is generally cloudy, and some irregularities and granularity are observed. ⁇ : The surface is entirely cloudy and covered with granular matter. (5-32) Adhesive strength A bovine mandibular anterior tooth was polished with No.
  • an adhesive test piece was prepared by a known method (see the method described in JP 2010-208964 A). The adhesive test piece was immersed in 37°C water for 24 hours, and the tensile adhesive strength was measured with an Instron universal testing machine (crosshead speed 2 mm/min) to determine the adhesive strength to the enamel and dentin, and the adhesive strength was evaluated according to the following criteria.
  • ⁇ The adhesive strength of both enamel and dentin is 20 MPa or more.
  • ⁇ The adhesive strength between enamel and dentin is 20 MPa or more in only one of the specimens.
  • ⁇ The adhesive strength of both enamel and dentin is 7 MPa or more.
  • ⁇ The adhesive strength between the enamel and the dentin was less than 7 MPa.
  • Examples 113 to 118 and Comparative Examples 20 and 21 Using the obtained photopolymerization initiator (A) and a known photopolymerization initiator (D), a polyfunctional monomer or oligomer (F), other components (G), and an organic solvent (H) were weighed in the proportions shown in Table 12, and mixed at 25° C. for 30 minutes to prepare an active energy ray-curable photosensitive composition. Using the obtained photosensitive composition, a photosensitive resin for evaluation was prepared in Examples 113 to 115 and Comparative Example 20 according to the following (5-33) Photosensitive Resin Production 1, and in Examples 116 to 118 and Comparative Example 21 according to the following (5-34) Photosensitive Resin Production 2, and the sensitivity, pattern formability, and storage stability of the photosensitive composition were evaluated.
  • ⁇ There is no distortion in the pattern, and chipping is observed at the edge portions.
  • ⁇ The pattern is distorted.
  • the photopolymerization initiator (A) (Examples 1 to 33) of the present disclosure has good compatibility with general-purpose monofunctional monomers, polyfunctional monomers, or oligomers, has high photoinitiation properties for various active energy rays from short wavelengths to long wavelengths, and the active energy ray-curable composition containing it has high curability. Both the obtained curable composition and the cured product had excellent transparency.
  • the photopolymerization initiator (A) is not easily inhibited by oxygen, and the initiation reaction and photopolymerization reaction by long-wavelength light in air can proceed at a sufficient speed.
  • the curable composition containing the photopolymerization initiator (A) (Examples 34 to 72) had high curability even when exposed to long-wavelength light in the air or in the absence of oxygen.
  • the active energy ray-curable composition (Examples 73 to 118) adjusted for various applications has good adhesion, tackiness, and adhesiveness in various forms after curing, and also has high physical properties such as hardness and strength.
  • the cured product obtained by curing had very little odor, bleed-out, outgassing, yellowing over time, or deterioration, and the cured product obtained had high yellowing resistance, water resistance, durability, heat resistance, and sealing properties.
  • compositions containing known photopolymerization initiators had low curing properties with long wavelength light, and the cured products obtained had low physical properties such as adhesion, tackiness, adhesion, hardness, and strength, as well as low yellowing resistance, water resistance, durability, and heat resistance. Therefore, the photopolymerization initiator disclosed herein and the active energy ray-curable composition containing it can be used suitably for various applications.
  • a photopolymerization initiator having one or more benzopheno groups and a saturated or unsaturated 5-membered or larger cyclic substituent having one or more heteroatoms in the molecule, and having one or more saturated or unsaturated 5-membered or larger cyclic substituents having heteroatoms bonded to one or more carbon atoms of the aryl groups of at least one of the benzopheno groups via a carboxylic acid ester group or a carboxylic acid amide group.
  • cyclic substituent is one or more groups selected from a piperidine group, a pyrrolidine group, a piperazine group, a pyridine group, a morpholine group, a tetrahydrofuran group, a hydrofuran group, a crown ether group, and a tetrahydrothiopyran group.
  • the photopolymerization initiator according to claim 1 or 2 wherein the cyclic substituent is one or more groups selected from the group consisting of a piperidine group, a pyrrolidine group, a piperazine group, a pyridine group, a morpholine group, a tetrahydrofuran group, a hydrofuran group, a crown ether group, and a tetrahydrothiopyran group.
  • Q 1 and Q 3 are each independently a hydrogen atom or a monovalent organic group represented by general formula (2) or general formula (3), and at least one of Q 1 and Q 3 is a monovalent organic group having at least one saturated or unsaturated 5- or larger-membered cyclic substituent having a heteroatom;
  • Q 2 and Q 4 each independently represent a divalent organic group represented by general formula (4) or general formula (5);
  • L 1 and L 2 are each independently a direct bond or a divalent organic group containing at least one of a urethane group, a urea group, an ester group, an amide group, and an imide group.
  • Q 2 -L 1 -R 5 and Q 4 -L 2 -R 6 may be hydrogen atoms, except when Q 1 and Q 3 are both hydrogen atoms.
  • R 1 to R 9 and R 12 each independently represent a hydrogen atom or a linear or cyclic, saturated or unsaturated monovalent hydrocarbon group having 1 to 36 carbon atoms in which one or more hydrogen atoms may be substituted with a hydroxyl group, an amine group, a thiol group, or a halogen group, and one or more carbon atoms may be substituted with an ether group, an amino group, a thioether group, or a thioester group;
  • R 10 and R 11 each independently represent a direct bond or a linear or cyclic, saturated or unsaturated divalent hydrocarbon group having 1 to 36 carbon atoms in which one or more hydrogen atoms may be substituted with a hydroxyl group, an amine group, a thiol group, or a halogen group, and one
  • An active energy ray-curable nail cosmetic composition containing the photopolymerization initiator according to any one of (1) to (5) above.
  • An active energy ray-curable dental material composition containing the photopolymerization initiator according to any one of (1) to (5) above.
  • An active energy ray-curable photosensitive composition containing the photopolymerization initiator according to any one of (1) to (5) above.
  • An active energy ray-curable hydrogel composition containing the photopolymerization initiator according to any one of (1) to (5) above.
  • An active energy ray-curable intraocular implant material composition containing the photopolymerization initiator according to any one of (1) to (5) above.
  • the photopolymerization initiator (A) of the present disclosure has high photoinitiating properties, can be used with light sources of a wide variety of wavelengths, such as UV-LED lamps with wavelengths of 360 nm to 420 nm, and can initiate photopolymerization and perform a curing reaction with active energy rays in the presence of oxygen.
  • the photopolymerization initiator becomes a structural unit of the cured product after curing, and a cured product having good physical properties and durability can be obtained.
  • the photopolymerization initiator of the present invention can be combined with various unsaturated group-containing compounds to produce active energy ray-curable compositions that correspond to various applications, and can impart various physical properties such as high adhesion, surface hardness, yellowing resistance, and water resistance, and can be suitably used as an active energy ray-curable composition, an active energy ray-curable ink composition, an active energy ray-curable pressure-sensitive adhesive composition, an active energy ray-curable adhesive composition, an active energy ray-curable coating composition, an active energy ray-curable sealant composition, an active energy ray-curable inkjet ink composition, an active energy ray-curable ink composition for three-dimensional modeling, an active energy ray-curable nail cosmetic composition, an active energy ray-curable dental composition, an active energy ray-curable photosensitive composition, an active energy ray-curable hydrogel composition, an active energy ray-curable intraocular implant material composition, an active energy ray-curable pressure-sensitive adhesive composition for skin, an

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010208964A (ja) 2009-03-09 2010-09-24 Tokuyama Dental Corp 歯科用光硬化性材料
CN103926794A (zh) * 2014-04-29 2014-07-16 常州强力电子新材料股份有限公司 一种含有二苯甲酮衍生物光引发剂的光固化组合物
CN111138290A (zh) * 2019-12-25 2020-05-12 山西大学 一种含芳香环二苯甲酮衍生物及其制备方法和应用
CN111205203A (zh) * 2019-12-02 2020-05-29 山西大学 含有二苯氨基甲酸酯基的二苯甲酮衍生物及其制备和应用
WO2023074620A1 (ja) * 2021-10-25 2023-05-04 Ｋｊケミカルズ株式会社 活性エネルギー線硬化性組成物

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010208964A (ja) 2009-03-09 2010-09-24 Tokuyama Dental Corp 歯科用光硬化性材料
CN103926794A (zh) * 2014-04-29 2014-07-16 常州强力电子新材料股份有限公司 一种含有二苯甲酮衍生物光引发剂的光固化组合物
CN111205203A (zh) * 2019-12-02 2020-05-29 山西大学 含有二苯氨基甲酸酯基的二苯甲酮衍生物及其制备和应用
CN111138290A (zh) * 2019-12-25 2020-05-12 山西大学 一种含芳香环二苯甲酮衍生物及其制备方法和应用
WO2023074620A1 (ja) * 2021-10-25 2023-05-04 Ｋｊケミカルズ株式会社 活性エネルギー線硬化性組成物

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