Benzoylformic acid amide derivative

Abstract

To provide a benzoylformic acid amide derivative, wherein the benzoylformic acid amide derivative has good photopolymerization initiation properties and photosensitization effect with respect to long-wavelength ultraviolet light, and a cured product obtained from a curable composition that contains the benzoylformic acid amide derivative has an extremely low content of a low molecular weight component, and exhibits high yellowing resistance, durability and safety.SOLUTION: The present invention provides a benzoylformic acid amide derivative.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to novel benzoylformamide derivatives. The benzoylformamide derivatives can be used as photoinitiators and photosensitizers. Further, the present invention relates to an active energy ray curable composition containing a benzoylformamide derivative, an active energy ray curable ink composition, an inkjet ink, an ink for three-dimensional modeling, an adhesive composition, an adhesive composition, a sealing material composition, a photosensitive composition, a nail cosmetic composition, a dental material composition, a coating agent composition, and an aqueous composition.

Background Art

[0002] Photopolymerization and photocuring using active energy rays such as ultraviolet rays (UV) generally generate active species such as radicals and ions by irradiating a composition containing a photoinitiator with UV, causing a polymerization reaction, and solidifying (curing) a liquid composition in a short time. This technology is currently utilized in a wide range of fields, including paints, coating agents, adhesives, sealants, elastomer-based materials, inkjet inks, sealing materials, encapsulants, dental hygiene materials, and optical materials. In particular, due to the ability to cure at arbitrary locations and in arbitrary shapes, its use as a nail cosmetic such as gel nails and its application in 3D printers as a material for three-dimensional optical modeling are expanding.

[0003] Photoinitiators that generate radicals by active energy rays can be classified into intramolecular cleavage type and hydrogen abstraction type. The former is a type that generates radicals by cleavage within the molecule, and the latter is a type that generates radicals by abstracting hydrogen from a hydrogen donor. In the intramolecular cleavage type, since the decomposition products derived from the initiator remain in the cured product, problems such as a decrease in the durability of the cured product, odor generation, and coloring over time occur, and there is also a problem of low safety. Although many of the hydrogen abstraction type have low efficiency of photoinitiation, they have recently attracted increased attention because there are no decomposition products derived from the initiator.

[0004] In addition, due to their high safety, long-wavelength UV-LED lamps and LED lamps have been increasingly used. Although the development of photoinitiators and photosensitizers applicable to these light sources has been actively carried out, there have been problems such as low photoinitiation effect and photosensitization effect, and the resulting cured products are prone to yellowing.

Summary of the Invention

Problems to be Solved by the Invention

[0005] The first object of the present invention is to provide a benzoylformamide derivative. The benzoylformamide derivative has a high photoinitiation property for active energy rays, particularly light rays of 360 to 420 nm irradiated by an LED lamp, and there are no decomposition products of the benzoylformamide derivative in the resulting cured product. The second object is to provide the benzoylformamide derivative as a highly safe photoinitiator. The third object is to provide a highly curable active energy ray-curable composition containing the benzoylformamide derivative as a photoinitiator. The fourth object is to provide a highly safe ink composition, an inkjet ink composition, a three-dimensional shaping ink composition, an adhesive composition, an adhesive composition, a sealing agent composition, a photosensitive composition, a nail cosmetic composition, a dental material composition, a coating agent composition, an aqueous composition, a hydrogel composition, and an intraocular implant material composition containing the benzoylformamide derivative, having high compatibility, excellent adhesion to a substrate, and little yellowing and bleed-out over time.

[0006] The benzoylformamide derivative has photosensitivity to active energy rays, particularly light rays in the range of 360 to 420 nm irradiated by an LED lamp, and a cured product that does not cause yellowing can be obtained. The fifth problem is to provide a benzoylformamide derivative as a photosensitizer. Further, the sixth problem is to provide an active energy ray-curable composition having high curability and high compatibility containing the benzoylformamide derivative as a photosensitizer. The seventh problem is to provide an ink composition, an inkjet ink composition, a three-dimensional shaping ink composition, an adhesive composition, an adhesive composition, a sealing agent composition, a photosensitive composition, a nail cosmetic composition, a dental material composition, a coating agent composition, an aqueous composition, a hydrogel composition, and an intraocular implant material composition, which contain a benzoylformamide derivative and can obtain a cured product having excellent adhesion to a substrate and excellent durability with little yellowing over time.

Means for Solving the Problems

[0007] As a result of intensive studies, the present inventors have found a benzoylformamide derivative having a benzoylformamide group represented by the general formula (1) and have reached the present invention. JPEG2025100963000001.jpg3364Q 1 ~Q 3 each independently represents a hydrogen atom, a substituent represented by Formula (Chemical Formula 2) to (Chemical Formula 8), a halogen group, or a nitrile group, and is bonded at an arbitrary position of the 2nd to 6th positions. JPEG2025100963000002.jpg11539R 1 ~R 10 each independently 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, or a cyclic alkenyl group having 3 to 18 carbon atoms, * represents the bonding position.

Effects of the Invention

[0008] The benzoylformamide derivatives of the present disclosure have high initiation efficiency (also referred to as polymerization initiation or photoinitiation) with respect to long-wavelength light rays of 360 to 420 nm and light rays having wavelengths typified by, for example, 365 nm, 385 nm, 395 nm, and 405 nm irradiated from an LED lamp, and at the same time, the radicals generated have high activity and can be used as a photoinitiator. The active energy ray-curable composition containing the benzoylformamide derivative as a photoinitiator can easily obtain a cured product that is completely cured at low energy (low integrated light amount) and high speed (short curing time) even in an industrial manufacturing environment under an air atmosphere without using additives such as a co-initiator hydrogen donor, a general-purpose photosensitizer, and a curing accelerator in combination. Further, the obtained cured product does not have decomposition products of the benzoylformamide derivative used as a photoinitiator, has low odor, yellowing over time, and bleed-out, and has high durability and safety. The benzoylformamide derivative can be suitably used in a variety of applications such as an active energy ray-curable ink composition, an inkjet ink composition, an ink composition for three-dimensional modeling, an adhesive composition, an adhesive composition, a sealing material composition, a photosensitive composition, a nail cosmetic composition, a dental material composition, a coating agent composition, an aqueous composition, a hydrogel composition, and a material composition for an intraocular implant.

[0009] The benzoylformamide derivatives of the present disclosure absorb long-wavelength light rays of 360 to 420 nm, and light rays of 365 nm, 385 nm, 395 nm, and 405 nm irradiated from an LED lamp, and have a photosensitizing effect on other general photo radical polymerization initiators and photoionic polymerization initiators. It can be used as a photosensitizer that hardly causes yellowing by photocuring. The active energy ray-curable composition containing the benzoylformamide derivative as a photosensitizer is used in combination with a photopolymerization initiator that has poor curability with long-wavelength light rays of 360 to 420 nm and light rays of 365 nm, 385 nm, 395 nm, and 405 nm irradiated from an LED lamp. Even in an industrial manufacturing environment under an air atmosphere, a cured product with complete curing can be easily obtained at low energy (low integrated light amount) and high speed (short curing time). Further, the obtained cured product has low odor, yellowing over time, and bleed-out, and has high durability and safety. The benzoylformamide derivative can be suitably used in a variety of applications such as active energy ray-curable ink compositions, inkjet ink compositions, ink compositions for three-dimensional modeling, adhesive compositions, adhesive compositions, sealant compositions, photosensitive compositions, nail cosmetic compositions, dental material compositions, coating agent compositions, aqueous compositions, hydrogel compositions, and material compositions for intraocular implants.

Embodiments for Carrying Out the Invention

[0010] Hereinafter, embodiments of the present disclosure will be described in detail. However, the scope of the present invention is not limited to the embodiments described here, and various modifications can be made without departing from the spirit of the present invention. Further, when a plurality of upper limit values and lower limit values are described for specific parameters, any upper limit value and lower limit value can be combined to form a suitable numerical range.

[0011] One embodiment of the present disclosure is a benzoylformamide derivative (D) having one or more benzoylformamide groups represented by the general formula (1) in the molecule.

[0012] Q of the general formula (1) 1 ~Q 3are, independently of each other, 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, an alkoxy group, 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, and a nitrile group. Q 1 ~Q 3 is bonded to an arbitrary position at the 2nd to 6th positions of the benzene ring. Q 1 ~Q 3 When ~Q is a hydrogen atom, the benzoylformic acid amide derivative (D) exhibits good photopolymerization initiation property and photosensitization property with respect to a high-pressure mercury lamp and a UV-LED light source of 360 nm to 410 nm, and has low coloring by light irradiation. Q 1 ~Q 3 When ~Q is an electron-donating alkyl group, alkoxy group, amino group, alkylamino group, dialkylamino group, alkyl ester group, or alkylamide group, the absorption wavelength of the benzoylformic acid amide derivative (D) shifts to the long wavelength side, and since it has high sensitivity even with respect to a light source of 390 nm to 420 nm, it is more preferably used as both a photopolymerization initiator and a photosensitizer. Although these electron-donating substituents may be colored by light irradiation, from the viewpoint of maintaining the coloring of D at a low level at a practical level, Q 1 ~Q 3 is particularly preferably an alkoxy group or an alkyl ester group.

[0013] The benzoylformamide group of the benzoylformamide derivative (D) is a monosubstituted amide group or a disubstituted amide group of benzoylformic acid. Both the monosubstituted amide group of benzoylformic acid and the disubstituted amide group of benzoylformic acid have photopolymerization initiation properties and photosensitization properties, and the photopolymerization initiation property is higher for the monosubstituted amide group of benzoylformic acid. The monosubstituted amide group of benzoylformic acid has a hydrogen atom bonded to its nitrogen atom. While it is a hydrogen abstraction type photoinitiating functional group, it is also a hydrogen donating group, and active radicals are efficiently generated by hydrogen abstraction within the molecule and / or between molecules. Therefore, D having a monosubstituted amide group of benzoylformic acid has high photopolymerization initiation property and polymerization initiation property for highly safe ultraviolet rays of 360 to 420 nm without the need to use in combination an easily colorable amine hydrogen donor or the like.

[0014] As the benzoylformamide derivative (D) of the present disclosure, it is preferably at least one compound represented by any one of general formulas (2) to (4).

[0015] JPEG2025100963000003.jpg3564In the formula, Q 1 ~Q 3 is the same as the definition described in general formula (1), B 1 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, B 2 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 group or a benzoylformamide group.

[0016] JPEG2025100963000004.jpg3677In the formula, Q 1 ~Q 3 is the same as the definition described in general formula (1), B 3 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 atoms, R 12 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 atoms of any carbon atom or hydrogen atom 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, m represents an integer from 1 to 10.

[0017] JPEG2025100963000005.jpg4283In the formula, Q 1 ~Q 3 is the same as the definition described in general formula (1), A 1 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 B 5 independently of each other 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, and either or both of B 4 B 5 represents a monovalent organic group containing one or more ethylenically unsaturated bonds, R 13represents 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 14 represents a trivalent hydrocarbon group that is linear and saturated with 1 to 8 carbon atoms, a trivalent hydrocarbon group that is linear and unsaturated with 2 to 8 carbon atoms, a trivalent hydrocarbon group that is branched and saturated or unsaturated with 3 to 8 carbon atoms, a trivalent hydrocarbon group that is alicyclic and saturated or unsaturated with 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 atoms of any carbon atom or hydrogen atom 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 15 represents a divalent hydrocarbon group that is linear and saturated with 1 to 18 carbon atoms, a divalent hydrocarbon group that is linear and unsaturated with 2 to 18 carbon atoms, a divalent hydrocarbon group that is branched and saturated or unsaturated with 3 to 8 carbon atoms, a divalent hydrocarbon group that is alicyclic and saturated or unsaturated with 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 atoms of any carbon atom or hydrogen atom 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, n represents an integer from 1 to 100.

[0018] When the benzoylformamide derivative (D) is represented by the general formula (2), the benzoylformamide group has a hydrophobic benzene ring and a hydrophilic formamide group and is amphiphilic. B 1 and B 2 (which are independent of each other.) By adjusting the polarity according to the purpose, D has high compatibility with other components used in the curable composition, and the resulting curable composition and the cured product obtained by curing it have high transparency. B 1 and / or B 2 has 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, which is preferable because the polarity is easy to adjust. Also, B 1 and B2 It is more preferable that it has an ether group, an ester group, a urethane group, or an amide group. B 1 When B is a hydrogen atom, D has a benzoylformic acid mono-substituted amide group and has higher photopolymerization initiating property, so it is more preferable.

[0019] B 1 and B 2 may further have a benzoylformic acid amide group represented by the general formula (1). In that case, the benzoylformic acid amide derivative (D) has a plurality of benzoylformic acid amide groups and is preferable because it has higher photopolymerization initiating property and photosensitizing property. The benzoylformic acid amide groups contained in D may be the same or different.

[0020] The benzoylformic acid amide derivative (D) represented by the general formula (2) can be used as a photosensitizer for photoionic polymerization. In that case, B 1 and B 2 having a cyclic ether group is preferable 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.

[0021] B 1 and B 2 preferably further has an ethylenically unsaturated group. In that case, the benzoylformic acid amide derivative (D) is preferable as a photopolymerization initiator or photosensitizer having an ethylenically unsaturated group because D is incorporated into the cured product via a covalent bond by photoradical polymerization. It is preferable to have one or more ethylenically unsaturated groups, and more preferable to have two or more ethylenically unsaturated groups. The ethylenically unsaturated groups may be a single type alone or a plurality of types.

[0022] B 1 and B 2When it has a urethane group, the benzoylformamide derivative (D) has good compatibility with other components used in the curable composition, and the resulting curable composition and its cured product have high transparency. The ratio of the number (total) of urethane groups in D to the number (total) of benzoylformamide groups is preferably 0.1 or more, and more preferably 0.5 or more. Also, when the number of urethane groups increases, the viscosity of D increases, and the above ratio is preferably 10.0 or less.

[0023] More preferably, the benzoylformamide derivative (D) has a urethane group represented by the general formula (3) or the general formula (4). The urethane group has a hydrogen atom bonded to its nitrogen atom and can function as a hydrogen-donating group, and D has good photopolymerization initiation properties with respect to highly safe ultraviolet rays of 360 to 420 nm.

[0024] When the benzoylformamide derivative (D) has one or more urethane groups, the number of atoms directly connecting between the nitrogen atom of the benzoylformamide group and the nitrogen atom of the nearest urethane group is preferably 3 to 20. When the number of directly connecting atoms is 3 or more, both the hydrogen abstraction ability of the benzoylformamide group and the hydrogen donating ability of the urethane group are improved due to the interaction between the benzoylformamide group and the urethane group. Also, when the number of directly connecting atoms is 20 or less, the benzoylformamide group and the urethane group in the molecule are likely to approach each other and are likely to cause a hydrogen abstraction reaction. From these viewpoints, the number of the directly connecting atoms is more preferably 4 to 10, and even more preferably 4 to 6.

[0025] 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 resulting curable composition and its cured product have high transparency. Also, from the viewpoint of further improving the compatibility of the curable composition, B 3It preferably 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 ratio is preferably 10.0 or less, more preferably 6.0 or less, and particularly preferably 4.0 or less.

[0026] R in the general formula (3) 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. R 11 When R is a hydrogen atom, the benzoylformamide derivative (D) has a benzoylformic acid monosubstituted amide group and is more preferable because of excellent photopolymerization initiation properties.

[0027] R in the general formula (3) 12 is 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 atoms of these hydrocarbon groups, either a carbon atom or a hydrogen atom, 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 linear saturated divalent hydrocarbon group having 1 to 8 carbon atoms, a linear unsaturated divalent hydrocarbon group having 2 to 8 carbon atoms, or a branched saturated or unsaturated divalent hydrocarbon group having 3 to 18 carbon atoms, and more preferably a linear saturated divalent hydrocarbon group having 2 to 4 carbon atoms or a branched saturated divalent hydrocarbon group having 3 to 8 carbon atoms.

[0028] The benzoylformamide group is amphiphilic, and B 3By adjusting the polarity of [component D] according to the purpose, D has high compatibility with other components used in the curable composition, and the resulting curable composition and the cured product obtained by curing it have high transparency. Component B 3 When [component B] 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, it is easy to adjust its polarity, which is preferable.

[0029] The benzoylformamide derivative (D) represented by the general formula (3) can also be used as a photosensitizer for photoionic polymerization. In that case, component B 3 Preferably has 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.

[0030] Component B 3 Preferably further has an ethylenically unsaturated group. In that case, the benzoylformamide derivative (D) is preferably a photopolymerization initiator or photosensitizer having an ethylenically unsaturated group, because D is incorporated into the cured product via a covalent bond by photoradical polymerization. It is preferable to have one or more ethylenically unsaturated groups, and more preferable to have two or more ethylenically unsaturated groups. The ethylenically unsaturated group may be a single type alone or may have a plurality of types.

[0031] m in the general formula (3) is an integer of 1 to 10. When m is 1 or more, the benzoylformamide derivative (D) has one or more benzoylformamide groups in the molecule and can function as both a photopolymerization initiator and a photosensitizer. When 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 of 2 to 4.

[0032] The benzoylformic acid amide derivative (D) represented by the general formula (3) can be produced by synthesizing a benzoylformic acid amide monoalcohol through an amidation reaction of benzoylformic acid and aminoalkyl alcohol, and then further performing a urethanization reaction with an isocyanate compound. As the aminoalkyl alcohol, 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 are preferred, 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, 2-amino-1-hexanol, 7-aminoheptanol, 2-amino-1-octanol, 2-amino-1-decanol, 2-amino-1-dodecanol, 2-amino-1-octadecanol are more preferred, and 2-aminoethanol, 2-aminopropanol, 2-amino-2-methyl-1-propanol are even more preferred.

[0033] The benzoylformic acid amide derivative (D) represented by the general formula (4) has one or more benzoylformic acid amide 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 curable composition containing D and the cured product obtained by curing it have high transparency. From this viewpoint, A 1 , B 4 and B 5It is preferable that any one or more of them further have one or more urethane groups. The ratio of the number (total) of urethane groups to the number (total) of benzoylformic acid amide groups in D is preferably 2.0 or more, more preferably 2.5 or more. Also, when the number of urethane groups increases, the viscosity of D increases. Therefore, the above ratio is preferably 15.0 or less, more preferably 8.0 or less, and particularly preferably 5.0 or less.

[0034] R in the general formula (4) 13 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. When R 13 is a hydrogen atom, the benzoylformic acid amide derivative (D) has a benzoylformic acid monosubstituted amide group and is preferable because of excellent photopolymerization initiation properties.

[0035] R in the general formula (4) 14 is a trivalent hydrocarbon group that is linear and saturated having 1 to 8 carbon atoms, a trivalent hydrocarbon group that is linear and unsaturated having 2 to 8 carbon atoms, a trivalent hydrocarbon group that is branched and saturated or unsaturated having 3 to 8 carbon atoms, a trivalent hydrocarbon group that is alicyclic and saturated or unsaturated 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 atoms of any carbon atom or hydrogen atom 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. From the viewpoint that the number of atoms directly connecting between the nitrogen atom of the benzoylformic acid amide group and the nitrogen atom of the nearest urethane group is preferably 3 to 10, R 14 is preferably a trivalent hydrocarbon group that is linear and saturated having 1 to 8 carbon atoms, a trivalent hydrocarbon group that is linear and unsaturated having 2 to 8 carbon atoms, a trivalent hydrocarbon group that is branched and saturated or unsaturated having 3 to 8 carbon atoms, a trivalent hydrocarbon group that is alicyclic and saturated or unsaturated having 3 to 8 carbon atoms, more preferably a trivalent hydrocarbon group that is linear and saturated having 2 to 4 carbon atoms, or a trivalent hydrocarbon group that is branched and saturated having 3 to 4 carbon atoms.

[0036] R in the general formula (4)15 represents a divalent hydrocarbon group that is linear and saturated with 1 to 18 carbon atoms, a divalent hydrocarbon group that is linear and unsaturated with 2 to 18 carbon atoms, a divalent hydrocarbon group that is branched and saturated or unsaturated with 3 to 18 carbon atoms, a divalent hydrocarbon group that is alicyclic and saturated or unsaturated with 3 to 8 carbon atoms, a divalent aromatic hydrocarbon group with 6 to 8 carbon atoms, or a divalent organic group in which any one or more atoms of any carbon atom or hydrogen atom 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. A 1 From the perspective of facilitating the introduction of the urethane group bonded to R 15 is preferably an alkylene group having 1 to 18 carbon atoms.

[0037] The benzoylformamide group is amphiphilic, and by adjusting A 1 according to the purpose of the polarity, D has high compatibility with other components used in the curable composition, and the resulting curable composition and the cured product obtained by curing it have high transparency. A 1 If A has 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 easy to adjust its polarity, which is preferable. Furthermore, when A 1 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 it is preferable because the polarity of A 1 can be adjusted more easily.

[0038] 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. Either one or both of B 4 and B 5 is a monovalent organic group containing one or more ethylenically unsaturated bonds.

[0039] The benzoylformamide derivative (D) represented by the general formula (4) can also be used as a photosensitizer for photoionic polymerization. In that case, B 4and / or B 5 When 5 has a cyclic ether group, it is preferable 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.

[0040] B 4 B 5 Since one or both of 4 and 5 have one or more ethylenically unsaturated bonds, 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 4 and 5 have an ethylenically unsaturated group. The ethylenically unsaturated group may be a single type or a plurality of types. 4 and B 5 Both preferably have an ethylenically unsaturated group. The ethylenically unsaturated group may be a single type or a plurality of types.

[0041] B 4 and B 5 The polarities of 4 and 5 can be adjusted according to the purpose. 4 and B 5 4 and 5 preferably 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 because their polarities can be easily adjusted. Furthermore, when 4 and 5 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 polarities of 4 and 5 can be more easily adjusted, which is preferable. 4 and B 5 4 and 5 preferably have an ether group, a thioether group, an ester group, a carbonate group or a urethane group because the number of these groups can be easily adjusted, and the polarities of 4 and 5 can be more easily adjusted. 4 and B 5 4 and 5 preferably have an ether group, a thioether group, an ester group, a carbonate group or a urethane group because the number of these groups can be easily adjusted, and the polarities of 4 and 5 can be more easily adjusted.

[0042] n in the general formula (4) is an integer from 1 to 100. When n is 1 or more, the benzoylformamide derivative (D) has one or more benzoylformamide groups and can function as both a photoinitiator and a photosensitizer. Also, when n is 2 or more, it is preferable because both the photoinitiation property and the photosensitization property are high. When n exceeds 100, 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 n is an integer from 2 to 50, and particularly preferably an integer from 2 to 20.

[0043] The general formula (4) can be produced by synthesizing benzoylformic acid amide diol through an amidation reaction of benzoylformic acid and aminoalkyl alcohol, and then further through a urethanization reaction with an isocyanate compound. As the aminoalkyl diol, 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, 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, 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, 2-amino-2-ethyl-1,3-propanediol are more preferred.

[0044] The benzoylformamide derivative (D) is a hydrogen abstraction type photoinitiator and does not generate decomposition products upon photopolymerization. When the benzoylformamide derivative (D) is used as a photosensitizer, no decomposition products are generated upon photopolymerization. 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 bleeding out of D from the cured product hardly occurs. A higher molecular weight of D is preferable because of higher safety, but if it exceeds 200,000, the viscosity of D and the viscosity of the curable composition containing it may become extremely high, resulting in a decrease in handleability. 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 referred to as a low molecular weight component. Since many low molecular weight components have high volatility and low safety, when the low molecular weight component is present in the cured product, it bleeds out from the cured product over time, causing problems such as deterioration of the appearance of the cured product and generation of odor.

[0045] The benzoylformic acid amide derivative (D) can be synthesized by the following method. Benzoylformic acid or a benzoylformic acid ester (hereinafter collectively referred to as raw material (a1)) and an amine compound (hereinafter also referred to as an amino group-containing compound and used as raw material (a2)) are subjected to an amidation reaction to obtain a benzoylformic acid amide derivative (D) represented by the general formula (2). Further, raw material (a2) can have a plurality of amino groups and, in addition to the amino group, a hydroxyl group, a carboxyl group, a urethane group, a urea group, or an amide group. It is preferable that a2 has a reactive group such as a hydroxyl group, an amino group, or a carboxyl group. After the amidation reaction of a1 and a2, these reactive groups can be used to react with various compounds. It is more preferable that the reactive group of a2 is a hydroxyl group. When having a hydroxyl group, after reacting a1 and a2 to form a benzoylformic acid amide, an etherification reaction, an esterification reaction, or a urethanization reaction can be easily carried out using the hydroxyl group. The above-mentioned urethanization reaction can be used to synthesize a benzoylformic acid amide derivative (D) represented by the general formula (3) or the general formula (4) by using a compound having an ethylenically unsaturated group, a hydroxyl group, an amino group, a carboxyl group, an isocyanate group, etc. as a raw material.

[0046] Benzoylformic acid or benzoylformic acid ester (a1) includes benzoylformic acid, benzoylformic acid alkyl (linear 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) ester, benzoylformic acid alkenyl (linear 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) ester. Further, substituents represented by (Chemical Formula 2) to (Chemical Formula 8) are bonded to any position of the benzene ring at the 2nd to 6th positions of benzoylformic acid, benzoylformic acid alkyl ester, and benzoylformic acid alkenyl ester of a1. Specifically, 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-ethoxycarbonylbenzoylformate, methyl 4-butoxycarbonylbenzoylformate, methyl 3,5-dimethoxybenzoylformate, methyl 2,4-dimethoxybenzoylformate, methyl 2,4-diethoxybenzoylformate, methyl 2,4-dibutoxybenzoylformate, methyl 3,4,5-trimethoxybenzoylformate, methyl 4-methoxycarbonylbenzoylformate, methyl 4-acetoxybenzoylformate, methyl 4-dimethylaminobenzoylformate, methyl 2-acetamidobenzoylformate, methyl 3-chlorobenzoylformate, methyl 4-chlorobenzoylformate, methyl 3-bromobenzoylformate, methyl 4-bromobenzoylformate, ethyl 3-bromobenzoylformate, ethyl 4-bromobenzoylformate, methyl 4-nitrilebenzoylformate, ethyl 4-nitrilebenzoylformate can be mentioned. These a1 may be used alone or in combination of multiple kinds.

[0047] The amino group-containing compound (a2) includes amine compounds such as alkylamine, alkenylamine, dialkylamine, dialkenylamine, alkylalkenylamine, arylamine, aminoalkyl monoalcohol, aminoalkyl diol, aminoalkyl triol, aminoalkyl tetraol, aminoalkyl pentanol, N-alkyl-aminoalkyl monoalcohol, N-alkyl-aminoalkyl diol, N-alkyl-aminoalkyl triol, N-alkyl-aminoalkyl tetraol, N-alkyl-aminoalkyl pentanol, N,N-bis(hydroxyalkyl)amine, N,N-bis(dihydroxyalkyl)amine, hydroxyalkyl arylamine and other amine compounds having a hydroxyl group, aminoalkyl thiol, aminoalkenyl thiol and other amine compounds having a thiol group, (aminoalkoxy) alkanol, dialkylene glycol monoamine, trialkylene glycol monoamine, polyalkylene glycol monoamine and other amine compounds having an ether group, alkylenediamine, polyalkyleneimine, dialkylene glycol diamine, trialkylene glycol diamine, polyalkylene glycol diamine, diamino alkanol and other amine compounds having a plurality of amino groups, amino acids, amino benzoic acid and other amine compounds having a carboxyl group. The above-mentioned 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, and 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. These amino group-containing compounds may be used alone or in combination of multiple kinds.

[0048] When the amino group-containing compound (a2) has a hydroxyl group, a carboxyl group, a thiol group, or a plurality of amino groups, a benzoylformic acid amide derivative (D) having a hydroxyl group, a carboxyl group, a thiol group, or an amino group can be obtained. D can be further subjected to urethanization, thiourethanization, etherification, esterification, ureatization, amidation, or imidization by utilizing these reactive groups. Urethanization is the reaction of a hydroxyl group with an isocyanate group, thiourethanization is the reaction of a thiol group with an isocyanate group, etherification is the reaction of a hydroxyl group with an organic halogen, esterification is the reaction of a hydroxyl group with a carboxyl group or the reaction of a carboxyl group with an epoxy group, ureatization is the reaction of an amino group with an isocyanate group, amidation is the reaction of an amino group with a carboxyl group or the reaction of a carboxyl group with an isocyanate group, and imidization is the reaction of an amino group with a carboxylic anhydride group. By appropriately selecting and combining the raw materials having the various functional groups, D represented by the general formula (3) and the general formula (4) can be synthesized.

[0049] The amidation reaction of benzoylformic acid or a benzoylformic acid ester (a1) with an amino group-containing compound (a2) is preferably carried out under conditions of blocking light. Specifically, it can be carried out under light shielding, in an environment where ultraviolet rays are cut off such as in a yellow room, under a fluorescent lamp that does not irradiate ultraviolet rays, or under a red safelight for a darkroom. The reaction can proceed under mild conditions of normal pressure and 100 °C or lower. The reaction may use 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, dimethyl sulfoxide, 2-pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone. Also, a polymerizable (radical-based, cationic or anionic polymerization by light or heat) compound 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 the polymerizable compound solvent include N-(meth)acryloylmorpholine, a linear alkyl group or alkoxy group having 1 to 18 carbon atoms, a branched or cyclic alkyl group or alkoxy group having 3 to 18 carbon atoms, a (meth)acrylic acid ester having an alkoxy group, N-substituted (meth)acrylamide and N,N-disubstituted (meth)acrylamide, etc.

[0050] When synthesizing a benzoylformic acid amide derivative (D) by an amidation reaction of a benzoylformic acid ester (a1) and an amino group-containing compound (a2), alcohol is by-produced, and D containing alcohol is obtained as a crude product. When a solvent (c) is used, D containing alcohol and c is obtained as a crude product. These crude products can be used as they are in the curable composition, or alcohol and c can be removed and used in the curable composition. When the obtained D has a hydroxyl group, a carboxyl group, a thiol group, or an amino group, a new D can be synthesized using these groups. In that case, the reaction can be carried out while containing alcohol and c, or the reaction can be carried out after removing alcohol and c. Examples of the method for removing alcohol and c include distillation under normal pressure or reduced pressure, bubbling with an inert gas such as dry air or nitrogen, and freeze-drying method.

[0051] The benzoylformic acid amide 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, a compound having an ethylenically unsaturated group and a hydroxyl group. Also, D can react with a polyol via a polyisocyanate. By using a polyol having an ether group, a thioether group, an ester group, a carbonate group, a siloxane group, an amide group, or an imide group, these functional groups can be easily introduced into D. Further, D can introduce a cyclic ether group into D by reacting with a polyisocyanate and a compound having a cyclic ether group and a hydroxyl group. When D having an ethylenically unsaturated group and / or a cyclic ether group is used as a photoinitiator or a photosensitizer in a curable composition, D is incorporated into the cured product of photoradical polymerization and / or photoionic polymerization through a chemical bond. In this case, even if the molecular weight of D is less than 300, no bleed-out from the cured product occurs, and D is suitably used for each application as both a photoinitiator and a photosensitizer.

[0052] The ethylenically unsaturated group of the benzoylformic acid amide derivative (D) is one or more groups selected from (meth)acrylate group, (meth)acrylamide group, vinyl group, vinyl ether group, alkyl vinyl ether group, allyl group, (meth)allyl ether group, styryl group and maleimide group. Further, from the viewpoint of high polymerizability, (meth)acrylate group and (meth)acrylamide group are preferable, from the viewpoint of high active energy ray curability, acrylate group and acrylamide group are more preferable, and from the viewpoint of forming hydrogen bonds in addition to covalent bonds within and between molecules, acrylamide group is particularly preferable. Furthermore, when D is used as a photoinitiator, N-mono-substituted acrylamide group is most preferable from the viewpoint of being a hydrogen donor. When D is used as a photosensitizer, acrylate group and N,N-disubstituted acrylamide group are most preferable from the viewpoint of low viscosity of the curable composition containing D and D.

[0053] The compounds used in the reaction with the benzoylformic acid amide derivative (D) having a hydroxyl group include isocyanate compound (b1), compound having a hydroxyl group (b2), compound having an ethylenically unsaturated group and a reactive group (b3), and compound having a cyclic ether group and a reactive group (b4). The reactive groups of b3 and b4 include hydroxyl group, acid halide, halogen, isocyanate group, acid anhydride group, and epoxy group. b1 includes general-purpose polyisocyanate, polyisocyanate having a polyol skeleton, and polyisocyanate having an isocyanurate ring.

[0054] The isocyanate compound (b1) is a compound having two or more isocyanate groups in the molecule. Specifically, 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, aromatic polyisocyanates such as 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4-diphenylmethane diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, alicyclic polyisocyanates such as cyclopentylene diisocyanate, cyclohexylene diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 1,3-hydrogenated xylylene diisocyanate, 1,4-hydrogenated xylylene diisocyanate, 2,5-norbornane diisocyanate, 2,6-norbornane diisocyanate, or multimers such as adducts, isocyanurate bodies, and burette bodies of these polyisocyanates can be mentioned. These b1s may be used alone or in combination of two or more.

[0055] The compound (b2) having a hydroxyl group is an alcohol or a polyol. Alcohols include monohydric alcohols using linear alkyl groups having 1 to 18 carbon atoms, branched or cyclic alkyl groups having 3 to 18 carbon atoms such as methanol, ethanol, isopropanol, octanol, isostearyl alcohol, and alkylene glycols having 2 to 18 carbon atoms in a straight chain, 3 to 18 carbon atoms in a branched chain, and 3 to 18 carbon atoms in a cyclic form such as ethylene glycol, 1,2-propylene glycol, and polyhydric alcohols such as glycerin, trimethylolpropane, pentaerythritol, and dipentaerythritol.

[0056] The polyols of b2 include polyether polyols, polyester polyols, polycarbonate polyols, carbinol-modified silicones, polyolefin polyols, etc. Examples of 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. Examples of the polyolefin polyols include hydrogenated polyalkadiene polyols and polyalkadiene polyols. These b2s may be used alone or in combination of two or more.

[0057] When the reactive group of the compound (b3) having an ethylenically unsaturated group and a reactive group is an acid anhydride group or an acid chloride group, examples of b3 include (meth)acrylic acid chloride, (meth)acrylic anhydride, maleic anhydride, itaconic anhydride, etc. When the reactive group is an epoxy group, examples of b3 include glycidyl (meth)acrylate, glycidyl 4-hydroxybutyl (meth)acrylate, etc. When the reactive group is an isocyanate group, examples of b3 include 2-(meth)acryloyloxyethyl isocyanate, etc. When the reactive group is a hydroxyl group, examples of b3 include hydroxyalkyl (meth)acrylate, N-hydroxyalkyl (meth)acrylamide, N-alkyl-N-hydroxyalkyl (meth)acrylamide, hydroxyalkyl (meth)vinyl ether, hydroxyalkyl (meth)allyl ether, hydroxyalkyl maleimide, hydroxyalkyl styrene, 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, alkenyl alcohol, glycerin mono(meth)acrylate, glycerin mono(meth)acrylamide, glycerin di(meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, glycerin mono(meth)acrylamide, trimethylolpropane di(meth)acrylamide, pentaerythritol tri(meth)acrylamide, dipentaerythritol penta(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; and 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. These b3s may be used individually or in combination of multiple types.

[0058] When the reactive group of the compound (b4) having a cyclic ether group and a reactive group is a halogen, b4 is exemplified by epichlorohydrin. When 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. For example, hydroxyalkyl glycidyl ether and hydroxyalkyl epoxide having 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 7-oxabicyclo[4.1.0]heptane-3-methanol as a compound containing an alicyclic epoxy group and a hydroxyl group. These b4s may be used individually or in combination of multiple types.

[0059] The method for introducing a urethane group (urethane formation) 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. If necessary, a solvent (c), a urethane formation catalyst, and other additives may be used. Also, a polymerizable compound can be used as a solvent instead of c. Examples of the polymerizable compound solvent include N-(meth)acryloylmorpholine, alkyl (meth)acrylate, alkenyl (meth)acrylate, aryl (meth)acrylate, alkylene di(meth)acrylate, dialkylene glycol di(meth)acrylate, trialkylene glycol di(meth)acrylate, polyalkylene glycol di(meth)acrylate, N-substituted (meth)acrylamide, and N,N-disubstituted (meth)acrylamide. The above-mentioned alkyl 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 is a linear alkenyl group having 2 to 18 carbon atoms and a cyclic alkenyl group having 3 to 18 carbon atoms. The aryl is an aryl group having 6 to 8 carbon atoms. The urethane formation reaction is preferably carried out in an environment where light is blocked. Specifically, it can be carried out under light shielding, in an environment where ultraviolet rays are cut off such as in a yellow room, under a fluorescent lamp that does not irradiate ultraviolet rays, or under a red safelight for a darkroom.

[0060] After the urethane formation reaction, a crude product D containing the solvent (c) or the polymerizable compound used instead of c is obtained. The crude product can be directly used in the curable composition, or it can also be used in the curable composition after removing c or the polymerizable compound. Examples of the method for removing c include distillation under normal pressure or reduced pressure, bubbling with an inert gas such as dry air or nitrogen, and freeze-drying.

[0061] The reaction catalysts used in the urethanization reaction include quaternary ammonium salts, tertiary phosphine derivatives, tertiary amine derivatives, organometallic compounds, etc. Examples of quaternary ammonium salts include tetrabutylammonium bromide, triethylbenzylammonium chloride, tetrabutylphosphonium bromide, tetraphenylphosphonium bromide, etc. Examples of tertiary phosphines include triarylphosphines such as triphenylphosphine, tribenzylphosphine, and tritolylphosphine, tricycloalkylphosphines such as tricyclohexylphosphine, and trialkylphosphines such as triethylphosphine, tripropylphosphine, tributylphosphine, and trioctylphosphine. Examples of tertiary amines include trialkylamines such as triethylamine and tributylamine, dialkylarylamines such as dimethylbenzylamine and diethylbenzylamine, and triethanolamine. Organometallic compounds include metal salts of metals such as zinc, tin, lead, zirconium, bismuth, cobalt, manganese, and iron with organic acids such as octenoic acid and naphthenic acid, metal chelate compounds such as dibutyltin dilaurate, dioctyltin dilaurate, tin 2-ethylhexanoate, dibutyltin diacetylacetonate, zirconium tetraacetylacetonate, titanium acetylacetonate, aluminum acetylacetonate, cobalt acetylacetonate, iron acetylacetonate, copper acetylacetonate, and zinc acetylacetonate, potassium or sodium salts of alkylphosphonic acids, and sodium and potassium salts of fatty acids having 8 to 20 carbon atoms. Also, these may be used alone or in combination of multiple types. Among them, quaternary ammonium salts, tertiary phosphine derivatives, tin-based, bismuth-based, zirconium-based, and iron-based organometallic compounds with high catalytic effects are more preferable.

[0062] The usage amount of the urethanization reaction catalyst 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 rapidly. When it is 10% by mass or less, the coloring by the catalyst is low. More preferably, it is 0.01 to 1.00% by mass.

[0063] The benzoylformamide derivative (D) of the present disclosure generates radicals, which are growth active species, upon irradiation with active energy rays. The active energy rays include light energy rays such as visible light, electron beams, ultraviolet rays, infrared rays, X-rays, α-rays, β-rays, and γ-rays. Among them, it is preferable to use ultraviolet rays in view of the balance between the active energy ray generating device, the photopolymerization initiation rate, and safety. Examples of the ultraviolet light source include a xenon lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, a UV-LED lamp, and a microwave-excited excimer lamp. A UV-LED lamp capable of irradiating high-safety ultraviolet rays in the range of 360 to 420 nm with high output is preferable. Further, an LED lamp capable of irradiating light rays of 365 nm, 385 nm, 395 nm, and 405 nm is preferably used.

[0064] The irradiation energy required for radical generation of the benzoylformamide derivative (D) of the present disclosure can be represented by the integrated light quantity. The integrated light quantity is preferably in the range of 5 to 50,000 mJ / cm 2 and more preferably in the range of 10 to 20,000 mJ / cm 2 . If the irradiation energy is within this range, a sufficient number of growth active species can be generated from the photopolymerization initiator.

[0065] The benzoylformamide derivative (D) of the present disclosure is contained in an active energy ray-curable composition as a photoinitiator and can be used in 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% by mass or more. When D is contained at 0.1% by mass or more, photopolymerization can be immediately initiated by irradiation with active energy rays, and the curable composition can be sufficiently cured. When D does not contain an ethylenically unsaturated group, the content of D in the curable composition is preferably 50% by mass or less, although it varies depending on the structure and molecular weight of D. Further, from the viewpoint of easily adjusting the balance between the curability (curing rate) of the curable composition and the physical properties of the obtained cured product, the content of D is more preferably 0.5 to 20% by mass, and particularly preferably 1 to 10% by mass, based on the entire curable composition. When D contains an ethylenically unsaturated group, since a cured product can be formed from D alone, D can be contained at 100% by mass. Further, from the viewpoint that the curable composition can be sufficiently cured and the physical properties of the obtained cured product are good, D is a compound having one ethylenically unsaturated group in the molecule as another polymerizable compound (h) (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)). In that case, the content of D is more preferably 0.5 to 90% by mass, and particularly preferably 1 to 70% by mass, based on the entire curable composition.

[0066] The benzoylformamide derivative (D) of the present disclosure can be contained in an 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% by mass or more. When D is contained at 0.1% by mass or more, D is excited by irradiation with active energy rays, the photoinitiator in the curable composition is activated, and photopolymerization can be immediately started, and the curable composition can be sufficiently cured. D exhibits photosensitivity with respect to both a photo radical polymerization initiator and a photoionic polymerization initiator (photo cationic polymerization or photo anionic polymerization), and thus can be used in combination with these photoinitiators. When D does not contain an ethylenically unsaturated group or a cyclic ether group, the content of D in the curable composition is preferably 30% by mass or less, although it varies depending on the structure and molecular weight of D. Further, from the viewpoint of easily adjusting the balance between the curability of the curable composition and the physical properties of the obtained cured product, the content of D is more preferably 0.5 to 20% by mass, and particularly preferably 1 to 10% by mass with respect to the entire curable composition. When D contains an ethylenically unsaturated group and / or a cyclic ether group, since a cured product can be formed from D alone, D can be contained at 100% by mass. Further, from the viewpoint that the curable composition can be sufficiently cured and the physical properties of the obtained cured product are good, D can be used in combination with a compound having a cyclic ether group in the molecule as another polymerizable compound (h) (hereinafter referred to as a cyclic ether-containing compound (h3)). In that case, the content of D is more preferably 0.5 to 90% by mass, and particularly preferably 1 to 70% by mass with respect to the entire curable composition.

[0067] The benzoylformamide derivative (D) of the present disclosure can be used alone as a photoinitiator and as a photosensitizer, and D having different structures can be appropriately combined as a photoinitiator or a photosensitizer. When D is used as a photoinitiator and a photosensitizer, the total content of D in the curable composition is 0.5 to 80% by mass, preferably 1 to 75% by mass, more preferably 2 to 50% by mass, and particularly preferably 3 to 30% by mass.

[0068] The coincident compound (h) includes a monofunctional unsaturated compound (h1), a polyfunctional unsaturated compound (h2), and a cyclic ether-containing compound (h3) other than D. The content of h is 0 to 99.9% by mass based on the whole curable composition. Also, from the viewpoint of suitably adjusting the physical properties of the cured product, the content of h is preferably 10 to 99.5% by mass, and more preferably 30 to 99% by mass.

[0069] 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. The content of h1 is preferably 0 to 90% by mass, more preferably 5 to 70% by mass, and particularly preferably 10 to 50% by mass based on the whole curable composition. h1 usually has a low viscosity, and by containing it, the effects of reducing the viscosity of the curable composition and improving the handleability can be expected.

[0070] The monofunctional unsaturated compound (h1) containing a (meth)acrylate group includes alkyl (meth)acrylates, hydroxyalkyl (meth)acrylates, alkyl carboxylic acid (meth)acrylates, alkyl sulfonic acid (meth)acrylates, alkyl phosphoric acid (meth)acrylates, alkoxy (hereinafter also referred to as alkoxy) alkylene glycol (meth)acrylates, alkoxydialkylene glycol (meth)acrylates, alkoxytrialkylene glycol (meth)acrylates, alkoxypolyalkylene glycol (meth)acrylates, phenoxyalkylene glycol (meth)acrylates, phenoxydialkylene glycol (meth)acrylates, phenoxytrialkylene glycol (meth)acrylates, phenoxypolyalkylene glycol (meth)acrylate, N-alkylamino (meth)acrylates, N-alkylaminoalkyl (meth)acrylates, N,N-dialkylaminoalkyl (meth)acrylates, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyl oxyethyl (meth)acrylate, bornyl (meth)acrylate, isobornyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate, (meth)acrylates into which a cyclic structure such as N-(meth)acryloyloxyethyl norbornene carboxamide is introduced. 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, and the alkylene is an alkylene group having 1 to 4 carbon atoms.

[0071] The monofunctional unsaturated compound (h1) containing a (meth)acrylamide group includes (meth)acrylamide, mono- or di-substituted (meth)acrylamide, N-(meth)acryloylmorpholine, diacetone (meth)acrylamide, and the like. Further, the mono- or di-substituted (meth)acrylamide includes 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-sulfoalkyl acrylamide, N-alkylamino (meth)acrylamide, N-alkylaminoalkyl (meth)acrylamide, N,N-dialkylaminoalkyl (meth)acrylamide, and the like. 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.

[0072] The monofunctional unsaturated compound (h1) containing a vinyl group includes vinyl carboxylates having a carboxyl group with 1 to 18 carbon atoms, alkyl vinyl ethers, vinyl chloride, N-vinylpyrrolidone, N-vinylcaprolactam, N-vinyl oxazoline, maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, monoalkyl maleate, dialkyl maleate, monoalkyl maleamide, dialkyl maleamide, alkyl maleimide, monoalkyl fumarate, dialkyl fumarate, monoalkyl fumaramide, dialkyl fumaramide, monoalkyl itaconate, dialkyl itaconate, monoalkyl itaconamide, dialkyl itaconamide, alkyl itaconimide, vinyl carboxylic acid, vinyl sulfonic acid, vinyl phosphoric acid, 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.

[0073] The monofunctional unsaturated compound (h1) containing an allyl group includes allyl carboxylates having a carboxyl group with 1 to 18 carbon atoms, alkyl allyl ethers, phenyl allyl ether, alkyl phenyl allyl ether, allyl amine, mono- or dialkyl allyl amine, 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.

[0074] The monofunctional unsaturated compound (h1) containing a styryl group includes styrene, α-alkylstyrene, α-methylstyrene dimer, o-alkylstyrene, m-alkylstyrene, p-alkylstyrene, p-styrene sulfonic acid, 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.

[0075] The polyfunctional unsaturated compound (h2) includes compounds containing two or more unsaturated groups such as (meth)acrylate group, (meth)acrylamide group, vinyl group, allyl group, styryl group, and acetylene group. These unsaturated groups may be contained in a compound alone or in combination of two or more kinds. Further, in order to obtain good curability, 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 with respect to the whole curable composition. By containing h2, the strength and hardness of the cured product obtained are high, and excellent durability can be expected.

[0076] The polyfunctional unsaturated compound (h2) includes allyl (meth)acrylate, allyloxyalkoxy (meth)acrylate, allyl (meth)acrylamide, allyloxyalkoxy (meth)acrylamide, vinyloxyalkoxy (meth)acrylate, diallylamine, alkyldiallylamine, dialkyldiallylammonium quaternary salt, alkylene glycol di(meth)acrylates, polyalkylene glycol di(meth)acrylates, bisphenol A diglycidyl ether (meth)acrylate 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(meth)acrylate, dipentaerythritol tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tri(meth)acryloyloxyethoxytrimethylolpropane, glycerin polyglycidyl ether poly(meth)acrylate, ethylene oxide-modified isocyanuric acid tri(meth)acrylate, ethylene oxide-modified dipentaerythritol penta(meth)acrylate, ethylene oxide-modified dipentaerythritol hexa(meth)acrylate, ethylene oxide-modified pentaerythritol tri(meth)acrylate, ethylene oxide-modified pentaerythritol tetra(meth)acrylate, succinic acid-modified pentaerythritol tri(meth)acrylate, etc. 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, and the alkylene is an alkylene group having 1 to 4 carbon atoms.

[0077] The number average molecular weight of the polyfunctional unsaturated compound (h2) is preferably from 100 to 50,000. When the molecular weight is 100 or more, the cured product obtained has low curing shrinkage, which is preferable. When the molecular weight is 50,000 or less, the viscosity of the curable composition is low and the handleability is excellent, which is preferable. From these viewpoints, the molecular weight of h2 is more preferably from 200 to 20,000, and particularly preferably from 300 to 15,000.

[0078] The 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 containing a plurality of these cyclic ether groups, only one type may be contained, or two or more types may be contained in combination. Examples of the compound having one cyclic ether group for h3 include alkyl glycidyl ether, alkyl epoxide, aryl glycidyl ether, epoxy cycloalkane, alkyl oxetane, glycidyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, vinyl glycidyl ether. Examples of the compound having a plurality of cyclic ether groups for h3 include alkylene glycol diglycidyl ether, aryl diglycidyl ether, trimethylolpropane triglycidyl ether, (3,4-epoxycyclohexylmethyl) 3,4-epoxycyclohexanecarboxylate, 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, 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, a cyclic alkylene group having 3 to 18 carbon atoms, and the aryl is an aryl group having 6 to 18 carbon atoms. These h3 may be used alone or in combination of multiple types.

[0079] 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 with respect to the whole curable composition. h3 usually has a low viscosity, and by containing it, the effects of reducing the viscosity of the curable composition and improving the handleability can be expected.

[0080] The benzoylformamide derivative (D) of the present disclosure has high photoinitiating properties in photoradical polymerization and can be suitably used for various applications as a photoinitiator. When further higher photoinitiating properties are required, D can be used in combination with other photoinitiators. The photoinitiators that can be used in combination are not particularly limited. For example, 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, benzoic acid 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) can be mentioned. The combined photoinitiator can be used in combination with D at an arbitrary ratio as required, and may be used alone or in combination of multiple types.

[0081] The benzoylformic acid amide derivative (D) can be used in a hybrid polymerization system of photo radical polymerization and thermal radical polymerization. The thermal polymerization initiator that can be used in combination with D is not particularly limited. For example, 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, 1,1-di(t-butylperoxy)cyclohexane, hydroperoxides such as 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, p-menthane hydroperoxide, dialkyl peroxides such as dicumyl peroxide, di-t-butyl peroxide, diacyl peroxides such as dilauroyl peroxide, dibenzoyl peroxide, peroxydicarbonates such as di(4-t-butylcyclohexyl) peroxydicarbonate, di(2-ethylhexyl) peroxydicarbonate, peroxy esters such as t-butyl peroxy-2-ethylhexanoate, t-hexyl peroxyisopropyl monocarbonate, t-butyl peroxybenzoate, 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate, azo initiators such as bis(1-phenyl-1-methylethyl) peroxide, 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2-methylbutyronitrile), dimethyl 2,2'-azobis(isobutyrate), 1,1'-azobis(cyclohexane-1-carbonitrile), polymer azo polymerization initiators containing polydimethylsiloxane units (manufactured by Fujifilm Wako Pure Chemical Corporation, VPS-1001N), polymer azo polymerization initiators containing polyethylene glycol units (manufactured by Fujifilm Wako Pure Chemical Corporation, VPE-0201), etc. These thermal polymerization initiators can be used in combination with D at an arbitrary ratio as needed, and may be used alone or in combination of multiple types.

[0082] The benzoylformic acid amide derivative (D) has a sufficient photosensitizing effect on radical photopolymerization and can be suitably used for various applications as a photosensitizer for radical photopolymerization. When a further photosensitizing effect is required, it can be used in combination with other photosensitizers. The photosensitizers that can be used in combination with D are not particularly limited. For example, benzophenones, unsaturated ketones typified by anthracene derivatives, 1,2-diketone derivatives typified by benzyl and camphorquinone, benzoin derivatives, anthraquinone derivatives, thioxanthone derivatives, coumarin derivatives, thiols, disulfides, etc. can be mentioned. These photosensitizers can be used in combination with D at an arbitrary ratio as required, and may be used alone or in combination of multiple types.

[0083] The benzoylformic acid amide derivative (D) can be suitably used for various applications as a photosensitizer for ionic photopolymerization. When D is used for ionic photopolymerization, the ionic photopolymerization 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 photo-cationic polymerization initiators such as antimony-based and triarylsulfonium salt-based ones. In the photoanionic polymerization system or the photo-cationic polymerization system, one kind of the polymerization initiator of each polymerization system may be used alone, or multiple kinds may be used.

[0084] The benzoylformic acid amide derivative (D) also has a sufficient photosensitizing effect on ionic photopolymerization and can be used alone as a photosensitizer for ionic photopolymerization. When a further photosensitizing effect is required, it can be used in combination with other photosensitizers for ionic photopolymerization. The ionic photopolymerization initiators that can be used in combination with D are not particularly limited, and as long as they are photosensitizers that can be used for radical photopolymerization, they can be similarly suitably used as photosensitizers for ionic photopolymerization. Also, other photosensitizers can be used in combination with D at an arbitrary ratio as required, and may be used alone or in combination of multiple types.

[0085] Depending on the use method and purpose of the curable composition and the resulting cured product, the curable composition may further contain an organic solvent and water. In that case, the polymerization reaction (curing) may be carried out after previously removing the organic solvent and water, or the polymerization reaction may be carried out while 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 not particularly limited, and from the viewpoints of energy saving and high efficiency, it is preferably 80% by mass or less, and more preferably 50% by mass or less based on the entire curable composition.

[0086] Organic solvents used in the curable composition include alcohols such as methanol, ethanol, and isopropanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; esters such as ethyl acetate, propyl acetate, butyl acetate, methyl lactate, and ethyl lactate; alkylene glycols such as ethylene glycol and propylene glycol; polyalkylene glycols such as polyethylene glycol and polypropylene glycol; glycol ethers such as ethoxydiethylene glycol and methoxypropylene glycol; glycol esters such as propylene glycol acetate; ethers such as tetrahydrofuran, methyltetrahydrofuran, cyclopentyl methyl ether, methyltetrahydropyran, methyl-tert-butyl ether, and 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 β-methoxy-N,N-dimethylpropionamide and 3-butoxy-N,N-dimethylpropionamide; pyrrolidones such as 2-pyrrolidone and N-methylpyrrolidone; piperidines such as N-methylpiperidine; halogenated hydrocarbons such as methylene chloride, chloroform, and dichloroethane; sulfoxides such as dimethyl sulfoxide; and imidazolidinones such as 1,3-dimethyl-2-imidazolidinone. These organic solvents may be used alone or in combination of two or more.

[0087] The benzoylformamide derivative (D) of the present disclosure is used in UV flexo ink, UV offset ink, UV screen ink, UV inkjet ink, active energy ray-curable nail cosmetic composition (gel nail), UV curable adhesive, UV curable adhesive, active energy ray-curable sealant used for sealing materials or sealants, active energy ray-curable coating agent used for paints or coating agents for automobiles, electrical appliances, furniture, etc., active energy ray-curable decorative sheet resin composition used for decorative sheets used for surface coating of automobiles, electrical appliances, etc., coating agent having self-healing properties, three-dimensional shaped articles, nail decorative materials, functional members such as automobile exterior protection, decorative films, etc., active energy ray-curable self-healing material resin composition used for devices, etc., transparent adhesive sheet, buffer material, packing, anti-vibration material, sound-absorbing material, printing plate, sealing material, active energy ray-curable elastomer composition for elastomers used for abrasives, etc., active energy ray-curable three-dimensional shaping ink composition used for model materials or support materials for 3D printers, active energy ray-curable vehicle coating agent composition such as automobile paints, active energy ray-curable compositions used in various coating fields such as ship bottom paints, anti-fogging materials, antifouling paints, etc., active energy ray-curable compositions used in the medical device surface coating field, active energy ray-curable dental material composition, active energy ray-curable photosensitive composition, active energy ray-curable hydrogel composition, active energy ray-curable intraocular implant material composition, etc. can be suitably used. Further, the obtained hydrogel composition can also be suitably used as a material in various fields such as superabsorbent resins, paper diapers, soft contact lenses, etc. in the sanitary field, artificial organs, etc. in the medical field, soil conditioners, etc. in the civil engineering and construction field, water retention materials, etc. in the agricultural field, impact absorption materials, etc.

Examples

[0088] Hereinafter, the present invention will be described in detail with reference to examples. However, these examples are merely illustrative for preferably explaining the present invention and do not limit the present invention in any way. Further, in the following, "parts" and "%" are all based on mass unless otherwise specified.

[0089] The following describes the analysis methods used in the examples and comparative examples of the present disclosure, including the devices used and the analysis conditions. (1) Fourier transform infrared spectroscopy (FT-IR analysis) The FT-IR analysis was performed using the following device. Nicolet iS50 (manufactured by Thermo Fisher Scientific K.K.) (2) Liquid chromatography-mass spectrometry (LC-MS analysis) The conditions for LC-MS analysis are as follows. Column: XBride C18, 4.6 mm - 150 mm, 3.5 μm (manufactured by Waters Japan K.K.) Eluent conditions: water / methanol / 1% formic acid aqueous solution = 60 / 30 / 10 Measurement wavelength: 258 nm Column oven: 40 °C (3) Nuclear magnetic resonance spectroscopy ( 1 1H-NMR analysis) 1 The 1H-NMR analysis was performed using a 400 MHz device manufactured by JEOL Ltd., with the resonance frequency of the methyl group of tetramethylsilane set to 0.0 ppm. (4) Gel permeation chromatography analysis (GPC analysis) The conditions for GPC analysis are as follows. Device: Prominence-I LC-2030C (manufactured by Shimadzu Corporation) Guard column: Shodex KF-G 1 (manufactured by Showa Denko K.K.) Column: Shodex KF-803 1 (manufactured by Showa Denko K.K.) Column temperature: 40 °C Mobile phase: tetrahydrofuran (THF) Flow rate: 0.5 mL / min Standard sample: polystyrene (5) High performance liquid chromatography analysis (HPLC analysis) The conditions for HPLC analysis are as follows. Device: Prominence-I LC-2030C (manufactured by Shimadzu Corporation) Column: Mightysil RP-18GP, 4.6 mm - 250 mm, 5 μm (manufactured by Kanto Chemical Co., Inc.) Eluent condition: methanol / 10 mM phosphoric acid aqueous solution = 50 / 50 Measurement wavelength: 258 nm Column oven: 40 °C

[0090] The various raw materials and solvents used in the examples and comparative examples are shown below. (1) Benzoylformic acid compound (a1) a1-1: Methyl benzoylformate a1-2: Methyl 3,4,5-trimethoxybenzoylformate a1-3: Methyl 4-methoxycarbonylbenzoylformate a1-4: Methyl 4-acetoxybenzoylformate a1-5: Methyl 4-dimethylaminobenzoylformate a1-6: Ethyl 4-methylbenzoylformate a1-7: Methyl 2-acetaminobenzoylformate a1-8: Methyl 4-methoxybenzoylformate a1-9: Methyl 3,5-dimethoxybenzoylformate a1-10: Methyl 3-methoxybenzoylformate a1-11: Ethyl 3-butoxybenzoylformate a1-12: Methyl 4-bromobenzoylformate (2) Amino group-containing compound (a2) a2-1: (2S,3S,4R)-2-amino-1,3,4-octadecanetriol a2-2: Diethanolamine a2-3: 3-Piperidinemethanol a2-4: Dimethylamine (11% methanol solution, 2.0 mol / L) a2-5: 8-Amino-1-octanol a2-6: Aminoethanol a2-7: 2-Amino-2-methyl-1-propanol a2-8: 1,3-Diamino-2-propanol a2-9: DL-2-Amino-1-butanol a2-10: 4-Aminobenzyl alcohol a2-11: 2-(2-Aminoethoxy)ethanol a2-12: Tris(hydroxymethyl)aminomethane a2-13: D-Glucamine a2-14: 3-Amino-1,2-propanediol a2-15: 2-Amino-1,3-propanediol a2-16: 2-Amino-2-ethyl-1,3-propanediol (3) Isocyanate compound (b1) b1-1: Isophorone diisocyanate b1-2: Trimethylhexamethylene diisocyanate b1-3: 1,3,5-Tris[(5-isocyanato-1,3,3-trimethylcyclohexyl)methyl]-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione (isocyanurate form of isophorone diisocyanate) b1-4: 1,3,5-Tris(6-isocyanatohex-1-yl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (isocyanurate form of hexamethylene diisocyanate) b1-5: Hexamethylene diisocyanate b1-6: Methylene bisphenyl isocyanate b1-7: Pentamethylene diisocyanate (Stabio PDI, manufactured by Mitsui Chemicals, Inc.) b1-8: Dicyclohexylmethane-4,4-diisocyanate (4) Compound having a hydroxyl group (b2) b2-1: Polyethylene glycol (number average molecular weight 300) b2-2: Hydrogenated poly-1,2-butadiene with hydroxyl groups at both ends (number average molecular weight 1,000) (GI-1000, manufactured by Nippon Soda Co., Ltd.) b2-3: ETERNACOLL UH-50 (number average molecular weight 500) (manufactured by Ube Industries, Ltd.) ​b2-4: Silicone modified with hydroxyl groups at both ends (number average molecular weight 1,700) (Shin-Etsu Silicone KF-6001, manufactured by Shin-Etsu Chemical Co., Ltd.) b2-5: 1,4-Butanediol b2-6: Isopropanol b2-7: Isostearyl alcohol b2-8: Adeka Polyether BPX-2000 (manufactured by Adeka Corporation) b2-9: Kuraray Polyol P-1010 (number average molecular weight 1,000) (manufactured by Kuraray Co., Ltd.) b2-10: Unionol TG330 (polyoxypropylene glyceryl ether, molecular weight 330, manufactured by NOF Corporation) b2-11: Polypropylene glycol (number average molecular weight 1,000) b2-12: Kuraray Polyol P-6010 (number average molecular weight 6,000) (manufactured by Kuraray Co., Ltd.) b2-13: Polytetramethylene glycol (number average molecular weight 650) (BioPTMG650, manufactured by Mitsubishi Chemical Corporation) (5) Compound having an ethylenically unsaturated group and a reactive group (b3) b3-1: 2-Acryloyloxyethyl isocyanate b3-2: N-(2-Hydroxyethyl)acrylamide (registered trademark "Kohshylmer", "HEAA", manufactured by KJ Chemicals Corporation) b3-3: Acrylic acid chloride b3-4: Allyl chloride b3-5: Acrylonitrile b3-6: Unsaturated polyester diol (polyester composed of 1,5-methylpentanediol / maleic acid / adipic acid = 4 / 1 / 2 (molar ratio)) b3-7: 2-Hydroxyethyl maleimide b3-8: Hydroxyethyl acrylate b3-9: N-(Hydroxymethyl)acrylamide b3-10: 4-Hydroxybutyl acrylate b3-11: Pentaerythritol triacrylate b3-12: Hydroxyethyl methacrylate b3-13: N-(2-Hydroxyethyl) methacrylamide b3-14: 4-Hydroxybutyl vinyl ether b3-15: Oleyl alcohol b3-16: Polypropylene glycol (6) monoacrylate b3-17: Dipentaerythritol pentaacrylate (6) Compound (b4) having a cyclic ether group and a reactive group b4-1: Epichlorohydrin b4-2: 7-Oxabicyclo[4.1.0]heptane-3-methanol b4-3: 2-Hydroxyethyl glycidyl ester (7) Solvent (c) c-1: Toluene c-2: 1,2-Dichloroethane c-3: Ethyl acetate c-4: 4-Methyltetrahydrofuran c-5: 3-Methoxy-N,N-dimethylpropionamide (registered trademark "Kohshylvent", "KJCMPA", manufactured by KJ Chemicals Co., Ltd.)

[0091] The monofunctional unsaturated compound (h1), polyfunctional unsaturated compound (h2), cyclic ether-containing compound (h3), photoinitiator (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. (8) Polymerizable compound (h) (8-1) Monofunctional unsaturated compound (h1) h1-1: N-Acryloylmorpholine (registered trademark "Kohshylmer", "ACMO", manufactured by KJ Chemicals Co., Ltd.) h1-2: Isobornyl acrylate h1-3: N,N-Diethylacrylamide (registered trademark "Kohshylmer", "DEAA", manufactured by KJ Chemicals Co., Ltd.) h1-4: 4-Hydroxybutyl acrylate h1-5: Methyl 3-acryloylaminopropionate h1-6: N-Acryloyloxyethylnorbornene carboxamide (Registered trademark "Kohshylmer", manufactured by KJ Chemicals Co., Ltd.) h1-7: N-Octylacrylamide (Registered trademark "Kohshylmer", manufactured by KJ Chemicals Co., Ltd.) h1-8: N-(2-Hydroxyethyl)acrylamide (Registered trademark "Kohshylmer", "HEAA", manufactured by KJ Chemicals Co., Ltd.) h1-9: t-Butylcyclohexyl acrylate (Registered trademark "Kohshylmer", manufactured by KJ Chemicals Co., Ltd.) h1-10: Tetrahydrofurfuryl acrylate h1-11: N-Vinylpyrrolidone h1-12: N-Oleylacrylamide (Registered trademark "Kohshylmer", manufactured by KJ Chemicals Co., Ltd.) h1-13: Diacetoneacrylamide (Registered trademark "Kohshylmer", manufactured by KJ Chemicals Co., Ltd.) h1-14: N,N-Dimethylacrylamide (Registered trademark "Kohshylmer", "DMAA", manufactured by KJ Chemicals Co., Ltd.) h1-15: Hydroxyethyl methacrylate h1-16: Phenoxyethyl acrylate h1-17: Lauryl acrylate h1-18: Isobornyl methacrylate h1-19: 2-Methacryloyloxyethyl acid phosphate (8-2) Polyfunctional unsaturated compound (h2) h2-1: Hexanediol diacrylate h2-2: Dipentaerythritol hexaacrylate h2-3: Quick Cure 8100 (Registered trademark "Quick Cure", manufactured by KJ Chemicals Co., Ltd.) h2-4: Quick Cure 7100 (Registered trademark "Quick Cure", manufactured by KJ Chemicals Co., Ltd.) h2-5: Polyethylene glycol (14) diacrylate h2-6: Urethane diacrylate (Violet UV3000, manufactured by Mitsubishi Chemical Corporation) h2-7: Trimethylolpropane triacrylate h2-8: Pentaerythritol triacrylate h2-9: Quick Cure 7300 (registered trademark "Quick Cure", manufactured by KJ Chemicals Co., Ltd.) h2-10: Dimethylol-tricyclodecane diacrylate h2-11: Urethane diacrylate (Violet UV6630, manufactured by Mitsubishi Chemical Corporation) h2-12: Polyethylene glycol (20) introduced bisphenol A diacrylate h2-13: 2-(2-Vinyloxyethoxy)ethyl acrylate h2-14: Diethylene glycol divinyl ether h2-15: Bisphenol A epoxy acrylate oligomer (Miramer PE-210, manufactured by MIWON) h2-16: Polyethylene glycol (10) introduced bisphenol A diacrylate h2-17: 2,4-Dimethyl-1,6-hexanediyl bis[carbamic acid 2-(methacryloyloxy)ethyl] h2-18: Ethylene bisacrylamide h2-19: Triethylene glycol dimethacrylate (9) Cyclic ether-containing compound (h3) h3-1: 2-Ethylhexyl glycidyl ether h3-2: Bisphenol A diglycidyl ether h3-3: 1,6-Hexanediol diglycidyl ether h3-4: Trimethylolpropane triglycidyl ether h3-5: Butyl glycidyl ether h3-6: 4-Hydroxybutyl acrylate glycidyl ether (10) Photoinitiator (E) E-1: Oligomer of 2-hydroxy-1-(4-isopropenylphenyl)-2-methylpropan-1-one (ESACURE KIP 150, manufactured by IGM Resin B.V.) E-2: Methyl benzoylformate (Omnirad MBF, manufactured by IGM Resin B.V.) E-3: 2,4,6-Trimethylbenzoyldiphenylphosphine oxide (Omnirad TPO, manufactured by IGM Resin B.V.) E-4: Kohshylex-I 3003 (registered trademark "Kohshylex", manufactured by KJ Chemicals Co., Ltd.) E-5: 1-Hydroxycyclohexyl phenyl ketone (Omnirad 184, manufactured by IGM Resin B.V.) E-6: 2-Hydroxy-2-methylpropiophenone (Omnirad 1173, manufactured by IGM Resin B.V.) E-7: 1-[4-(2-Hydroxyethyl)-phenyl]-2-hydroxy-methylpropanone (Omnirad 2959, manufactured by IGM Resin B.V.) E-8: Benzophenone E-9: α-[(4-Benzoylphenoxy)acetyl]-ω-{[(4-benzoylphenoxy)acetyl]oxy}poly(oxybutane-1,4-diyl) (Omnipol BP, manufactured by IGM Resin B.V.) E-10: 1,5,7-Triazabicyclo[4.4.0]dec-5-ene 2-(9-oxoxanthen-2-yl)propionate E-11: 1,2-Dicyclohexyl-4,4,5,5-tetramethylbiguanidium n-butyltriphenylborate (11) Photosensitizer (I) I-1: Poly(ethylene glycol) bis(p-dimethylaminobenzoate) (Omnipol ASA, manufactured by IGM Resin B.V.) I-2: Bis N,N-[2-(4-dimethylaminobenzoyl)oxyethylene-1-yl]methylamine (Esacure A 198, manufactured by IGM Resin B.V.) I-3: Isopropylthioxanthone I-4: 2-Ethylanthraquinone I-5: Polytetramethylene glycol (3) carboxymethoxythioxanthone diester (Omnipol TX, manufactured by IGM Resin B.V.) (12) Thermal polymerization initiator (J) J-1: Azobisisobutyronitrile (13) Other additives (k) k-1: Pentaerythritol tetrakis(3-mercaptobutyrate) k-2: Methyl-5-norbornene-2,3-dicarboxylic anhydride k-3: BYK JET9151 (Pigment dispersant, maleimide-styrene copolymer having an ammonium salt structure, manufactured by BYK Chemie) k-4: Carbon black dispersion (manufactured by Mitsubishi Chemical Corporation) k-5: Pigment Yellow 155 k-6: VALIFAST BLUE1613 (manufactured by ORIENT CHEMICAL INDUSTRIES Co., LTD.) k-7: BYK-331 (Leveling agent, polyether-modified polydimethylsiloxane, manufactured by BYK Chemie) k-8: Petrotack 100V (manufactured by Tosoh Corporation) k-9: Trimethylsilyl group surface-modified silica (AEROSIL RX200, manufactured by Nippon Aerosil Co., Ltd.) k-10: Hydrogenated rosin (Non-polymerizable polymer, Tackifier Fire KE-359, manufactured by Arakawa Chemical Industries) k-11: Rheoseal QS-30 (manufactured by Tokuyama Corporation) k-12: Inorganic filler (titanium oxide) k-13: Methacrylic acid / methyl methacrylate / styrene copolymer binder k-14: Polyvinyl alcohol JC-25 (manufactured by Nippon Vinylon K.K.) k-15: Elemineol JS-20 (manufactured by Sanyo Chemical Industries, Ltd.)

[0092] Example 1 Synthesis of Benzoylformamide Derivative (D-1) 197.0 g (1.20 mol) of methyl benzoylformate (a1-1), 317.5 g (1.00 mol) of (2S,3S,4R)-2-amino-1,3,4-octadecatriol (a2-1), 500 g of toluene (c-1) as a solvent, and 1.0 g (0.01 mol) of triethylamine (TEA) as a catalyst were added to a 1,000 mL flask equipped with a reflux condenser, a stirrer, a thermometer, and a dropping funnel. The temperature was raised to 70 °C with stirring. After reacting at 70 °C for 8 hours, unreacted raw materials, the solvent, by-produced methanol, and the catalyst were removed by distillation under reduced pressure to obtain a benzoylformamide derivative (D-1) as a pale yellow solid (yield 85%). The identification of D-1 was 1 performed by 1H-NMR analysis, and the chemical shift values of representative protons are shown in Table 1-1. The molecular weight of the product was 450 (the molecular ion peak in the mass spectrum was 451) by liquid chromatography-mass spectrometry (LC-MS analysis). 1 From the results of 1H-NMR and LC-MS analysis, it was confirmed that the product was the benzoylformamide derivative (D-1) shown in Table 1-1.

[0093] Examples 2, 3, 5 to 20 Synthesis of Benzoylformamide Derivatives (D-2), (D-3), (D-5) to (D-20) Reactions were carried out under the same conditions as in Example 1 according to the raw materials and charge ratios shown in Table 1-1 and Table 1-2 to obtain benzoylformamide derivatives (D-2), (D-3), (D-5) to (D-20). The identification of the obtained benzoylformamide (D) was similarly 1 performed by 1H-NMR analysis and LC-MS analysis, and the chemical shift values of representative protons, the molecular weight, and the yield of the product are shown in Table 1-1 and Table 1-2. 1 From the results of 1H-NMR and LC-MS analysis, it was confirmed that the products were the benzoylformamide derivatives (D-2), (D-3), (D-5) to (D-20) shown in Table 1-1 and Table 1-2.

[0094] Example 4 Synthesis of Benzoylformamide Derivative (D-4) The catalyst TEA in Example 1 was changed to sodium methoxide, and the reaction and purification of methyl 4-acetoxybenzoylformate (a1-4) and dimethylamine were carried out under the same conditions as in Example 1 to obtain a benzoylformamide derivative (D-4) as a pale yellow solid (yield 75%). 1 The identification of D-4 was performed by 1H-NMR and LC-MS analysis, and the respective analysis data and the chemical formula of D-4 are shown in Table 1-1.

[0095] Example 21 Synthesis of benzoylformamide derivative (D-21) 243.1 g (1.00 mol) of methyl 4-bromobenzoylformate (a1-12), 143.0 g (1.20 mol) of 2-amino-2-ethyl-1,3-propanediol (a2-16), and 362 g 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. Then, nitrogen gas was passed at a flow rate of 100 cm 3 / min at 25 °C for 10 minutes (bubbling) to remove unreacted raw materials and by-produced methanol, and a solution of benzoylformamide derivative (D-21) in b2-8 was obtained (yield 84%). The identification of D-21 was similarly 1 performed by 1H-NMR analysis, and the chemical shift values of representative protons are shown in Table 1-2. The molecular weight of D-21 was confirmed by LC-MS analysis, and it was also confirmed that the obtained solution was a mixture of D-21 and b2-8 with a mass ratio of 1 / 1.

[0096] Example 22 Synthesis of benzoylformamide derivative (D-22) Into a 300 mL flask equipped with a reflux condenser, a stirrer, a thermometer and a dropping funnel, 45.7 g of the benzoylformamide derivative (D-2) synthesized in Example 2, 54.3 g of 2-acryloyloxyethyl isocyanate (b3-1), and 50 g of ethyl acetate (c-3) were added and mixed. 0.02 g of bismuth tris(2-ethylhexanoate) was added to the mixture as a catalyst, and the reaction was carried out for 4 hours with stirring at 70 °C. The disappearance of the isocyanate group was confirmed by FT-IR analysis, and the solvent was removed under reduced pressure to obtain a pale yellow viscous solid product (yield 98%). The presence of urethane groups and benzoylformamide groups (disubstituted) derived from D-2 in the product was confirmed by FT-IR analysis of the product. 1 The presence of acrylate groups (5.85 ppm, 6.20 ppm, 6.45 ppm) was confirmed by 1H-NMR analysis. Furthermore, it was confirmed by LC-MS analysis that the molecular weight of the product was 520, and the product was the benzoylformamide derivative (D-22) shown in Table 2-1. Table 2-1 shows the chemical formula, molecular weight, number of benzoylformamide groups per molecule, number of atoms directly connecting 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 benzoylformamide groups per molecule of D-22.

[0097] Example 23 Synthesis of benzoylformamide derivative (D-23) Except for not using a reaction solvent, the reaction of 50.0 g of benzoylformamide derivative (D-3), 32.9 g of isophorone diisocyanate (b1-1) and 17.1 g of N-(2-hydroxyethyl)acrylamide (b3-2) was carried out in the presence of 0.01 g of the catalyst dibutyltin dilaurate in the same manner as in Example 22 to obtain a pale yellow viscous solid product (yield 96%). The presence of urethane groups and benzoylformamide groups (disubstituted) derived from D-3 in the product was confirmed by FT-IR analysis of the product. 1 The presence of acrylamide groups (5.60 ppm, 6.10 ppm, 6.50 ppm) was confirmed by 1H-NMR analysis. Furthermore, it was confirmed by LC-MS analysis that the molecular weight of the product was 675, and the product was the benzoylformamide derivative (D-23) shown in Table 2-1. The chemical formula and other data of D-23 are summarized in Table 2-1.

[0098] Example 24 Synthesis of Benzoylformic Acid Amide Derivative (D-24) 74.7 g of the benzoylformic acid amide 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 25.3 g of acryloyl chloride (b3-3) was added dropwise while maintaining the temperature at -10 to 0°C to cause a reaction. Then, extraction was performed with an alkaline aqueous solution, and the solvent in the organic layer was removed under reduced pressure to obtain a pale yellow viscous liquid product (yield 84%). The presence of a benzoylformic acid amide group (monosubstituted) derived from D-5 was confirmed by FT-IR analysis of the product, 1 and the presence of an acrylate group was confirmed by 1H-NMR analysis. Furthermore, it was confirmed by LC-MS analysis that the molecular weight of the product was 331. The chemical formula and other data of the product D-24 are summarized in Table 2-1.

[0099] Example 25 Synthesis of Benzoylformic Acid Amide Derivative (D-25) 6.0 g of sodium hydride and 50 g of 4-methyltetrahydrofuran (c-4) were placed in a 500 mL flask equipped with a reflux condenser, a stirrer, a thermometer, and a dropping funnel. 63.6 g of the benzoylformic acid amide derivative (D-18) was dissolved in 50 g of c-4, placed in the dropping funnel, and added dropwise over 30 minutes while checking the amount of hydrogen gas generated. After completion of the dropwise addition, 36.4 g of allyl chloride (b3-4) was added, and the reaction was carried out at 25°C for 24 hours. Then, 100 mL of ion-exchanged water was added to deactivate the remaining sodium hydride, c-4 was separated, and extraction was further performed three times with saturated brine. The extract was concentrated with an evaporator, purified by silica gel column chromatography, and the solvent was removed under reduced pressure to obtain a pale yellow viscous liquid product (yield 43%). The presence of a benzoylformic acid amide group (monosubstituted) derived from D-18 was confirmed by FT-IR analysis of the product. 1The presence of allyl ether groups (5.00 ppm, 5.05 ppm, 5.85 ppm, 3.85 ppm) was confirmed by 1H-NMR analysis. Also, it was confirmed by LC-MS analysis that the molecular weight of the product was 347. The chemical formula of D-25 and other data are summarized in Table 2-1.

[0100] 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, stirrer, thermometer, and dropping funnel. While cooling, 4.8 g of ion-exchanged water was added and mixed 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 added dropwise to the flask at 40 °C over 2 hours. After completion of the reaction, extraction was performed twice with ion-exchanged water, the organic layer was concentrated, and purification was carried out by silica gel column chromatography. Further, the solvent was removed under reduced pressure to obtain a pale yellow viscous liquid product (yield 38%). The presence of a benzoylformamide group (monosubstituted) derived from D-9 was confirmed by FT-IR analysis of the product, 1 The presence of an acrylamide group and the presence of two benzoylformamide groups were confirmed by 1H-NMR analysis. Also, it was confirmed by LC-MS analysis that the molecular weight of the product was 407. The chemical formula of D-26 and other data are summarized in Table 2-1.

[0101] Examples 27, 28, 30, 32, 36 - 39 Synthesis of Benzoylformamide Derivatives (D-27), (D-28), (D-30), (D-32), (D-36) - (D-39) Using the raw materials shown in Tables 2-1 to 2-3, the synthesis of benzoylformamide derivative (D) was carried out in the same manner as in Example 22. The product was identified by FT-IR analysis, 1 1H-NMR analysis, and LC-MS analysis, and the chemical formula of the product and other data are summarized in Tables 2-1 to 2-3. Specifically, 1The presence of maleimide groups (7.05 ppm), acrylate groups (5.85 ppm, 6.20 ppm, 6.45 ppm), and acrylamide groups (5.60 ppm, 6.10 ppm, 6.50 ppm) was confirmed by 1H-NMR analysis.

[0102] Example 29 Synthesis of benzoylformic acid amide derivative (D-29) Using the same reaction apparatus as in Example 23, 18.8 g of benzoylformic 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 tetrakisacetylacetonate as a catalyst were mixed and reacted at 60 °C for 5 hours with stirring. The disappearance of isocyanate groups was confirmed by FT-IR analysis of the reaction solution, and a pale yellow viscous liquid product was obtained (yield 96%). The presence of urethane groups and benzoylformic acid amide groups was confirmed by FT-IR analysis of the product. 1 The presence of maleate groups (6.30 ppm) was confirmed by 1H-NMR analysis. The number average molecular weight (Mn) was calculated to be 2,700 by GPC analysis. The chemical formula and other data of the benzoylformic acid amide derivative (D-29) confirmed from these results are shown in Table 2-1.

[0103] Examples 31, 34, 35, 40 - 46, 48 - 54 Synthesis of benzoylformic acid amide derivatives (D-31), (D-34), (D-35), (D-40) - (D-46), (D-48) - (D-54) Using the raw materials shown in Tables 2-2 to 2-6, the benzoylformic acid amide derivative (D) was synthesized in the same manner as in Example 23. The presence of urethane groups and benzoylformic acid amide groups was confirmed by FT-IR analysis. 1The 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 was confirmed by 1H-NMR analysis. Furthermore, the number-average molecular weight (Mn) of the product was calculated by GPC analysis. The chemical formulas and other data of benzoylformamide derivatives (D-31), (D-34), (D-35), (D-40) to (D-46), and (D-48) to (D-54) are summarized in Tables 2-2 to 2-6. Also, since D-41 was synthesized from biomass diisocyanate (b1-7), the bio-based content was 27.0%. Since D-53 was synthesized from biomass polyol (b2-13), the bio-based content was 24.9%. The bio-based content was calculated by the method described in ISO 16620-1.

[0104] 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), and 20.6 g of N-(hydroxymethyl)acrylamide (b3-9) were used in the same manner as in Example 22. Instead of solvent (c), 100.0 g of polymerizable compound N-acryloylmorpholine (h1-1) and 0.02 g of bismuth tris(2-ethylhexanoate) as a catalyst were mixed and reacted at 60 °C with stirring for 6 hours. The disappearance of the isocyanate group was confirmed by FT-IR analysis of the reaction solution, and a pale yellow liquid product was obtained (yield 99%). The presence of urethane groups and benzoylformamide groups was confirmed by FT-IR analysis of the product. 1 The presence of acrylamide groups (5.60 ppm, 6.10 ppm, 6.50 ppm) derived from b3-9 was confirmed by 1H-NMR analysis. Also, by LC-MS analysis, it was confirmed that the molecular weight of D-33 having no methoxy group after standing for 24 hours was 588, and a solution of D-33 in h1-1 (50% by mass) was obtained. These analysis results are shown in Table 2-2.

[0105] Example 47 Synthesis of Benzoylformamide Derivative (D-47) Using the same reaction apparatus as in Example 23, 19.8 g of a b2-8 solution of benzoylformamide derivative (D-21) (D-21 / b2-8 = 1 / 1, mass ratio), 15.7 g of trimethylhexamethylene diisocyanate (b1-2), 58.8 g of b2-8, 1.7 g of N-(hydroxyethyl)acrylamide (b3-2), 4.0 g of oleyl alcohol (b3-15), and 0.01 g of the catalyst dibutyltin dilaurate were mixed and reacted for 6 hours while stirring at 60°C. The disappearance of the isocyanate group was confirmed by FT-IR analysis of the reaction solution, and a pale yellow liquid product was obtained (yield 95%). The presence of urethane groups and benzoylformamide groups was confirmed by FT-IR analysis of the product, 1 and the presence of acrylamide groups derived from b3-2 (5.60 ppm, 6.10 ppm, 6.50 ppm) and the unsaturated groups of the oleyl group derived from b3-15 (5.35 ppm) was confirmed by 1H-NMR analysis. Furthermore, the number average molecular weight (Mn) of D-47 was calculated to be 7,200 by GPC analysis. The chemical formula and other data of D-47 confirmed from these results are shown in Table 2-4.

[0106] Example 55 Synthesis of Benzoylformamide Derivative (D-55) 67.6 g of benzoylformamide derivative (D-6) and 50.0 g of 4-methyltetrahydrofuran (c-4) were placed in a 300 mL flask equipped with a reflux condenser, stirrer, thermometer, and dropping funnel, mixed, and then 21.6 g of epichlorohydrin (b4-1) was added. After adding 0.5 g of boron trifluoride diethyl ether while maintaining the temperature at 20°C, 10.8 g of b4-1 was further added dropwise over 1 hour, and the reaction was continued for 2 hours after the addition was complete. The reaction solution was filtered, the filtrate was washed with ion-exchanged water, and the solvent was removed under reduced pressure from the organic layer to obtain a pale yellow liquid product (yield 65%). The presence of benzoylformamide groups was confirmed by FT-IR analysis of the product, 1The presence of glycidyl groups (3.00 ppm, 3.85 ppm) was confirmed by 1H-NMR analysis. Furthermore, it was confirmed by LC-MS analysis that the molecular weight of the product was 249. From these results, it was confirmed that the product was the benzoylformamide derivative (D-55) shown in Table 2-6.

[0107] 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, 1 and the presence of cyclic ethers and unsaturated groups was confirmed by 1H-NMR analysis. Specifically, 1 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 1H-NMR analysis. Furthermore, in Example 56, the molecular weight of the product was measured by LC-MS analysis, and in Examples 57 and 58, the number average molecular weight (Mn) of the product was calculated by GPC analysis and is shown in Table 2-6. The chemical formulas and other data of the benzoylformamide derivatives (D-56) to (D-58) are summarized in Table 2-6.

[0108]

Table 1-1

[0109]

Table 1-2

[0110]

Table 2-1

[0111]

Table 2-2

[0112]

Table 2-3

[0113]

Table 2-4

[0114]

Table 2-5

[0115]

Table 2-6

[0116] 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 photoinitiators (E-1) to (E-3) as comparative examples, the monofunctional unsaturated compound (h1), polyfunctional unsaturated compound (h2), photosensitizer (I), and other components (k) were weighed in the proportions shown in Tables 3-1 and 3-2, mixed at 25°C for 30 minutes, and an active energy ray-curable composition (hereinafter abbreviated as curable composition) was obtained. The compatibility of the obtained curable composition and its curability with respect to light rays of different wavelengths were evaluated. Also, a photocured product of the curable composition was prepared, and the content rate of low molecular weight components derived from the photoinitiator in the cured product, the light resistance yellowing property, and the durability of the cured product were evaluated by the following methods, and the results are shown in Tables 3-1 and 3-2.

[0117] <Compatibility> The state of the curable composition was visually observed, and the compatibility was evaluated by dividing it into four levels. ++: High transparency, no turbidity or phase separation was confirmed at all. +: High transparency, but slight turbidity was observed. ±: No phase separation was confirmed, but turbidity was confirmed. -: Both turbidity and phase separation were confirmed.

[0118] <Sclerosing> The sclerosing composition was applied to a polyethylene terephthalate film (Cosmo Shine A - 4100, corona - treated surface, thickness 100 μm, manufactured by Toyobo Co., Ltd.) (hereinafter referred to as PET film) with a bar coater so that the film thickness became 20 μm. The coating film was irradiated with light rays of different wavelengths to cure the coating film, and the integrated light quantity until the tack disappeared when touching the cured product was determined, and the sclerosing property was evaluated by dividing it into four grades. Three types of lamps for ultraviolet irradiation were used as follows: 1) - 3). Also, the lower the integrated light quantity required until the tack disappears, the higher the sclerosing property. 1) High - pressure mercury lamp: wavelength 200 - 450 nm, illuminance 100 mW / cm 2 2) UV - LED lamp: wavelength 385 nm, illuminance 100 mW / cm 2 3) UV - LED lamp: wavelength 405 nm, illuminance 100 mW / cm 2 ++: The integrated light quantity was less than 500 mJ / cm 2 and the tack disappeared. +: The integrated light quantity was 500 mJ / cm 2 or more and less than 1,000 mJ / cm 2 and the tack disappeared. ±: The integrated light quantity was 1,000 mJ / cm 2 or more and less than 5,000 mJ / cm 2 and the tack disappeared. -: The integrated light quantity was 5,000 mJ / cm 2 but the tack remained.

[0119] <Low - molecular - weight component content> The sclerosing composition was applied to a polyester - based heavy - release film (E7001, thickness 75 μm, manufactured by Toyobo Co., Ltd.) (hereinafter referred to as heavy - release film). Using a table - top roll - type laminator (RSL - 382S manufactured by Royal Sovereign), it was laminated to a thickness of 20 μm without trapping air bubbles with a polyester - based light - release film (E7002, thickness 50 μm, manufactured by Toyobo Co., Ltd.) (hereinafter referred to as light - release film), and then irradiated with ultraviolet rays (high - pressure mercury lamp, illuminance 100 mW / cm2 , integrated light quantity of 5,000 mJ / cm 2 ). Then, the release film was peeled off, and three test pieces with a size of 5 cm 2 were cut out, dried at 90 °C for 2 minutes, weighed, and used as the mass of the pre-extraction cured film. 25 g of acetone and the weighed cured film were placed in an ultraviolet-impermeable brown glass bottle. The glass bottle was sealed and rotated at 30 °C for 48 hours to extract the soluble components in the cured film. The solution after extraction was filtered through a 0.45 μm filter, subjected to HPLC analysis, the low molecular weight components were quantified based on the calibration curve, the content rate of the low molecular weight components was calculated according to the following formula, and the evaluation was carried out as follows. Content rate of low molecular weight components (%) = (mass of extracted low molecular weight components / mass of pre-extraction cured film) × 100% ++: The content rate of the low molecular weight components was 1.0% or less. +: The content rate of the low molecular weight components was more than 1.0% and 2.0% or less. ±: The content rate of the low molecular weight components was more than 2.0% and 4.0% or less. -: The content rate of the low molecular weight components was more than 4.0%.

[0120] <Lightfast yellowing resistance> The double-release film was adhered to a horizontally placed glass plate, and a silicone spacer with an internal volume of 10 mm × 10 mm × 0.5 mm (when the material is not specified hereinafter, silicone is used) was placed thereon, and the spacer was filled with the curable composition. The release film was covered on the liquid surface of the spacer so as not to entrap air bubbles, and irradiated with ultraviolet rays using a UV-LED lamp (wavelength 405 nm, illuminance 100 mW / cm 2 , integrated light quantity of 20,000 mJ / cm 2 ). Then, the release film was peeled off, the cured product was taken out from the spacer, visually observed, and the lightfast yellowing resistance was evaluated according to the following criteria. ++: No yellowing was confirmed at all. +: Slight yellowing was confirmed. ±: Yellowing was confirmed. -: Obvious yellowing was confirmed.

[0121] <Durability> Change the integrated light quantity to 5,000 mJ / cm 2 Except for this change, a cured product of the curable composition was prepared in the same manner as in the lightfast yellowing resistance evaluation. Then, it was left standing in a thermo-hygrostat at a temperature of 40°C and a relative humidity of 50% for 168 hours, and the presence or absence of bleed-out on the surface of the cured product was visually observed, and the durability was evaluated according to the following criteria. ++: No bleed-out was observed at all. +: A very slight bleed-out was observed. ±: A slight bleed-out was observed. -: A severe bleed-out was observed.

[0122]

Table 3-1

[0123]

Table 3-2

[0124] As is clear from the evaluation results in Table 3-1 and Table 3-2, the curable compositions of each example using the benzoylformic acid amide derivative (D) of the present disclosure had good compatibility, and not only with a high-pressure mercury lamp but also with respect to the light rays of 385 nm and 405 nm of a UV-LED lamp, the curability was high. The cured products obtained in the examples had a low content of low-molecular-weight components, high safety, and excellent light resistance to yellowing and durability. Also, 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. Among Ds in which the number of atoms directly connecting between the nitrogen atom of the benzoylformic acid amide group and the nitrogen atom of the nearest urethane group was 10 (D-30 of Example 76), 7 (D-36 of Example 82), and 4 (D-40 of Example 86), the numbers 7 and 4 showed higher curability than the number 10, and the number 4 showed the highest curability. D-42 (Example 88) and D-43 (Example 89) having a methoxy group on the benzene ring of the benzoylformic acid amide group showed higher curability than D-44 (Example 90) not having a methoxy group. Also, D-22 (Example 68), D-23 (Example 69), D-27 (Example 73), D-28 (Example 74), D-33 (Example 79), and D-40 (Example 86) having a urethane group with a molecular weight of less than 1,000 showed good compatibility. Furthermore, 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), D-53 (Example 99) having a urethane group with a molecular weight of 1,000 or more and an alkylene structural unit, polyether structural unit, polyester structural unit, polycarbonate structural unit, polyolefin structural unit, polysiloxane structural unit derived from a polyol showed good compatibility while having a high molecular weight. The content of low-molecular-weight components in the cured products obtained in these examples was low, and both the light resistance to yellowing and durability of the cured products were high.On the one hand, in Comparative Example 1 using Esacure KIP 150 (E-1) as a photoinitiator, the curability was low with light of wavelength 405 nm, and both the residual amount (unpolymerized) of the polymerizable compound (h) and the decomposition products generated by the intramolecular cleavage of E-1 remained in the cured product, resulting in a high content of low molecular weight components in the cured product. In Comparative Example 2 using methyl benzoylformate (E-2) and Comparative Example 3 using 2,4,6-trimethylbenzoyldiphenylphosphine oxide (E-3), curing was possible with light of 405 nm. However, since E-2 itself with a molecular weight of 164 is a low molecular weight component and E-3 is an intramolecular cleavage type photoinitiator, the cured products of Comparative Examples 2 and 3 both had a high content of low molecular weight components. Also, in Comparative Examples 1 to 3, the lightfast yellowing resistance and durability of the cured products were both low.

[0125] Examples 101 to 137 and Comparative Examples 4 to 10 (Preparation and Evaluation of Photo-Radical Polymerization-Type Active Energy Ray-Curable Compositions) Using the benzoylformamide derivatives (D-2) to (D-57) obtained in each example and commercially available photosensitizers (I-3), (I-4) as comparative examples, the monofunctional unsaturated compound (h1), polyfunctional unsaturated compound (h2), and radical photoinitiator (E) were weighed in the compositions shown in Tables 4-1 and 4-2, mixed at 25 °C for 30 minutes, and a photo-radical polymerization-type active energy ray-curable composition (hereinafter also referred to as a radical-type curable composition) was prepared. The compatibility of the obtained radical-type curable composition, the curability with light of different wavelengths, the lightfast yellowing resistance and durability of the obtained cured product were evaluated in the same manner as the evaluation of the curable composition, and the results are shown in Tables 4-1 and 4-2. The higher the curability of the curable composition, the higher the photosensitivity (sensitivity) of D.

[0126] [Table 4-1]

[0127] [Table 4-2]

[0128] Examples 138 to 143 and Comparative Examples 11 to 15 (Preparation and Evaluation of Photoionization Polymerization-Type Active Energy Ray-Curable Compositions) Using the benzoylformamide derivatives (D) obtained in each example and commercially available photosensitizers (I-3) to (I-5), the cyclic ether compound (h3), photoionization polymerization initiator (E-10) or (E-11), and other additives (k) were weighed in the compositions shown in Table 5, mixed at 25°C for 30 minutes, and a photoionization polymerization-type active energy ray-curable composition (hereinafter also referred to as an ionic curable composition) was prepared. The compatibility of the obtained ionic curable composition, the curability with respect to light rays of different wavelengths, the lightfast yellowing resistance and durability of the obtained cured product were evaluated by the following methods, and the results are shown in Table 5. The higher the curability of the curable composition, the higher the photosensitivity of D.

[0129] <Compatibility> The compatibility of the photoionization polymerization-type curable composition was evaluated by the same method and evaluation criteria as those for the compatibility evaluation of the above-mentioned photoradical polymerization-type curable composition.

[0130] <Curability> Similar to the curability evaluation of the above-mentioned photoradical polymerization-type curable composition, a coating film with a thickness of 20 μm was formed on a PET film, and active energy rays were irradiated under the following conditions using the following various light sources 4) to 6). Thereafter, it was left standing in a constant temperature machine at 70°C for 1 hour to obtain a film-shaped cured product. The integrated light quantity at which the tack disappeared when touching the surface of the obtained cured product was determined, and the curability was evaluated according to the following criteria. The lower the integrated light quantity required until the tack disappears, the higher the curability. 4) High-pressure mercury lamp: wavelength 200 to 450 nm, illuminance 500 mW / cm 2 5) UV-LED lamp: wavelength 385 nm, illuminance 500 mW / cm 2 6) UV-LED lamp: wavelength 405 nm, illuminance 500 mW / cm 2 ++: Integrated light quantity less than 5,000 mJ / cm 2 and the tack disappeared. +: Integrated light quantity of 10,000 mJ / cm 2 and the tack disappeared upon irradiation. +: When the integrated light quantity was 50,000 mJ / cm 2 the tack disappeared upon irradiation. -: When the integrated light quantity was 50,000 mJ / cm 2 the tack remained even after irradiation.

[0131] <Lightfast yellowing resistance> A photoionically cured product was prepared in the same manner as the evaluation of the curability of the photoion polymerization curable composition, except that the curing conditions were changed as follows. The lightfast yellowing resistance of the obtained cured product was evaluated in the same manner as the evaluation of the lightfast yellowing resistance of the photoradical polymerization cured product. Curing conditions: UV-LED lamp: wavelength 405 nm, illuminance 1,000 mW / cm 2 , integrated light quantity 100,000 mJ / cm 2 irradiated, and then left standing at 70 °C for 1 hour.

[0132] <Durability> A cured product was prepared in the same manner as the photoion polymerization curable composition, except that the curing condition was changed to irradiation with an integrated light quantity of 50,000 mJ / cm 2 . The durability of the obtained cured product was evaluated in the same manner as the evaluation of the lightfast yellowing resistance of the photoion polymerization curable composition.

[0133]

Table 5

[0134] Examples 144 to 151 and Comparative Examples 16 to 18 (Preparation of a photo hybrid polymerization active energy ray curable composition and evaluation of a photosensitizer) Using the benzoylformamide derivative (D) synthesized in the examples and commercially available photosensitizers (I-3), (I-5), and commercially available photoinitiator (E-5) as comparative examples, unsaturated compounds (h1), (h2), cyclic ether compound (h3) and photoionization initiator (E-10) or (E-11), and other additives (k) were weighed in the proportions shown in Table 6, and a photo hybrid polymerization system active energy ray curable composition and a cured product were obtained in the same manner as the evaluation of the photosensitizer of the photoionization polymerization system. In the same manner as the evaluation of the photosensitizer of the photoionization polymerization system, the compatibility and curability of the curable composition, and the light fastness yellowing resistance and durability of the cured product were evaluated, and the results are shown in Table 6. The higher the curability of the curable composition, the higher the photosensitivity of D.

[0135]

Table 6

[0136] As is clear from the results of Tables 4-1, 4-2, 5, and 6, the curable compositions of each example using benzoylformamide derivative (D) as a photosensitizer showed good compatibility. D showed photosensitivity to continuous light of a wide range of wavelengths of a high-pressure mercury lamp, as well as to light of wavelengths 385 nm and 405 nm of a UV-LED lamp, and the curable composition containing D showed high curability. It was confirmed that D has high photosensitivity even when used in combination with one or more of a general-purpose photo radical polymerization initiator, a general-purpose photoionic photo polymerization initiator, or a photo radical polymerization initiator D. All of the photo radical-based, photoionic-based, and photo hybrid-based curable compositions had high curability, and it was possible to obtain a cured product with good light fastness yellowing resistance and durability. Also, D-3 (Example 102), D-17 (Example 110), D-18 (Example 111), D-41 to D-43 (Examples 127 to 129) having a methoxy group had a very high photosensitizing effect on light of wavelengths 385 nm and 405 nm, and it was clear that the absorption wavelength of D was shifted to the long wavelength side by containing an electron-donating methoxy group. D-55 to D-58 (Examples 140 to 143) having a cyclic epoxy group showed photosensitivity to a photoionic polymerization initiator, and at the same time was incorporated into the cured product by photoionic polymerization, the curability of the curable composition was high, and a cured product with high durability could be obtained. Examples 144, 145, 147 to 151 were photo hybrid polymerization systems of photo radical polymerization and photoionic polymerization using a photoionic polymerization initiator and D in combination. Also in these examples, the curability of the curable composition was high, and the light fastness yellowing resistance and durability of the obtained cured product were good. That is, it was confirmed that D has an effect as both a photo radical polymerization initiator and a photosensitizer for photoionic polymerization. On the other hand, in Comparative Examples 4 to 8, 11, and 16 without using a photosensitizer, the sensitivity to light of wavelengths 385 nm and 405 nm was low, and the curability of the curable composition was low. In the case of Comparative Examples 9 and 10 using isopropylthioxanthone (I-3) and 2-ethylanthraquinone (I-4) as photosensitizers, the curability of the curable composition was good, but the light fastness yellowing resistance and durability of the obtained cured product were low. Similar results to those of the radical-based were confirmed also in the ionic-based and hybrid-based comparative examples.Comparative Example 15 and Comparative Example 18 using polymer thioxanthone (I-5) had lower photosensitivity, lower curability of the curable composition, yellowing of the obtained cured product, and lower durability of the cured product than when using low-molecular-weight I-3.

[0137] Examples 152 to 161 and Comparative Examples 19 to 21 (Active Energy Ray-Curable Ink Composition and Its Evaluation) According to the ratio described in Table 7 (in terms of solid content), the benzoylformic acid amide derivative (D), the curable composition (F) containing D, a commercially available photoinitiator (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 the ink composition). The viscosity and curability of the ink composition were evaluated by the following methods. Also, inkjet printing was performed using the ink composition, and the ink ejection stability, blocking resistance of the printed matter, sharpness, and bleed-out resistance were evaluated as printing suitability by the following methods. Furthermore, using the ink composition, a cured product for evaluating the low-molecular-weight component content was prepared, and the low-molecular-weight component content in the cured product of the ink composition was evaluated in the same manner as the evaluation of the low-molecular-weight component content in the cured product of the curable composition. The results of these evaluations are shown in Table 7.

[0138] <Viscosity> The viscosity of the ink composition was measured using a cone and plate viscometer (RE550 viscometer manufactured by Toki Sangyo Co., Ltd.) in accordance with ISO 2884-1. The viscosity of the ink composition for inkjet printing was evaluated in four grades as follows. ++: The viscosity was 5 mPa·s or more and less than 50 mPa·s. +: The viscosity was 50 mPa·s or more and less than 100 mPa·s. ±: The viscosity was 100 mPa·s or more and less than 200 mPa·s. -: The viscosity was 200 mPa·s or more.

[0139] <Method for Producing Printed Matter by Ultraviolet Irradiation> An ink composition was used to form a coating film with a thickness of 20 μm on a PET film using a bar coater, and the coating was cured by ultraviolet irradiation (UV-LED lamp: wavelength 395 nm, illuminance 1,000 mW / cm 2 ) to produce a printed matter.

[0140] <Curability> When producing the printed matter, the integrated light quantity until the ink composition was completely cured (non-sticky state) was measured, and the curability of the ink composition was evaluated according to the following criteria. ++: The integrated light quantity was less than 1,000 mJ / cm 2 and it was completely cured. +: The integrated light quantity was 1,000 mJ / cm 2 or more and less than 2,000 mJ / cm 2 and it was completely cured. ±: The integrated light quantity was 2,000 mJ / cm 2 or more and less than 5,000 mJ / cm 2 and it was completely cured. -: The integrated light quantity required to be completely cured was 5,000 mJ / cm 2 or more.

[0141] <Printing suitability> The obtained ink composition was filled into an inkjet printer (manufactured by Fujifilm Corporation, LuxelJetUV350GTW), and a solid image was printed using coated paper, and the ejection stability of the ink was evaluated as the printing suitability.

[0142] <Ejection stability> The printing state of the printed matter was visually observed, and the ejection stability was evaluated according to the following criteria. ++: There was no nozzle clogging and it was printed well. +: There was slightly nozzle clogging. -: There was nozzle clogging in a wide range.

[0143] <Blocking resistance> The printed matter was left standing in an environment of 23°C at room temperature and 50% relative humidity for 5 minutes, a high-quality paper was placed on the printed surface, and a load of 1 Kg / cm 2Apply the load for 1 minute, visually observe the degree of ink transfer to the paper, and evaluate the blocking resistance according to the following criteria. ++: The ink dried and there was no transfer to the paper at all. +: The ink dried and there was a slight transfer to the paper. ±: The ink was almost dry and there was transfer to the paper. -: The ink hardly dried and there was a lot of transfer to the paper. <Color clarity> Visually observe the image color clarity of the printed matter obtained from the ink composition containing the pigment, and evaluate the color clarity according to the following criteria. ++: There was no bleeding of the ink at all and the image was clear. +: There was almost no bleeding of the ink and the image was good. -: Bleeding of the ink was observed.

[0144] <Bleed-out resistance> Place the printed matter in a thermo-hygrostat set at a temperature of 40 °C and a relative humidity of 50% for 168 hours, visually observe the surface of the printed matter, and evaluate the bleed-out resistance according to the following criteria. ++: No bleed-out was observed at all. +: Slight bleed-out was observed. -: Severe bleed-out was observed.

[0145] As is clear from the results in Table 7, the ink compositions of the examples had high curability, there were no low molecular weight components in the resulting cured films (printed matter), the cured films had good drying properties, little bleed-out, and it was possible to produce printed matter with high durability. On the other hand, the ink composition of Comparative Example 19 had low curability. In Comparative Examples 20 and 21, curing was possible, but in both cases, there were many low molecular weight components in the printed matter, and the blocking resistance, bleed-out resistance, and clarity of the printed matter were poor. Also, in Comparative Example 20 using Esacure KIP 150 (E-1), the ejection stability of the ink was low and the printability was poor. Also, in the examples in which pigments were blended, clear printed matter could be obtained. This is considered to be because the pigments were uniformly dispersed or uniformly dissolved in the ink compositions of the examples. Furthermore, the viscosity of the ink compositions of the examples was low, the ejection stability was high, and they were suitable for inkjet printing.

[0146]

Table 7

[0147] Examples 162 to 170 and Comparative Examples 22 and 23 (Preparation and Evaluation of Active Energy Ray Curable Pressure Sensitive Adhesive Compositions) According to the proportions described in Table 8 (in terms of solid content), the benzoylformamide derivative (D), the curable composition (F) containing D, a commercially available photoinitiator (E), a monofunctional unsaturated compound (h1), a 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 pressure sensitive adhesive composition (hereinafter also referred to as a pressure sensitive adhesive composition). Using the pressure sensitive adhesive composition, a pressure sensitive adhesive sheet having a pressure sensitive adhesive layer was produced by the following method, and the curability of the pressure sensitive adhesive composition and the adhesiveness (adhesive strength) to various substrates were evaluated. The low molecular weight component content, transparency, bleed-out resistance, reworkability, and light yellowing resistance (by the same method as the evaluation of the curable composition) of the obtained pressure sensitive adhesive layer (cured product of the pressure sensitive adhesive composition) were evaluated. The results of these evaluations are shown in Table 8.

[0148] <Curability> A release film was adhered to a horizontally installed glass plate, a spacer with a thickness of 1 mm and an internal space of 60 mm × 100 mm was installed, and the adhesive compositions of the examples and comparative examples prepared were filled inside the spacer. A release film was overlaid on the filled composition, and irradiation was performed with a UV-LED lamp having a wavelength of 405 nm and an illuminance of 100 mW / cm 2 so that the integrated light quantity became 1,000 mJ / cm 2 to cure the adhesive composition. Thereafter, the release film was peeled off to obtain an adhesive sheet composed of a cured product (adhesive layer) of the adhesive composition and a release film. The curability of the adhesive composition was evaluated according to the following criteria by touching the adhesive layer. ++: A cured product that could maintain its shape was obtained, and there was no liquid deposit at all. +: A cured product that could maintain its shape was obtained, and there was a slight amount of liquid deposit. ±: A cured product that could maintain its shape was obtained, and there was liquid adhesion. -: Curing was insufficient, and a cured product that could maintain its shape was not obtained.

[0149] <Low molecular weight component content> In the same manner as the evaluation of the low molecular weight component content in the cured product of the curable composition, the low molecular weight component content of the obtained adhesive layer was evaluated.

[0150] <Transparency> In an environment of a temperature of 23°C and a relative humidity of 50%, the adhesive layer was transferred from the obtained adhesive sheet to a glass substrate, and the total light transmittance of the glass substrate and the adhesive layer was measured in accordance with ISO 14782 using a haze meter (manufactured by Nippon Denshoku Industries Co., Ltd., NDH-8000). Thereafter, the transmittance of the glass plate was measured in the same manner, and the transmittance of the adhesive layer itself was calculated by subtracting the transmittance of the glass plate from the total light transmittance of the glass substrate and the adhesive layer. The transparency of the adhesive layer was evaluated according to the following criteria. ++: The transmittance was 90% or more. +: The transmittance was 85% or more and less than 90%. ±: The transmittance was 50% or more and less than 85%. -: The transmittance was less than 50%.

[0151] <Bleed-out resistance> The obtained pressure-sensitive adhesive sheet was allowed to stand in a thermo-hygrostat at a temperature of 40 °C and a relative humidity of 50% for 168 hours. Then, it was left for 30 minutes in an environment at a temperature of 23 °C and a relative humidity of 50%. The bleed-out resistance of the pressure-sensitive adhesive layer on the surface of the pressure-sensitive adhesive sheet was evaluated according to the following criteria by touching the pressure-sensitive adhesive layer. ++: There was no liquid deposit, and no bleed-out was observed. +: There was a very small amount of liquid deposit, and very slight bleed-out was observed. ±: There was a slight liquid deposit, and slight bleed-out was observed. -: There was a liquid deposit, and bleed-out was observed.

[0152] <Adhesive strength> In an environment at a temperature of 23 °C and a relative humidity of 50%, the pressure-sensitive adhesive layer was transferred from the obtained pressure-sensitive adhesive sheet to a film or plate of the following base material, and pressure-bonded by reciprocating twice using a pressure roller weighing 2 kg, and then left for 30 minutes in the same environment. Then, using a tensile tester (manufactured by ORIENTE, Tensilon RTA-100, hereinafter also referred to as a universal testing machine), the 180° peel strength (N / 25 mm) (peel rate: 300 mm / min) was measured according to ISO 29862, 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 Seya Co., Ltd.) GL: Glass (plate) (Eagle XG, manufactured by Corning Incorporated) ++: The 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). -: The peel strength was less than 5 (N / 25 mm).

[0153] <Reworkability> Similar to the adhesion evaluation, the adhesive layer was transferred onto films or plates of different base materials, pressure-bonded, and then left standing in a constant-temperature bath at 80°C for 24 hours. After that, it was left standing for 30 minutes in an environment with a temperature of 23°C and a relative humidity of 50%. Then, the adhesive layer was peeled off, and the remaining state of the adhesive layer (paste) on the surface of the base material was visually observed, and the reworkability of the adhesive layer was evaluated according to the following criteria. ++: No paste residue. +: There was a very slight paste residue. ±: There was a slight paste residue. -: There was paste residue.

[0154] <Durability> The adhesive layer of the adhesive sheet was transferred onto a glass substrate and left standing in a constant-temperature and humidity chamber at a temperature of 85°C and a relative humidity of 85% for 100 hours. After that, it was left standing for 30 minutes in an environment with a temperature of 23°C and a relative humidity of 50%. Then, the state of the adhesive layer was visually observed, and the durability was evaluated according to the following criteria. ++: The adhesive layer was transparent, without lifting or bubbles. +: The adhesive layer was slightly cloudy, without lifting or bubbles. -: The adhesive layer was cloudy, lifted, or had bubbles.

[0155]

Table 8

[0156] As is clear from the results in Table 8, the adhesive composition of the examples had high curability, and the adhesive layer obtained by curing it had high transparency and high adhesiveness (adhesion) to various base materials. Also, the cured product (adhesive layer) obtained in the examples had a low content of low-molecular-weight components, high anti-bleed-out property, durability, and light yellowing resistance, and also had good reworkability when the cured product was peeled off from the substrate. On the other hand, the curability of the adhesive composition of the comparative examples was low, the content of low-molecular-weight components in the obtained cured product was high, the adhesion of the adhesive layer was low, and both the anti-bleed-out property, durability, light yellowing resistance, and reworkability were low.

[0157] Examples 171 to 177 and Comparative Examples 24 and 25 (Preparation and Evaluation of Active Energy Ray-Curable Adhesive Compositions) According to the ratio described in Table 9 (in terms of solid content), the benzoylformamide derivative (D), the curable composition (F) containing D, a commercially available photoinitiator (E), a monofunctional unsaturated compound (h1), a 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 the adhesive composition). The curability of the adhesive composition and the content rate of low molecular weight components in the obtained cured product were evaluated. Also, various base materials were adhered using the adhesive composition to prepare a laminate, and the adhesive strength and durability of the laminate were evaluated. The evaluation results are shown in Table 9.

[0158] <Curability> A PET film was adhered closely onto a horizontally installed glass plate, and the adhesive compositions of the examples and comparative examples were coated to a thickness of 20 μm using a bar coater, and a light release film was overlaid, and ultraviolet irradiation was performed using a UV-LED lamp with a wavelength of 405 nm and an illuminance of 50 mW / cm 2 to cure the adhesive composition. Then, the light release film was removed, the presence or absence of tack on the surface of the cured film was confirmed, and based on the necessary integrated light quantity until the tack disappeared, the curability of the adhesive composition was evaluated according to the following criteria. ++: The integrated light quantity was less than 500 mJ / cm 2 and the tack disappeared. +: The integrated light quantity was 500 mJ / cm 2 or more and less than 1,000 mJ / cm 2 and the tack disappeared. ±: The integrated light quantity was 1,000 mJ / cm 2 or more and less than 5,000 mJ / cm 2 and the tack disappeared. -: The integrated light quantity was 5,000 mJ / cm 2 but the tack remained.

[0159] <Laminate Preparation> The adhesive composition was coated onto various film-like or plate-like base materials (substrates) shown below, and using a tabletop roll laminator (RSL-382S) so as not to entrap air bubbles with a PET film, they were laminated so that the adhesive layer had a thickness of 20 μm, and ultraviolet rays were irradiated (wavelength 405 nm, illuminance 50 mW / cm2 UV-LED lamp with an integrated light quantity of 2,000 mJ / cm 2 ) and a laminate was produced. Base material (substrate) PET3: polyethylene terephthalate film (Cosmoshine E5100, corona treated, manufactured by Toyobo Co., Ltd.) PMMA: polymethyl methacrylate (sheet) (Comglas P, manufactured by Kuraray Co., Ltd.) PC: polycarbonate (sheet) (PC1600, manufactured by Takiron Seia Co., Ltd.)

[0160] <Adhesion strength> Using a universal testing machine, the 180° peel strength (N / 25 mm) (peel rate: 300 mm / min) of the laminate was measured in accordance with ISO 29862, and the adhesion strength was evaluated according to the following criteria. ++: The 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). -: The peel strength was less than 5 (N / 25 mm).

[0161] <Durability> Similar to the evaluation of the curability of the adhesive composition, a cured product (adhesive layer) was produced on a glass substrate (integrated light quantity: 2,000 mJ / cm 2 ) and left standing in a thermo-hygrostat at a temperature of 85°C and a relative humidity of 85% for 100 hours. Then, it was left standing for 30 minutes in an environment at a temperature of 23°C and a relative humidity of 50%, and the state of the laminate was visually observed, and the durability was evaluated according to the following criteria. ++: The laminate was transparent and there was no peeling or bubbling. +: The laminate had very slight cloudiness, but there was no peeling or bubbling. ±: The laminate had slight cloudiness, peeling, or bubbling. -: The laminate had extreme cloudiness, peeling, or bubbling.

[0162] <Content of low molecular weight components> Similar to the evaluation of the curability of the adhesive composition, 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 / cm 2 , integrated light quantity: 2,000 mJ / cm 2 ), and the PET film having the obtained adhesive layer was cut into test pieces of size 5 cm 2 . Similar to the evaluation of the content rate of low-molecular-weight components in the cured product of the curable composition, the content rate of low-molecular-weight components in the adhesive layer was evaluated.

[0163]

Table 9

[0164] As is clear from the results in Table 9, the adhesive compositions of the examples had high curability, and the laminates (adherends) obtained by curing them had high adhesive strength for both the same type and different types of base materials. Also, the content rate of low-molecular-weight components in the cured product (adhesive layer) was low, and the durability of the laminate was good. Such adhesive compositions exhibited properties suitable as adhesives. On the other hand, the adhesive compositions of the comparative examples had low curability, a large amount of residual low-molecular-weight components in the adhesive layer, and low adhesive strength and durability of the adherend.

[0165] Examples 178 to 184 and Comparative Examples 26 and 27 (Preparation and evaluation of an active energy ray curable encapsulant composition) According to the proportions described in Table 10 (in terms of solid content), a benzoylformic acid amide derivative (D), a commercially available photoinitiator (E), a monofunctional unsaturated compound (h1), a 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 encapsulant composition (hereinafter also referred to as the encapsulant composition). A cured product of the encapsulant composition was prepared, and the curability of the encapsulant composition, the transparency, moisture and heat resistance yellowing resistance, water resistance, outgassing resistance, heat cycle resistance, and corrosion resistance of the obtained cured product were evaluated. Also, similar to the cured product of the curable composition, the content rate of low-molecular-weight components in the cured product of the encapsulant composition was evaluated. These evaluation results are shown in Table 10.

[0166] <Preparation of cured product of encapsulant composition> A spacer (30 mm × 15 mm × 3 mm) was set on a glass plate, a copper foil (5 mm in length × 50 mm in width × 80 μm in thickness) was placed inside the spacer, and the prepared sealant composition was injected. After sufficient degassing, ultraviolet rays were irradiated (UV-LED lamp with a wavelength of 405 nm and an illuminance of 500 mW / cm 2 and an integrated light quantity of 1,000 mJ / cm 2 ) to obtain a cured product of the sealant composition.

[0167] <Curability> The cured product was evaluated according to the following criteria for curability evaluation. ++: A cured product that could maintain its shape was obtained, and there was no tackiness when touching the cured product. +: A cured product that could maintain its shape was obtained, and there was tackiness when touching the cured product. ±: A cured product that could maintain its shape was obtained, but there was a liquid deposit when touching the cured product. -: Curing was insufficient, and a cured product that could maintain its shape was not obtained.

[0168] <Transparency> In an environment with a temperature of 23 °C and a relative humidity of 50%, after the cured product was left stationary for 24 hours, 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. +: The transmittance was 85% or more and less than 90%. ±: The transmittance was 50% or more and less than 85%. -: The transmittance was less than 50%.

[0169] <Moisture and heat resistance yellowing> After leaving the cured product to stand for 24 hours in an environment of a temperature of 23°C and a relative humidity of 50%, the transmission spectrum of the cured product was measured using a transmission color measurement dedicated machine (manufactured by Nippon Denshoku Industries Co., Ltd., TZ-6000), and the initial b value was obtained. Thereafter, the cured product was left to stand in a thermo-hygrostat set at a temperature of 85°C and a relative humidity of 85% for 500 hours to conduct an accelerated test for hygrothermal yellowing degradation. After the test, the cured product was left to stand for 24 hours in an environment of a temperature of 23°C and a relative humidity of 50%, and transmission color measurement was performed to obtain the b value after hygrothermal treatment. The difference between the b value after hygrothermal treatment and the initial b value was defined as the change value Δb (Δb = b value after hygrothermal treatment - initial b value). The hygrothermal yellowing degradation of the cured product was evaluated according to the following criteria. ++: Both the initial b value and the b value after hygrothermal treatment were 0.2 or less, and Δb was 0.1 or less. +: One or more of the initial b value and the b value after hygrothermal treatment exceeded 0.2, but both were 0.5 or less, and Δb was 0.2 or less. ±: One or more of the initial b value and the b value after hygrothermal treatment exceeded 0.5, but both were 1.0 or less, and Δb was 0.3 or less. -: One or more of the initial b value and the b value after hygrothermal treatment exceeded 1.0, or Δb exceeded 0.3.

[0170] <Water resistance> 1 g was cut out from the cured product to obtain a test piece, which was left to stand in a thermo-hygrostat at a temperature of 85°C and a relative humidity of 95%. After leaving it to stand for 48 hours, the weight of the test piece was measured again. The water absorption rate was calculated according to the following formula, and the water resistance was evaluated according to the following criteria. The lower the water absorption rate, the higher the water resistance of the cured product. Water absorption rate (%) = (weight after water absorption - weight before water absorption) / weight before water absorption × 100% ++: The water absorption rate was less than 1.0%. +: The 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%. -: The water absorption rate was 3.0% or more.

[0171] <Outgassing resistance> 1 g was cut from the cured product and left as a test piece in a thermostatic bath set at a temperature of 100 °C, and a dry nitrogen stream was passed for 24 hours. Then, the weight of the test piece was measured again. The outgas generation rate was calculated by the following formula, and the outgas resistance was evaluated according to the following criteria. The lower the outgas generation rate, the higher the outgas resistance. Outgas generation rate (%) = (weight after test - weight before test) / weight before test × 100% ++: The outgas generation rate was less than 0.1%. +: The outgas generation rate was 0.1% or more and less than 0.2%. ±: The outgas generation rate was 0.2% or more and less than 0.3%. -: The outgas generation rate was 0.3% or more.

[0172] <Heat cycle resistance> A treatment of leaving at -40 °C for 30 minutes and then at 100 °C for 30 minutes was defined as one heat cycle, and the cured product was repeatedly treated 100 times. Then, the cured product was visually observed, and the heat cycle resistance was evaluated according to the following criteria. ++: No change was observed at all. +: Slight generation of bubbles was observed, but neither clouding nor crack generation was observed. ±: Some bubbles or cracks were generated, and there was slight clouding. -: Bubbles or cracks were generated all over, and it was in a translucent state.

[0173] <Corrosion resistance> After the above-mentioned damp heat yellowing test, the surface of the copper foil was visually observed, and the corrosion resistance of the cured product was evaluated according to the following criteria. The lower the corrosion of the copper foil, the lower the metal corrosiveness of the cured product and the higher the corrosion resistance of the cured product. ++: There was no corrosion on the copper foil in the cured product. +: There was slight corrosion on the copper foil in the cured product. ±: There was a little corrosion on the copper foil in the cured product. -: There was significant corrosion on the copper foil in the cured product.

[0174]

Table 10

[0175] As is clear from the results in Table 10, the sealant composition of the examples had high curability, the content rate of low-molecular-weight components in the obtained cured product (sealant) was low, the cured product had high transparency, high resistance to moisture and heat-induced yellowing, high water resistance, little outgas generation, and good heat cycle resistance and corrosion resistance. On the other hand, the sealant composition of the comparative examples had low curability, a large amount of low-molecular-weight components remained in the sealant, and the sealant could not satisfy any two or more physical properties among transparency, resistance to moisture and heat-induced yellowing, water resistance, outgas resistance, heat cycle resistance, and corrosion resistance.

[0176] Examples 185 to 192 and Comparative Examples 28 and 29 (Preparation and Evaluation of Active Energy Ray-Curable Coating Agent Composition) According to the proportions described in Table 11 (in terms of solid content), a benzoylformamide derivative (D), a commercially available photoinitiator (E), a monofunctional unsaturated compound (h1), a 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 agent composition (hereinafter also referred to as the coating agent composition). Using the coating agent composition, a coating layer was formed by the following method, and the curability of the coating agent composition, the adhesion, light yellowing resistance, bending resistance, chemical resistance, scratch resistance, durability, and low-molecular-weight component content rate of the obtained coating layer were evaluated, and the results are shown in Table 11.

[0177] <Curability> The curability of the coating agent composition was evaluated by the same method and evaluation criteria as those of the above adhesive composition.

[0178] <Coating Layer Formation> A PET film was adhered to a horizontally placed glass plate, and the coating agent compositions of the examples and comparative examples were coated to a thickness of 5 μm with a bar coater, and under a nitrogen atmosphere, irradiated with ultraviolet light having a wavelength of 385 nm and an illuminance of 500 mW / cm 2 and an integrated light amount of 2,000 mJ / cm 2 to form a coating layer on the PET film.

[0179] <Adhesion evaluation> In accordance with the cross-cut method described in ISO 2409, cut marks were made on the surface of the coating layer with a cutter knife to produce 100 meshes of 1 mm × 1 mm, which were used as test pieces. After attaching a commercially available cellophane tape onto the test pieces and then peeling it off, the number of meshes remaining on the test pieces was counted, and the adhesion was evaluated according to the following criteria. ++: 100 meshes remained. +: 90 or more and 99 or less meshes remained. -: The number of remaining meshes was 89 or less.

[0180] <Lightfast yellowing resistance> Similarly, for the evaluation of the lightfast yellowing resistance of the cured product of the curable composition, ultraviolet rays were irradiated onto the coating layer using a UV-LED (wavelength 405 nm, illuminance 100 mW / cm 2 , integrated light quantity 20,000 mJ / cm 2 ), and the lightfast yellowing resistance of the coating layer was evaluated.

[0181] <Flexural resistance> In accordance with the cylindrical mandrel method described in ISO 1519, it was bent while contacting a mandrel (10 mm φ) so that the coating layer was on the outside. Then, the coating layer was visually observed, and the flexural resistance was evaluated according to the following criteria. ++: There was neither whitening nor cracking at the bent part. +: The bent part was partially whitened. ±: The bent part was partially cracked. -: The bent part was cracked.

[0182] <Chemical resistance> Using the prepared coating layer, oleic acid was applied onto the surface of the coating layer to a diameter of about 1 cm, held at 23°C for 1 hour, then washed away with a neutral detergent, and the surface state was visually observed, and the chemical resistance was evaluated according to the following criteria. ++: No trace of oleic acid was seen at all. +: A very thin whitened trace was slightly seen at the part where oleic acid was applied. +: The part coated with oleic acid turned white, and swelling was observed on the surface. -: The part coated with oleic acid was sticky, and surface peeling was observed.

[0183] <Scratch resistance> Under the environment of room temperature 23°C and humidity 50%, the surface of the coating layer was scraped 10 times back and forth with steel wool (#0000, weighted 100 g), the surface of the coating layer was visually observed, and the scratch resistance was evaluated according to the following criteria. ++: No scratches were observed on the coating layer. +: Slight thin scratches were observed on a part of the coating layer. ±: Streak-like scratches were observed on the entire coating layer. -: Peeling of the coating layer was observed.

[0184] <Durability> The durability of the coating layer was evaluated in the same manner as the durability evaluation of the cured product of the above adhesive composition.

[0185] <Low molecular weight component content> The light source was a UV-LED lamp with a wavelength of 385 nm and an illuminance of 1,000 mW / cm 2 Except that the integrated light quantity was 10,000 mJ / cm 2 The low molecular weight component content of the coating layer was evaluated in the same manner as the evaluation of the low molecular weight component content in the cured product of the above curable composition.

[0186]

Table 11

[0187] As is clear from the results in Table 11, the coating agent composition of the example had high curability with respect to long-wavelength light, and the obtained cured product (coating layer) had good adhesion, light yellowing resistance, flexural resistance, chemical resistance and durability. Such a coating agent composition had properties suitable for vehicle use, indoor and outdoor coating agents, and coating agents for decoration. On the other hand, the coating agent composition of the comparative example had low curability with respect to long-wavelength light, a large amount of low molecular weight components remained in the obtained coating layer, and various physical properties of the coating layer were low.

[0188] Examples 193 to 202 and Comparative Examples 30 and 31 (Preparation and Evaluation of Ink Composition for Active Energy Ray Curable Three-Dimensional Modeling) In accordance with the proportions described in Table 12 (in terms of solid content), the benzoylformamide derivative (D), the curable composition (F) containing D, a commercially available photoinitiator (E), a monofunctional unsaturated compound (h1), and a polyfunctional unsaturated compound (h2) were weighed and mixed at 25°C for 30 minutes to prepare an ink composition for active energy ray curable 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 molded article was produced by the following molding method, and the resistance to curing shrinkage and the content rate of low molecular weight components in the molded article were evaluated. The strength, heat resistance, molding accuracy, light yellowing resistance, and bleed-out resistance of the obtained molded article were evaluated. The results of these evaluations are shown in Table 12.

[0189] <Viscosity> In accordance with ISO 2884-1, the viscosity of the ink composition for three-dimensional modeling was measured with a cone and plate viscometer (RE550 viscometer) and evaluated according to the following criteria. ++: The viscosity was 5 mPa·s or more and less than 500 mPa·s. +: The viscosity was 500 mPa·s or more and less than 2,000 mPa·s. -: The viscosity was 2,000 mPa·s or more.

[0190] <Curability> The curability of the ink composition for three-dimensional modeling was evaluated in the same manner as 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 / cm 2 The curability of the ink composition for three-dimensional modeling was evaluated in the same manner as 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.

[0191] <Production of Molded Article> A peeling film was adhered closely to a horizontally installed glass plate, and spacers with an internal size of 6 mm × 60 mm × 60 mm were installed thereon. The three-dimensional shaping ink compositions of each example and comparative example were each filled into the spacers so as to form a layer with a thickness of 0.3 mm. After standing in a thermostat at 60 °C for 1 minute, ultraviolet rays (wavelength 405 nm, illuminance 5 mW / cm 2 , integrated light quantity 100 mJ / cm 2 ) were irradiated with a UV-LED lamp to cure. Similarly, the three-dimensional shaping ink composition was 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 × 60 mm × 60 mm). Ultraviolet rays (wavelength 405 nm, illuminance 100 mW / cm 2 , integrated light quantity 2,000 mJ / cm 2 ) were irradiated onto the cured product with a UV-LED lamp to obtain a shaped product after post-curing treatment.

[0192] <Low molecular weight component content> A test piece with a thickness of 0.5 m was cut out from the shaped product, and 0.5 g was weighed. The low molecular weight component content in the shaped product was evaluated in the same manner as the evaluation of the low molecular weight component content of the cured product of the curable composition.

[0193] <Hardening shrinkage resistance> The density of the three-dimensional shaping ink composition was measured using a Gay-Lussac type specific gravity bottle in accordance with ISO 758. The density of the shaped product was measured using an electronic specific gravity meter (MDS-300 manufactured by Alpha Mirage Co., Ltd.) in accordance with ISO 1183-1. The hardening shrinkage rate was calculated from the density of the three-dimensional shaping ink composition and the density of the shaped product by the following formula, and the hardening shrinkage resistance of the three-dimensional shaping ink composition was evaluated according to the following criteria. The lower the hardening shrinkage rate, the higher the hardening shrinkage resistance. Hardening shrinkage rate (%) = (Ds - Dl) / D1 × 100% (In the formula, Ds is the density of the shaped product, and Dl is the density of the three-dimensional shaping ink composition.) ++: The hardening shrinkage rate was less than 6%. +: The hardening shrinkage rate was 6% or more and less than 7%. ±: The hardening shrinkage rate was 7% or more and less than 8%. -: The hardening shrinkage rate was 8% or more.

[0194] <Strength> In accordance with ISO 48, the Shore D hardness of the shaped article was measured, and the strength of the three-dimensional shaped article was evaluated according to the following criteria. ++: The Shore D hardness was 60 or more. +: The Shore D hardness was 40 or more and less than 60. -: The Shore D hardness was less than 40.

[0195] <Heat resistance> The glass transition temperature (Tg) of the shaped article was measured with a differential scanning calorimeter (manufactured by Shimadzu Corporation, DSC-60plus), and the heat resistance of the shaped article was evaluated according to the following criteria. ++: Tg was 60°C or more. +: Tg was 40°C or more and less than 60°C. -: Tg was less than 40°C.

[0196] <Shaping accuracy> The side surface of the shaped article was visually observed, and the height of the shaped article was measured. Combining these results, the shaping accuracy was evaluated according to the following criteria. ++: The height was less than 6 mm ± 0.1 mm, and there were no irregularities on the side surface. +: The height was 6 mm ± 0.1 mm or more and less than ± 0.2 mm, or there were slight irregularities on the side surface. ±: The height was 6 mm ± 0.2 mm or more and less than ± 0.3 mm, or there were some irregularities on the side surface. -: The height was 6 mm ± 0.3 mm or more, or there were obvious irregularities on the side surface.

[0197] <Lightfast yellowing resistance> The shaped article was further irradiated with ultraviolet rays (UV-LED lamp, wavelength 405 nm, 100 mW / cm 2 , integrated light quantity 20,000 mJ / cm 2 ), and the lightfast yellowing resistance of the shaped article was evaluated in the same manner as that of the cured product of the curable composition.

[0198] <Bleed-out resistance> The shaped article was left standing in a thermo-hygrostat at a temperature of 40 °C and a relative humidity of 50% for 168 hours, and then the side surface of the shaped article was visually observed to evaluate the bleed-out resistance of the shaped article in the same manner as the bleed-out resistance of the cured film of the ink composition.

[0199]

Table 12

[0200] As is clear from Table 12, the ink composition for three-dimensional shaping of the examples had high curability with respect to long-wavelength light, low shrinkage during curing, and high shaping accuracy of the obtained shaped article. Further, the shaped articles obtained in the examples had high strength and heat resistance, and good bleed-out resistance and light yellowing resistance. On the other hand, the curability of the ink composition for three-dimensional shaping of the comparative examples was low, and the shaping accuracy of the obtained shaped articles was low. The shaped articles of the comparative examples contained many low-molecular-weight components, and the strength, heat resistance, and light yellowing resistance of the shaped articles were not satisfactory, and the bleed-out resistance was particularly low.

[0201] Examples 203 to 208 and Comparative Examples 32 and 33 (Preparation and Evaluation of an Actinic Energy Ray-Curable Nail Cosmetic Composition) According to the proportions described in Table 13 (in terms of solid content), a benzoylformic acid amide derivative (D), a commercially available photoinitiator (E), a monofunctional unsaturated compound (h1), a polyfunctional unsaturated compound (h2), a photosensitizer (I), and other components (k) were weighed and mixed at 25 °C for 30 minutes to prepare an actinic energy ray-curable nail cosmetic composition (hereinafter also referred to as a nail cosmetic composition). The curability of the nail cosmetic composition, the adhesion to a nylon substrate, the surface hardness, surface glossiness, light yellowing resistance of the obtained cured film, and the content of low-molecular-weight components in the cured film were evaluated, and the results are shown in Table 13.

[0202] <Curability> The nail cosmetic composition was applied onto a test piece of nylon 6 (manufactured by Toray Plastics (Kogyo) Co., Ltd., SHT-N6 (NC)) using a separator so that the film thickness became 100 μm. Ultraviolet irradiation was performed using a UV-LED lamp for gel nails (manufactured by Beauty Nailer, wavelength 405 nm, output 48 W) to produce a cured film. The time until the tack disappeared when touching the surface of the cured film was measured, and the curability was evaluated according to the following criteria. The shorter the time required until the tack disappeared, the higher the curability. ++: The tack disappeared in less than 1 minute. +: The tack disappeared in 1 minute or more and less than 3 minutes. ±: The tack disappeared in 3 minutes or more and less than 10 minutes. -: The tack did not disappear even after 10 minutes or more.

[0203] <Adhesion> Using the nail cosmetic composition, it was applied onto a nylon substrate in the same manner as the curability evaluation, and in the same manner, a cured film was produced by irradiating for 3 minutes using a UV-LED lamp for gel nails. In accordance with ISO 2409, the adhesion of the cured film obtained in the same manner as the coating layer adhesion evaluation of the coating agent composition was evaluated.

[0204] <Surface hardness> A cured film was produced in the same manner as the adhesion evaluation. The surface of the film was pressed against with a 750 g load at an angle of 45° using a pencil with a hardness of HB and pulled, and the change in the film surface was visually confirmed. The surface hardness was evaluated according to the following criteria. The higher the surface hardness, the less the occurrence of scratches and peeling on the film surface. +: Neither scratches nor peeling occurred. ±: No peeling occurred, but scratches occurred. -: Peeling occurred.

[0205] <Surface glossiness> A cured film was produced in the same manner as the adhesion evaluation and left standing in a thermo-hygrostat at a temperature of 40 °C and a relative humidity of 50% for 24 hours. Then, the gloss of the film surface was visually observed, and the surface glossiness of the cured film was evaluated according to the following criteria. +: There was gloss. ±: Reflection of light could be confirmed, but there were cloudy areas. -: No light reflection was confirmed, and there was no gloss.

[0206] <Low molecular weight component content> A cured film was prepared in the same manner as in the adhesion evaluation, and using a test piece of nylon 6 having the obtained cured film, the content of low molecular weight components in the cured film was evaluated in the same manner as the evaluation of the content of low molecular weight components in the cured product (adhesive layer) of the adhesive composition.

[0207] <Lightfast yellowing resistance> A cured film was prepared in the same manner as in the adhesion evaluation, set in a xenon fade meter, and irradiated with ultraviolet rays of 70 mW / cm 2 for 120 hours. Thereafter, the discoloration of the cured film was visually observed, and the lightfast yellowing resistance was evaluated according to the following criteria. ++: No yellowing was confirmed at all. +: Slight yellowing was confirmed. ±: Yellowing was confirmed. -: Obvious yellowing was confirmed.

[0208]

Table 13

[0209] As is clear from the results in Table 13, the nail cosmetic compositions of the examples had high curability with respect to a UV lamp for gel nails, and the obtained cured films had high adhesion to a nylon substrate (a material having a large number of amide bonds like nails mainly composed of protein). It was found that such nail cosmetic compositions can be suitably used as gel nails for base gels directly applied to nails. Also, the content of low molecular weight components in the cured film was low, and safety was ensured. The surface glossiness, surface hardness and lightfast yellowing resistance of the cured film were good, and it can be suitably used as gel nails for top coats. On the other hand, the nail cosmetic compositions of the comparative examples had low curability, contained many low molecular weight components in the obtained cured films, and had low adhesion, surface hardness, surface glossiness and lightfast yellowing resistance of the cured films.

[0210] Examples 209 to 214 and Comparative Examples 34 to 36 (Preparation and Evaluation of Actinic Energy Ray-Curable Dental Material Compositions) According to the proportions described in Table 14 (in terms of solid content), the benzoylformic acid amide derivative (D), a commercially available photoinitiator (E), a monofunctional unsaturated compound (h1), a polyfunctional unsaturated compound (h2), and other components (k) were weighed and mixed at 25°C for 30 minutes to prepare an actinic energy ray-curable dental material composition (hereinafter also referred to as a 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. The low molecular weight component content, hardness, surface smoothness, and flexural strength of the cured product were evaluated, and the results are shown in Table 14.

[0211] <Solubility (Dispersibility)> The state of the dental material composition was visually observed, and the solubility (dispersibility) was evaluated according to the following criteria. +: The obtained composition was in a uniform state. ±: A slightly non-uniform state was observed in the obtained composition. -: The obtained composition was in a non-uniform state.

[0212] <Storage Stability> The dental material composition was placed in a light-shielding screw tube, the lid was closed, and it was stored under two conditions: at 40°C for 1 month and at 80°C for 2 weeks. The dissolution or dispersion state of the composition after storage was confirmed, and the storage stability was evaluated according to the following criteria. +: There was no change in the state after storage under both conditions of 40°C for 1 month and 80°C for 2 weeks. ±: A change in the state after storage was confirmed under either one of the conditions of 40°C for 1 month or 80°C for 2 weeks. -: A change in the state after storage was confirmed under both conditions of 40°C for 1 month and 80°C for 2 weeks.

[0213] <Curability> A polytetrafluoroethylene mold (20 mm × 20 mm × 10 mm) having a 6-mm-diameter hole in the center was filled with the dental material composition and pressure-bonded with a polypropylene film. Ultraviolet rays (wavelength 405 nm, illuminance 50 mW / cm 2) was irradiated for 30 seconds, the polypropylene film was peeled off, and the cured product was touched by hand, and the curability was evaluated according to the following criteria. ++: There was no stickiness at all. +: There was some stickiness, but no fingerprint remained on the surface. ±: There was stickiness and a fingerprint remained on the surface. -: The stickiness was severe and the finger stuck to the surface.

[0214] <Low molecular weight component content> Using the cured product obtained in the curability evaluation, the low molecular weight component content of the cured product of the dental material composition was evaluated in the same manner as the evaluation of the low molecular weight component content of the curable composition.

[0215] <Hardness> The surface of the cured product obtained in the curability evaluation was buffed, and the Knoop hardness was measured at a temperature of 23 °C under the conditions of a load of 100 gf and a load application time of 20 seconds using a microhardness tester (manufactured by Matsuzawa Seiki Co., Ltd., DMH-2), and the hardness was evaluated according to the following criteria. ++: The Knoop hardness was 200 KHN or more. +: The Knoop hardness was 70 KHN or more and less than 200 KHN. -: The Knoop hardness was less than 70 KHN.

[0216] <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 shiny. +: The surface was almost smooth, and slight cloudiness or unevenness was observed. ±: The surface was cloudy as a whole, and some unevenness or granularity was confirmed. -: The surface was cloudy as a whole and covered with granular substances.

[0217] <Bending strength> The double - release film was adhered closely onto a horizontally placed glass plate, and spacers made of polytetrafluoroethylene (2 mm×2 mm×25 mm) were placed thereon, and then the dental material composition was filled. The light - release film was covered over the liquid surface of the spacers so as not to entrap air bubbles, and ultraviolet rays were irradiated with a UV - LED lamp (wavelength 405 nm, illuminance 50 mW / cm 2 , integrated light quantity 1,500 mJ / cm 2 ). Thereafter, the release films on both sides were peeled off, and the cured product was taken out from the spacers to obtain test specimens. The test specimens were immersed in water at 37°C for 24 hours and then subjected to a bending test with a universal testing machine. The test conditions conformed to ISO 4049, with a distance between supports of 20 mm and a cross - head 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.

[0218]

Table 14

[0219] As is clear from the results in Table 14, the dental material composition of the examples had high solubility or dispersibility, and high curability and storage stability. The content of low molecular weight components in the obtained cured product was low, and it was excellent in safety as a dental material. Also, both the hardness and flexural strength of the cured product were high, and the surface smoothness was good. On the other hand, the dental material composition of the comparative example had low curability, and insufficient solubility and storage stability. Also, the content of low molecular weight components in the cured product was high, and there were concerns about safety. The surface smoothness, hardness, and flexural strength of the cured product were low. The dental material composition of the present disclosure is suitable for use as a dental restoration material (crown composite resin, caries cavity filling composite resin, abutment construction composite resin, filling and restoration composite resin), denture base resin, luting resin, luting material (resin cement, resin-added glass ionomer cement), dental adhesive (orthodontic adhesive, cavity coating adhesive), denture base lining material, impression material, dental temporary filling material, dental fissure sealant, CAD / CAM resin block, temporary crown, and artificial tooth material.

[0220] Examples 215 to 220 and Comparative Examples 37 and 38 (Preparation and Evaluation of Actinic Energy Ray-Curable Photosensitive Composition) According to the proportions described in Table 15 (in terms of solid content), a benzoylformic acid amide derivative (D), a commercially available photopolymerization initiator (E), a monofunctional unsaturated compound (h1), a polyfunctional unsaturated compound (h2), a thermal polymerization initiator (J), a solvent (c), and other components (k) were weighed and mixed at 25°C for 30 minutes to prepare an actinic energy ray-curable photosensitive composition (hereinafter also referred to as a 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. Also, a pattern cured product was produced from the photosensitive composition, and the pattern formability of the obtained cured product and the content of low molecular weight components in the cured product were evaluated. These results are shown in Table 15.

[0221] <Production of Photosensitive Resin> Using the photosensitive compositions of the examples and comparative examples, they were applied with a spin coater to a film thickness of 15 μm and dried in an oven for 3 minutes. Then, ultraviolet light was irradiated for 3 minutes (wavelength 405 nm, illuminance 0.5 mW / cm 2, integrated light quantity 90 mJ / cm 2 ) and a photosensitive resin (cured product) was obtained. Drying of the photosensitive composition not containing the thermal polymerization initiator (J) was carried out at 80°C. Drying of the photosensitive composition containing the thermal polymerization initiator (J) was carried out at 40°C, and after irradiation with ultraviolet rays, heat treatment was carried out in an oven at 130°C for 30 minutes.

[0222] <Sensitivity> The photosensitive resin was touched by hand and the sensitivity was evaluated according to the following criteria. ++: There was no stickiness at all. +: There was some stickiness, but no fingerprint remained on the surface. ±: There was stickiness and a fingerprint remained on the surface. -: The stickiness was severe and the finger stuck to the surface.

[0223] <Storage stability> The photosensitive resin was allowed to stand in a thermostatic and humidistatic chamber at a temperature of 40°C and a relative humidity of 50% for 168 hours, the surface of the photosensitive resin was visually observed, and the storage stability was evaluated according to the following criteria. The less the bleed-out, the higher the storage stability. ++: No bleed-out was observed at all. +: Slight bleed-out was observed. -: Severe bleed-out was observed.

[0224] <Low molecular weight component content> Three test pieces with a size of 5 cm were cut out from the photosensitive resin and dried at 130°C for 30 minutes. Then, the low molecular weight component content of the photosensitive resin (cured product of the photosensitive composition) was evaluated in the same manner as the evaluation of the low molecular weight component content of the cured product of the curable composition. 2

[0225] <Manufacture of pattern cured product> Using a negative photomask (pattern mask), cured products of the photosensitive compositions of the examples and comparative examples were manufactured in the same manner as the manufacture of the photosensitive resin. Then, the negative photomask was removed from the cured product, and the unexposed portion was removed with cyclopentanone to obtain a pattern cured product.

[0226] <Pattern formability> The pattern formability of the pattern cured product was evaluated according to the following criteria. ++: There was neither distortion of the pattern nor chipping at the edge part. +: There was no distortion of the pattern, and there was slight chipping at the edge part. ±: There was slight distortion of the pattern and chipping at the edge part. -: There were both distortion of the pattern and chipping at the edge part.

[0227]

Table 15

[0228] As is clear from the results in Table 15, the photosensitive composition of the examples had high curability (sensitivity), the cured product (photosensitive resin) obtained by curing it had high storage stability, and the content rate of low molecular weight components was low. In addition, the pattern cured product of the examples obtained using a pattern mask had excellent pattern formability. On the other hand, the photosensitive composition of the comparative examples had low sensitivity, the cured product obtained therefrom had a high content rate of low molecular weight components, and the storage stability was low. In addition, the pattern formability of the pattern cured product of the comparative examples obtained using a pattern mask was poor.

[0229] Examples 221 to 227 and Comparative Examples 39 and 40 (Preparation and Evaluation of Active Energy Ray Curable Hydrogel Composition) According to the ratio described in Table 16 (in terms of solid content), the benzoylformamide derivative (D), a commercially available photopolymerization initiator (E), a monofunctional unsaturated compound (h1), a 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 a hydrogel composition). The compatibility and curability of the hydrogel composition were evaluated, and the appearance and low molecular weight component content rate of the obtained cured product (hydrogel) were evaluated, and the results are shown in Table 16.

[0230] <Compatibility> The prepared hydrogel composition was evaluated by the same method and evaluation criteria as those for the compatibility evaluation of the active energy ray curable composition.

[0231] <Curability> Using a bar coater, the hydrogel composition was applied onto a PET film so that the film thickness became 20 μm. The coating film was cured by irradiating ultraviolet rays under the following conditions 7) to 9), and the curability was evaluated according to the following criteria by touching the cured product. 7) High-pressure mercury lamp: wavelength 200 to 450 nm, illuminance 100 mW / cm 2 , 1,000 mJ / cm 2 8) UV-LED lamp: wavelength 385 nm, illuminance 100 mW / cm 2 , 1,000 mJ / cm 2 9) UV-LED lamp: wavelength 405 nm, illuminance 100 mW / cm 2 , 1,000 mJ / cm 2 ++: A gel was formed overall and was in a slightly hard state. +: A gel was formed overall and was in a slightly soft state. ±: A partial gel was formed. -: A gel was not formed.

[0232] <Appearance of cured product> The appearance of the cured product obtained by the curability evaluation under the ultraviolet ray irradiation condition 9) was visually observed and evaluated according to the following criteria. +: There was neither turbidity nor phase separation. ±: There was no phase separation but there was turbidity. -: There were both turbidity and phase separation.

[0233] <Content rate of low molecular weight component> Using the cured product obtained by the curability evaluation under the ultraviolet ray irradiation condition 9), the content rate of the low molecular weight component (excluding water) of the cured product (hydrogel) was evaluated in the same manner as the evaluation of the content rate of the low molecular weight component of the cured product of the curable composition.

[0234]

Table 16

[0235] As is clear from the results in Table 16, the hydrogel compositions of the examples contained water-soluble or hydrophilic acrylmorpholine (h1-1), N-(2-hydroxyethyl)acrylamide (h1-7), or N-vinylpyrrolidone (h1-11) and water, showed good compatibility, and were in an aqueous solution state. The hydrogel compositions of the examples had high curability, and the cured products obtained by curing them formed gels as a whole (hydrogels). Also, the content rate of low molecular weight components in the cured products (hydrogels) was low and the safety was high. Such hydrogels can be suitably used as sanitary materials and medical materials. On the other hand, the hydrogel compositions of the comparative examples had low compatibility and curability, and could not form a uniform hydrogel even when irradiated with ultraviolet rays, and the evaluation of the content rate of low molecular weight components could not be performed. Also, in the comparative examples in which a hydrogel was partially formed, the content rate of low molecular weight components in the hydrogel was high.

[0236] Examples 228 to 234 and Comparative Examples 41 and 42 (Preparation and Evaluation of Actinic Energy Ray-Curable Aqueous Compositions) According to the proportions described in Table 17 (in terms of solid content), a benzoylformic acid amide derivative (D), a commercially available photoinitiator (E), a monofunctional unsaturated compound (h1), a polyfunctional unsaturated compound (h2), ion-exchanged water, and other components (k) were weighed and mixed at 25°C for 30 minutes to prepare an actinic energy ray-curable aqueous composition (hereinafter also referred to as an aqueous composition). The dispersibility and curability of the aqueous composition were evaluated, and the appearance and the content rate of low molecular weight components of the obtained cured product were evaluated, and the results are shown in Table 17.

[0237] <Dispersibility> After allowing the aqueous composition to stand in a constant temperature bath 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 and uniform emulsion. ±: The aqueous composition was partially aggregated and was a non-uniform emulsion. -: The aqueous composition was phase-separated.

[0238] <Sclerosing> A coating film of the aqueous composition was prepared in the same manner as the evaluation of the curability of the sclerosing composition, dried at 80°C for 5 minutes, and then irradiated with ultraviolet rays to evaluate the curability.

[0239] <Appearance of cured product> The cured product obtained by the curability evaluation under the ultraviolet irradiation condition 3) was visually observed, and the appearance of the cured product was evaluated according to the following criteria. +: The cured product had no turbidity or phase separation. ±: The cured product had turbidity. -: The cured product was phase-separated.

[0240] <Content rate of low molecular weight component> Using the cured product obtained by the curability evaluation under the ultraviolet irradiation condition 3), the content rate of the low molecular weight component of the cured product of the aqueous composition was evaluated in the same manner as the evaluation of the content rate of the low molecular weight component of the sclerosing composition.

[0241]

Table 17

[0242] As is clear from the results in Table 17, the aqueous composition of the example had good dispersibility, could maintain a good emulsion state, and had high curability even when using long-wavelength light rays. The obtained cured product had a low content rate of low molecular weight components. On the other hand, the aqueous composition of the comparative example had low dispersibility and curability, and the obtained cured product contained many low molecular weight components.

[0243] This disclosure contains the following contents. (1) A benzoylformamide derivative having a benzoylformamide group represented by the general formula (1). JPEG2025100963000031.jpg3364In the formula, Q 1 ~Q 3 each independently represents a hydrogen atom, a substituent represented by Formula (Chemical Formula 2) to (Chemical Formula 8), a halogen group, or a nitrile group, and is bonded to any position from the 2nd to the 6th position. JPEG2025100963000032.jpg11539R 1~R 10 each independently 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, or a cyclic alkenyl group having 3 to 18 carbon atoms, * represents the bonding position. (2) The benzoylformic acid amide derivative is the benzoylformic acid amide derivative according to the above (1), which is at least one compound represented by any one of general formulas (2) to (4). JPEG2025100963000033.jpg3564 In the formula, Q 1 ~Q 3 is the same as the definition described in general formula (1), B 1 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 benzoylformic acid amide group, B 2 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 benzoylformic acid amide group. JPEG2025100963000034.jpg3677 In the formula, Q 1 ~Q 3 is the same as the definition described in general formula (1), B 3 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 11represents 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 12 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 atoms of these hydrocarbon groups, either a carbon atom or a hydrogen atom, are substituted with an oxygen atom, a nitrogen atom, a sulfur atom, a hydroxyl group, a thiol group, or an amine group, m represents an integer from 1 to 10. In the formula JPEG2025100963000035.jpg4283, Q 1 ~Q 3 is the same as the definition described in the general formula (1), A 1 represents a divalent organic group that 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, and either 4 one or both of 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 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 14represents a trivalent hydrocarbon group with 1 to 8 carbon atoms in a straight-chain saturated form, a trivalent hydrocarbon group with 2 to 8 carbon atoms in a straight-chain unsaturated form, a trivalent hydrocarbon group with 3 to 8 carbon atoms in a branched saturated or unsaturated form, a trivalent hydrocarbon group with 3 to 8 carbon atoms in an alicyclic saturated or unsaturated form, a trivalent aromatic hydrocarbon group with 6 to 8 carbon atoms, or a trivalent organic group in which any one or more atoms of any carbon atom or hydrogen atom 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 15 represents a divalent hydrocarbon group with 1 to 18 carbon atoms in a straight-chain saturated form, a divalent hydrocarbon group with 2 to 18 carbon atoms in a straight-chain unsaturated form, a divalent hydrocarbon group with 3 to 8 carbon atoms in a branched saturated or unsaturated form, a divalent hydrocarbon group with 3 to 8 carbon atoms in an alicyclic saturated or unsaturated form, a divalent aromatic hydrocarbon group with 6 to 8 carbon atoms, or a divalent organic group in which any one or more atoms of any carbon atom or hydrogen atom 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. n represents an integer from 1 to 100. (3) Q of the benzoylformamide group represented by the general formula (1) 1 ~Q 3 are each independently a hydrogen atom, a substituent represented by formula (Chemical Formula 3), or a substituent represented by formula (Chemical Formula 6), the benzoylformamide derivative according to (1) or (2) above. (4) having one or more ethylenically unsaturated bonds in the molecule, and the ethylenically unsaturated bond is 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, the benzoylformamide derivative according to any one of (1) to (3) above. (5) The ethylenically unsaturated bond is an acrylate group or an acrylamide group, the benzoylformamide derivative according to any one of (2) to (4) above. (6) having one or more urethane groups in the molecule, and the number of atoms directly connecting between the nitrogen atom of the benzoylformamide group and the nitrogen atom of the nearest urethane group is 3 to 20, the benzoylformamide derivative according to any one of (2) to (5) above. (7) A benzoylformamide derivative according to any one of (2) to (6) above, which has one or more urethane groups in the molecule and the number of atoms directly connecting between the nitrogen atom of the benzoylformamide group and the nitrogen atom of the nearest urethane group is 4 to 10. (8) A benzoylformamide derivative according to any one of (2) to (7) above, wherein m in the benzoylformamide derivative represented by the general formula (3) is an integer of 1 to 4. (9) A benzoylformamide derivative according to any one of (2) to (8) above, wherein n in the benzoylformamide derivative represented by the general formula (4) is an integer of 2 to 50. (10) A benzoylformamide derivative according to any one of (2) to (9) above, wherein the ratio of the total number of urethane groups to the total number of benzoylformamide groups in the benzoylformamide derivative represented by the general formula (3) is 0.5 to 10.0. (11) A benzoylformamide derivative according to any one of (2) to (10) above, wherein the ratio of the total number of urethane groups to the total number of benzoylformamide groups in the benzoylformamide derivative represented by the general formula (4) is 2.0 to 15.0. (12) A benzoylformamide derivative according to any one of (1) to (11) above, which is a photoinitiator. (13) The photoinitiator according to (12) above, wherein the benzoylformamide group represented by the general formula (1) is a benzoylformic acid mono-substituted amide. (14) A benzoylformamide derivative according to any one of (1) to (11) above, which is a photosensitizer for photoradical polymerization and / or a photosensitizer for photoion polymerization. (15) An active energy ray curable composition containing a benzoylformamide derivative according to any one of (1) to (12) and (14) above. (16) An active energy ray curable ink composition containing a benzoylformamide derivative according to any one of (1) to (12) and (14) above. (17) An active energy ray curable adhesive composition containing a benzoylformamide derivative according to any one of (1) to (12) and (14) above. (18) An active energy ray-curable adhesive composition containing the benzoylformamide derivative according to any one of (1) to (12) and (14). (19) An active energy ray-curable encapsulant composition containing the benzoylformamide derivative according to any one of (1) to (12) and (14). (20) An active energy ray-curable photosensitive composition containing the benzoylformamide derivative according to any one of (1) to (12) and (14). (21) An active energy ray-curable nail cosmetic composition containing the benzoylformamide derivative according to any one of (1) to (12) and (14). (22) An active energy ray-curable dental material composition containing the benzoylformamide derivative according to any one of (1) to (12) and (14). (23) An active energy ray-curable coating agent composition containing the benzoylformamide derivative according to any one of (1) to (12) and (14). (24) An active energy ray-curable aqueous composition containing the benzoylformamide derivative according to any one of (1) to (12) and (14). (25) An active energy ray-curable inkjet ink composition containing the benzoylformamide derivative according to any one of (1) to (12) and (14). (26) An active energy ray-curable elastomer composition containing the benzoylformamide derivative according to any one of (1) to (12) and (14). (27) An active energy ray-curable resin composition for a decorative sheet containing the benzoylformamide derivative according to any one of (1) to (12) and (14). (28) An active energy ray-curable architectural paint composition containing the benzoylformamide derivative according to any one of (1) to (12) and (14). (29) An active energy ray-curable medical device surface coating agent composition containing the benzoylformamide derivative according to any one of (1) to (12) and (14). (30) An active energy ray-curable ink composition for three-dimensional modeling containing the benzoylformic acid amide derivative according to any one of (1) to (12) and (14). (31) An active energy ray-curable flexographic ink composition containing the benzoylformic acid amide derivative according to any one of (1) to (12) and (14). (32) An active energy ray-curable offset ink composition containing the benzoylformic acid amide derivative according to any one of (1) to (12) and (14). (33) An active energy ray-curable screen ink composition containing the benzoylformic acid amide derivative according to any one of (1) to (12) and (14). (34) A resin composition for an active energy ray-curable self-healing material containing the benzoylformic acid amide derivative according to any one of (1) to (12) and (14). Industrial applicability

[0244] As described above, the benzoylformamide 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. In particular, even when using UV-LED lamps of 385 nm, 395 nm, and 405 nm, it shows high photoinitiation, photosensitivity, and curability. Also, by containing a urethane group and an ethylenically unsaturated group in the molecule, these individual properties and effects of D are further improved. In particular, by containing D having an ethylenically unsaturated group, the low molecular weight components in the cured product obtained are extremely few, the safety is high, and the adhesion to various materials is also high. Various physical properties such as surface hardness, light fastness to yellowing, durability, and transparency are also good. The benzoylformamide derivative (D) of the present disclosure is an active energy ray curable ink composition, an active energy ray curable inkjet ink composition, an active energy ray curable flexo 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 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 composition, an active energy ray curable ink composition for three-dimensional modeling, an active energy ray curable vehicle coating agent composition, an active energy ray curable nail cosmetic composition, an active energy ray curable resin composition for self-healing materials, an active energy ray curable architectural paint composition, ship bottom paint, anti-fogging materials, anti-fouling paints, and other active energy ray curable compositions used in various coating fields, 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 aqueous dispersion composition. It can be preferably used. Also, the obtained hydrogel composition and aqueous composition can be preferably used as materials in various fields such as high water-absorbing resins, paper diapers, soft contact lenses, and other sanitary fields, medical device surface coatings and artificial organs, and other medical fields, soil improvers, and other civil engineering and construction fields, water retention materials, and other agricultural fields, shock absorption materials, and other diverse fields.

Claims

1. A benzoylformamide derivative having a benzoylformamide group represented by the general formula (1). Q 1 ~Q 3 each independently represents a hydrogen atom, a substituent represented by Formula (Chemical Formula 2) to (Chemical Formula 8), a halogen group, or a nitrile group, and is bonded to any position of the 2nd to 6th positions. R 1 ~R 10 each independently 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, or a cyclic alkenyl group having 3 to 18 carbon atoms, * represents the bonding position.

2. The benzoylformamide derivative according to claim 1, wherein the benzoylformamide derivative is at least one compound represented by any one of the general formulas (2) to (4). where Q 1 to Q 3 is the same as the definition described in General Formula (1). B 1 represents a monovalent organic group which may have a hydrogen atom or 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, B 2 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. where Q 1 to Q 3 is the same as the definition described in general formula (1). B 3 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 atoms, R 12 represents a divalent hydrocarbon group having 1 to 18 carbon atoms and being linear and saturated, a divalent hydrocarbon group having 2 to 18 carbon atoms and being linear and unsaturated, a divalent hydrocarbon group having 3 to 18 carbon atoms and being branched and saturated or unsaturated, a divalent hydrocarbon group having 3 to 8 carbon atoms and being alicyclic and saturated or unsaturated, a divalent aromatic hydrocarbon group having 6 to 8 carbon atoms, or a divalent organic group in which any one or more atoms of any carbon atom or hydrogen atom 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, m represents an integer of 1 to 10. where Q 1 to Q 3 is the same as the definition described in general formula (1). A 1 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, and B 4 and B 5 either one or both of them 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 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 14 represents a trivalent hydrocarbon group that is linear and saturated with 1 to 8 carbon atoms, a trivalent hydrocarbon group that is linear and unsaturated with 2 to 8 carbon atoms, a branched saturated or unsaturated trivalent hydrocarbon group with 3 to 8 carbon atoms, an alicyclic saturated or unsaturated trivalent hydrocarbon group with 3 to 8 carbon atoms, a trivalent aromatic hydrocarbon group with 6 to 8 carbon atoms, or a trivalent organic group in which any one or more atoms of any carbon atom or hydrogen atom 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 15 represents a divalent hydrocarbon group having 1 to 18 carbon atoms and being linear and saturated, a divalent hydrocarbon group having 2 to 18 carbon atoms and being linear and unsaturated, a divalent hydrocarbon group having 3 to 8 carbon atoms and being branched and saturated or unsaturated, a divalent hydrocarbon group having 3 to 8 carbon atoms and being alicyclic and saturated or unsaturated, a divalent aromatic hydrocarbon group having 6 to 8 carbon atoms, or a divalent organic group in which any one or more atoms of any carbon atom or hydrogen atom 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, n represents an integer of 1 to 100.

3. The benzoylformamide derivative according to claim 1 or 2, which has one or more ethylenically unsaturated bonds in the molecule, and the ethylenically unsaturated bond is 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.

4. The benzoylformamide derivative according to any one of claims 1 to 3, which has one or more urethane groups in the molecule, and the number of atoms directly connecting between the nitrogen atom of the benzoylformamide group and the nitrogen atom of the nearest urethane group is 3 to 20.

5. The benzoylformamide derivative according to any one of claims 1 to 4, which is a photoinitiator.

6. The benzoylformamide derivative according to any one of claims 1 to 4, which is a photosensitizer for photoradical polymerization and / or a photosensitizer for photoionic polymerization.

7. An active energy ray curable composition containing the benzoylformamide derivative according to any one of claims 1 to 6.

8. An active energy ray curable ink composition containing the benzoylformamide derivative according to any one of claims 1 to 6.

9. An active energy ray curable adhesive composition containing the benzoylformamide derivative according to any one of claims 1 to 6.

10. An active energy ray curable bonding agent composition containing the benzoylformamide derivative according to any one of claims 1 to 6.

11. An active energy ray curable encapsulant composition containing the benzoylformamide derivative according to any one of claims 1 to 6.

12. An active energy ray curable photosensitive composition containing the benzoylformamide derivative according to any one of claims 1 to 6.

13. An active energy ray curable nail cosmetic composition containing the benzoylformamide derivative according to any one of claims 1 to 6.

14. An active energy ray-curable dental material composition containing a benzoylformic acid amide derivative according to any one of claims 1 to 6.

15. An active energy ray-curable coating agent composition containing a benzoylformic acid amide derivative according to any one of claims 1 to 6.

16. An active energy ray-curable aqueous composition containing a benzoylformic acid amide derivative according to any one of claims 1 to 6.

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