Classifications

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  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C235/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms
  • C07C235/70—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups and doubly-bound oxygen atoms bound to the same carbon skeleton
  • C07C235/72—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups and doubly-bound oxygen atoms bound to the same carbon skeleton with the carbon atoms of the carboxamide groups bound to acyclic carbon atoms
  • C07C235/76—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups and doubly-bound oxygen atoms bound to the same carbon skeleton with the carbon atoms of the carboxamide groups bound to acyclic carbon atoms of an unsaturated carbon skeleton
  • C07C235/78—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups and doubly-bound oxygen atoms bound to the same carbon skeleton with the carbon atoms of the carboxamide groups bound to acyclic carbon atoms of an unsaturated carbon skeleton the carbon skeleton containing rings
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  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K6/00—Preparations for dentistry
  • A61K6/30—Compositions for temporarily or permanently fixing teeth or palates, e.g. primers for dental adhesives
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  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K6/00—Preparations for dentistry
  • A61K6/60—Preparations for dentistry comprising organic or organo-metallic additives
  • A61K6/62—Photochemical radical initiators
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  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K6/00—Preparations for dentistry
  • A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
  • A61K6/884—Preparations for artificial teeth, for filling teeth or for capping teeth comprising natural or synthetic resins
  • A61K6/887—Compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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  • 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
  • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
  • A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
  • A61K8/42—Amides
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  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q3/00—Manicure or pedicure preparations
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  • C07C237/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups
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  • C07C237/20—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atoms of the carboxamide groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton containing six-membered aromatic rings
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  • C07C237/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups
  • C07C237/02—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atoms of the carboxamide groups bound to acyclic carbon atoms of the carbon skeleton
  • C07C237/22—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atoms of the carboxamide groups bound to acyclic carbon atoms of the carbon skeleton having nitrogen atoms of amino groups bound to the carbon skeleton of the acid part, further acylated
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  • C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
  • C07C271/06—Esters of carbamic acids
  • C07C271/08—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms
  • C07C271/10—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms
  • C07C271/16—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of hydrocarbon radicals substituted by singly-bound oxygen atoms
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  • C07C271/06—Esters of carbamic acids
  • C07C271/08—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms
  • C07C271/10—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms
  • C07C271/20—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of hydrocarbon radicals substituted by nitrogen atoms not being part of nitro or nitroso groups
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  • C07D207/44—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members
  • C07D207/444—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members having two doubly-bound oxygen atoms directly attached in positions 2 and 5
  • C07D207/448—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members having two doubly-bound oxygen atoms directly attached in positions 2 and 5 with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms, e.g. maleimide
  • C07D207/452—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members having two doubly-bound oxygen atoms directly attached in positions 2 and 5 with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms, e.g. maleimide with hydrocarbon radicals, substituted by hetero atoms, directly attached to the ring nitrogen atom
• • C—CHEMISTRY; METALLURGY
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  • C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
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  • C07D211/06—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
  • C07D211/08—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms
  • C07D211/18—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms with substituted hydrocarbon radicals attached to ring carbon atoms
  • C07D211/20—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms with substituted hydrocarbon radicals attached to ring carbon atoms with hydrocarbon radicals, substituted by singly bound oxygen or sulphur atoms
  • C07D211/22—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms with substituted hydrocarbon radicals attached to ring carbon atoms with hydrocarbon radicals, substituted by singly bound oxygen or sulphur atoms by oxygen atoms
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  • C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
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  • C07D295/16—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms
  • C07D295/18—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms by radicals derived from carboxylic acids, or sulfur or nitrogen analogues thereof
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  • C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links
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  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
  • C09J133/24—Homopolymers or copolymers of amides or imides
  • C09J133/26—Homopolymers or copolymers of acrylamide or methacrylamide
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J201/00—Adhesives based on unspecified macromolecular compounds
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • 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
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • 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
  • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
  • G03F7/031—Organic compounds not covered by group G03F7/029
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
  • A61K2800/80—Process related aspects concerning the preparation of the cosmetic composition or the storage or application thereof
  • A61K2800/81—Preparation or application process involves irradiation
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q3/00—Manicure or pedicure preparations
  • A61Q3/02—Nail coatings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2601/00—Systems containing only non-condensed rings
  • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
  • C07C2601/14—The ring being saturated

Definitions

• the present invention relates to a novel benzoyl formic acid amide derivative.
• the benzoyl formic acid amide derivative can be used as a photopolymerization initiator or a photosensitizer.
• the present invention also relates to an active energy ray curable composition, an active energy ray curable ink composition, an inkjet ink, an ink for three-dimensional modeling, a pressure sensitive adhesive composition, an adhesive composition, a sealant composition, a photosensitive composition, a nail cosmetic composition, a dental material composition, a coating composition, and an aqueous composition, which contain the benzoyl formic acid amide derivative.
• Photopolymerization and photocuring using ultraviolet (UV) and other active energy rays generally involve irradiating a composition containing a photopolymerization initiator with UV light to generate active species such as radicals and ions, which initiate a polymerization reaction and solidify (cure) the liquid composition in a short period of time.
• This technology is currently used in a wide range of fields, including paints, coatings, pressure sensitive adhesives, adhesives, elastomer materials, inkjet inks, sealing materials, sealants, dental hygiene materials, and optical materials.
• it can be cured in any location and shape, it is increasingly being used as a nail cosmetic for gel nails and as a material for three-dimensional photo-modeling in 3D printers.
• Photopolymerization initiators that generate radicals when exposed to active energy rays can be classified into intramolecular cleavage type and hydrogen abstraction type.
• 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 leaves decomposition products derived from the initiator remaining 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.
• Hydrogen abstraction types often have low efficiency in initiating photopolymerization, but they have been attracting attention in recent years because they do not produce decomposition products derived from the initiator.
• UV-LED lamps and LED lamps have become widespread.
• photopolymerization initiators and photosensitizers that can be used with these light sources, but there has been an issue that the photopolymerization initiation effect and photosensitization effect are low, and the resulting cured product is prone to yellowing.
• the first object of the present invention is to provide a benzoyl formic acid amide derivative.
• the benzoyl formic acid amide derivative has high photopolymerization initiation properties with respect to active energy rays, particularly light rays of 360 to 420 nm irradiated by an LED lamp, and the resulting cured product does not contain any decomposition products of the benzoyl formic acid amide derivative.
• the second object of the present invention is to provide the benzoyl formic acid amide derivative as a highly safe photopolymerization initiator.
• the third object of the present invention is to provide a highly curable active energy ray curable composition containing the benzoyl formic acid amide derivative as a photopolymerization initiator.
• the fourth object of the present invention is to provide a highly safe ink composition, inkjet ink composition, ink composition for three-dimensional modeling, adhesive composition, adhesive composition, sealant composition, photosensitive composition, nail cosmetic composition, dental material composition, coating composition, aqueous composition, hydrogel composition, and material composition for intraocular implants, which contain the benzoyl formic acid amide derivative and have high compatibility, excellent adhesion to substrates, and produce cured products with little yellowing and bleed-out over time.
• the benzoyl formic acid amide derivative has photosensitivity to active energy rays, particularly light rays of 360 to 420 nm irradiated by an LED lamp, and a cured product that does not yellow is obtained.
• the fifth objective is to provide a benzoyl formic acid amide derivative as a photosensitizer.
• the sixth objective is to provide an active energy ray curable composition that contains the benzoyl formic acid amide derivative as a photosensitizer and has high curing properties and high compatibility.
• the seventh objective is to provide an ink composition, inkjet ink composition, ink composition for three-dimensional modeling, pressure sensitive adhesive composition, adhesive composition, sealant composition, photosensitive composition, nail cosmetic composition, dental material composition, coating composition, aqueous composition, hydrogel composition, or material composition for intraocular implant that contains a benzoyl formic acid amide derivative and that can provide a cured product that has excellent adhesion to a substrate, is less likely to yellow over time, and is excellent in durability.
• Q 1 to Q 3 each independently represent a hydrogen atom, a substituent represented by formulae (2) to (8), a halogen group, or a nitrile group, and are bonded to any of the 2- to 6-positions.
• R 1 to R 10 each independently represent a hydrogen atom, a linear alkyl group having 1 to 18 carbon atoms, a linear alkenyl group having 2 to 18 carbon atoms, a branched alkyl group having 3 to 18 carbon atoms, a branched alkenyl group having 3 to 18 carbon atoms, a cyclic alkyl group having 3 to 18 carbon atoms, or a cyclic alkenyl group having 3 to 18 carbon atoms, where * indicates the bonding position.
• the benzoyl formic acid amide derivative disclosed herein has high initiation efficiency (also called polymerization initiation or photoinitiation) for long wavelength light of 360 to 420 nm, and light of wavelengths such as 365 nm, 385 nm, 395 nm, and 405 nm irradiated from an LED lamp, and the activity of the radicals generated at the same time is high, so it can be used as a photopolymerization initiator.
• initiation efficiency also called polymerization initiation or photoinitiation
• An active energy ray curable composition containing the benzoyl formic acid amide derivative as a photopolymerization initiator can easily obtain a completely cured product with low energy (low cumulative light amount) and high speed (short curing time) even in an industrial manufacturing environment under an air atmosphere, without the need for additives such as a hydrogen donor of a co-initiator, a general-purpose photosensitizer, or a curing accelerator.
• the obtained cured product does not contain decomposition products of the benzoyl formic acid amide derivative used as a photopolymerization initiator, has low odor, yellowing over time, and bleed-out, and is highly durable and safe.
• the benzoyl formic acid amide derivative can be suitably used in a wide variety of applications, such as active energy ray-curable ink compositions, inkjet ink compositions, ink compositions for three-dimensional modeling, pressure-sensitive adhesive compositions, adhesive compositions, sealant compositions, photosensitive compositions, nail cosmetic compositions, dental material compositions, coating compositions, aqueous compositions, hydrogel compositions, and material compositions for intraocular implants.
• the benzoyl formic acid amide derivative disclosed herein has a photosensitizing effect on other general-purpose photoradical polymerization initiators and photoionic polymerization initiators when absorbing long-wavelength light of 360 to 420 nm, and light of 365 nm, 385 nm, 395 nm, and 405 nm irradiated from an LED lamp, and can be used as a photosensitizer that is unlikely to cause yellowing during photocuring.
• An active energy ray curable composition containing the benzoyl formic acid amide derivative as a photosensitizer can be used in combination with a photopolymerization initiator that has poor curing properties with long-wavelength light of 360 to 420 nm, and light of 365 nm, 385 nm, 395 nm, and 405 nm irradiated from an LED lamp, to easily obtain a completely cured product with low energy (low cumulative light amount) and high speed (short curing time) even in an industrial manufacturing environment under an air atmosphere.
• the obtained cured product has low odor, yellowing over time, and bleed-out, and is highly durable and safe.
• the benzoyl formic acid amide derivative can be suitably used in a wide variety of applications, such as active energy ray-curable ink compositions, inkjet ink compositions, ink compositions for three-dimensional modeling, pressure-sensitive adhesive compositions, adhesive compositions, sealant compositions, photosensitive compositions, nail cosmetic compositions, dental material compositions, coating compositions, aqueous compositions, hydrogel compositions, and material compositions for intraocular implants.
• One embodiment of the present disclosure is a benzoylformamide derivative (D) having one or more benzoylformamide groups represented by general formula (1) in the molecule.
• Q 1 to Q 3 in the general formula (1) are each independently a hydrogen atom, a linear alkyl group having 1 to 18 carbon atoms, a linear alkenyl group having 2 to 18 carbon atoms, a branched alkyl group having 3 to 18 carbon atoms, a branched alkenyl group having 3 to 18 carbon atoms, a cyclic alkyl group having 3 to 18 carbon atoms, an alkoxy group having a cyclic alkenyl group having 3 to 18 carbon atoms, an amino group, an alkylamino group, a dialkylamino group, an alkoxycarbonyl group, an alkyl ester group, an aminocarbonyl group, an alkylaminocarbonyl group, a dialkylaminocarbonyl group, an alkylamide group, a halogen group, or a nitrile group.
• Q 1 to Q 3 are bonded to any of the 2- to 6-positions of the benzene ring.
• the benzoylformamide derivative (D) exhibits good photopolymerization initiation and photosensitization to a high-pressure mercury lamp and a 360-410 nm UV-LED light source, and is low in coloration due to light irradiation.
• Q1 to Q3 are electron-donating alkyl, alkoxy, amino, alkylamino, dialkylamino, alkyl ester, or alkylamide groups
• the absorption wavelength of the benzoylformamide derivative (D) shifts to the longer wavelength side and has high sensitivity to light sources of 390 to 420 nm, making it more suitable for use as both a photopolymerization initiator and a photosensitizer.
• These electron-donating substituents may become colored by irradiation with light, but from the viewpoint of keeping the coloration of D at a practically low level, it is particularly preferred that Q1 to Q3 are alkoxy or alkyl ester groups.
• the benzoylformamide group of the benzoylformamide derivative (D) is a mono-substituted or di-substituted amide group of benzoylformic acid. Both the mono-substituted amide group of benzoylformic acid and the di-substituted amide group of benzoylformic acid have photopolymerization initiation and photosensitization properties, and the mono-substituted amide group of benzoylformic acid has higher photopolymerization initiation properties.
• the mono-substituted amide group of benzoylformic acid has a hydrogen atom bonded to its nitrogen atom, and while it is a photoinitiating functional group of the hydrogen abstraction type, it is also a hydrogen donor group, and active radicals are efficiently generated by intramolecular and/or intermolecular hydrogen abstraction. Therefore, even without the use of an amine hydrogen donor, which is prone to coloring, D having a mono-substituted amide group of benzoylformic acid has high photopolymerization initiation properties and polymerization initiation properties against highly safe ultraviolet rays of 360 to 420 nm.
• the benzoylformamide derivative (D) of the present disclosure is preferably at least one compound represented by any one of general formulas (2) to (4).
• Q 1 to Q 3 are defined as in general formula (1).
• B1 represents a monovalent organic group which may have a hydrogen atom, a hydroxyl group, an amino group, a thiol group, an ether group, a thioether group, an ester group, a carbonate group, a urethane group, a thiourethane group, a urea group, a siloxane group, an amide group, an imide group, an ethylenically unsaturated group, or a benzoylformamide group;
• B2 represents a monovalent organic group which may have a hydroxyl group, an amino group, a thiol group, an ether group, a thioether group, an ester group, a carbonate group, a urethane group, a thiourethane group, a urea group, a siloxane group, an amide group, an imide group, an ethylenically unsaturated
• Q 1 to Q 3 are defined as in general formula (1).
• B3 represents an m-valent organic group which may have an ethylenically unsaturated group, an ether group, a thioether group, an ester group, a carbonate group, a urethane group, a thiourethane group, an isocyanurate group, an allophanate group, a urea group, a siloxane group, an amide group, or an imide group;
• R 11 represents a hydrogen atom, a linear alkyl group having 1 to 18 carbon atoms, a linear alkenyl group having 2 to 18 carbon atoms, a branched alkyl group having 3 to 18 carbon atoms, a branched alkenyl group having 3 to 18 carbon atoms, a cyclic alkyl group having 3 to 18 carbon atoms, a cyclic alkenyl group having 3 to 18 carbon atoms, or an aryl group having 6 to 8 carbon
• A1 represents a divalent organic group which may have an ether group, a thioether group, an ester group, a carbonate group, a urethane group, a thiourethane group, a urea group, a siloxane group, an amide group, or an imide group
• B 4 and B 5 may each independently have an ethylenically unsaturated group, an ether group, a thioether group, an ester group, a carbonate group, a urethane group, a thiourethane group, an isocyanurate group, an allophanate group, a urea group, a siloxane group, an amide group, or an imide group
• B 4 and B 5 represent a monovalent organic group containing one or more ethylenically unsaturated bonds
• R 13 represents a hydrogen atom, a linear alkyl group having 1 to
• the benzoyl formic acid amide derivative (D) is represented by the general formula (2)
• the benzoyl formic acid amide group has a hydrophobic benzene ring and a hydrophilic formic acid amide group, and is amphiphilic.
• D has high compatibility with other components used in the curable composition, and the obtained curable composition and the cured product obtained by curing it have high transparency.
• B 1 and/or B 2 have an ether group, a thioether group, an ester group, a carbonate group, a urethane group, a thiourethane group, an isocyanurate group, an allophanate group, a urea group, a siloxane group, an amide group, or an imide group, since it is easy to adjust the polarity. It is more preferable that B 1 and B 2 have an ether group, an ester group, a urethane group, or an amide group.
• B 1 is a hydrogen atom
• D has a benzoyl formic acid mono-substituted amide group, and has higher photopolymerization initiation, which is more preferable.
• B1 and B2 may further have a benzoylformamide group represented by the general formula (1).
• the benzoylformamide derivative (D) has a plurality of benzoylformamide groups, and is preferable because it has higher photopolymerization initiation and photosensitization properties.
• the benzoylformamide groups contained in D may be the same or different.
• the benzoylformamide derivative (D) shown in general formula (2) can be used as a photosensitizer for photoionic polymerization.
• B1 and B2 have a cyclic ether group, because D is incorporated into the cured product via a covalent bond by photoionic polymerization. It may have one cyclic ether group or two or more cyclic ether groups.
• B1 and B2 further have an ethylenically unsaturated group.
• the benzoylformamide derivative (D) is preferable because it serves as a photopolymerization initiator or photosensitizer having an ethylenically unsaturated group, and D is incorporated into the cured product via a covalent bond by photoradical polymerization.
• the ethylenically unsaturated group has one or more, and more preferably has two or more.
• the ethylenically unsaturated group may have one type alone or multiple types.
• the benzoyl formate derivative (D) has good compatibility with other components used in the curable composition, and the obtained curable composition and its cured product have high transparency.
• the ratio of the number (total) of urethane groups to the number (total) of benzoyl formate groups in D is preferably 0.1 or more, more preferably 0.5 or more.
• the viscosity of D increases, and the ratio is preferably 10.0 or less.
• the benzoylformamide derivative (D) has a urethane group represented by general formula (3) or general formula (4).
• the urethane group has a hydrogen atom bonded to its nitrogen atom and can function as a hydrogen donor group, and D has good photopolymerization initiation properties against highly safe ultraviolet light of 360 to 420 nm.
• the number of atoms directly linked between the nitrogen atom of the benzoylformamide group and the nitrogen atom of the urethane group closest thereto is preferably 3 to 20.
• the number of directly linked atoms is 3 or more, the hydrogen abstraction ability of the benzoylformamide group and the hydrogen donating ability of the urethane group are both improved due to the interaction between the benzoylformamide group and the urethane group.
• the number of directly linked atoms is 20 or less, the benzoylformamide group and the urethane group in the molecule are easily close to each other, making it easy for a hydrogen abstraction reaction to occur. From these viewpoints, the number of directly linked atoms is more preferably 4 to 10, and even more preferably 4 to 6.
• the benzoylformamide derivative (D) represented by the general formula (3) has one or more benzoylformamide groups and one or more urethane groups in the molecule.
• the urethane group has good compatibility with other components used in the curable composition, and the obtained curable composition and its cured product have high transparency.
• B3 further has one or more urethane groups.
• the ratio of the number (total) of urethane groups to the number (total) of benzoylformamide groups in D is preferably 0.5 or more, more preferably 2.0 or more. When the number of urethane groups increases, the viscosity of D increases, and the above ratio is preferably 10.0 or less, more preferably 6.0 or less, and particularly preferably 4.0 or less.
• R 11 is a hydrogen atom, a linear alkyl group having 1 to 18 carbon atoms, a linear alkenyl group having 2 to 18 carbon atoms, a branched alkyl group having 3 to 18 carbon atoms, a branched alkenyl group having 3 to 18 carbon atoms, a cyclic alkyl group having 3 to 18 carbon atoms, a cyclic alkenyl group having 3 to 18 carbon atoms, or an aryl group having 6 to 8 carbon atoms.
• the benzoylformic acid amide derivative (D) has a benzoylformic acid mono-substituted amide group and is more preferred because it has excellent photopolymerization initiation properties.
• R 12 in general formula (3) is a divalent linear saturated hydrocarbon group having 1 to 18 carbon atoms, a divalent linear unsaturated hydrocarbon group having 2 to 18 carbon atoms, a divalent branched saturated or unsaturated hydrocarbon group having 3 to 18 carbon atoms, a divalent alicyclic saturated or unsaturated hydrocarbon group having 3 to 8 carbon atoms, a divalent aromatic hydrocarbon group having 6 to 8 carbon atoms, or a divalent organic group in which any one or more of the carbon atoms or hydrogen atoms of these hydrocarbon groups are substituted with an oxygen atom, a nitrogen atom, a sulfur atom, a hydroxyl group, a thiol group, or an amine group.
• R 12 is preferably a divalent linear saturated hydrocarbon group having 1 to 8 carbon atoms, a divalent linear unsaturated hydrocarbon group having 2 to 8 carbon atoms, or a divalent branched saturated or unsaturated hydrocarbon group having 3 to 18 carbon atoms, more preferably a divalent linear saturated hydrocarbon group having 2 to 4 carbon atoms, or a divalent branched saturated hydrocarbon group having 3 to 8 carbon atoms.
• the benzoylformamide group is amphiphilic, and by adjusting the polarity of B3 according to the purpose, D has high compatibility with other components used in the curable composition, and the obtained curable composition and the cured product obtained by curing the same have high transparency.
• B3 has an ethylenically unsaturated group, an ether group, a thioether group, an ester group, a carbonate group, a urethane group, a thiourethane group, an isocyanurate group, an allophanate group, a urea group, a siloxane group, an amide group, or an imide group, its polarity can be easily adjusted, which is preferable.
• Benzoylformamide derivatives (D) represented by general formula (3) can also be used as photosensitizers for photoionic polymerization.
• B3 has a cyclic ether group, since D is incorporated into the cured product via a covalent bond by photoionic polymerization. It may have one cyclic ether group or two or more cyclic ether groups.
• B3 further has an ethylenically unsaturated group.
• the benzoylformamide derivative (D) is preferable because it serves as a photopolymerization initiator or photosensitizer having an ethylenically unsaturated group, and D is incorporated into the cured product via a covalent bond by photoradical polymerization.
• the ethylenically unsaturated group has one or more, and more preferably has two or more.
• the ethylenically unsaturated group may have one type alone or multiple types.
• m is an integer from 1 to 10.
• the benzoylformamide derivative (D) has one or more benzoylformamide groups in the molecule, and can function both as a photopolymerization initiator and a photosensitizer.
• m exceeds 10, the molecular weight and viscosity of D are high, and the handleability of the curable composition containing D may decrease, which is not preferable. From these viewpoints, it is more preferable that m is an integer from 2 to 4.
• the benzoylformamide derivative (D) shown in general formula (3) can be produced by synthesizing benzoylformamide monool by an amidation reaction of benzoylformic acid with an aminoalkyl alcohol, and then further by a urethane reaction with an isocyanate compound.
• aminoalkyl alcohols include 4-aminobenzyl alcohol, 2-(2-aminoethoxy)ethanol, 2-aminoethanol, 2-aminopropanol, 2-amino-2-methyl-1-propanol, 2-amino-2-ethyl-1-propanol, 3-aminopropanol, 2-amino-1-butanol, 3-amino-1-butanol, 4-aminobutanol, 5-aminopentanol, 2-amino-1-hexanol, 6-aminohexanol, 7-aminoheptanol, 2-amino-1-octanol, 8-aminooctanol, 2-amino-1-decanol, 10-aminodecanol, 12-aminododecanol, 18-aminooctadecanol is preferred, 2-aminoethanol, 2-aminopropanol, 2-amino-2-methyl-1-propan
• the benzoylformamide derivative (D) represented by the general formula (4) has one or more benzoylformamide groups, two or more urethane groups, and one or more ethylenically unsaturated groups in the molecule.
• the urethane group has good compatibility with other components constituting the curable composition, and the transparency of the curable composition containing D and the cured product obtained by curing the same is high. From this viewpoint, it is preferable that at least one of A 1 , B 4 and B 5 further has one or more urethane groups.
• the ratio of the number (total) of urethane groups to the number (total) of benzoylformamide groups in D is preferably 2.0 or more, more preferably 2.5 or more. In addition, since the viscosity of D increases as the number of urethane groups increases, the ratio is preferably 15.0 or less, more preferably 8.0 or less, and particularly preferably 5.0 or less.
• R 13 in general formula (4) is a hydrogen atom, a linear alkyl group having 1 to 18 carbon atoms, a linear alkenyl group having 2 to 18 carbon atoms, a branched alkyl group having 3 to 18 carbon atoms, a branched alkenyl group having 3 to 18 carbon atoms, a cyclic alkyl group having 3 to 18 carbon atoms, a cyclic alkenyl group having 3 to 18 carbon atoms, or an aryl group having 6 to 8 carbon atoms.
• R 13 is a hydrogen atom
• the benzoylformic acid amide derivative (D) has a benzoylformic acid mono-substituted amide group and is preferred because it has excellent photopolymerization initiation properties.
• R 14 in general formula (4) is a linear saturated trivalent hydrocarbon group having 1 to 8 carbon atoms, a linear unsaturated trivalent hydrocarbon group having 2 to 8 carbon atoms, a branched saturated or unsaturated trivalent hydrocarbon group having 3 to 8 carbon atoms, an alicyclic saturated or unsaturated trivalent hydrocarbon group having 3 to 8 carbon atoms, a trivalent aromatic hydrocarbon group having 6 to 8 carbon atoms, or a trivalent organic group in which any one or more of the carbon atoms or hydrogen atoms of these hydrocarbon groups has been substituted with an oxygen atom, a nitrogen atom, a sulfur atom, a hydroxyl group, a thiol group, or an amine group.
• R 14 is preferably a linear saturated trivalent hydrocarbon group having 1 to 8 carbon atoms, a linear unsaturated trivalent hydrocarbon group having 2 to 8 carbon atoms, a branched saturated or unsaturated trivalent hydrocarbon group having 3 to 8 carbon atoms, or an alicyclic saturated or unsaturated trivalent hydrocarbon group having 3 to 8 carbon atoms, and more preferably a linear saturated trivalent hydrocarbon group having 2 to 4 carbon atoms or a branched saturated trivalent hydrocarbon group having 3 to 4 carbon atoms.
• R 15 represents a linear saturated divalent hydrocarbon group having 1 to 18 carbon atoms, a linear unsaturated divalent hydrocarbon group having 2 to 18 carbon atoms, a branched saturated or unsaturated divalent hydrocarbon group having 3 to 18 carbon atoms, an alicyclic saturated or unsaturated divalent hydrocarbon group having 3 to 8 carbon atoms, a divalent aromatic hydrocarbon group having 6 to 8 carbon atoms, or a divalent organic group in which any one or more of the carbon atoms or hydrogen atoms of these hydrocarbon groups have been substituted with an oxygen atom, a nitrogen atom, a sulfur atom, a hydroxyl group, a thiol group, or an amine group.
• R 15 is preferably an alkylene group having 1 to 18 carbon atoms.
• the benzoylformamide group is amphiphilic, and the polarity of A1 can be adjusted according to the purpose, so that D has high compatibility with other components used in the curable composition, and the obtained curable composition and the cured product obtained by curing it have high transparency.
• A1 is preferably an ether group, a thioether group, an ester group, a carbonate group, a urethane group, a thiourethane group, a urea group, a siloxane group, an amide group, or an imide group, since the polarity can be easily adjusted.
• A1 is an ether group, a thioether group, an ester group, a carbonate group, or a urethane group
• the number of these groups can be easily adjusted, and the polarity of A1 can be more easily adjusted, which is preferable.
• B4 and B5 may each independently have an ethylenically unsaturated group, an ether group, a thioether group, an ester group, a carbonate group, a urethane group, a thiourethane group, an isocyanurate group, an allophanate group, a urea group, a siloxane group, an amide group or an imide group, and either or both of B4 and B5 are monovalent organic groups containing one or more ethylenically unsaturated bonds.
• the benzoylformamide derivative (D) represented by the general formula (4) can also be used as a photosensitizer for photoionic polymerization.
• B4 and/or B5 have a cyclic ether group, since D is incorporated into the cured product via a covalent bond by photoionic polymerization. It may have one cyclic ether group or two or more cyclic ether groups.
• the benzoylformamide derivative (D) is incorporated into the cured product via a covalent bond by photoradical polymerization. From the viewpoint of being more easily incorporated into the cured product, it is preferable that both B4 and B5 have an ethylenically unsaturated group.
• the ethylenically unsaturated group may be of one type alone or of multiple types.
• the polarity of B4 and B5 can be adjusted according to the purpose.
• B4 and B5 have an ether group, a thioether group, an ester group, a carbonate group, a urethane group, a thiourethane group, a urea group, a siloxane group, an amide group, or an imide group
• it is preferable that the polarity of B4 and B5 is easily adjusted.
• B4 and B5 are an ether group, a thioether group, an ester group, a carbonate group, or a urethane group
• the number of these groups can be easily adjusted, and the polarity of B4 and B5 can be more easily adjusted.
• n is an integer from 1 to 100.
• the benzoylformamide derivative (D) has one or more benzoylformamide groups and can function both as a photopolymerization initiator and a photosensitizer.
• n is 2 or more, it is preferable because it has high photopolymerization initiation and photosensitization properties.
• n exceeds 100, it is not preferable because the molecular weight and viscosity of D are high and the handleability of the curable composition containing D may decrease. From these viewpoints, it is more preferable that n is an integer from 2 to 50, and particularly preferable that n is an integer from 2 to 20.
• General formula (4) can be produced by synthesizing benzoylformic acid amide diol through an amidation reaction between benzoylformic acid and an aminoalkyl alcohol, and then further carrying out a urethane reaction with an isocyanate compound.
• aminoalkyl diols examples include 2-aminoethylene glycol, 2-amino-1,3-propanediol, 3-amino-1,2-propanediol, 2-amino-2-methyl-1,3-propanediol, 2-amino-2-ethyl-1,3-propanediol, 2-amino-2-butyl-1,3-propanediol, 2-amino-2-hexyl-1,3-propanediol, and 2-amino-2-octyl-1,3-propanediol.
• 2-amino-2-dodecyl-1,3-propanediol, 2-amino-2-octadecyl-1,3-propanediol, 2-amino-1,4-butanediol, and 2-amino-1,6-hexanediol are preferred, and 2-amino-1,3-propanediol, 3-amino-1,2-propanediol, 2-amino-2-methyl-1,3-propanediol, and 2-amino-2-ethyl-1,3-propanediol are more preferred.
• Benzoyl formic acid amide derivative (D) is a hydrogen abstraction type photopolymerization initiator, and does not generate decomposition products during photopolymerization. Benzoyl formic acid amide derivative (D) does not generate decomposition products during photopolymerization even when used as a photosensitizer.
• the molecular weight of D is preferably 300 or more, more preferably 500 or more, and particularly preferably 1,000 or more. If the molecular weight of D is 300 or more, the volatility of D is low, the odor of the resulting cured product is low, and D is less likely to bleed out from the cured product.
• a higher molecular weight of D is preferable because it is safer, but if it exceeds 200,000, the viscosity of D and the viscosity of the curable composition containing it may become significantly high, and the handleability decreases. From these viewpoints, the molecular weight of D is preferably 200,000 or less, more preferably 150,000 or less, and particularly preferably 100,000 or less. In the present invention, a compound having a molecular weight of less than 300 is called a low molecular weight component.
• low molecular weight components are highly volatile and have low safety, so if low molecular weight components are present in the cured product, they will bleed out from the cured product over time, causing problems such as a deterioration in the appearance of the cured product and the generation of odors.
• Benzoyl formic acid amide derivative (D) can be synthesized by the following method. Benzoyl formic acid or benzoyl formic acid ester (hereinafter collectively referred to as raw material (a1)) and amine compound (hereinafter also referred to as amino group-containing compound, raw material (a2)) are subjected to an amidation reaction to obtain benzoyl formic acid amide derivative (D) represented by general formula (2).
• Raw material (a2) can have multiple amino groups, or in addition to amino groups, hydroxyl groups, carboxyl groups, urethane groups, urea groups, and amide groups. It is preferable that a2 has a reactive group such as a hydroxyl group, amino group, or carboxyl group.
• these reactive groups can be used to further react with various compounds. It is more preferable that the reactive group of a2 is a hydroxyl group.
• the hydroxyl group can be used to easily carry out etherification reaction, esterification reaction, and urethanization reaction.
• a compound having an ethylenically unsaturated group, a hydroxyl group, an amino group, a carboxyl group, an isocyanate group, or the like can be used as a raw material to synthesize a benzoylformamide derivative (D) represented by general formula (3) or general formula (4).
• Benzoylformic acid or benzoylformic acid ester (a1) includes benzoylformic acid, benzoylformic acid alkyl ester (straight-chain alkyl group having 1 to 18 carbon atoms, branched alkyl group having 3 to 18 carbon atoms, cyclic alkyl group having 3 to 18 carbon atoms), and benzoylformic acid alkenyl ester (straight-chain alkenyl group having 2 to 18 carbon atoms, branched alkenyl group having 3 to 18 carbon atoms, cyclic alkenyl group having 3 to 18 carbon atoms).
• benzoylformic acid, benzoylformic acid alkyl ester, and benzoylformic acid alkenyl ester of a1 have the substituents shown in (chemical formula 2) to (chemical formula 8) bonded to any of the 2nd to 6th positions of the benzene ring.
• methyl benzoylformate ethyl benzoylformate, methyl 2-methylbenzoylformate, methyl 3-methylbenzoylformate, methyl 4-methylbenzoylformate, ethyl 4-methylbenzoylformate, methyl 4-ethylbenzoylformate, methyl 4-butylbenzoylformate, methyl 4-octylbenzoylformate, methyl 4-dodecylbenzoylformate, methyl 4-octadecylbenzoylformate, methyl 4-ethynylbenzoylformate, methyl 4-ethylbenzoylformate, methyl 2-methoxycarbonylbenzoylformate, methyl 3-methoxycarbonylbenzoylformate, methyl 4-methoxycarbonylbenzoylformate, methyl 3-ethoxycarbonylbenzoylformate, methyl 4-methoxycarbonylbenzoylformate,
• the amino group-containing compound (a2) is an amine compound such as an alkylamine, an alkenylamine, a dialkylamine, a dialkenylamine, an alkyl alkenylamine, or an arylamine, an aminoalkyl monool, an aminoalkyl diol, an aminoalkyl triol, an aminoalkyl tetraol, an aminoalkyl pentanol, an N-alkyl-aminoalkyl monool, an N-alkyl-aminoalkyl diol, an N-alkyl-aminoalkyl triol, an N-alkyl-aminoalkyl tetraol, an N-alkyl-aminoalkyl pentanol, an N,N-bis(hydroxyalkyl)amine, an N,N-bis(dihydroxyalkyl)amine, or a hydroxyalkyl diol.
• amine compounds having a hydroxyl group such as dialkylarylamine, amine compounds having a thiol group such as aminoalkylthiol and aminoalkenylthiol, amine compounds having an ether group such as (aminoalkoxy)alkanol, dialkylene glycol monoamine, trialkylene glycol monoamine, and polyalkylene glycol monoamine, amine compounds having multiple amino groups such as alkylenediamine, polyalkyleneimine, dialkylene glycol diamine, trialkylene glycol diamine, polyalkylene glycol diamine, and diaminoalkanol, and amine compounds having a carboxyl group such as amino acids and aminobenzoic acid.
• a hydroxyl group such as dialkylarylamine
• amine compounds having a thiol group such as aminoalkylthiol and aminoalkenylthiol
• amine compounds having an ether group such as (aminoalkoxy)alkanol
• the alkyl is a linear alkyl group having 1 to 18 carbon atoms, a branched alkyl group having 3 to 18 carbon atoms, or a cyclic alkyl group having 3 to 18 carbon atoms
• the alkenyl is a linear alkylene group having 2 to 18 carbon atoms, a branched alkylene group having 3 to 18 carbon atoms, or a cyclic alkylene group having 3 to 18 carbon atoms.
• the amino group-containing compound (a2) has a hydroxyl group, a carboxyl group, a thiol group, or multiple amino groups
• a benzoylformamide derivative (D) having a hydroxyl group, a carboxyl group, a thiol group, or an amino group.
• D can be further urethane-, thiourethane-, ether-, ester-, urea-, amid-, or imid-ized by utilizing these reactive groups.
• Urethane-ization is the reaction of a hydroxyl group with an isocyanate group
• thiourethane-ization is the reaction of a thiol group with an isocyanate group
• ether-ization is the reaction of a hydroxyl group with an organic halogen
• ester-ization is the reaction of a hydroxyl group with a carboxyl group or a carboxyl group with an epoxy group
• urea-ization is the reaction of an amino group with an isocyanate group
• amidation is the reaction of an amino group with a carboxyl group or a carboxyl group with an isocyanate group
• imidization is the reaction of an amino group with a carboxylic anhydride group.
• the amidation reaction of benzoylformic acid or benzoylformate (a1) with the amino group-containing compound (a2) is preferably carried out under light-shielded conditions. Specifically, it may be carried out in a light-shielded environment where ultraviolet rays are cut, such as in a yellow room, under fluorescent lights that do not irradiate ultraviolet rays, or under a red darkroom safelight.
• the reaction can proceed under mild conditions at normal pressure and below 100°C.
• the reaction may be carried out using a solvent (c).
• Examples of the solvent (c) include general-purpose solvents such as toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, tetrahydrofuran, 1,4-dioxane, chloroform, 1,2-dichloroethane, ethyl acetate, butyl acetate, N,N'-dimethylformamide, 3-methoxy-N,N'-dimethylpropionamide, 3-butoxy-N,N'-dimethylpropionamide, N,N'-dimethylpropionamide, dimethylacetamide, dimethylsulfoxide, 2-pyrrolidone, N-methyl-2-pyrrolidone, and 1,3-dimethyl-2-imidazolidinone.
• general-purpose solvents such as toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl
• a polymerizable compound (radical, cationic, or anionic polymerization by light or heat) that is liquid at the reaction temperature and does not react with the raw materials and products can also be used as the solvent (c).
• examples of polymerizable compound solvents include N-(meth)acroylmorpholine, (meth)acrylic acid esters having a linear alkyl group or alkoxy group with 1 to 18 carbon atoms, a branched or cyclic alkyl group or alkoxy group with 3 to 18 carbon atoms, N-substituted (meth)acrylamide, and N,N-disubstituted (meth)acrylamide.
• the alcohol and c can react while still containing the alcohol and c, or it can react after removing the alcohol and c.
• Methods for removing the alcohol and c include distillation at normal or reduced pressure, bubbling with dry air or an inert gas such as nitrogen, and freeze-drying.
• Benzoylformamide derivative (D) having a hydroxyl group can introduce a urethane group into the molecule of D by reacting with an isocyanate compound.
• D can introduce an ethylenically unsaturated group by reacting with an isocyanate compound having an ethylenically unsaturated group.
• D can introduce a urethane group and an ethylenically unsaturated group by reacting with a polyisocyanate compound or a compound having an ethylenically unsaturated group and a hydroxyl group.
• D can also react with a polyol via a polyisocyanate.
• D can introduce a cyclic ether group into D by reacting with a polyisocyanate or a compound having a cyclic ether group and a hydroxyl group.
• D having an ethylenically unsaturated group and/or a cyclic ether group is used as a photopolymerization initiator or a photosensitizer in a curable composition
• D is incorporated into the cured product of photoradical polymerization and/or photoionic polymerization via a chemical bond. In this case, even if the molecular weight of D is less than 300, there is no bleeding from the cured product, and D is suitable for use in various applications as both a photopolymerization initiator and a photosensitizer.
• the ethylenically unsaturated group of the benzoyl formic acid amide derivative (D) is one or more groups selected from the group consisting of (meth)acrylate, (meth)acrylamide, vinyl, vinyl ether, alkyl vinyl ether, allyl, (meth)allyl ether, styryl, and maleimide.
• (meth)acrylate and (meth)acrylamide groups are preferred, from the viewpoint of high active energy ray curability, acrylate and acrylamide groups are more preferred, and from the viewpoint of being able to form intramolecular and intermolecular hydrogen bonds in addition to covalent bonds, acrylamide groups are particularly preferred.
• N-monosubstituted acrylamide groups are most preferred from the viewpoint of being a hydrogen donor.
• acrylate and N,N-disubstituted acrylamide groups are most preferred from the viewpoint of low viscosity of D and curable compositions containing D.
• Compounds used in the reaction with the benzoylformamide derivative (D) having a hydroxyl group include an isocyanate compound (b1), a compound (b2) having a hydroxyl group, a compound (b3) having a group reactive with an ethylenically unsaturated group, and a compound (b4) having a group reactive with a cyclic ether group.
• the reactive groups of b3 and b4 include hydroxyl groups, acid halides, halogens, isocyanate groups, acid anhydride groups, and epoxy groups.
• b1 includes general-purpose polyisocyanates, polyisocyanates having a polyol skeleton, and polyisocyanates having an isocyanurate ring.
• Isocyanate compound (b1) is a compound having two or more isocyanate groups in the molecule.
• aliphatic polyisocyanates such as trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, etc.
• isocyanate examples include aromatic polyisocyanates such as 2,4-diphenylmethane diisocyanate, 1,3-xylylene diisocyanate, and 1,4-xylylene diisocyanate, cyclopentylene diisocyanate, cyclohexylene diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 1,3-hydrogenated xylylene diisocyanate, 1,4-hydrogenated xylylene diisocyanate, 2,5-norbornane diisocyanate, and 2,6-norbornane diisocyanate, as well as multimers such as adducts, isocyanurates, and biuret forms of these polyisocyanates. These b1s may be used alone or in combination.
• the compound (b2) having a hydroxyl group is an alcohol or a polyol.
• alcohols include monoalcohols using linear alkyl groups having 1 to 18 carbon atoms, such as methanol, ethanol, isopropanol, octanol, and isostearyl alcohol, and branched or cyclic alkyl groups having 3 to 18 carbon atoms; linear alkylene glycols having 2 to 18 carbon atoms, such as ethylene glycol and 1,2-propylene glycol, branched alkylene glycols having 3 to 18 carbon atoms, and cyclic alkylene glycols having 3 to 18 carbon atoms; and polyhydric alcohols such as glycerin, trimethylolpropane, pentaerythritol, and dipentaerythritol.
• the polyols of b2 include polyether polyols, polyester polyols, polycarbonate polyols, carbinol-modified silicones, polyolefin polyols, etc.
• the polyether polyols include linear polyalkylene glycols having 2 to 18 carbon atoms, branched polyalkylene glycols having 3 to 18 carbon atoms, and cyclic polyalkylene glycols having 3 to 18 carbon atoms
• the polyolefin polyols include hydrogenated polyalkadiene polyols and polyalkadiene polyols. These b2s may be used alone or in combination.
• examples of b3 include (meth)acrylic acid chloride, (meth)acrylic acid anhydride, maleic anhydride, itaconic anhydride, etc.
• examples of b3 include (meth)acrylic acid glycidyl ether, 4-hydroxybutyl (meth)acrylate glycidyl ether, etc.
• examples of b3 include 2-(meth)acryloyloxyethyl isocyanate, etc.
• b3 is a hydroxyalkyl (meth)acrylate, N-hydroxyalkyl (meth)acrylamide, N-alkyl-N-hydroxyalkyl (meth)acrylamide, hydroxyalkyl (meth)vinyl ether, hydroxyalkyl (meth)allyl ether, hydroxyalkylmaleimide, hydroxyalkylstyrene, polyalkylene glycol mono(meth)acrylate, N-polyalkylene glycol mono(meth)acrylamide, N-alkyl-N-polyalkylene glycol mono(meth)acrylamide, N,N-bis(polyalkylene glycol) (meth)acrylamide, polyalkylene glycol mono(meth)vinyl ether, polyalkylene Glycol mono(meth)allyl ether, polyalkylene glycol monomaleimide, hydroxyphenyl(meth)acrylate, hydroxyphenyl(meth)acrylamide, hydroxyphenyl(meth)acrylamide
• the alkyl is a linear alkyl group having 1 to 18 carbon atoms, a branched alkyl group having 3 to 18 carbon atoms, or a cyclic alkyl group having 3 to 18 carbon atoms
• the alkylene is an alkylene group having 1 to 9 carbon atoms
• the alkenyl is a linear alkenyl group having 2 to 18 carbon atoms, a branched alkenyl group having 3 to 18 carbon atoms, or a cyclic alkenyl group having 3 to 18 carbon atoms.
• b4 can be epichlorohydrin.
• the reactive group is a hydroxyl group, b4 is not particularly limited as long as it is a compound having one or more cyclic ether groups and one or more hydroxyl groups.
• hydroxyalkyl glycidyl ethers and hydroxyalkyl epoxides having a linear alkyl group with 1 to 18 carbon atoms, a branched alkyl group with 3 to 18 carbon atoms, or a cyclic alkyl group with 3 to 18 carbon atoms, and 7-oxabicyclo[4.1.0]heptane-3-methanol as a compound containing an alicyclic epoxy and a hydroxyl group can be mentioned.
• These b4s can be used alone or in combination.
• the method of introducing urethane groups is not particularly limited as long as it is a known method.
• the reaction temperature is preferably within the range of room temperature to 90°C.
• a solvent (c), a urethanization catalyst, or other additives may be used.
• a polymerizable compound can be used as a solvent instead of c.
• polymerizable compound solvents examples include N-(meth)acryloylmorpholine, alkyl(meth)acrylic acid esters, alkenyl(meth)acrylic acid esters, aryl(meth)acrylic acid esters, alkylene di(meth)acrylic acid esters, dialkylene glycol di(meth)acrylic acid esters, trialkylene glycol di(meth)acrylic acid esters, polyalkylene glycol di(meth)acrylic acid esters, N-substituted (meth)acrylamides, and N,N-disubstituted (meth)acrylamides.
• the alkyl group is a linear alkyl group having 1 to 18 carbon atoms, a branched alkyl group having 3 to 18 carbon atoms, and a cyclic alkyl group having 3 to 18 carbon atoms
• the alkenyl group is a linear alkenyl group having 2 to 18 carbon atoms
• the aryl group is an aryl group having 6 to 8 carbon atoms.
• the urethanization reaction is preferably carried out in a light-blocking environment. Specifically, the reaction can be carried out in a light-blocking environment, such as a yellow room where ultraviolet rays are blocked, under fluorescent lights that do not irradiate ultraviolet rays, or under a red darkroom safelight.
• a crude product D containing the solvent (c) or the polymerizable compound used in place of c is obtained, and the crude product can be used as is in the curable composition, or after removing c or the polymerizable compound, it can be used in the curable composition.
• Methods for removing c include distillation under normal or reduced pressure, bubbling with dry air, inert gas such as nitrogen, and freeze-drying.
• Reaction catalysts used in the urethanization reaction include quaternary ammonium salts, tertiary phosphine derivatives, tertiary amine derivatives, and organometallic compounds.
• quaternary ammonium salts include tetrabutylammonium bromide, triethylbenzylammonium chloride, tetrabutylphosphonium bromide, and tetraphenylphosphonium bromide.
• tertiary phosphines examples include triarylphosphines such as triphenylphosphine, tribenzylphosphine, and tritolylphosphine, tricycloalkylphosphines such as tricyclohexylphosphine, and trialkylphosphines such as triethylphosphine, tripropylphosphine, tributylphosphine, and trioctylphosphine.
• tertiary amines examples include trialkylamines such as triethylamine and tributylamine, dialkylarylamines such as dimethylbenzylamine and diethylbenzylamine, and triethanolamine.
• organometallic compound examples 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, dibutyltin dilaurate, dioctyltin dilaurate, tin 2-ethylhexanoate, dibutyltin diacetylacetonate, zirconium tetraacetylacetonate, titanium acetylacetonate, acetylacetone aluminum, acetylacetone cobalt, acetylacetone iron, acetylacetone copper, and acetylacetone zinc metal chelate compounds, potassium or sodium salts of alkylphosphonic acid, and sodium or potassium salts of fatty acids having 8 to 20 carbon atoms.
• metal salts of metals such as zinc, tin, lead, zirconium, bismuth, cobalt, manganes
• quaternary ammonium salts tertiary phosphine derivatives, and tin-, bismuth-, zirconium-, and iron-based organometallic compounds having a high catalytic effect are more preferred.
• the amount of the urethane reaction catalyst used is preferably 0.001 to 10% by mass based on the total mass of each raw material. If it is 0.001% by mass or more, the reaction can proceed quickly. If it is 10% by mass or less, coloring due to the catalyst is low. It is even more preferable that it is 0.01 to 1.00% by mass.
• the benzoyl formic acid amide derivative (D) of the present disclosure generates radicals, which are active species that grow, when exposed to active energy rays.
• active energy rays include light energy rays such as visible light, electron beams, ultraviolet rays, infrared rays, X-rays, alpha rays, beta rays, and gamma rays.
• ultraviolet rays are preferably used in terms of the balance between the active energy ray generator, the photopolymerization initiation rate, and safety.
• Examples of ultraviolet light sources include xenon lamps, low-pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, UV-LED lamps, and microwave excimer lamps.
• UV-LED lamps that can irradiate highly safe ultraviolet rays of 360 to 420 nm at high output are preferred. Also, LED lamps that can irradiate rays of 365 nm, 385 nm, 395 nm, and 405 nm are preferably used.
• the irradiation energy required for generating radicals from the benzoylformamide derivative (D) of the present disclosure can be expressed as an integrated light dose.
• the integrated light dose is preferably within the range of 5 to 50,000 mJ/ cm2 , and more preferably within the range of 10 to 20,000 mJ/ cm2 . If the irradiation energy is within this range, a sufficient number of growing active species can be generated from the photopolymerization initiator.
• the benzoyl formic acid amide derivative (D) of the present disclosure can be contained in an active energy ray curable composition as a photopolymerization initiator and used for various applications.
• the content of D in the curable composition varies depending on the structure of D and the composition of the curable composition, but is preferably 0.1 mass% or more.
• D is contained in an amount of 0.1 mass% or more, photopolymerization can be immediately initiated by irradiation with active energy rays, and the curable composition can be sufficiently cured.
• D does not contain an ethylenically unsaturated group
• the content of D in the curable composition varies depending on the structure and molecular weight of D, but is preferably 50 mass% or less.
• the content of D is more preferably 0.5 to 20 mass% and particularly preferably 1 to 10 mass% relative to the entire curable composition.
• D contains an ethylenically unsaturated group
• D can be contained in 100 mass% because D alone can form a cured product.
• D can be used in combination with another polymerizable compound (h), such as a compound having one ethylenically unsaturated group in the molecule (hereinafter referred to as a monofunctional unsaturated compound (h1)) and/or a compound having two or more ethylenically unsaturated groups in the molecule (hereinafter referred to as a polyfunctional unsaturated compound (h2)).
• a monofunctional unsaturated compound (h1)) and/or a compound having two or more ethylenically unsaturated groups in the molecule
• h2 a compound having two or more ethylenically unsaturated groups in the molecule
• the content of D in the entire curable composition is more preferably 0.5 to 90 mass%, and particularly preferably 1 to 70 mass%.
• the benzoylformamide derivative (D) of the present disclosure can be contained in the active energy ray curable composition as a photosensitizer.
• the content of D in the curable composition varies depending on the structure of D and the composition of the curable composition, but is preferably 0.1 mass% or more.
• D is contained at 0.1 mass% or more, D is excited by irradiation with active energy rays, activating the photopolymerization initiator in the curable composition, so that photopolymerization can be immediately initiated and the curable composition can be sufficiently cured.
• D exhibits photosensitivity to both photoradical polymerization initiators and photoionic polymerization initiators (photocationic polymerization or photoanionic polymerization), and can be used in combination with these photopolymerization initiators.
• D does not contain an ethylenically unsaturated group or a cyclic ether group
• the content of D in the curable composition varies depending on the structure and molecular weight of D, but is preferably 30 mass% or less.
• the content of D is more preferably 0.5 to 20 mass% and particularly preferably 1 to 10 mass% based on the entire curable composition.
• D contains an ethylenically unsaturated group and/or a cyclic ether group
• D alone can form a cured product, so D can be contained in an amount of 100 mass%.
• D can be used in combination with a compound having a cyclic ether group in the molecule (hereinafter referred to as a cyclic ether-containing compound (h3)) as another polymerizable compound (h).
• a compound having a cyclic ether group in the molecule hereinafter referred to as a cyclic ether-containing compound (h3)
• the content of D is more preferably 0.5 to 90 mass% and particularly preferably 1 to 70 mass% based on the entire curable composition.
• the benzoylformamide derivative (D) of the present disclosure can be used alone as a photopolymerization initiator or a photosensitizer, and Ds having different structures can be appropriately combined as a photopolymerization initiator or a photosensitizer.
• the total content of D in the curable composition is 0.5 to 80 mass%, preferably 1 to 75 mass%, more preferably 2 to 50 mass%, and particularly preferably 3 to 30 mass%.
• the polymerizable compound (h) includes a monofunctional unsaturated compound (h1) other than D, a polyfunctional unsaturated compound (h2), and a cyclic ether-containing compound (h3).
• the content of h is 0 to 99.9 mass% based on the total curable composition. From the viewpoint of being able to suitably adjust the physical properties of the cured product, the content of h is preferably 10 to 99.5 mass%, and more preferably 30 to 99 mass%.
• Examples of the monofunctional unsaturated compound (h1) include compounds containing a (meth)acrylate group, a (meth)acrylamide group, a vinyl group, an allyl group, a styryl group, and an acetylene group. These groups may be used alone or in combination of two or more types.
• the content of h1 is preferably 0 to 90 mass% of the entire curable composition, more preferably 5 to 70 mass%, and particularly preferably 10 to 50 mass%.
• h1 usually has a low viscosity, and by containing it, it is expected to have the effect of lowering the viscosity of the curable composition and improving the handleability.
• Monofunctional unsaturated compounds (h1) containing a (meth)acrylate group include alkyl (meth)acrylates, hydroxyalkyl (meth)acrylates, (meth)acrylic acid alkyl carboxylic acids, (meth)acrylic acid alkyl sulfonic acids, (meth)acrylic acid alkyl phosphoric acids, alkyloxy (hereinafter also referred to as alkoxy) alkylene glycol (meth)acrylates, alkoxy dialkylene glycol (meth)acrylates, alkoxy trialkylene glycol (meth)acrylates, alkoxy polyalkylene glycol (meth)acrylates, phenoxy alkylene glycol (meth)acrylates, phenoxy dialkylene glycol (meth)acrylates, phenoxy trialkylene glycol (meth)acrylates, phenoxy polyalkylene glycol (meth)acrylates, Examples of the aryloxyethyl (meth)acrylate include (meth)acrylates having a
• the alkyl group is a linear alkyl group having 1 to 18 carbon atoms, a branched alkyl group having 3 to 18 carbon atoms, or a cyclic alkyl group having 3 to 18 carbon atoms, and the alkylene group is an alkylene group having 1 to 4 carbon atoms.
• Examples of monofunctional unsaturated compounds (h1) containing a (meth)acrylamide group include (meth)acrylamide, mono- or di-substituted (meth)acrylamide, N-(meth)acroylmorpholine, diacetone (meth)acrylamide, etc.
• examples of mono- or di-substituted (meth)acrylamides include N-alkyl(meth)acrylamide, N,N-dialkyl(meth)acrylamide, N-hydroxyalkyl(meth)acrylamide, N,N-di(hydroxyalkyl)(meth)acrylamide, N-hydroxyalkyl-N-(4-hydroxyphenyl)(meth)acrylamide, N-alkyl-N-hydroxyalkyl(meth)acrylamide, N-alkyl-N-(4-hydroxyphenyl)(meth)acrylamide, 4-hydroxyphenyl(meth)acrylamide, N,N-di(4-hydroxyphenyl)(meth)acrylamide, N-alkoxyalkyl(meth)acrylamide, N,N-di(alkoxyalkyl)(meth)acrylamide, N-alkyl-N-alkoxyalkyl(meth)acrylamide, N-sulfoalkylacrylamide, N-alkylamin
• Examples of the monofunctional unsaturated compound (h1) containing a vinyl group include vinyl carboxylates having a carboxyl group with 1 to 18 carbon atoms, alkyl vinyl ethers, vinyl chloride, N-vinylpyrrolidone, N-vinylcaprolactam, N-vinyloxazoline, maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, maleic acid monoalkyl esters, maleic acid dialkyl esters, maleic acid monoalkyl amides, maleic acid dialkyl amides, maleic acid alkyl imides, fumaric acid monoalkyl esters, fumaric acid dialkyl esters, fumaric acid monoalkyl amides, fumaric acid dialkyl amides, itaconic acid monoalkyl esters, itaconic acid dialkyl esters, itaconic acid monoalkyl amides, itaconic acid dialkyl amides, itac
• the monofunctional unsaturated compound (h1) containing an allyl group includes carboxylic acid allyl esters having a carboxyl group with 1 to 18 carbon atoms, alkyl allyl ethers, phenyl allyl ethers, alkyl phenyl allyl ethers, allylamines, mono- or dialkyl allylamines, etc.
• the alkyl is a linear alkyl group with 1 to 18 carbon atoms, a branched alkyl group with 3 to 18 carbon atoms, or a cyclic alkyl group with 3 to 18 carbon atoms.
• Examples of monofunctional unsaturated compounds (h1) containing styryl groups include styrene, ⁇ -alkylstyrene, ⁇ -methylstyrene dimer, o-alkylstyrene, m-alkylstyrene, p-alkylstyrene, and p-styrenesulfonic acid.
• the alkyl group is a linear alkyl group having 1 to 18 carbon atoms, a branched alkyl group having 3 to 18 carbon atoms, or a cyclic alkyl group having 3 to 18 carbon atoms.
• the polyfunctional unsaturated compound (h2) may be a compound containing two or more unsaturated groups such as a (meth)acrylate group, a (meth)acrylamide group, a vinyl group, an allyl group, a styrene group, or an acetylene group.
• the compound may contain one type of unsaturated group alone, or may contain two or more types in combination.
• it is more preferable that the unsaturated group contains one or more (meth)acrylate groups or (meth)acrylamide groups.
• the content of h2 is preferably 0 to 99% by mass, more preferably 1 to 70% by mass, and particularly preferably 5 to 50% by mass, based on the total curable composition. By containing h2, the strength and hardness of the cured product obtained are high, and excellent durability can be expected.
• Polyfunctional unsaturated compounds (h2) include allyl(meth)acrylate, allyloxyalkoxy(meth)acrylate, allyl(meth)acrylamide, allyloxyalkoxy(meth)acrylamide, vinyloxyalkoxy(meth)acrylate, diallylamine, alkyl diallylamine, dialkyl diallyl ammonium quaternary salt, alkylene glycol di(meth)acrylates, polyalkylene glycol di(meth)acrylates, bisphenol A diglycidyl ether (meth)acrylic acid adducts, alkoxylated bisphenol A di(meth)acrylates, polyester di(meth)acrylates, polycarbonate di(meth)acrylates, polyurethane di(meth)acrylates, polyurethane di(meth)acrylamides, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, trimethylolpropane tri
• the alkyl group is a linear alkyl group having 1 to 18 carbon atoms, a branched alkyl group having 3 to 18 carbon atoms, or a cyclic alkyl group having 3 to 18 carbon atoms, and the alkylene group is an alkylene group having 1 to 4 carbon atoms.
• the number average molecular weight of the polyfunctional unsaturated compound (h2) is preferably 100 to 50,000.
• the molecular weight is 100 or more, the resulting cured product has low cure shrinkage, which is preferable.
• the molecular weight is 50,000 or less, the viscosity of the curable composition is low, which is preferable because it has excellent handleability. From these perspectives, it is more preferable that the molecular weight of h2 is 200 to 20,000, and particularly preferably 300 to 15,000.
• Cyclic ether-containing compound (h3) is a compound having one or more cyclic ether groups in the molecule, and the cyclic ether groups of h3 include epoxy groups, glycidyl groups, and oxetane groups. When multiple cyclic ether groups are contained, only one type may be contained, or two or more types may be contained in combination.
• Examples of compounds having one cyclic ether group in h3 include alkyl glycidyl ether, alkyl epoxide, aryl glycidyl ether, epoxy cycloalkane, alkyl oxetane, glycidyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, and vinyl glycidyl ether.
• Examples of compounds having multiple cyclic ether groups in h3 include alkylene glycol diglycidyl ether, aryl diglycidyl ether, trimethylolpropane triglycidyl ether, (3,4-epoxycyclohexylmethyl) 3,4-epoxycyclohexane carboxylate, and alkylene bisoxetane.
• the alkyl is a linear alkyl group having 1 to 18 carbon atoms, a branched alkyl group having 3 to 18 carbon atoms, or a cyclic alkyl group having 3 to 18 carbon atoms
• the alkylene is a linear alkylene group having 1 to 18 carbon atoms, a branched alkylene group having 3 to 18 carbon atoms, or a cyclic alkylene group having 3 to 18 carbon atoms
• the aryl is an aryl group having 6 to 18 carbon atoms.
• the content of the cyclic ether-containing compound (h3) is preferably 0 to 99% by mass, more preferably 5 to 90% by mass, and particularly preferably 10 to 50% by mass, based on the total mass of the curable composition.
• h3 usually has a low viscosity, and by including it, it is expected to have the effect of lowering the viscosity of the curable composition and improving its handleability.
• the benzoyl formic acid amide derivative (D) disclosed herein has high photopolymerization initiation properties in photoradical polymerization and can be suitably used as a photopolymerization initiator for various applications. When even higher photopolymerization initiation properties are required, D can be used in combination with other photopolymerization initiators.
• the photopolymerization initiators that can be used in combination are not particularly limited, and examples thereof include benzoins such as benzoin and benzoin alkyl ethers, acetophenones such as 2-hydroxy-2-methyl-1-phenylpropan-1-one, acylphosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide, benzoyl formate esters such as methyl benzoylformate, aminoacetophenones such as 2-methyl-2-morpholino(4-thiomethylphenyl)propan-1-one, and oxime esters such as 1-(9,9-dimethyl-9H-fluoren-2-yl)-1,2-propanedione 2-(O-acetoxime).
• the photopolymerization initiator used in combination with D can be used in any ratio as necessary, and one type may be used alone or multiple types may be used in combination.
• Benzoylformamide derivatives (D) can be used in a hybrid polymerization system of photoradical polymerization and thermal radical polymerization.
• thermal polymerization initiators include ketone peroxides such as methyl ethyl ketone peroxide, peroxyketals such as 1,1-di(t-hexylperoxy)-3,3,5-trimethylcyclohexane, 1,1-di(t-hexylperoxy)cyclohexane, and 1.1-di(t-butylperoxy)cyclohexane, hydroperoxides such as 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, and p-menthane hydroperoxide, dialkyl peroxides such as dicumyl peroxide and di-t-butyl peroxide, diacyl peroxides such as dilauroyl
• the initiator examples include peroxy esters such as t-butylperoxy-2-ethylhexanoate, t-hexylperoxyisopropyl monocarbonate, t-butylperoxybenzoate, and 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate; azo initiators such as bis(1-phenyl-1-methylethyl)peroxide, 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(isobutyric acid)dimethyl, and 1,1'-azobis(cyclohexane-1-carbonitrile); and polymeric azo polymerization initiators such as a polydimethylsiloxane unit-containing polymeric azo polymerization initiator (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd., VPS-1001N) and a polyethylene glycol unit-containing polymeric
• the benzoyl formic acid amide derivative (D) has sufficient photosensitizing effect for photoradical polymerization and can be suitably used for various applications as a photosensitizer for photoradical polymerization. If further photosensitizing effect is required, it can be used in combination with other photosensitizers.
• Photosensitizers that can be used in combination with D are not particularly limited, and examples include benzophenones, unsaturated ketones represented by anthracene derivatives, 1,2-diketone derivatives represented by benzil and camphorquinone, benzoin derivatives, anthraquinone derivatives, thioxanthone derivatives, coumarin derivatives, thiols, disulfides, etc. These photosensitizers can be used in combination with D in any ratio as necessary, and one type may be used alone or multiple types may be used.
• the benzoyl formate amide derivative (D) can be suitably used as a photosensitizer for photoionic polymerization in various applications.
• the photoionic polymerization initiator is not particularly limited, and examples include photoanionic polymerization initiators such as 2-(9-oxoxanthen-2-yl)propionic acid, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, and 1,2-dicyclohexyl-4,4,5,5-tetramethylbiguanidium, N-butyltriphenylborate, and photocationic polymerization initiators of antimony and triarylsulfonium salt types.
• the polymerization initiator of each polymerization system may be used alone or in combination.
• the benzoylformamide derivative (D) has sufficient photosensitizing effect for photoionic polymerization and can be used alone as a photosensitizer for photoionic polymerization. If a further photosensitizing effect is required, it can be used in combination with other photosensitizers for photoionic polymerization.
• the photoionic polymerization initiators that can be used in combination with D, and any photosensitizer that can be used for photoradical polymerization can be suitably used as a photosensitizer for photoionic polymerization.
• other photosensitizers can be used in combination with D in any ratio as necessary, and one type can be used alone or multiple types can be used.
• the curable composition may further contain an organic solvent and water depending on the method and purpose of use of the curable composition and the resulting cured product.
• the organic solvent and water may be removed beforehand before carrying out the polymerization reaction (curing), or the polymerization reaction may be carried out while still containing the organic solvent and water, and the organic solvent and water may be removed after curing.
• the content of the organic solvent and water is preferably 80 mass% or less, and more preferably 50 mass% or less, of the entire curable composition.
• the organic solvents used in the curable composition include alcohols such as methanol, ethanol, isopropanol, etc.; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.; esters such as ethyl acetate, propyl acetate, butyl acetate, methyl lactate, ethyl lactate, etc.; alkylene glycols such as ethylene glycol, propylene glycol, etc.; polyalkylene glycols such as polyethylene glycol, polypropylene glycol, etc.; glycol ethers such as ethoxydiethylene glycol, methoxypropylene glycol, etc.; glycol esters such as propylene glycol acetate, tetrahydrofuran, methyltetrahydrofuran, cyclopentyl methyl ether, methyltetrahydrofuran ...
• alcohols such as
• organic solvent examples include ethers such as dropyrane and methyl-tert-butyl ether toluene, aromatic hydrocarbons such as xylene, aliphatic hydrocarbons such as hexane and cyclohexane, amides such as N,N'-dimethylformamide, dimethylacetamide, and N,N-dimethylpropionamide, 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.
• aromatic hydrocarbons such as
• the benzoyl formate derivative (D) disclosed herein is useful in a wide variety of applications, including UV flexographic ink, UV offset ink, UV screen ink, UV inkjet ink, active energy ray curable nail cosmetic composition (gel nail), UV curable pressure sensitive adhesive, UV curable adhesive, active energy ray curable sealant used in sealing material or sealant, active energy ray curable coating agent used in paint or coating agent for automobiles, electrical appliances, furniture, etc., active energy ray curable resin composition for decorative sheet used in decorative sheet used for surface coating of automobiles, electrical appliances, etc., coating agent having self-repairing properties, three-dimensional object, nail decoration material, automobile exterior protection, functional parts such as decorative film, resin composition for active energy ray curable self-repairing material used in devices, etc., transparent
• the active energy ray curable elastomer composition for elastomers used in adhesive sheets, cushioning materials, packing, vibration-proofing materials, sound-absorbing materials, printing plates, sealing materials, abrasives, etc., active energy
• the obtained hydrogel composition can also be suitably used as a material in a wide variety of fields such as the hygiene field such as superabsorbent resins, paper diapers, and soft contact lenses, the medical field such as artificial organs, the civil engineering and construction field such as soil conditioners, the agricultural field such as water-retaining materials, and shock absorbing materials.
• the hygiene field such as superabsorbent resins, paper diapers, and soft contact lenses
• the medical field such as artificial organs
• the civil engineering and construction field such as soil conditioners
• the agricultural field such as water-retaining materials, and shock absorbing materials.
• FT-IR analysis Fourier transform infrared spectroscopy
• FT-IR analysis was carried out using the following equipment.
• Nicolet iS50 Thermo Fisher Scientific
• LC-MS analysis Liquid chromatography-mass spectrometry
• the monofunctional unsaturated compound (h1), polyfunctional unsaturated compound (h2), cyclic ether-containing compound (h3), photopolymerization initiator (E), photosensitizer (I), thermal polymerization initiator (J), and other additives (k) used in the active energy ray-curable compositions of the Examples and Comparative Examples are shown below.
• Example 1 Synthesis of Benzoylformamide Derivative (D-1) 197.0g (1.20 mol) of methyl benzoylformate (a1-1), 317.5g (1.00 mol) of (2S,3S,4R)-2-amino-1,3,4-octadecanetriol (a2-1), 500g of toluene (c-1) as a solvent, and 1.0g (0.01 mol) of triethylamine (TEA) as a catalyst were added to a 1,000mL flask equipped with a reflux condenser, a stirrer, a thermometer, and a dropping funnel, and the mixture was heated to 70°C while stirring.
• TEA triethylamine
• Examples 2, 3, 5-20 Synthesis of benzoyl formic acid amide derivatives (D-2), (D-3), (D-5)-(D-20)
• the reaction was carried out under the same conditions as in Example 1 according to the raw materials and charge ratios shown in Tables 1-1 and 1-2, to obtain benzoyl formic acid amide derivatives (D-2), (D-3), (D-5)-(D-20).
• the identification of the obtained benzoyl formic acid amide (D) was similarly carried out by 1 H-NMR analysis and LC-MS analysis, and the representative proton chemical shift values, and the molecular weight and yield of the product are shown in Tables 1-1 and 1-2. From the results of 1 H-NMR and LC-MS analysis, it was confirmed that the products were the benzoyl formic acid amide derivatives (D-2), (D-3), (D-5)-(D-20) shown in Tables 1-1 and 1-2.
• Example 4 Synthesis of Benzoylformamide Derivative (D-4)
• the catalyst TEA in Example 1 was replaced with sodium methoxide, and 4-acetoxybenzoylmethylformate (a1-4) was reacted with dimethylamine and purified under the same conditions as in Example 1 to obtain a pale yellow solid, Benzoylformamide Derivative (D-4) (75% yield).
• D-4 was identified by 1 H-NMR and LC-MS analysis, and the analytical data and the chemical formula of D-4 are shown in Table 1-1.
• Example 21 Synthesis of Benzoylformamide Derivative (D-21) 243.1g (1.00 mol) of 4-bromobenzoylmethylformate (a1-12), 143.0g (1.20 mol) of 2-amino-2-ethyl-1,3-propanediol (a2-16), and 362g of Adeka polyether BPX-2000 (b2-8) were added instead of the solvent (c), and the reaction was carried out under the same conditions as in Example 1.
• Example 22 Synthesis of Benzoylformamide Derivative (D-22) 45.7g of the benzoylformamide derivative (D-2) synthesized in Example 2, 54.3g of 2-acryloyloxyethyl isocyanate (b3-1), and 50g of ethyl acetate (c-3) were added to a 300mL flask equipped with a reflux condenser, a stirrer, a thermometer, and a dropping funnel, and mixed. 0.02g of bismuth tris(2-ethylhexanate) was added as a catalyst to the mixture, and the mixture was reacted for 4 hours while stirring at 70°C.
• Table 2-1 shows the chemical formula, molecular weight, and number of benzoylformamide groups per molecule of D-22, the number of atoms directly linked between the nitrogen atom of the benzoylformamide group and the nitrogen atom of the nearest urethane group, and the ratio of the number of urethane groups to the number of benzoylformamide groups per molecule.
• Example 23 Synthesis of Benzoylformamide Derivative (D-23)
• 32.9 g of isophorone diisocyanate (b1-1) and 17.1 g of N-(2-hydroxyethyl)acrylamide (b3-2) were reacted in the presence of 0.01 g of catalyst dibutyltin dilaurate to obtain a pale yellow viscous solid product (yield 96%).
• FT-IR analysis of the product confirmed the presence of urethane groups and benzoylformamide groups (di-substituted) derived from D-3.
• Example 24 Synthesis of Benzoylformamide Derivative (D-24) 74.7 g of the benzoylformamide derivative (D-5) synthesized in Example 5 and 100 g of 1,2-dichloroethane (c-2) were added to a 300 mL flask equipped with a reflux condenser, a stirrer, a thermometer, and a dropping funnel, and mixed. The mixture was cooled to -10°C, and while maintaining the temperature at -10 to 0°C, 25.3 g of acrylic acid chloride (b3-3) was added dropwise to react.
• D-24 74.7 g of the benzoylformamide derivative (D-5) synthesized in Example 5 and 100 g of 1,2-dichloroethane (c-2) were added to a 300 mL flask equipped with a reflux condenser, a stirrer, a thermometer, and a dropping funnel, and mixed. The mixture was cooled to -10°C, and while maintaining the temperature at -10
• Example 25 Synthesis of Benzoylformamide Derivative (D-25) 6.0g of sodium hydride and 50g of 4-methyltetrahydrofuran (c-4) were placed in a 500mL flask equipped with a reflux condenser, a stirrer, a thermometer and a dropping funnel. 63.6g of benzoylformamide derivative (D-18) was dissolved in 50g of c-4, placed in the dropping funnel and dropped over 30 minutes while checking the amount of hydrogen gas generated. After the dropwise addition was completed, 36.4g of allyl chloride (b3-4) was added and reacted at 25°C for 24 hours.
• D-25 6.0g of sodium hydride and 50g of 4-methyltetrahydrofuran (c-4) were placed in a 500mL flask equipped with a reflux condenser, a stirrer, a thermometer and a dropping funnel. 63.6g of benzoylformamide derivative (D-18) was dissolved in 50g of c-4,
• Example 26 Synthesis of Benzoylformamide Derivative (D-26) 40.4 g of trifluoromethanesulfonic acid was placed in a 500 mL flask equipped with a reflux condenser, a stirrer, a thermometer and a dropping funnel, and 4.8 g of ion-exchanged water was added and mixed while cooling to obtain trifluoromethanesulfonic acid hydrate. A solution of 86.6 g of benzoylformamide derivative (D-9), 13.4 g of acrylonitrile (b3-5) and 100 g of 4-methyltetrahydrofuran (c-4) was dropped into the flask at 40°C over 2 hours.
• D-9 benzoylformamide derivative
• b3-5 acrylonitrile
• c-4 4-methyltetrahydrofuran
• Example 29 Synthesis of Benzoyl Formic Acid Amide Derivative (D-29) Using the same reaction apparatus as in Example 23, 18.8 g of benzoyl formic acid amide derivative (D-7), 23.5 g of trimethylhexamethylene diisocyanate (b1-2), 57.7 g of unsaturated polyester diol (b3-6), and 0.05 g of zirconium tetrakis acetylacetonate as a catalyst were mixed and reacted for 5 hours while stirring at 60°C. The disappearance of the isocyanate group was confirmed by FT-IR analysis of the reaction liquid, and a pale yellow viscous liquid product was obtained (yield 96%).
• FT-IR analysis confirmed the presence of urethane and benzoylformamide groups
• 1 H-NMR analysis confirmed the presence of acrylate groups (5.85 ppm, 6.20 ppm, 6.45 ppm), methacrylate groups (5.65 ppm, 6.20 ppm), acrylamide groups (5.60 ppm, 6.10 ppm, 6.50 ppm), methacrylamide groups (5.60 ppm, 6.20 ppm), vinyl ether groups (4.75 ppm, 4.80 ppm, 6.75 ppm), and various unsaturated groups.
• GPC analysis was used to calculate the number average molecular weight (Mn) of the product.
• Example 33 Synthesis of Benzoylformamide Derivative (D-33) Using the raw materials shown in Table 2-2, 39.6 g of benzoylformamide derivative (D-10), 39.8 g of isophorone diisocyanate (b1-1), 20.6 g of N-(hydroxymethyl)acrylamide (b3-9), 100.0 g of polymerizable compound N-acryloylmorpholine (h1-1) instead of solvent (c), and 0.02 g of bismuth tris(2-ethylhexanoate) as a catalyst were mixed in the same manner as in Example 22, and the mixture was reacted for 6 hours while stirring at 60°C.
• Example 55 Synthesis of Benzoylformamide Derivative (D-55) 67.6g of benzoylformamide derivative (D-6) and 50.0g of 4-methyltetrahydrofuran (c-4) were placed in a 300mL flask equipped with a reflux condenser, a stirrer, a thermometer and a dropping funnel, mixed, and then 21.6g of epichlorohydrin (b4-1) was added. While maintaining the temperature at 20°C, 0.5g of boron trifluoride diethyl ether was added, and then 10.8g of b4-1 was added dropwise over 1 hour, and the reaction was continued for another 2 hours after the end of the dropwise addition.
• b4-1 epichlorohydrin
• Examples 56 to 58 Synthesis of Benzoylformamide Derivatives (D-56) to (D-58) Using the raw materials shown in Table 2-6, the benzoylformamide derivative (D) was synthesized in the same manner as in Example 23. The presence of urethane groups and benzoylformamide groups was confirmed by FT-IR analysis, and the presence of cyclic ethers and unsaturated groups was confirmed by 1 H-NMR analysis. Specifically, the presence of alicyclic epoxy groups (2.95 ppm, 3.05 ppm), glycidyl groups (3.00 ppm, 3.85 ppm), and acrylate groups (5.85 ppm, 6.20 ppm, 6.45 ppm) was confirmed by 1 H-NMR analysis.
• Examples 59 to 100 and Comparative Examples 1 to 3 (Preparation and Evaluation of Active Energy Ray-Curable Compositions) Using the benzoylformamide derivatives (D-1) to (D-54) synthesized as examples and the commercially available photopolymerization initiators (E-1) to (E-3) as comparative examples, the monofunctional unsaturated compound (h1), the polyfunctional unsaturated compound (h2), the photosensitizer (I), and other components (k) were weighed in the proportions shown in Tables 3-1 and 3-2, and mixed at 25°C for 30 minutes to obtain an active energy ray curable composition (hereinafter abbreviated as curable composition). The compatibility of the obtained curable composition and its curability against light of different wavelengths were evaluated.
• the curable composition was applied to a polyethylene terephthalate film (Cosmoshine A-4100, corona-treated surface, thickness 100 ⁇ m, manufactured by Toyobo Co., Ltd.) (hereinafter referred to as PET film) using a bar coater to a film thickness of 20 ⁇ m.
• PET film polyethylene terephthalate film
• the coating film was irradiated with light of different wavelengths to cure the coating film, and the cumulative amount of light required until the tackiness disappeared when touched was determined, and the curability was evaluated into four stages.
• the following three types of ultraviolet irradiation lamps 1) to 3) were used. Furthermore, the lower the cumulative amount of light required until the tackiness disappeared, the higher the curability.
• the curable composition was applied to a polyester-based heavy release film (E7001, thickness 75 ⁇ m, manufactured by Toyobo Co., Ltd.) (hereinafter referred to as a heavy release film), and a polyester-based light release film (E7002, thickness 50 ⁇ m, manufactured by Toyobo Co., Ltd.) was applied to the film.
• the film was laminated to a thickness of 20 ⁇ m using a tabletop roll laminator (Royal Sovereign RSL-382S) to avoid trapping air bubbles.
• the sample was irradiated with light (high pressure mercury lamp, illuminance 100 mW/ cm2 , cumulative light quantity 5,000 mJ/ cm2 ).
• the light release film was peeled off, and three test pieces with a size of 5 cm2 were cut out and dried at 90°C for 2 minutes.
• the mixture was then weighed and the mass of the cured film before extraction was determined. 25 g of acetone and the weighed cured film were placed in a UV-opaque brown glass bottle, which was then sealed and rotated at 30°C for 48 hours to extract the soluble components in the cured film.
• the extracted solution was filtered to remove 0.45 ⁇ m water.
• the mixture was filtered through a filter and subjected to HPLC analysis. The amount of low molecular weight components was quantified based on the calibration curve, and the content of low molecular weight components was calculated according to the following formula, and evaluation was performed as described below.
• Low molecular weight component content (%) (mass of extracted low molecular weight components/mass of cured film before extraction) x 100% ++: The content of low molecular weight components was 1.0% or less. +: The content of low molecular weight components was more than 1.0% and less than 2.0%. ⁇ : The content of low molecular weight components was more than 2.0% and 4.0% or less. -: The content of low molecular weight components was greater than 4.0%.
• a heavy release film was attached to a horizontally placed glass plate, a silicone spacer (if no material is specified hereafter, silicone is used) with an internal volume of 10 mm x 10 mm x 0.5 mm was placed on top of it, and the curable composition was filled into the spacer.
• a light release film was placed over the liquid surface of the spacer to avoid trapping air bubbles, and ultraviolet light was irradiated from a UV-LED lamp (wavelength 405 nm, illuminance 100 mW/cm 2 , cumulative light amount 20,000 mJ/cm 2 ).
• the light release film was then peeled off, the cured product was removed from the spacer, and the product was visually observed, and the light yellowing resistance was evaluated according to the following criteria. ++: No yellowing was observed. +: Very slight yellowing was observed. ⁇ : Yellowing was observed. -: Obvious yellowing was observed.
• a cured product of the curable composition was prepared in the same manner as in the evaluation of light yellowing resistance, except that the accumulated light amount was changed to 5,000 mJ/ cm2 .
• the product was then left to stand in a thermo-hygrostat at a temperature of 40°C and a relative humidity of 50% for 168 hours, and the surface of the cured product was visually observed for the presence or absence of bleeding out, and durability was evaluated according to the following criteria.
• + Very little bleeding was observed.
• ⁇ Slight bleed-out was observed.
• - Severe bleeding out was observed.
• the curable compositions of each Example using the benzoylformic acid amide derivative (D) of the present disclosure had good compatibility and high curability not only with high-pressure mercury lamps but also with 385 nm and 405 nm light from UV-LED lamps.
• the cured products obtained in the Examples had a low content of low molecular weight components, high safety, and excellent resistance to yellowing and durability.
• D-20 (Example 66) having a benzoylformic acid mono-substituted amide group showed higher curability than D-3 (Example 60) having a benzoylformic acid di-substituted amide group.
• D-40 (Example 86) containing a urethane group showed higher compatibility and curability than D-24 (Example 70) not containing a urethane group.
• D having 10 (D-30 in Example 76), 7 (D-36 in Example 82) and 4 (D-40 in Example 86) atoms directly connected between the nitrogen atom of the benzoyl formic acid amide group and the nitrogen atom of the nearest urethane group the 7 and 4 atoms showed higher curability than the 10 atoms, and the 4 atoms showed the highest curability.
• D-29 (Example 75), D-32 (Example 78), D-34 (Example 80), D-35 (Example 81), D-45 to D-49 (Examples 91 to 95), D-48 and D-52 (Example 98), and D-53 (Example 99), which have a urethane group with a molecular weight of 1,000 or more and an alkylene structural unit derived from a polyol, a polyether structural unit, a polyester structural unit, a polycarbonate structural unit, a polyolefin structural unit, and a polysiloxane structural unit, showed good compatibility despite their high molecular weight.
• Comparative Example 1 which used Esacure KIP 150 (E-1) as the photopolymerization initiator, had low curing properties with light of 405 nm wavelength, and both the remaining (unpolymerized) polymerizable compound (h) and decomposition products generated by intramolecular cleavage of E-1 remained in the cured product, resulting in a high content of low molecular weight components in the cured product.
• Comparative Example 2 which used methyl benzoylformate (E-2) and Comparative Example 3, which used 2,4,6-trimethylbenzoyldiphenylphosphine oxide (E-3), were able to cure with light of 405 nm, but since E-2, which has a molecular weight of 164, itself is a low molecular weight component, and E-3 is an intramolecular cleavage type photopolymerization initiator, the cured products of Comparative Examples 2 and 3 both had high contents of low molecular weight components. Furthermore, Comparative Examples 1 to 3 all had low light yellowing resistance and durability of the cured products.
• Examples 101 to 137 and Comparative Examples 4 to 10 (Preparation and Evaluation of Photoradical Polymerization-Based Active Energy Ray-Curable Compositions) Benzoylformamide derivatives (D-2) to (D-57) obtained in each Example and commercially available photosensitizers (I-3) and (I-4) as comparative examples were used, and the monofunctional unsaturated compound (h1), the polyfunctional unsaturated compound (h2) and the radical photopolymerization initiator (E) were weighed in the compositions shown in Tables 4-1 and 4-2, and mixed at 25°C for 30 minutes to prepare photoradical polymerization active energy ray curable compositions (hereinafter also referred to as radical curable compositions).
• radical curable compositions photoradical polymerization active energy ray curable compositions
• Examples 138 to 143 and Comparative Examples 11 to 15 (Preparation and Evaluation of Photoionically Polymerizable Active Energy Ray-Curable Compositions) Using the benzoyl formic acid amide derivative (D) obtained in each Example and commercially available photosensitizers (I-3) to (I-5), the cyclic ether compound (h3), photoionic polymerization initiator (E-10) or (E-11), and other additives (k) were weighed in the composition shown in Table 5, and mixed at 25°C for 30 minutes to prepare a photoionic polymerization active energy ray curable composition (hereinafter also referred to as an ionic curable composition).
• a photoionic polymerization active energy ray curable composition hereinafter also referred to as an ionic curable composition.
• ⁇ Curability> As in the evaluation of the curability of the photoradical polymerization curable composition described above, a coating film with a thickness of 20 ⁇ m was prepared on a PET film and irradiated with active energy rays under the following conditions using various light sources 4) to 6) below. The coating was then left to stand for 1 hour in a thermostatic chamber at 70°C to obtain a film-like cured product. The cumulative amount of light required to remove tack when the surface of the obtained cured product was touched was determined, and the curability was evaluated according to the following criteria. The lower the cumulative amount of light required to remove tack, the higher the curability.
• High pressure mercury lamp Wavelength 200-450nm, Illuminance 500mW/ cm2 5)
• UV-LED lamp Wavelength 385nm, Illuminance 500mW/ cm2 6)
• UV-LED lamp Wavelength 405nm, Illuminance 500mW/ cm2 ++: Tack was lost when the accumulated light amount was less than 5,000 mJ/ cm2 . +: Tack disappeared after irradiation with an accumulated light amount of 10,000 mJ/ cm2 .
• ⁇ Tack disappeared after irradiation with an accumulated light amount of 50,000 mJ/ cm2 .
• - Tack remained even after irradiation with an accumulated light dose of 50,000 mJ/ cm2 .
• a photoionic cured product was prepared in the same manner as in the evaluation of the curability of the photoionic polymerization curable composition, except that the curing conditions were changed as follows.
• the photoyellowing resistance of the obtained cured product was evaluated in the same manner as in the evaluation of the photoyellowing resistance of the photoradical polymerization cured product.
• Curing conditions UV-LED lamp: wavelength 405 nm, illuminance 1,000 mW/cm 2 , cumulative light quantity 100,000 mJ/cm 2 was irradiated, and then left to stand at 70°C for 1 hour.
• a cured product was prepared in the same manner as in the photoionically polymerizable curable composition, except that the curing conditions were changed to an accumulated light dose of 50,000 mJ/cm 2.
• the durability of the obtained cured product was evaluated in the same manner as in the evaluation of the photoyellowing resistance of the photoionically polymerizable curable composition.
• Examples 144 to 151 and Comparative Examples 16 to 18 (Preparation of Photohybrid Polymerization-Based Active Energy Ray-Curable Compositions and Evaluation of Photosensitizers)
• the benzoyl formic acid amide derivative (D) synthesized in the examples and the commercially available photosensitizers (I-3), (I-5), and the commercially available photopolymerization initiator (E-5) were used as comparative examples, and the unsaturated compounds (h1), (h2), cyclic ether compounds (h3), and photoionic polymerization initiators (E-10) or (E-11), and other additives (k) were weighed in the proportions shown in Table 6, and a photohybrid polymerization system active energy ray curable composition and a cured product were obtained in the same manner as in the evaluation of the photoionic polymerization system photosensitizer.
• the curable compositions of each Example using the benzoylformamide derivative (D) as a photosensitizer showed good compatibility.
• D showed photosensitivity to the wide range of wavelengths of continuous light from a high-pressure mercury lamp and to the 385 nm and 405 nm wavelengths of light from a UV-LED lamp, and the curable compositions containing D showed high curability. It was confirmed that D has high photosensitivity when used in combination with one or more photopolymerization initiators, including a general-purpose photoradical polymerization initiator, a general-purpose photoionic photopolymerization initiator, and the photoradical polymerization initiator D.
• one or more photopolymerization initiators including a general-purpose photoradical polymerization initiator, a general-purpose photoionic photopolymerization initiator, and the photoradical polymerization initiator D.
• the photoradical, photoionic, and photohybrid curable compositions all had high curability, and cured products with good photoyellowing resistance and durability were obtained.
• D-3 (Example 102), D-17 (Example 110), D-18 (Example 111), and D-41 to D-43 (Examples 127 to 129) having a methoxy group had a very high photosensitizing effect against light rays of 385 nm and 405 nm, and it was clear that the absorption wavelength of D shifted to the long wavelength side due to the inclusion of an electron-donating methoxy group.
• Example 140 to 143 having a cyclic epoxy group showed photosensitizing properties to a photoionic polymerization initiator, and was simultaneously incorporated into the cured product by photoionic polymerization, resulting in high curability of the curable composition and a cured product with high durability.
• Examples 144, 145, and 147 to 151 are photohybrid polymerization systems of photoradical polymerization and photoionic polymerization using a photoionic polymerization initiator and D in combination, and in these examples as well, the curable composition had high curability, and the obtained cured product had good photoyellowing resistance and durability.
• Examples 152 to 161 and Comparative Examples 19 to 21 (Active Energy Ray-Curable Ink Compositions and Evaluations Thereof) According to the proportions shown in Table 7 (solid content equivalent), the benzoylformic acid amide derivative (D), the curable composition (F) containing D, the commercially available photopolymerization initiator (E), the curable composition (G) containing E, the monofunctional unsaturated compound (h1), the polyfunctional unsaturated compound (h2) and other components (k) were weighed and mixed at 25 ° C for 30 minutes to obtain an active energy ray curable ink composition (hereinafter also referred to as an ink composition). The viscosity and curability of the ink composition were evaluated by the following method.
• ink jet printing was performed using the ink composition, and the ink discharge stability, blocking resistance, clarity and bleed-out resistance of the printed matter were evaluated as printability by the following method.
• a cured product for evaluating the low molecular weight component content was prepared using the ink composition, and the low molecular weight component content in the cured product of the ink composition was evaluated by the same method as the evaluation of the low molecular weight component content in the cured product of the curable composition.
• Viscosity was 5 mPa ⁇ s or more and less than 50 mPa ⁇ s.
• Viscosity was 50 mPa ⁇ s or more and less than 100 mPa ⁇ s.
• Viscosity was 100 mPa ⁇ s or more and less than 200 mPa ⁇ s.
• Viscosity was 200 mPa ⁇ s or more.
• the ink composition was applied to a PET film using a bar coater to form a coating having a thickness of 20 ⁇ m, and cured by exposure to ultraviolet light (UV-LED lamp: wavelength 395 nm, illuminance 1,000 mW/cm 2 ) to produce a print.
• UV-LED lamp wavelength 395 nm, illuminance 1,000 mW/cm 2
• ⁇ Curability> When producing a printed matter, the integrated amount of light until the ink composition was completely cured (until it became non-sticky) was measured, and the curability of the ink composition was evaluated according to the following criteria. ++: Completely cured with an integrated light dose of less than 1,000 mJ/ cm2 . +: Completely cured with an accumulated light amount of 1,000 mJ/ cm2 or more and less than 2,000 mJ/ cm2 . ⁇ : Completely cured with an accumulated light amount of 2,000 mJ/ cm2 or more and less than 5,000 mJ/ cm2 . -: A cumulative light dose of 5,000 mJ/ cm2 or more was required for complete curing.
• the obtained ink composition was filled into an inkjet printer (LuxelJetUV350GTW, manufactured by Fujifilm Corporation), and a solid image was printed on coated paper to evaluate the ejection stability of the ink as the printability.
• ⁇ Discharge stability> The printing condition of the printed matter was visually observed, and the ejection stability was evaluated according to the following criteria. ++: There were no missing nozzles and printing was excellent. +: There was a slight nozzle dropout. -: Nozzle missing occurred over a wide area.
• ⁇ Blocking resistance> The printed material was left to stand for 5 minutes in an environment with a room temperature of 23°C and a relative humidity of 50%, then a piece of high-quality paper was placed over the printed surface and a load of 1 kg/ cm2 was applied for 1 minute. The extent of ink transfer to the paper was visually observed and blocking resistance was evaluated according to the following criteria. ++: The ink was dry and there was no transfer to the paper. +: The ink was dried and there was a small amount of transfer onto the paper. ⁇ : The ink was almost dry and was transferred to the paper. -: The ink barely dried and a lot of it was transferred to the paper.
• ⁇ Bleed-out resistance> The print was left to stand in a thermo-hygrostat set at a temperature of 40° C. and a relative humidity of 50% for 168 hours, and the surface of the print was visually observed and evaluated for bleed-out resistance according to the following criteria. ++: No bleeding out was observed at all. +: Slight bleed-out was observed. -: Severe bleeding out was observed.
• the ink compositions of the Examples had high curability, and the resulting cured film (printed matter) was free of low molecular weight components, and the cured film dried well with little bleed-out, making it possible to produce highly durable prints.
• the ink composition of Comparative Example 19 had low curability. Curing was possible in Comparative Examples 20 and 21, but both had a high content of low molecular weight components in the printed matter, and the cured film had poor blocking resistance, bleed-out resistance, and clarity of the printed matter.
• Comparative Example 20 which used Esacure KIP 150 (E-1)
• the ink had low ejection stability and poor printability.
• clear prints could be obtained. This is believed to be because the pigment was uniformly dispersed or dissolved in the ink compositions of the Examples.
• the ink compositions of the Examples had low viscosity and high ejection stability, making them suitable for inkjet printing.
• Examples 162 to 170 and Comparative Examples 22 and 23 Preparation and Evaluation of Active Energy Ray-Curable Pressure-Sensitive Adhesive Compositions
• the benzoylformamide derivative (D) the curable composition (F) containing D
• the commercially available photopolymerization initiator (E) the monofunctional unsaturated compound (h1), the polyfunctional unsaturated compound (h2) and other components (k) were weighed and mixed at 25 ° C for 30 minutes to prepare an active energy ray curable adhesive composition (hereinafter also referred to as adhesive composition).
• an adhesive sheet having an adhesive layer was produced by the following method, and the curability of the adhesive composition and the adhesiveness (adhesive strength) to various substrates were evaluated.
• a heavy release film was attached to a horizontally placed glass plate, a spacer with a thickness of 1 mm and an internal dimension of 60 mm x 100 mm was placed, and the adhesive composition prepared in the examples and comparative examples was filled inside the spacer.
• a light release film was placed on the filled composition, and the adhesive composition was cured by irradiating it with a UV-LED lamp with a wavelength of 405 nm and an illuminance of 100 mW/ cm2 so that the accumulated light amount was 1,000 mJ/ cm2 . Thereafter, the light release film was peeled off to obtain an adhesive sheet consisting of a cured product (adhesive layer) of the adhesive composition and the heavy release film.
• the curability of the adhesive composition was evaluated according to the following criteria by touching the adhesive layer. ++: A cured product that was able to maintain its shape was obtained, and no liquid deposits were observed. +: A cured product that was able to maintain its shape was obtained, and there was a small amount of liquid adhesion. ⁇ : A cured product that was able to maintain its shape was obtained, and liquid adhesion was observed. -: Curing was insufficient, and a cured product capable of maintaining its shape was not obtained.
• the adhesive layer was transferred from the obtained adhesive sheet to a glass substrate in an environment of 23°C temperature and 50% relative humidity, and the total light transmittance of the glass substrate and adhesive layer was measured using a haze meter (NDH-8000, manufactured by Nippon Denshoku Industries Co., Ltd.) in accordance with ISO 14782.
• the transmittance of the glass plate was then measured in the same manner and subtracted from the total light transmittance of the glass substrate and adhesive layer to calculate the transmittance of the adhesive layer itself, and the transparency of the adhesive layer was evaluated according to the following criteria.
• ++ The transmittance was 90% or more.
• ⁇ The transmittance was 50% or more and less than 85%.
• ⁇ Bleed-out resistance> The obtained pressure-sensitive adhesive sheet was left to stand for 168 hours in a thermo-hygrostat at a temperature of 40° C. and a relative humidity of 50%, and then left to stand for 30 minutes in an environment at a temperature of 23° C. and a relative humidity of 50%, and the pressure-sensitive adhesive layer on the surface of the pressure-sensitive adhesive sheet was touched to evaluate the bleed-out resistance of the pressure-sensitive adhesive layer according to the following criteria. ++: No liquid deposit was observed and no bleeding out was observed. +: There was very little liquid adhesion, and very little bleeding out was observed. ⁇ : A small amount of liquid adhesion was observed, and a small amount of bleeding out was observed. -: Liquid adhesion was observed and bleeding out was observed.
• the adhesive layer was transferred from the obtained adhesive sheet to the following substrate film or plate in an environment of 23°C temperature and 50% relative humidity, and pressure-applied by two reciprocating motions using a 2 kg pressure roller, and left in the same environment for 30 minutes. Thereafter, the 180° peel strength (N/25 mm) (peel speed 300 mm/min) was measured in accordance with ISO 29862 using a tensile tester (ORIENTE, Tensilon RTA-100, hereinafter also referred to as universal testing machine), and the adhesive strength was evaluated according to the following criteria.
• PET2 Polyethylene terephthalate film (Cosmoshine A4160, corona treated, manufactured by Toyobo Co., Ltd.)
• PC Polycarbonate (plate) (PC1600, manufactured by Takiron C.I. Co., Ltd.)
• GL Glass (plate) (Eagle XG, Corning)
• Peel strength was 20 (N/25 mm) or more. +: The peel strength was 10 (N/25 mm) or more and less than 20 (N/25 mm). ⁇ : The peel strength was 5 (N/25 mm) or more and less than 10 (N/25 mm).
• - Peel strength was less than 5 (N/25 mm).
• the adhesive layer was transferred to a film or plate of a different substrate, pressed and attached, and left to stand for 24 hours in a thermostatic chamber at 80°C. After that, it was left for 30 minutes in an environment with a temperature of 23°C and a relative humidity of 50%, and the adhesive layer was peeled off. The remaining state of the adhesive layer (glue) on the substrate surface was visually observed, and the reworkability of the adhesive layer was evaluated according to the following criteria. ++: No adhesive residue was left. +: There was a very small amount of glue remaining. ⁇ : A small amount of glue was left behind. -: There was glue residue.
• the adhesive layer of the adhesive sheet was transferred to a glass substrate and left to stand in a thermo-hygrostat at a temperature of 85°C and a relative humidity of 85% for 100 hours, then left to stand for 30 minutes in an environment at a temperature of 23°C and a relative humidity of 50%, and the condition of the adhesive layer was visually observed and durability was evaluated according to the following criteria.
• ++ The adhesive layer was transparent and had no lifting or bubbles.
• + The adhesive layer was slightly cloudy, but there was no lifting or bubbles.
• - The adhesive layer was cloudy or floating, and air bubbles were present.
• the adhesive compositions of the Examples had high curability, and the adhesive layers obtained by curing them had high transparency and high adhesion (adhesive strength) to various substrates.
• the cured products (adhesive layers) obtained in the Examples had a low content of low molecular weight components, high bleed-out resistance, durability, and light yellowing resistance, and also had good reworkability when the cured products were peeled off from the substrate.
• the adhesive compositions of the Comparative Examples had low curability, a high content of low molecular weight components in the obtained cured products, low adhesive strength of the adhesive layers, and low bleed-out resistance, durability, light yellowing resistance, and reworkability.
• Examples 171 to 177 and Comparative Examples 24 and 25 (Preparation and Evaluation of Active Energy Ray-Curable Adhesive Compositions) According to the proportions shown in Table 9 (solid content conversion), the benzoyl formic acid amide derivative (D), the curable composition (F) containing D, the commercially available photopolymerization initiator (E), the monofunctional unsaturated compound (h1), the polyfunctional unsaturated compound (h2) and other components (k) were weighed and mixed at 25 ° C for 30 minutes to prepare an active energy ray curable adhesive composition (hereinafter also referred to as adhesive composition). The curability of the adhesive composition and the content of low molecular weight components in the obtained cured product were evaluated. In addition, various substrates were bonded using the adhesive composition to prepare a laminate, and the adhesive strength and durability of the laminate were evaluated. These evaluation results are shown in Table 9.
• a PET film was attached to a horizontally placed glass plate, and the adhesive compositions of the Examples and Comparative Examples were coated to a thickness of 20 ⁇ m using a bar coater, and a light-release film was placed on top of the adhesive composition.
• the adhesive composition was cured by irradiating it with ultraviolet light using a UV-LED lamp with a wavelength of 405 nm and an illuminance of 50 mW/ cm2 .
• the light-release film was then removed, and the presence or absence of tack on the surface of the cured film was confirmed.
• the curability of the adhesive composition was evaluated according to the following criteria based on the accumulated amount of light required until the tack disappeared.
• Tack was lost when the accumulated light amount was less than 500 mJ/ cm2 .
• + Tack was lost when the accumulated light amount was 500 mJ/ cm2 or more and less than 1,000 mJ/ cm2 .
• ⁇ Tack was lost when the accumulated light amount was 1,000 mJ/ cm2 or more and less than 5,000 mJ/ cm2 .
• - Tack remained even with an accumulated light dose of 5,000 mJ/ cm2 .
• the adhesive composition was coated onto various film- or plate-shaped base materials (substrates) as shown below, and the PET film was used to bond them together using a tabletop roll laminator (RSL-382S), taking care not to trap air bubbles, so that the adhesive layer was 20 ⁇ m thick.
• the laminate was then irradiated with ultraviolet light (UV-LED lamp with wavelength 405 nm and illuminance 50 mW/ cm2 , cumulative light amount: 2,000 mJ/ cm2 ) to produce a laminate.
• ultraviolet light UV-LED lamp with wavelength 405 nm and illuminance 50 mW/ cm2 , cumulative light amount: 2,000 mJ/ cm2
• Base material (substrate) PET3 Polyethylene terephthalate film (Cosmoshine E5100, corona treatment, manufactured by Toyobo Co., Ltd.)
• PMMA Polymethyl methacrylate (plate) (COMOGLAS P, manufactured by Kuraray Co., Ltd.)
• PC Polycarbonate (plate) (PC1600, manufactured by Takiron C.I. Co., Ltd.)
• a cured product (adhesive layer) was prepared on a glass substrate (accumulated light amount 2,000 mJ/ cm2 ) and left to stand for 100 hours in a thermo-hygrostat chamber at a temperature of 85°C and a relative humidity of 85%. It was then left to stand for 30 minutes in an environment at a temperature of 23°C and a relative humidity of 50%, and the condition of the laminate was visually observed and its durability was evaluated according to the following criteria.
• ++ The laminate was transparent and had no peeling or bubbles.
• + The laminate was slightly cloudy, but there was no peeling or bubbles.
• ⁇ The laminate was slightly cloudy or peeled off, and air bubbles were present.
• - The laminate was extremely cloudy or peeled off, and bubbles were present.
• a cured product (adhesive layer) was prepared on a PET film (UV-LED with a wavelength of 405 nm and an illuminance of 50 mW/ cm2 , cumulative light amount: 2,000 mJ/ cm2 ).
• the PET film having the adhesive layer was cut into a test piece having a size of 5 cm2 , and the content of low molecular weight components in the adhesive layer was evaluated in the same manner as in the evaluation of the content of low molecular weight components in the cured product of the curable composition. .
• the adhesive compositions of the Examples had high curing properties, and the laminates (adhesive bodies) obtained by curing them had high adhesive strength to both homogeneous and heterogeneous substrates.
• the content of low molecular weight components in the cured product (adhesive layer) was low, and the durability of the laminate was good.
• Such adhesive compositions showed properties suitable for use as an adhesive.
• the adhesive compositions of the Comparative Examples had low curing properties, and there was a large amount of low molecular weight components remaining in the adhesive layer, resulting in low adhesive strength and durability of the adhesive body.
• Examples 178 to 184 and Comparative Examples 26 and 27 (Preparation and Evaluation of Active Energy Ray-Curable Sealant Compositions) According to the proportions shown in Table 10 (solid content equivalent), the benzoyl formic acid amide derivative (D), the commercially available photopolymerization initiator (E), the monofunctional unsaturated compound (h1), the polyfunctional unsaturated compound (h2) and other components (k) were weighed and mixed at 25 ° C for 30 minutes to prepare an active energy ray curable sealant composition (hereinafter also referred to as a sealant composition).
• a sealant composition an active energy ray curable sealant composition
• a cured product of the sealant composition was prepared, and the curability of the sealant composition, the transparency of the obtained cured product, the resistance to wet heat yellowing, the water resistance, the outgassing resistance, the heat cycle resistance and the corrosion resistance were evaluated.
• the low molecular weight component content in the cured product of the sealant composition was evaluated in the same manner as the cured product of the curable composition.
• ⁇ Preparation of cured product of sealant composition A spacer (30 mm x 15 mm x 3 mm) was placed on a glass plate, and copper foil (5 mm length x 50 mm width x 80 ⁇ m thickness) was placed inside the spacer, and the prepared sealant composition was poured in. After sufficient degassing, ultraviolet light was irradiated (UV-LED lamp with wavelength of 405 nm and illuminance of 500 mW/ cm2 , cumulative light amount: 1,000 mJ/ cm2 ) to obtain a cured product of the sealant composition.
• UV-LED lamp with wavelength of 405 nm and illuminance of 500 mW/ cm2 , cumulative light amount: 1,000 mJ/ cm2
• ⁇ Curability> The cured product was evaluated according to the following criteria to evaluate curability. ++: A cured product was obtained that was able to maintain its shape, and the cured product was not tacky when touched. +: A cured product was obtained that was able to maintain its shape, and the cured product was tacky when touched. ⁇ : A cured product was obtained that was able to maintain its shape, but liquid matter was found to adhere to the cured product when touched. -: Curing was insufficient, and a cured product capable of maintaining its shape was not obtained.
• ⁇ Transparency> The cured product was left to stand for 24 hours in an environment of 23° C. and 50% relative humidity, after which the transmittance of the cured product was measured using the same haze meter as above, and the transparency was evaluated according to the following criteria. ++: The transmittance was 90% or more. +: Transmittance was 85% or more and less than 90%. ⁇ : The transmittance was 50% or more and less than 85%. -: Transmittance was less than 50%.
• ⁇ Resistance to wet heat yellowing> The cured product was left to stand for 24 hours in an environment with a temperature of 23°C and a relative humidity of 50%, and then the transmission spectrum of the cured product was measured using a dedicated transmission color measuring device (TZ-6000, manufactured by Nippon Denshoku Industries Co., Ltd.) and recorded as the initial b value.
• the cured product was then left to stand for 500 hours in a thermohygrostat set at a temperature of 85°C and a relative humidity of 85%, and an accelerated test of humidity and heat yellowing resistance was performed.
• the cured product was left to stand for 24 hours in an environment with a temperature of 23°C and a relative humidity of 50%, and the transmission color was measured and recorded as the post-humid heat b value.
• the humidity and heat yellowing resistance of the cured product was evaluated according to the following criteria. ++: Both the initial b value and the b value after moist heat treatment were 0.2 or less, and ⁇ b was 0.1 or less.
• Water absorption rate (weight after water absorption - weight before water absorption) / weight before water absorption x 100% ++: Water absorption was less than 1.0%. +: Water absorption rate was 1.0% or more and less than 2.0%. ⁇ : The water absorption rate was 2.0% or more and less than 3.0%. -: Water absorption rate was 3.0% or more.
• Outgassing resistance A 1g piece was cut out from the cured product and placed in a thermostatic chamber set at 100°C as a test piece, and a dry nitrogen gas flow was passed through it for 24 hours, after which the weight of the test piece was measured again.
• the outgassing rate was calculated using the following formula, and the outgassing resistance was evaluated according to the following criteria. The lower the outgassing rate, the higher the outgassing resistance.
• Outgassing rate (%) (weight after test - weight before test)/weight before test x 100% ++: The outgassing rate was less than 0.1%. +: The outgassing rate was 0.1% or more and less than 0.2%. ⁇ : The outgassing rate was 0.2% or more and less than 0.3%. -: Outgassing rate was 0.3% or more.
• ⁇ Heat cycle resistance> The cured product was subjected to 100 cycles of leaving at -40°C for 30 minutes and then leaving at 100°C for 30 minutes, which constituted one heat cycle. After that, the cured product was visually observed and the heat cycle resistance was evaluated according to the following criteria. ++: No change was observed. +: A small amount of bubbles were observed, but neither cloudiness nor cracks were observed. ⁇ : A few bubbles or cracks were observed, and there was slight cloudiness. -: Bubbles or cracks were observed over the entire surface, and the product was semi-transparent.
• the sealant compositions of the Examples had high curability, the content of low molecular weight components in the resulting cured products (sealants) was low, and the cured products had high transparency, high resistance to moist heat yellowing, and water resistance, little outgassing, and good heat cycle resistance and corrosion resistance.
• the sealant compositions of the Comparative Examples had low curability, a large amount of low molecular weight components remained in the sealant, and the sealant was not satisfactory in two or more of the physical properties of transparency, resistance to moist heat yellowing, water resistance, outgassing resistance, heat cycle resistance, and corrosion resistance.
• Examples 185 to 192 and Comparative Examples 28 and 29 (Preparation and Evaluation of Active Energy Ray-Curable Coating Compositions) According to the proportions shown in Table 11 (solid content equivalent), benzoyl formic acid amide derivative (D), commercially available photopolymerization initiator (E), monofunctional unsaturated compound (h1), polyfunctional unsaturated compound (h2) and other components (k) were weighed and mixed at 25 ° C for 30 minutes to prepare an active energy ray curable coating composition (hereinafter also referred to as coating composition).
• coating composition an active energy ray curable coating composition
• a coating layer was prepared by the following method, and the curability of the coating composition, the adhesion of the obtained coating layer, photo-yellowing resistance, bending resistance, chemical resistance, scratch resistance, durability, and low molecular weight component content were evaluated, and the results are shown in Table 11.
• a PET film was placed on a horizontally placed glass plate, and the coating compositions of the Examples and Comparative Examples were applied to a thickness of 5 ⁇ m using a bar coater. Under a nitrogen atmosphere, the film was irradiated with ultraviolet light from a UV-LED lamp with a wavelength of 385 nm at an illuminance of 500 mW/ cm2 and an accumulated light quantity of 2,000 mJ/ cm2 to produce a coating layer on the PET film.
• ⁇ Adhesion evaluation> According to the cross-cut method described in ISO 2409, the surface of the coating layer was scored with a cutter knife to create 100 1 mm x 1 mm squares to prepare test pieces. A commercially available cellophane tape was applied to the test piece and then peeled off, and the number of squares remaining on the test piece was counted to evaluate the adhesion according to the following criteria. ++: 100 squares remaining. +: 90 to 99 squares remain. -: Fewer than 89 squares remained.
• the light yellowing resistance of the cured product of the curable composition was evaluated by irradiating the coating layer with ultraviolet light using a UV-LED (wavelength 405 nm, illuminance 100 mW/cm 2 , cumulative light quantity 20,000 mJ/cm 2 ) and evaluating the light yellowing resistance of the coating layer.
• a UV-LED wavelength 405 nm, illuminance 100 mW/cm 2 , cumulative light quantity 20,000 mJ/cm 2
• ⁇ Chemical resistance> Using the prepared coating layer, oleic acid was applied to the surface of the coating layer to a diameter of approximately 1 cm, and after keeping it at 23°C for 1 hour, it was washed off with a neutral detergent. The surface condition was visually observed and the chemical resistance was evaluated according to the following criteria. ++: No trace of oleic acid was found. +: A very slight white mark was observed in the area where oleic acid was applied. ⁇ : The area where oleic acid was applied turned white, and swelling was observed on the surface. -: The area where oleic acid was applied was sticky, and surface peeling was observed.
• ⁇ Scratch resistance> The surface of the coating layer was scraped back and forth 10 times with steel wool (#0000, weight 100 g) in an environment of room temperature 23° C. and humidity 50%, and the surface of the coating layer was visually observed and evaluated for scratch resistance according to the following criteria. ++: No scratches were observed on the coating layer. +: Slight fine scratches were observed in part of the coating layer. ⁇ : Streaky scratches were observed throughout the entire coating layer. -: Peeling of the coating layer was observed.
• ⁇ Low molecular weight component content> The same evaluation as for the content of low molecular weight components in the cured product of the curable composition was performed except that the light source was a UV-LED lamp with a wavelength of 385 nm and an illuminance of 1,000 mW/ cm2 and the cumulative light amount was 10,000 mJ/ cm2 .
• the content of low molecular weight components in the coating layer was evaluated by the method.
• the coating compositions of the examples had high curing properties to long wavelength light, and the resulting cured products (coating layers) had good adhesion, resistance to yellowing due to light, resistance to bending, resistance to chemicals, and durability.
• Such coating compositions had properties suitable for use as coatings for vehicles, indoor and outdoor use, and decorative coatings.
• the coating compositions of the comparative examples had low curing properties to long wavelength light, and a large amount of low molecular weight components remained in the resulting coating layer, resulting in poor physical properties of the coating layer.
• Examples 193 to 202 and Comparative Examples 30 and 31 (Preparation and Evaluation of Active Energy Ray-Curable Ink Compositions for Three-Dimensional Modeling) According to the proportions shown in Table 12 (solid content conversion), the benzoyl formate derivative (D), the curable composition (F) containing D, the commercially available photopolymerization initiator (E), the monofunctional unsaturated compound (h1) and the polyfunctional unsaturated compound (h2) were weighed and mixed at 25 ° C for 30 minutes to prepare an active energy ray curable ink composition for three-dimensional modeling (hereinafter also referred to as an ink composition for three-dimensional modeling). The viscosity and curability of the ink composition for three-dimensional modeling were evaluated.
• a three-dimensional model was produced by the following modeling method, and the curing shrinkage resistance and the content of low molecular weight components in the model were evaluated. The strength, heat resistance, modeling accuracy, light yellowing resistance, and bleed-out resistance of the obtained model were evaluated. These evaluation results are shown in Table 12.
• Viscosity was 5 mPa ⁇ s or more and less than 500 mPa ⁇ s.
• Viscosity was 500 mPa ⁇ s or more and less than 2,000 mPa ⁇ s.
• Viscosity was 2,000 mPa ⁇ s or more.
• the curability of the ink composition for three-dimensional modeling was evaluated in the same manner as for the curable composition, except that the light source was a UV-LED lamp with a wavelength of 405 nm and an illuminance of 5 mW/ cm2 .
• a heavy release film was attached to a horizontally placed glass plate, and a spacer with an internal size of 6 mm x 60 mm x 60 mm was placed on top of it.
• the ink composition for three-dimensional modeling of each Example and Comparative Example was filled into the spacer so as to form a layer with a thickness of 0.3 mm. After leaving it in a thermostatic chamber at 60°C for 1 minute, it was irradiated with ultraviolet light (wavelength 405 nm, illuminance 5 mW/cm 2 , accumulated light amount 100 mJ/cm 2 ) from a UV-LED lamp and cured.
• the ink composition for three-dimensional modeling was similarly filled (thickness 0.3 mm) on the cured film (first layer) in the spacer and cured. The same operation was repeated to obtain a total of 20 layers of cured products (6 mm x 60 mm x 60 mm).
• the cured product was irradiated with ultraviolet light (wavelength 405 nm, illuminance 100 mW/cm 2 , cumulative light quantity 2,000 mJ/cm 2 ) from a UV-LED lamp to obtain a modeled product after post-cure treatment.
• ⁇ Cure shrinkage resistance> The density of the ink composition for three-dimensional modeling was measured using a Gay-Lussac pycnometer in accordance with ISO 758. The density of the modeled object was measured using an electronic pycnometer (MDS-300 manufactured by Alpha Mirage Co., Ltd.) in accordance with ISO 1183-1. The cure shrinkage rate was calculated from the density of the ink composition for three-dimensional modeling and the density of the modeled object using the following formula, and the cure shrinkage resistance of the ink composition for three-dimensional modeling was evaluated according to the following criteria. The lower the cure shrinkage rate, the higher the cure shrinkage resistance.
• Curing shrinkage rate (%) (Ds - Dl)/D1 x 100% (In the formula, Ds is the density of the object, and Dl is the density of the ink composition for three-dimensional modeling.) ++: The cure shrinkage was less than 6%. +: The cure shrinkage rate was 6% or more and less than 7%. ⁇ : The cure shrinkage rate was 7% or more and less than 8%. -: The cure shrinkage rate was 8% or more.
• the Shore D hardness of the molded objects was measured in accordance with ISO 48, and the strength of the three-dimensional molded objects was evaluated according to the following criteria. ++: Shore D hardness was 60 or more. +: Shore D hardness was 40 or more and less than 60. -: Shore D hardness was less than 40.
• Tg glass transition temperature
• the shaped object was further irradiated with ultraviolet light (UV-LED lamp, wavelength 405 nm, 100 mW/cm 2 , cumulative light amount 20,000 mJ/cm 2 ), and the light yellowing resistance of the shaped object was evaluated in the same manner as the light yellowing resistance of the cured product of the curable composition described above.
• ultraviolet light UV-LED lamp, wavelength 405 nm, 100 mW/cm 2 , cumulative light amount 20,000 mJ/cm 2
• the ink composition for three-dimensional modeling of the Examples had high curing properties against long wavelength light, low shrinkage during curing, and high modeling precision of the resulting objects. Furthermore, the objects obtained in the Examples had high strength and heat resistance, and good resistance to bleed-out and yellowing due to light. On the other hand, the ink composition for three-dimensional modeling of the Comparative Example had low curing properties, and the resulting objects had low modeling precision.
• the objects of the Comparative Example contained many low molecular weight components, and the strength, heat resistance, and yellowing resistance of the objects were not satisfactory, and the bleed-out resistance was particularly low.
• Examples 203 to 208 and Comparative Examples 32 and 33 (Preparation and Evaluation of Active Energy Ray-Curable Nail Cosmetic Compositions) Benzoylformamide derivative (D), commercially available photopolymerization initiator (E), monofunctional unsaturated compound (h1), polyfunctional unsaturated compound (h2), photosensitizer (I), and other components (k) were weighed out in the proportions (based on solid content) shown in Table 13 and mixed for 30 minutes at 25° C. to prepare an active energy ray-curable nail cosmetic composition (hereinafter also referred to as nail cosmetic composition). The nail cosmetic composition was evaluated for curability, adhesion to nylon substrates, surface hardness, surface gloss, and photo-yellowing resistance of the resulting cured film, and the content of low molecular weight components in the cured film. The results are shown in Table 13.
• the nail cosmetic composition was applied to a nylon 6 test piece (SHT-N6(NC) manufactured by Toray Plastics Precision Co., Ltd.) using a separator to a thickness of 100 ⁇ m.
• a cured film was produced by irradiating ultraviolet light using a UV-LED lamp for gel nails (manufactured by Beauty Nailer, wavelength 405 nm, output 48 W).
• the time it took for the tackiness to disappear when the surface of the cured film was touched was measured, and the curability was evaluated according to the following criteria. The shorter the time required for the tackiness to disappear, the higher the curability.
• ++ Lost tack in less than a minute.
• + Tack disappeared in 1 minute or more but less than 3 minutes.
• ⁇ Tack disappeared in 3 minutes or more but less than 10 minutes.
• - The tack did not disappear even after 10 minutes or more.
• ⁇ Adhesion> The nail cosmetic composition was applied to a nylon substrate in the same manner as in the curing evaluation, and a cured film was produced by irradiating the substrate with a UV-LED lamp for gel nails for 3 minutes.
• the adhesion of the resulting cured film was evaluated in accordance with ISO 2409 in the same manner as in the evaluation of the coating layer adhesion of the coating composition.
• ⁇ Surface hardness> A cured film was prepared in the same manner as in the adhesion evaluation, and a 750 g load of an HB hardness pencil was pressed against the surface of the film at an angle of 45° and pulled, and changes in the film surface were confirmed visually, and the surface hardness was evaluated according to the following criteria: The fewer scratches and peeling that occurred on the film surface, the higher the surface hardness. +: No scratches or peeling occurred. ⁇ : No peeling occurred, but scratches occurred. -: Peeling occurred.
• ⁇ Surface gloss> A cured film was prepared in the same manner as in the adhesion evaluation and allowed to stand for 24 hours in a thermo-hygrostat at a temperature of 40° C. and a relative humidity of 50%. Thereafter, the gloss of the film surface was visually observed, and the surface gloss of the cured film was evaluated according to the following criteria. +: Shiny. ⁇ : Light reflection was observed, but there were some cloudy areas. -: No light reflection was observed and there was no gloss.
• a cured film was prepared in the same manner as in the adhesion evaluation, and the nylon 6 test pieces having the obtained cured film were used to evaluate the content of low molecular weight components in the cured product (adhesive layer) of the adhesive composition in the same manner as in the evaluation of the adhesive composition. The content of low molecular weight components in the cured film was evaluated.
• a cured film was prepared in the same manner as in the adhesion evaluation, and was set in a xenon fade meter and irradiated with ultraviolet light at an intensity of 70 mW/cm 2 for 120 hours. Thereafter, the discoloration of the cured film was visually observed, and the light yellowing resistance was evaluated according to the following criteria. ++: No yellowing was observed. +: Very slight yellowing was observed. ⁇ : Yellowing was observed. -: Obvious yellowing was observed.
• the nail cosmetic composition of the example had high curing properties under a UV lamp for gel nails, and the obtained cured film had high adhesion to a nylon substrate (a material that has many amide bonds like nails, which are mainly composed of proteins). It was found that such a nail cosmetic composition can be suitably used as a gel nail base gel that is applied directly to the nail. In addition, the content of low molecular weight components in the cured film was low, ensuring safety. The surface gloss, surface hardness, and light yellowing resistance of the cured film were good, making it suitable for use as a gel nail top coat. On the other hand, the nail cosmetic composition of the comparative example had low curing properties, and the obtained cured film contained many low molecular weight components, and the adhesion, surface hardness, surface gloss, and light yellowing resistance of the cured film were low.
• Examples 209 to 214 and Comparative Examples 34 to 36 (Preparation and Evaluation of Active Energy Ray-Curable Dental Material Compositions) According to the proportions shown in Table 14 (solid content basis), the benzoyl formic acid amide derivative (D), the commercially available photopolymerization initiator (E), the monofunctional unsaturated compound (h1), the polyfunctional unsaturated compound (h2) and other components (k) were weighed and mixed at 25°C for 30 minutes to prepare an active energy ray-curable dental material composition (hereinafter also referred to as the dental material composition). The solubility (dispersibility), storage stability and curability of the dental material composition were evaluated. The dental material composition was cured to obtain a cured product, and the low molecular weight component content, hardness, surface smoothness and bending strength in the cured product were evaluated. The results are shown in Table 14.
• ⁇ Storage stability> The dental material compositions were placed in light-shielding screw tubes, the lids were closed, and the compositions were stored under two conditions: one month at 40° C. and two weeks at 80° C. After storage, the dissolution or dispersion state of the compositions was confirmed, and the storage stability was evaluated according to the following criteria. +: No change in condition after storage at 40°C for one month and at 80°C for two weeks. ⁇ : No change in condition was observed after storage at either 40°C for one month or at 80°C for two weeks. -: No change in condition was observed after storage under both conditions: 40°C for one month and 80°C for two weeks.
• the dental material composition was filled into a polytetrafluoroethylene mold (20 mm x 20 mm x 10 mm) with a hole of 6 mm diameter in the center, and pressed with a polypropylene film. It was irradiated with ultraviolet light (wavelength 405 nm, illuminance 50 mW/ cm2 ) for 30 seconds, the polypropylene film was peeled off, and the cured product was touched with a hand to evaluate the curability according to the following criteria. ++: No stickiness at all. +: There was some stickiness, but finger marks were not left on the surface. ⁇ : Sticky and finger marks left on the surface. -: It was very sticky and my fingers stuck to the surface.
• the cured product obtained in the curability evaluation was used to evaluate the content of low molecular weight components in the dental material composition cured product in the same manner as in the evaluation of the content of low molecular weight components in the hardenable composition.
• ⁇ Hardness> The surface of the cured product obtained in the curability evaluation was buffed, and the Knoop hardness was measured using a microhardness tester (DMH-2, manufactured by Matsuzawa Seiki Co., Ltd.) at a temperature of 23°C and a load of 100 gf for 20 seconds. The hardness was evaluated according to the following criteria. ++: Knoop hardness was 200KHN or more. +: The Knoop hardness was 70 KHN or more and less than 200 KHN. -: Knoop hardness was less than 70KHN.
• ⁇ Surface smoothness> The surface of the cured product obtained in the curability evaluation was visually observed, and the surface smoothness was evaluated according to the following criteria. ++: The surface was smooth and glossy. +: The surface was almost smooth, with slight cloudiness or irregularities observed. ⁇ : The surface was generally cloudy, and some irregularities or graininess were observed. -: The entire surface was cloudy and covered with granular matter.
• a heavy release film was attached to a horizontally placed glass plate, a polytetrafluoroethylene spacer (2 mm x 2 mm x 25 mm) was placed on top of it, and the dental material composition was filled.
• a light release film was placed over the liquid surface of the spacer to prevent air bubbles from being trapped, and ultraviolet rays were irradiated from a UV-LED lamp (wavelength 405 nm, illuminance 50 mW/cm 2 , cumulative light amount 1,500 mJ/cm 2 ). Then, the release films on both sides were peeled off, and the cured product was taken out of the spacer to be used as a test specimen.
• the test specimen was immersed in water at 37°C for 24 hours, and then a bending test was performed using a universal testing machine.
• the test conditions were in accordance with ISO 4049, with a support distance of 20 mm and a crosshead speed of 1 mm/min.
• the bending strength was evaluated according to the following criteria. ++: The bending strength was 100 MPa or more. +: The bending strength was 90 MPa or more and less than 100 MPa. ⁇ : The bending strength was 80 MPa or more and less than 90 MPa. -: The bending strength was less than 80 MPa.
• the dental material compositions of the Examples had high solubility or dispersibility, and were high in hardenability and storage stability.
• the content of low molecular weight components in the obtained cured products was low, making them safe as dental materials.
• the cured products also had high hardness and flexural strength, and good surface smoothness.
• the dental material compositions of the Comparative Examples had low hardenability, and insufficient solubility and storage stability.
• the content of low molecular weight components in the cured products was high, raising safety concerns.
• the cured products also had low surface smoothness, hardness, and flexural strength.
• the dental material composition of the present disclosure can be suitably used as dental restorative materials (composite resins for crowns, composite resins for filling caries cavities, composite resins for core construction, composite resins for filling and restoring), denture base resins, bonding resins, bonding materials (resin cements, resin-added glass ionomer cements), dental adhesives (orthodontic adhesives, cavity application adhesives), denture base lining materials, impression materials, dental temporary sealing materials, fissure sealants, CAD/CAM resin blocks, temporary crowns, and artificial tooth materials.
• dental restorative materials composite resins for crowns, composite resins for filling caries cavities, composite resins for core construction, composite resins for filling and restoring
• denture base resins bonding resins, bonding materials (resin cements, resin-added glass ionomer cements), dental adhesives (orthodontic adhesives, cavity application adhesives), denture base lining materials, impression materials, dental temporary sealing materials, fissure sealants
• Examples 215 to 220 and Comparative Examples 37 and 38 (Preparation and Evaluation of Active Energy Ray-Curable Photosensitive Compositions) According to the proportions shown in Table 15 (solid content conversion), benzoyl formic acid amide derivative (D), commercially available photopolymerization initiator (E), monofunctional unsaturated compound (h1), polyfunctional unsaturated compound (h2), thermal polymerization initiator (J), solvent (c) and other components (k) were weighed and mixed at 25 ° C for 30 minutes to prepare an active energy ray curable photosensitive composition (hereinafter also referred to as photosensitive composition). Using the photosensitive composition, a photosensitive resin was produced by the following method, and the sensitivity (curability) and storage stability of the obtained photosensitive resin were evaluated. In addition, a patterned cured product was produced from the photosensitive composition, and the pattern formability of the obtained cured product and the low molecular weight component content of the cured product were evaluated. These results are shown in Table 15.
• the photosensitive compositions of the examples and comparative examples were applied to a film thickness of 15 ⁇ m using a rotary coater, and dried in an oven for 3 minutes. After that, ultraviolet light was irradiated for 3 minutes (wavelength 405 nm, illuminance 0.5 mW/cm 2 , cumulative light amount 90 mJ/cm 2 ) to obtain a photosensitive resin (cured product).
• the photosensitive composition not containing a thermal polymerization initiator (J) was dried at 80°C.
• the photosensitive composition containing a thermal polymerization initiator (J) was dried at 40°C, and after ultraviolet light irradiation, heat treatment was performed in an oven at 130°C for 30 minutes.
• ⁇ Sensitivity> The photosensitive resin was touched with a hand and the sensitivity was evaluated according to the following criteria. ++: No stickiness at all. +: There was some stickiness, but finger marks were not left on the surface. ⁇ : Sticky and finger marks left on the surface. -: It was very sticky and my fingers stuck to the surface.
• ⁇ Storage stability> The photosensitive resin was allowed to stand in a thermo-hygrostat at a temperature of 40° C. and a relative humidity of 50% for 168 hours, and the surface of the photosensitive resin was visually observed to evaluate the storage stability according to the following criteria. The less bleeding out, the higher the storage stability. ++: No bleeding out was observed at all. +: Slight bleed-out was observed. -: Severe bleeding out was observed.
• ⁇ Low molecular weight component content> Three test pieces each having a size of 5 cm2 were cut out from the photosensitive resin and dried at 130°C for 30 minutes. Thereafter, the photosensitive resin (photosensitive composition) was subjected to the same evaluation as in the evaluation of the content of low molecular weight components in the cured product of the curable composition. The content of low molecular weight components in the cured product was evaluated.
• Patterned Cured Product Using a negative photomask (pattern mask), cured products of the photosensitive compositions of the Examples and Comparative Examples were produced in the same manner as in the production of the photosensitive resin. The negative photomask was then removed from the cured products, and the unexposed areas were removed with cyclopentanone to obtain patterned cured products.
• a negative photomask pattern mask
• ⁇ Pattern Formability> The pattern formability of the patterned cured product was evaluated according to the following criteria. ++: There was no distortion of the pattern or chipping of the edges. +: There was no distortion of the pattern, and there was slight chipping at the edges. ⁇ : The pattern was slightly distorted and had chipping at the edges. -: The pattern was distorted and the edges were chipped.
• the photosensitive compositions of the Examples had high curability (sensitivity), and the cured products (photosensitive resins) obtained by curing them had high storage stability and a low content of low molecular weight components. Furthermore, the patterned cured products of the Examples obtained using a pattern mask had excellent pattern formability. On the other hand, the photosensitive compositions of the Comparative Examples had low sensitivity, and the cured products obtained from them had a high content of low molecular weight components and low storage stability. Furthermore, the patterned cured products of the Comparative Examples obtained using a pattern mask had poor pattern formability.
• Examples 221 to 227 and Comparative Examples 39 and 40 Preparation and Evaluation of Active Energy Ray-Curable Hydrogel Compositions
• the benzoylformamide derivative (D) the commercially available photopolymerization initiator (E), the monofunctional unsaturated compound (h1), the polyfunctional unsaturated compound (h2), ion-exchanged water and other components (k) were weighed and mixed at 25°C for 30 minutes to prepare an active energy ray-curable hydrogel composition (hereinafter also referred to as the hydrogel composition).
• the compatibility and curability of the hydrogel composition were evaluated, and the appearance and low molecular weight component content of the obtained cured product (hydrogel) were evaluated. The results are shown in Table 16.
• the prepared hydrogel composition was evaluated by the same method and evaluation criteria as in the evaluation of compatibility of the active energy ray-curable composition.
• the hydrogel composition was applied to a PET film using a bar coater to a film thickness of 20 ⁇ m.
• the coating was cured by irradiating it with ultraviolet light under the conditions 7) to 9) below, and the cured product was touched to evaluate its curability according to the following criteria.
• High pressure mercury lamp Wavelength 200-450nm, Illuminance 100mW/ cm2 , 1,000mJ/ cm2 8)
• UV-LED lamp wavelength 385nm, illuminance 100mW/cm 2 , 1,000mJ/cm 2 9)
• UV-LED lamp wavelength 405nm, illuminance 100mW/cm 2 , 1,000mJ/cm 2 ++: Gel was formed overall and the mixture was in a slightly hard state. +: Gel was formed overall and the product was in a slightly soft state. ⁇ : A partial gel was formed. -: No gel was formed.
• ⁇ Appearance of the cured product> The appearance of the cured product obtained in the curing evaluation under UV irradiation condition 9) was visually observed and rated according to the following criteria. +: No turbidity or phase separation. ⁇ : No phase separation, but turbidity was observed. -: Turbidity and phase separation were observed.
• the cured product obtained in the curability evaluation under the ultraviolet irradiation conditions in 9) was used to evaluate the low molecular weight component content of the cured product (hydrogel) in the same manner as in the evaluation of the low molecular weight component content of the cured product of the curable composition. (excluding water) was evaluated.
• the hydrogel compositions of the examples contain water-soluble or hydrophilic acroylmorpholine (h1-1), N-(2-hydroxyethyl)acrylamide (h1-7) or N-vinylpyrrolidone (h1-11) and water, and show good compatibility and are in an aqueous solution state.
• the hydrogel compositions of the examples have high curing properties, and the cured products obtained by curing them form a gel overall (hydrogel).
• the cured products (hydrogels) have a low content of low molecular weight components and are highly safe. Such hydrogels can be suitably used as sanitary materials and medical materials.
• the hydrogel compositions of the comparative examples have low compatibility and curing properties, and cannot form a uniform hydrogel even when irradiated with ultraviolet light, so the low molecular weight component content could not be evaluated.
• the comparative examples in which hydrogels were partially formed had a high content of low molecular weight components in the hydrogels.
• Examples 228 to 234 and Comparative Examples 41 and 42 Preparation and Evaluation of Active Energy Ray-Curable Aqueous Compositions
• the benzoyl formic acid amide derivative (D) the commercially available photopolymerization initiator (E), the monofunctional unsaturated compound (h1), the polyfunctional unsaturated compound (h2), ion-exchanged water and other components (k) were weighed and mixed at 25°C for 30 minutes to prepare an active energy ray-curable aqueous composition (hereinafter also referred to as the aqueous composition).
• the dispersibility and curability of the aqueous composition were evaluated, and the appearance and low molecular weight component content of the obtained cured product were evaluated. The results are shown in Table 17.
• ⁇ Dispersibility> After the aqueous composition was allowed to stand in a thermostatic chamber at 40° C. for 24 hours, the state of the aqueous composition was visually observed, and the dispersibility was evaluated according to the following criteria. +: The aqueous composition was a stable homogeneous emulsion. ⁇ : The aqueous composition was partially aggregated and was a non-uniform emulsion. -: The aqueous composition was phase separated.
• a coating film of the aqueous composition was prepared in the same manner as in the evaluation of the curability of the curable composition, and after drying at 80° C. for 5 minutes, it was irradiated with ultraviolet light to evaluate the curability.
• the aqueous compositions of the Examples had good dispersibility, were able to maintain a good emulsion state, and had high curing properties even when using long-wavelength light.
• the cured products obtained had a low content of low molecular weight components.
• the aqueous compositions of the Comparative Examples had low dispersibility and curing properties, and the cured products obtained contained a large amount of low molecular weight components.
• a benzoylformamide derivative having a benzoylformamide group represented by general formula (1) includes the following: (1) A benzoylformamide derivative having a benzoylformamide group represented by general formula (1).
• Q 1 to Q 3 each independently represent a hydrogen atom, a substituent represented by formulae (Chemical Formula 2) to (Chemical Formula 8), a halogen group, or a nitrile group, and are bonded to any of the 2- to 6-positions.
• R 1 to R 10 each independently represent a hydrogen atom, a linear alkyl group having 1 to 18 carbon atoms, a linear alkenyl group having 2 to 18 carbon atoms, a branched alkyl group having 3 to 18 carbon atoms, a branched alkenyl group having 3 to 18 carbon atoms, a cyclic alkyl group having 3 to 18 carbon atoms, or a cyclic alkenyl group having 3 to 18 carbon atoms; * indicates the bond position.
• the benzoylformamide derivative according to (1) above which is at least one compound represented by any one of general formulas (2) to (4).
• Q 1 to Q 3 are defined as in general formula (1).
• B1 represents a monovalent organic group which may have a hydrogen atom, a hydroxyl group, an amino group, a thiol group, an ether group, a thioether group, an ester group, a carbonate group, a urethane group, a thiourethane group, a urea group, a siloxane group, an amide group, an imide group, an ethylenically unsaturated group, or a benzoylformamide group;
• B2 represents a monovalent organic group which may have a hydroxyl group, an amino group, a thiol group, an ether group, a thioether group, an ester group, a carbonate group, a urethane group, a thiourethane group, a urea group, an amide group, an imide group, a siloxane group, an ethylenically unsaturated group, or a benzoylformamide group.
• Q 1 to Q 3 are defined as in general formula (1).
• B3 represents an m-valent organic group which may have an ethylenically unsaturated group, an ether group, a thioether group, an ester group, a carbonate group, a urethane group, a thiourethane group, an isocyanurate group, an allophanate group, a urea group, a siloxane group, an amide group, or an imide group;
• R 11 represents a hydrogen atom, a linear alkyl group having 1 to 18 carbon atoms, a linear alkenyl group having 2 to 18 carbon atoms, a branched alkyl group having 3 to 18 carbon atoms, a branched alkenyl group having 3 to 18 carbon atoms, a cyclic alkyl group having 3 to 18 carbon atoms, a cyclic alkenyl group having 3 to 18 carbon atoms, or an aryl group having 6 to 8 carbon
• A1 represents a divalent organic group which may have an ether group, a thioether group, an ester group, a carbonate group, a urethane group, a thiourethane group, a urea group, a siloxane group, an amide group, or an imide group
• B 4 and B 5 may each independently have an ethylenically unsaturated group, an ether group, a thioether group, an ester group, a carbonate group, a urethane group, a thiourethane group, an isocyanurate group, an allophanate group, a urea group, a siloxane group, an amide group, or an imide group
• B 4 and B 5 represent a monovalent organic group containing one or more ethylenically unsaturated bonds
• R 13 represents a hydrogen atom
• the benzoylformamide derivative according to any one of (1) to (3) which has one or more ethylenically unsaturated bonds in the molecule, and the ethylenically unsaturated bonds are one or more groups selected from a (meth)acrylate group, a (meth)acrylamide 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.
• An actinic ray-curable ink composition comprising the benzoylformamide derivative according to any one of (1) to (12) and (14).
• An active energy ray-curable pressure-sensitive adhesive composition comprising the benzoylformamide derivative according to any one of (1) to (12) and (14).
• An active energy ray-curable adhesive composition containing the benzoylformamide derivative according to any one of (1) to (12) and (14).
• An active energy ray-curable dental material composition containing the benzoylformamide derivative according to any one of (1) to (12) and (14).
• An active energy ray-curable coating composition comprising the benzoylformamide derivative according to any one of (1) to (12) and (14).
• An active energy ray-curable aqueous composition containing the benzoylformamide derivative according to any one of (1) to (12) and (14).
• An actinic ray-curable ink-jet ink composition comprising the benzoylformamide derivative according to any one of (1) to (12) and (14).
• An active energy ray-curable elastomer composition containing the benzoylformamide derivative according to any one of (1) to (12) and (14).
• An active energy ray-curable resin composition for decorative sheets comprising the benzoylformamide derivative according to any one of (1) to (12) and (14).
• An active energy ray-curable screen ink composition containing the benzoylformamide derivative according to any one of (1) to (12) and (14).
• a resin composition for an active energy ray-curable self-repairing material comprising the benzoylformamide derivative according to any one of (1) to (12) and (14).
• the benzoyl formic acid amide derivative (D) of the present disclosure exhibits high curability against ultraviolet rays of various wavelengths, including long-wavelength ultraviolet rays with wavelengths of 360 to 420 nm, and in particular exhibits high photopolymerization initiation, photosensitization, and curability even when using UV-LED lamps with wavelengths of 385 nm, 395 nm, and 405 nm.
• these individual performances and effects of D are further improved.
• the amount of low molecular weight components in the cured product obtained is extremely small, and the safety and adhesion to various materials are high, and various physical properties such as surface hardness, light yellowing resistance, durability, and transparency are also good.
• the benzoylformamide derivative (D) of the present disclosure can be used in an active energy ray-curable ink composition, an active energy ray-curable inkjet ink composition, an active energy ray-curable flexographic ink composition, an active energy ray-curable offset ink composition, an active energy ray-curable screen ink composition, an active energy ray-curable nail cosmetic composition, an active energy ray-curable pressure-sensitive adhesive composition, an active energy ray-curable adhesive composition, an active energy ray-curable sealant composition, an active energy ray-curable coating agent composition, an active energy ray-curable resin composition for decorative sheets, an active energy ray-curable elastomer ...
• the composition can be suitably used as an active energy ray curable ink composition for three-dimensional modeling, an active energy ray curable coating composition for vehicles, an active energy ray curable nail cosmetic composition, an active energy ray curable resin composition for self-repairing materials, an active energy ray curable architectural coating composition, an active energy ray curable composition used in various coating fields such as ship bottom paint, anti-fogging material, and antifouling paint, an active energy ray curable composition used in the medical device surface coating field, an active energy ray curable dental material composition, an active energy ray curable photosensitive composition, an active energy ray curable hydrogel composition, and an active energy ray curable water dispersion composition.
• the obtained hydrogel composition and aqueous composition can also be suitably used as a material in a wide variety of fields such as superabsorbent resins, paper diapers, and soft contact lenses in the hygiene field, medical device surface coatings and artificial organs in the medical field, soil conditioners in the civil engineering and construction fields, water-retaining materials in the agricultural field, and shock absorbing materials.

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