Benzoylcarboxamide derivatives

Abstract

The present invention addresses the problem of providing a benzoyl formamide derivative. The benzoyl formamide derivative has good photopolymerization initiation and photosensitive effect on long-wavelength ultraviolet rays, and a cured product obtained from the curable composition containing the benzoyl formamide derivative has extremely low content of low-molecular-weight components, yellowing resistance, high durability and high safety. [Solution] The present invention provides a benzoylformamide derivative.

Description

Technical Field

[0001] The present invention relates to a novel benzoylformamide derivative. The benzoylformamide derivative can be used as a photoinitiator and a photosensitizer. In addition, 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, a bonding agent 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] In general, photopolymerization and photocuring using active energy rays typified by ultraviolet rays (UV) generate active species such as free radicals and ions by irradiating a composition containing a photoinitiator with UV, causing a polymerization reaction, and converting the liquid composition into a solid (curing) in a short time. This technology is currently applied in a wide range of fields and is used in coatings, coating agents, adhesives, bonding agents, materials for elastic systems, inkjet inks, materials for sealing, sealing materials, dental hygiene materials, and optical materials. In particular, in terms of being able to cure in any place and in any shape, its use in nail cosmetics such as gel nails and its application in 3D printers as materials for three-dimensional optical modeling are constantly expanding.

[0003] Photoinitiators that generate free radicals through active energy rays can be classified into intramolecular cleavage type and hydrogen abstraction type. The former is a type that generates free radicals by intramolecular cleavage, and the latter is a type that generates free radicals by abstracting hydrogen from a hydrogen donor. In the case of 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, generation of odors, and coloring over time occur. In addition, there is a problem of low safety. In most cases, the hydrogen abstraction type has low photoinitiation efficiency, but since there are no decomposition products derived from the initiator, it has been attracting increasing attention in recent years.

[0004] In addition, due to high safety, long-wavelength UV-LED (Light Emitting Diode) lamps and LED lamps are actively used. The industry is actively developing photoinitiators and photosensitizers suitable for these light sources, but there are problems such as low photoinitiation effect, low photosensitization effect, and easy yellowing of the obtained cured product. Summary of the Invention

[0005] Technical Problems to be Solved by the Present Invention

[0006] A first object of the present invention is to provide a benzoylformamide derivative. The benzoylformamide derivative has high photoinitiating properties for actinic energy rays (especially for light rays of 360 nm to 420 nm irradiated by an LED lamp), and there is no decomposition product of the benzoylformamide derivative in the obtained cured product. Therefore, a second object of the present invention is to provide a benzoylformamide derivative as a highly safe photoinitiator. In addition, a third object of the present invention is to provide a highly curable actinic energy ray curable composition containing the above benzoylformamide derivative as a photoinitiator. A fourth object of the present invention is to provide a highly safe ink composition, inkjet ink composition, ink composition for three-dimensional modeling, adhesive composition, adhesive composition, sealant composition, photosensitive composition, nail cosmetic composition, dental material composition, coating agent composition, aqueous composition, hydrogel composition, material composition for intraocular implant, which contains a benzoylformamide derivative, has high miscibility, and can obtain a cured product having excellent adhesion to a substrate, little yellowing over time and little bleed out.

[0007] The benzoylformamide derivative has photosensitivity to actinic energy rays (especially for light rays of 360 nm to 420 nm irradiated by an LED lamp), and a cured product without yellowing can be obtained. Therefore, a fifth object of the present invention is to provide a benzoylformamide derivative as a photosensitizer. In addition, a sixth object of the present invention is to provide a highly curable and highly miscible actinic energy ray curable composition containing the above benzoylformamide derivative as a photosensitizer. A seventh object of the present invention is to provide an ink composition, inkjet ink composition, ink composition for three-dimensional modeling, adhesive composition, adhesive composition, sealant composition, photosensitive composition, nail cosmetic composition, dental material composition, coating agent composition, aqueous composition, hydrogel composition, material composition for intraocular implant, which contains a benzoylformamide derivative, and can obtain a cured product having excellent adhesion to a substrate, little yellowing over time and excellent durability.

[0008] Technical means for solving technical problems

[0009] The inventors of the present invention repeatedly conducted dedicated research and as a result, found a benzoylformamide derivative having a benzoylformamide group represented by the general formula (1), thereby completing the present invention.

[0010]

[0011] Q 1 to Q 3 Each independently represents a hydrogen atom, a substituent represented by formula (Chemical formula 2) to formula (Chemical formula 8), a halogen group, or a nitrile group, and is bonded to any position among the 2nd to 6th positions.

[0012]

[0013] R 1 to 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;

[0014] * represents the bonding position.

[0015] Advantages of the Invention

[0016] The benzoylformamide derivative of the present invention has high initial efficiency (also referred to as polymerization initiation property or photoinitiation property) for long-wavelength light of 360 nm to 420 nm and light having wavelengths represented 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 energy ray-curable composition containing the benzoylformamide derivative as a photoinitiator can easily obtain a completely cured product with low energy (low cumulative light amount) and high speed (short curing time) even without using additives such as a hydrogen donor of a co-initiator, a general photosensitizer, and a curing accelerator, and even in an industrial manufacturing environment under an air atmosphere. In addition, the obtained cured product does not have decomposition products of the benzoylformamide derivative used as a photoinitiator, has low odor, yellowing over time, and exudation, and has high durability and safety. The benzoylformamide derivative can be suitably used in various applications such as 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 compositions, aqueous compositions, hydrogel compositions, and material compositions for intraocular implants.

[0017] The benzoylformamide derivatives of the present invention can be used as photosensitizers as follows: when absorbing long-wavelength light of 360 nm to 420 nm, light of 365 nm, 385 nm, 395 nm, and 405 nm irradiated from an LED lamp, they have a photosensitizing effect on other common photo radical polymerization initiators and photo ionic polymerization initiators, and are not easily yellowed due to photocuring. The active energy ray curable composition containing the benzoylformamide derivative as a photosensitizer can be easily obtained a completely cured product with low energy (low cumulative light amount) and high speed (short curing time) even in an industrial manufacturing environment under an air atmosphere by using it in combination with a photopolymerization initiator lacking curability for long-wavelength light of 360 nm to 420 nm, light of 365 nm, 385 nm, 395 nm, and 405 nm irradiated from an LED lamp. In addition, the obtained cured product has low odor, yellowing over time, and exudation, and high durability and safety. The benzoylformamide derivative can be suitably used in various 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. Detailed Description of the Invention

[0018] Hereinafter, embodiments of the present invention will be described in detail, but the scope of the present invention is not limited to the embodiments described herein, and various modifications can be made without departing from the gist of the present invention. In addition, regarding specific parameters, when a plurality of upper limit values and lower limit values are described, any upper limit value and lower limit value among these upper limit values and lower limit values can be combined to set an appropriate numerical range.

[0019] One embodiment of the present invention is a benzoylformamide derivative (D) having one or more benzoylformamide groups represented by the general formula (1) in the molecule.

[0020] Q in the general formula (1) 1 to Q 3 are each independently a hydrogen atom, a straight-chain alkyl group having 1 to 18 carbon atoms, a straight-chain alkenyl group having 2 to 18 carbon atoms, a branched alkyl group having 3 to 18 carbon atoms, a branched alkenyl group having 3 to 18 carbon atoms, a cyclic alkyl group having 3 to 18 carbon atoms, an alkoxy group of a cyclic alkenyl group having 3 to 18 carbon atoms, an amino group, an alkylamino group, a dialkylamino group, an alkoxycarbonyl group, an alkyl ester group, an aminocarbonyl group, an alkylaminocarbonyl group, a dialkylaminocarbonyl group, an alkylamide group, and a halogen group, a nitrile group. Q 1 to Q 3 are bonded to any position of the 2nd to 6th positions of the benzene ring. Among Q 1 to Q 3In the case where it is a hydrogen atom, the benzoylformamide derivative (D) exhibits good photopolymerization initiation property and photosensitivity with respect to a high-pressure mercury lamp and a UV-LED light source of 360 nm to 410 nm, and has low coloring due to light irradiation. In Q 1 to Q 3 In the case where it 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 benzoylformamide derivative (D) is shifted to the long wavelength side, and the sensitivity with respect to a light source of 390 nm to 420 nm is also high. Therefore, it can be more suitably used both as a photopolymerization initiator and as a photosensitizer. Sometimes these electron-donating substituents are colored due to light irradiation, but from the viewpoint of being able to maintain the coloring of D at a low level in practical use, Q 1 to Q 3 Particularly preferably, it is an alkoxy group or an alkyl ester group.

[0021] The benzoylformamide group of the benzoylformamide derivative (D) is a monosubstituted (monosubstitution) amide group or a disubstituted (disubstitution) amide group of benzoylformic acid. Both the monosubstituted amide group of benzoylformic acid and the disubstituted amide group of benzoylformic acid have photopolymerization initiation property and photosensitivity, and the photopolymerization initiation property is higher in the monosubstituted amide group of benzoylformic acid. The monosubstituted amide group of benzoylformic acid has a hydrogen atom bonded to its nitrogen atom. Although it is a hydrogen abstraction type photoinitiating functional group, it is also a hydrogen donating group, and highly efficiently generates active free radicals through intramolecular and / or intermolecular hydrogen abstraction. Therefore, even without using an easily colored amine hydrogen donor or the like in combination, the photopolymerization initiation property of D having a monosubstituted amide group of benzoylformic acid is high, and it has polymerization initiation property with respect to highly safe ultraviolet rays of 360 nm to 420 nm.

[0022] As the benzoylformamide derivative (D) of the present invention, at least one compound represented by any one of the general formulas (2) to (4) is preferred.

[0023]

[0024] In the formula, Q 1 to Q 3 is the same as the definition described in the general formula (1);

[0025] B 1 represents a hydrogen atom or a monovalent organic group that may have a hydroxyl group, an amino group, a thiol group, an ether group, a thioether group, an ester group, a carbonate group, a carbamate group, a thiocarbamate group, a urea group, a siloxanyl group, an amide group, an imide group, an ethylenically unsaturated group, or a benzoylformamide group;

[0026] B 2Represents a monovalent organic group that may have a hydroxyl group, an amino group, a thiol group, an ether group, a thioether group, an ester group, a carbonate group, a carbamate group, a thiocarbamate group, a urea group, a siloxane group, an amide group, an imide group, an ethylenically unsaturated group, or a benzoylmethamide group.

[0027]

[0028] In the formula, Q 1 to Q 3 Has the same definition as described in the general formula (1);

[0029] B 3 Represents an m-valent organic group that may have an ethylenically unsaturated group, an ether group, a thioether group, an ester group, a carbonate group, a carbamate group, a thiocarbamate group, an isocyanurate group, a urethane group, a urea group, a siloxane group, an amide group, or an imide group;

[0030] R 11 Represents a hydrogen atom, a straight-chain alkyl group having 1 to 18 carbon atoms, a straight-chain alkenyl group having 2 to 18 carbon atoms, a branched-chain alkyl group having 3 to 18 carbon atoms, a branched-chain 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;

[0031] R 12 Represents a straight-chain saturated divalent hydrocarbon group having 1 to 18 carbon atoms, a straight-chain unsaturated divalent hydrocarbon group having 2 to 18 carbon atoms, a branched-chain 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 amino group;

[0032] m represents an integer from 1 to 10.

[0033]

[0034] In the formula, Q 1 to Q 3 Has the same definition as described in the general formula (1);

[0035] A 1 Represents a divalent organic group that may have an ether group, a thioether group, an ester group, a carbonate group, a carbamate group, a thiocarbamate group, a urea group, a siloxane group, an amide group, or an imide group;

[0036] B 4 、B 5Each independently represents a monovalent 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 thiocarbamate group, an isocyanurate group, a urethane group, a siloxane group, an amide group or an imide group, and B 4 、B 5 Any one or both of which contain one or more ethylenically unsaturated bonds;

[0037] 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;

[0038] R 14 represents a linear saturated trivalent hydrocarbon group having 1 to 8 carbon atoms, a linear unsaturated trivalent hydrocarbon group having 2 to 8 carbon atoms, a branched saturated or unsaturated trivalent hydrocarbon group having 3 to 8 carbon atoms, a cycloaliphatic saturated or unsaturated trivalent hydrocarbon group having 3 to 8 carbon atoms, a trivalent aromatic hydrocarbon group having 6 to 8 carbon atoms, or a trivalent organic group in which any one or more 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 amino group;

[0039] R 15 represents a linear saturated divalent hydrocarbon group having 1 to 18 carbon atoms, a linear unsaturated divalent hydrocarbon group having 2 to 18 carbon atoms, a branched saturated or unsaturated divalent hydrocarbon group having 3 to 8 carbon atoms, a cycloaliphatic 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 amino group;

[0040] n represents an integer from 1 to 100.

[0041] 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. By adjusting the polarity of B 1 and B 2 (independently of each other), the miscibility of D with other components of the curable composition is high, and the transparency of the obtained curable composition and the cured product obtained by curing the curable composition is high. If B 1 and / or B 2If it has an ether group, a thioether group, an ester group, a carbonate group, a carbamate group, a thiocarbamate group, an isocyanurate group, a urethane group, a urea group, a siloxane group, an amide group or an imide group, the polarity can be easily adjusted, so it is preferred. Additionally, B is more preferred. 1 and B 2 has an ether group, an ester group, a carbamate group, and an amide group. In the case of B 1 being a hydrogen atom, D has a benzoylformic acid monosubstituted amide group, and the photoinitiating property is higher, so it is more preferred.

[0042] B 1 and B 2 may further have a benzoylformamide group represented by the general formula (1). In this case, the benzoylformamide derivative (D) has multiple benzoylformamide groups, and both the photoinitiating property and photosensitivity are higher, so it is preferred. The benzoylformamide groups contained in D may be the same or different.

[0043] The benzoylformamide derivative (D) represented by the general formula (2) can be used as a photosensitizer for photoionic polymerization. In this case, if B 1 and B 2 has a cyclic ether group, D is incorporated into the cured product via a covalent bond by photoionic polymerization, so it is preferred. It may have 1 cyclic ether group or 2 or more.

[0044] B 1 and B 2 is preferably further provided with an ethylenically unsaturated group. In this case, the benzoylformamide derivative (D) is incorporated into the cured product via a covalent bond by photoradical polymerization as a photoinitiator or photosensitizer having an ethylenically unsaturated group, so it is preferred. It is preferably provided with 1 or more ethylenically unsaturated groups, and more preferably 2 or more ethylenically unsaturated groups. The ethylenically unsaturated groups may be of a single type or multiple types.

[0045] In the case of B 1 and B 2 having a carbamate group, the benzoylformamide derivative (D) has good compatibility with other components of the curable composition, and the obtained curable composition and its cured product have high transparency. The ratio of the total number of carbamate groups of D to the total number of benzoylformamide groups of D is preferably 0.1 or more, and more preferably 0.5 or more. Additionally, if the number of carbamate groups increases, the viscosity of D becomes higher, and the above ratio is preferably 10.0 or less.

[0046] More preferably, the benzoylformamide derivative (D) has a carbamate group represented by the general formula (3) or the general formula (4). The carbamate 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 for highly safe ultraviolet rays of 360 nm to 420 nm.

[0047] When the benzoylformamide derivative (D) has one or more carbamate groups, the number of atoms directly bonded between the nitrogen atom of the benzoylformamide group and the nitrogen atom of the nearest carbamate group is preferably 3 to 20. When the number of directly bonded atoms is 3 or more, the hydrogen abstraction ability of the benzoylformamide group and the hydrogen-donating ability of the carbamate group are both enhanced by the interaction between the benzoylformamide group and the carbamate group. In addition, when the number of directly bonded atoms is 20 or less, the benzoylformamide group and the carbamate group in the molecule are easily accessible, and the hydrogen abstraction reaction is likely to occur. From these viewpoints, the number of the above-mentioned directly bonded atoms is more preferably 4 to 10, and further preferably 4 to 6.

[0048] The benzoylformamide derivative (D) represented by the general formula (3) has one or more benzoylformamide groups and one or more carbamate groups in the molecule. The carbamate group has good miscibility with other components of the curable composition, and the obtained curable composition and its cured product have high transparency. In addition, from the viewpoint of further improving the miscibility of the curable composition, B 3 Preferably, it further has one or more carbamate groups. The ratio of the total number of carbamate groups of D to the total number of benzoylformamide groups is preferably 0.5 or more, and more preferably 2.0 or more. If the number of carbamate groups increases, the viscosity of D becomes higher, and the above ratio is preferably 10.0 or less, more preferably 6.0 or less, and particularly preferably 4.0 or less.

[0049] 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. When R11 is a hydrogen atom, the benzoylformamide derivative (D) has a benzoylformic acid monosubstituted amide group and has excellent photopolymerization initiation properties, so it is more preferably used.

[0050] R in the general formula (3) 12is 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 mercapto group, or an amino group. R 12 Preferably, it is 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. More preferably, it is 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.

[0051] The benzoylamino group is amphiphilic. By adjusting the polarity of B 3 according to the purpose, the miscibility of D with other components of the curable composition is high, and the transparency of the obtained curable composition and the cured product obtained by curing the curable composition is high. When B 3 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, a urethane group, a siloxane group, an amide group, or an imide group, it is easy to adjust the polarity of B 3 and is therefore preferred.

[0052] The benzoylamine derivative (D) represented by the general formula (3) can also be used as a photosensitizer for photoionization polymerization. In this case, if B 3 has a cyclic ether group, D is incorporated into the cured product via a covalent bond by photoionization polymerization, and is therefore preferred. It may have 1 cyclic ether group or 2 or more cyclic ether groups.

[0053] B 3 Preferably, it further has an ethylenically unsaturated group. In this case, the benzoylamine derivative (D) is incorporated into the cured product via a covalent bond by photoradical polymerization as a photopolymerization initiator or photosensitizer having an ethylenically unsaturated group, and is therefore preferred. It is preferably has 1 or more ethylenically unsaturated groups, and more preferably has 2 or more ethylenically unsaturated groups. It may have a single type of ethylenically unsaturated group or multiple types of ethylenically unsaturated groups.

[0054] In the general formula (3), m is an integer of 1 to 10. When m is 1 or more, one or more benzoylformamide groups are present in the molecule of the benzoylformamide derivative (D), and it can function both as a photoinitiator and as a photosensitizer. In addition, when m exceeds 10, both the molecular weight and viscosity of D are high, and the operability of the curable composition containing D may be reduced, so it is not preferred. From these viewpoints, it is more preferably an integer of 2 to 4 for m.

[0055] The benzoylformamide derivative (D) represented by the general formula (3) can be synthesized by amidation reaction of benzoylformic acid with aminoalkyl alcohol to obtain benzoylformamide monoalcohol, and then by carbamate 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.

[0056] The benzoylformamide derivative (D) represented by the general formula (4) has one or more benzoylformamide groups, two or more urethane groups and one or more ethylenically unsaturated groups in the molecule. The urethane group has good miscibility with other components constituting the curable composition, and the curable composition containing D and the cured product obtained by curing the curable composition have high transparency. From this viewpoint, it is preferred that any one or more of A 1 , B 4 and B 5 further has one or more urethane groups. The ratio of the total number of urethane groups of D to the total number of benzoylformamide groups is preferably 2.0 or more, more preferably 2.5 or more. In addition, if the number of urethane groups increases, the viscosity of D becomes high, so the above ratio is preferably 15.0 or less, more preferably 8.0 or less, and particularly preferably 5.0 or less.

[0057] R of 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 benzoylformamide derivative (D) has a monosubstituted amide group of benzoylformic acid and is excellent in photopolymerization initiation property, and thus is preferred.

[0058] R of the general formula (4) 14 is a linear saturated trivalent hydrocarbon group having 1 to 8 carbon atoms, a linear unsaturated trivalent hydrocarbon group having 2 to 8 carbon atoms, a branched saturated or unsaturated trivalent hydrocarbon group having 3 to 8 carbon atoms, a cycloaliphatic saturated or unsaturated trivalent hydrocarbon group having 3 to 8 carbon atoms, a trivalent aromatic hydrocarbon group having 6 to 8 carbon atoms, or a trivalent organic group in which any one or more 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 mercapto group, or an amino group. In terms of the view that the number of atoms directly bonded between the nitrogen atom of the benzoylformamide group and the nitrogen atom of the nearest carbamate group is preferably 3 to 10, R 14 is preferably a linear saturated trivalent hydrocarbon group having 1 to 8 carbon atoms, a linear unsaturated trivalent hydrocarbon group having 2 to 8 carbon atoms, a branched saturated or unsaturated trivalent hydrocarbon group having 3 to 8 carbon atoms, a cycloaliphatic saturated or unsaturated trivalent hydrocarbon group having 3 to 8 carbon atoms, and more preferably a linear saturated trivalent hydrocarbon group having 2 to 4 carbon atoms, a branched saturated trivalent hydrocarbon group having 3 to 4 carbon atoms.

[0059] R of the general formula (4) 15 represents a linear saturated divalent hydrocarbon group having 1 to 18 carbon atoms, a linear unsaturated divalent hydrocarbon group having 2 to 18 carbon atoms, a branched saturated or unsaturated divalent hydrocarbon group having 3 to 18 carbon atoms, a cycloaliphatic 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 mercapto group, or an amino group. In terms of the view that it is easy to introduce a carbamate group bonded to A 1 , R 15 is preferably an alkylene group having 1 to 18 carbon atoms.

[0060] The benzoylformamide group is amphiphilic. By adjusting the polarity of A 1 according to the purpose, the compatibility of D with other components of the curable composition is high, and the transparency of the obtained curable composition and the cured product obtained by curing the curable composition is high. If A1 If it has an ether group, a thioether group, an ester group, a carbonate group, a urethane group, a thiocarbamate group, a urea group, a siloxane group, an amide group or an imide group, it is easy to adjust the polarity of A, so it is preferred. Further, when A is an ether group, a thioether group, an ester group, a carbonate group or a urethane group, the number of these groups can be easily adjusted, and the polarity of A can be more easily adjusted, so it is preferred. 1 1 1

[0061] B 4 and B 5 are each independently a monovalent 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 thiocarbamate group, an isocyanurate group, a urethane group, a siloxane group, an amide group or an imide group, and one or both of B 4 and B 5 contain one or more ethylenically unsaturated bonds.

[0062] The benzoylmethaneamide derivative (D) represented by the general formula (4) can also be used as a photosensitizer for photoionic polymerization. In this case, if B 4 and / or B 5 has a cyclic ether group, D is incorporated into the cured product via a covalent bond by photoionic polymerization, so it is preferred. It may have one cyclic ether group or two or more cyclic ether groups.

[0063] Since one or both of B 4 and B 5 have one or more ethylenically unsaturated bonds, the benzoylmethaneamide derivative (D) is incorporated into the cured product via a covalent bond by photoradical polymerization. From the viewpoint of easier incorporation into the cured product, it is preferred that both B 4 and B 5 have ethylenically unsaturated groups. It may have a single type of ethylenically unsaturated group or multiple types of ethylenically unsaturated groups.

[0064] The polarity of B 4 and B 5 can be adjusted according to the purpose. If B 4 and B 5 have an ether group, a thioether group, an ester group, a carbonate group, a urethane group, a thiocarbamate group, a urea group, a siloxane group, an amide group or an imide group, it is easy to adjust the polarity of these B 4 and B 5 so it is preferred. Further, in B 4 and B 5In the case of 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 B can be more easily adjusted. 4 and B 5 The polarity of is preferred.

[0065] n in the general formula (4) is an integer of 1 to 100. When n is 1 or more, the benzoylformamide derivative (D) has one or more benzoylformamide groups and can function both as a photopolymerization initiator and as a photosensitizer. In addition, when n is 2 or more, both the photopolymerization initiation property and the photosensitivity are high, so it is preferred. When n exceeds 100, the molecular weight and viscosity of D are high, and the operability of the curable composition containing D may be reduced, so it is not preferred. From these viewpoints, n is more preferably an integer of 2 to 50, and particularly preferably an integer of 2 to 20.

[0066] The general formula (4) can be produced by synthesizing benzoylformamide diol through an amidation reaction of benzoylformic acid and aminoalkyl alcohol, and then 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.

[0067] The benzoylformamide derivative (D) is a hydrogen abstraction type photoinitiator and does not produce decomposition products during photopolymerization. When the benzoylformamide derivative (D) is used as a photosensitizer, no decomposition products are produced during photopolymerization either. 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, D has low volatility, the cured product obtained has low odor, and exudation of D from the cured product is less likely to occur. D with a high molecular weight has high safety, so it is preferred. However, if it exceeds 200,000, the viscosity of D and the viscosity of the curable composition containing D may increase significantly, and the operability may decrease. 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 most low molecular weight components have high volatility and low safety, if low molecular weight components are present in the cured product, problems such as exudation from the cured product over time, poor appearance of the cured product, and generation of odor may occur.

[0068] The benzoylformamide derivative (D) can be synthesized by the following method. An amidation reaction is carried out between 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, designated as raw material (a2)) to obtain the benzoylformamide derivative (D) represented by the general formula (2). In addition, raw material (a2) may have a plurality of amino groups, and may have a hydroxyl group, a carboxyl group, a urethane group, a urea group, or an amide group in addition to the amino group. a2 preferably has a reactive group such as a hydroxyl group, an amino group, or a carboxyl group. After the amidation reaction of a1 and a2, further reactions with various compounds can be carried out using these reactive groups. More preferably, the reactive group of a2 is a hydroxyl group. In the case of having a hydroxyl group, after reacting a1 and a2 to form benzoylformamide, etherification reaction, esterification reaction, or urethanation reaction can be easily carried out using the hydroxyl group. 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 in the above urethanation reaction, the benzoylformamide derivative (D) represented by the general formula (3) or the general formula (4) can be synthesized.

[0069] Examples of benzoylformic acid or benzoylformate (a1) include: benzoylformic acid, alkyl (linear alkyl having 1 to 18 carbon atoms, branched alkyl having 3 to 18 carbon atoms, cyclic alkyl having 3 to 18 carbon atoms) esters of benzoylformic acid, alkenyl (linear alkenyl having 2 to 18 carbon atoms, branched alkenyl having 3 to 18 carbon atoms, cyclic alkenyl having 3 to 18 carbon atoms) esters of benzoylformic acid. Additionally, substituents represented by (Chemical Formula 2) to (Chemical Formula 8) are bonded at any position from the 2nd to the 6th position of the benzene ring of benzoylformic acid, alkyl esters of benzoylformic acid, and alkenyl esters of benzoylformic acid in a1. Specifically, examples include: 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-cyanobenzoylformate, ethyl 4-cyanobenzoylformate. These a1 can be used individually or in combination.

[0070] Examples of the amino group-containing compound (a2) include amine compounds such as alkylamine, alkenylamine, dialkylamine, dialkenylamine, alkylalkenylamine, and arylamine; amine compounds with hydroxyl groups such as aminoalkyl monohydric alcohol, aminoalkyl dihydric alcohol, aminoalkyl trihydric alcohol, aminoalkyl tetrahydric alcohol, aminoalkyl pentahydric alcohol, N-alkyl-aminoalkyl monohydric alcohol, N-alkyl-aminoalkyl dihydric alcohol, N-alkyl-aminoalkyl trihydric alcohol, N-alkyl-aminoalkyl tetrahydric alcohol, N-alkyl-aminoalkyl pentahydric alcohol, N,N-bis(hydroxyalkyl)amine, N,N-bis(dihydroxyalkyl)amine, and hydroxyalkylarylamine; amine compounds with mercapto groups such as aminoalkyl mercaptan and aminoalkenyl mercaptan; amine compounds with ether groups such as (aminoalkoxy)alkanols, dialkylene glycol monoamine, trialkylene glycol monoamine, and polyalkylene glycol monoamine; amine compounds with multiple amino groups such as alkylenediamine, polyalkylenimine, dialkylene glycol diamine, trialkylene glycol diamine, polyalkylene glycol diamine, and diaminoalkanol; and amine compounds with carboxyl groups such as amino acids and aminobenzoic acid. The above-mentioned alkyl groups are straight-chain alkyl groups having 1 to 18 carbon atoms, branched-chain alkyl groups having 3 to 18 carbon atoms, and cyclic alkyl groups having 3 to 18 carbon atoms, and the alkenyl groups are straight-chain alkenyl groups having 2 to 18 carbon atoms, branched-chain alkenyl groups having 3 to 18 carbon atoms, and cyclic alkenyl groups having 3 to 18 carbon atoms. These amino group-containing compounds can be used alone or in combination.

[0071] When the amino group-containing compound (a2) has hydroxyl groups, carboxyl groups, mercapto groups, or multiple amino groups, benzoylmethaneamide derivatives (D) having hydroxyl groups, carboxyl groups, mercapto groups, or amino groups can be obtained. D can be further subjected to carbamate esterification, thiocarbamate esterification, etherification, esterification, ureation, amidation, or imidization using these reactive groups. Carbamate esterification is the reaction of a hydroxyl group with an isocyanate group, thiocarbamate esterification is the reaction of a mercapto 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, ureation 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 raw materials having the above various functional groups, D represented by the general formula (3) and the general formula (4) can be synthesized.

[0072] The amidation reaction of benzoylformic acid or benzoylformate (a1) with an amino group-containing compound (a2) is preferably carried out under light-blocking conditions. Specifically, examples include: under light shielding, in an environment where ultraviolet rays are blocked such as a yellow light room, under a fluorescent lamp that does not irradiate ultraviolet rays, and under a red darkroom safety lamp. The reaction can be carried out under mild conditions at normal pressure and below 100 °C. A solvent (c) can be used in the reaction. Examples of the solvent (c) include: 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-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, N,N-dimethylpropanamide, dimethylacetamide, dimethyl sulfoxide, 2-pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone and other common solvents. In addition, a polymeric (radical-based, cationic-based or anionic-based polymerization using 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 polymeric compound solvent include: N-(methyl)acryloylmorpholine, (meth)acrylic acid esters having a straight-chain alkyl or alkoxy group with 1 to 18 carbon atoms, a branched or cyclic alkyl group or alkoxy group with 3 to 18 carbon atoms, N-substituted (meth)acrylamide and N,N-disubstituted (meth)acrylamide, etc.

[0073] In the case of synthesizing a benzoylformamide derivative (D) by the amidation reaction of benzoylformate (a1) with an amino group-containing compound (a2), an alcohol is produced as a by-product, and D containing the alcohol is obtained as a crude product. In addition, in the case of using a solvent (c), D containing the alcohol and c is obtained as a crude product. These crude products can be directly used in the curable composition, or the 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, new D can be synthesized using these groups. In this case, the reaction can be carried out in a state containing the alcohol and c, or the alcohol and c can be removed and the reaction can be carried out. Examples of the method for removing the alcohol and c include: a method of distillation under normal pressure or reduced pressure; a method of foaming using an inert gas such as dry air or nitrogen; a freeze-drying method.

[0074] The benzoylformamide derivative (D) having a hydroxyl group can introduce a urethane group into the molecule of D by reacting with an isocyanate compound. D can introduce an ethylenically unsaturated group by reacting with an isocyanate compound having an ethylenically unsaturated group. D can introduce a urethane group and an ethylenically unsaturated group by reacting with a polyisocyanate compound and a compound having an ethylenically unsaturated group and a hydroxyl group. In addition, 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 via a chemical bond. In this case, even if the molecular weight of D is less than 300, bleeding from the cured product does not occur, and D can be suitably used for each use both as a photoinitiator and as a photosensitizer.

[0075] The ethylenically unsaturated group of the benzoylformamide derivative (D) 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. Further, from the viewpoint of high polymerizability, a (meth)acrylate group and a (meth)acrylamide group are preferred, from the viewpoint of high active energy ray curability, an acrylate group and an acrylamide group are more preferred, and from the viewpoint of being able to form hydrogen bonds not only intramolecularly but also intermolecularly in addition to covalent bonds, an acrylamide group is particularly preferred. Further, when D is used as a photoinitiator, an N-monosubstituted acrylamide group is most preferred from the viewpoint of its being a hydrogen donor. When D is used as a photosensitizer, an acrylate group and an N,N-disubstituted acrylamide group are most preferred from the viewpoint of the low viscosity of D and the curable composition containing D.

[0076] Examples of the compound used in the reaction with the benzoylformamide derivative (D) having a hydroxyl group include an isocyanate compound (b1), a compound having a hydroxyl group (b2), a compound having an ethylenically unsaturated group and a reactive group (b3), and a compound having a cyclic ether group and a reactive group (b4). Examples of the reactive group of b3 and b4 include a hydroxyl group, an acyl halide, a halogen, an isocyanate group, an acid anhydride group, and an epoxy group. b1 includes a general polyisocyanate, a polyisocyanate having a polyol skeleton, and a polyisocyanate having an isocyanurate ring.

[0077] The isocyanate compound (b1) is a compound having two or more isocyanate groups in the molecule. Specifically, examples include: 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 polymers such as adducts, isocyanurates, and biurets of these polyisocyanates. These b1 can be used alone or in combination.

[0078] The compound (b2) having a hydroxyl group is an alcohol or a polyol. Examples of alcohols include: monohydric alcohols using a straight-chain alkyl group having 1 to 18 carbon atoms, a branched or cyclic alkyl group having 3 to 18 carbon atoms such as methanol, ethanol, isopropanol, octanol, isostearyl alcohol; alkylene glycols having 2 to 18 carbon atoms in a straight chain, 3 to 18 carbon atoms in a branched chain, 3 to 18 carbon atoms in a cyclic structure such as ethylene glycol, 1,2-propanediol; polyols such as glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol.

[0079] Examples of polyols of b2 include: polyether polyols, polyester polyols, polycarbonate polyols, methanol-modified silicones, polyolefin polyols. Examples of polyether polyols include: polyalkylene glycols having 2 to 18 carbon atoms in a straight chain, 3 to 18 carbon atoms in a branched chain, 3 to 18 carbon atoms in a cyclic structure. Examples of polyolefin polyols include: hydrogenated polybutadiene polyols, polybutadiene polyols. These b2 can be used alone or in combination.

[0080] When the reactive group of the compound (b3) having an ethylenically unsaturated group and a reactive group is an acid anhydride group or an acyl chloride group, examples of b3 include: (meth)acryloyl 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 mono maleimide, (meth)acrylic acid hydroxybenzyl ester, hydroxyphenyl (meth)acrylamide, enol, glycerol mono(meth)acrylate, glycerol mono(meth)acrylamide, glycerol di(meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, glycerol mono(meth)acrylamide, trimethylolpropane di(meth)acrylamide, pentaerythritol tri(meth)acrylamide, dipentaerythritol penta(meth)acrylamide. The above alkyl group is a straight-chain alkyl group having 1 to 18 carbon atoms, a branched-chain alkyl group having 3 to 18 carbon atoms, or a cyclic alkyl group having 3 to 18 carbon atoms, the alkylene group is an alkylene group having 1 to 9 carbon atoms, and the alkenyl group is a straight-chain alkenyl group having 2 to 18 carbon atoms, a branched-chain alkenyl group having 3 to 18 carbon atoms, or a cyclic alkenyl group having 3 to 18 carbon atoms. These b3 can be used alone or in combination.

[0081] When the reactive group of the compound (b4) having a cyclic ether group and a reactive group is a halogen, examples of b4 include: 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, it includes: hydroxyalkyl glycidyl ether and hydroxyalkyl epoxide having a straight-chain alkyl group having 1 to 18 carbon atoms, a branched-chain 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 b4 can be used alone or in combination.

[0082] The method for introducing a carbamate group (carbamoylation) is not particularly limited as long as it is a well-known method. The reaction temperature is preferably in the range of room temperature to 90 °C. If necessary, a solvent (c), a carbamoylation catalyst, and other additives may also be used. In addition, a polymerizable compound may be used instead of c as the solvent. Examples of the polymerizable compound solvent include N-(meth)acryloylmorpholine, (meth)acrylic acid alkyl ester, (meth)acrylic acid alkenyl ester, (meth)acrylic acid aryl ester, di(meth)acrylic acid alkylene ester, 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 alkyl group is a linear alkyl group having 1 to 18 carbon atoms, a branched alkyl group having 3 to 18 carbon atoms, and a cyclic alkyl group having 3 to 18 carbon atoms. The alkenyl group is a linear alkenyl group having 2 to 18 carbon atoms and a cyclic alkenyl group having 3 to 18 carbon atoms. The aryl group is an aryl group having 6 to 8 carbon atoms. The carbamoylation reaction is preferably carried out in an environment where light is blocked. Specifically, examples include carrying out the reaction under light shielding, in an environment where ultraviolet rays are cut off such as in a yellow light room, under a fluorescent lamp that does not irradiate ultraviolet rays, or under a red safety lamp for a dark room.

[0083] After the carbamoylation reaction, a crude product D containing the solvent (c) or the polymerizable compound used in place of c is obtained. The crude product can be directly used in the curable composition, or it can 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; a method of foaming with an inert gas such as dry air or nitrogen; and freeze-drying.

[0084] Examples of the reaction catalyst used in the carbamation 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 mesitylphosphine; tricycloalkylphosphines such as tricyclohexylphosphine; trialkylphosphines such as triethylphosphine, tripropylphosphine, tributylphosphine, and trioctylphosphine, etc. Examples of tertiary amines include trialkylamines such as triethylamine and tributylamine; dialkylarylamines such as dimethylbenzylamine and diethylbenzylamine; triethanolamine, etc. Examples of organometallic compounds include metal salts of metals such as zinc, tin, lead, zirconium, bismuth, cobalt, manganese, and iron with organic acids such as octenoic acid and naphthenic acid; metal chelate compounds of 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; sodium and potassium salts of fatty acids having 8 to 20 carbon atoms. In addition, these can be used alone or in combination. Among them, quaternary ammonium salts, tertiary phosphine derivatives, tin-based, bismuth-based, zirconium-based, and iron-based organometallic compounds with high catalyst effects are more preferred.

[0085] The usage amount of the above-mentioned carbamation reaction catalyst is preferably 0.001% by mass to 10% by mass relative to the total mass of each raw material. If it is 0.001% by mass or more, the reaction can proceed rapidly. When it is below 10% by mass, the coloring caused by the catalyst is low. Furthermore, it is more preferably 0.01% by mass to 1.00% by mass.

[0086] The benzoylamine derivative (D) of the present invention generates radicals belonging to growth active species by irradiation with active energy rays. Examples of 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, in terms of the balance of the active energy ray generation device, the photopolymerization initiation rate, and safety, it is preferable to use ultraviolet rays. Examples of ultraviolet light sources include xenon lamps, low-pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, UV-LED lamps, microwave-excited excimer lamps, etc. A UV-LED lamp that can irradiate ultraviolet rays of 360 nm to 420 nm with high output and high safety is preferred. In addition, LED lamps that can irradiate light of 365 nm, 385 nm, 395 nm, and 405 nm can be suitably used.

[0087] The irradiation energy required for the benzoylamine derivative (D) of the present invention to generate radicals can be represented by the cumulative light amount. The cumulative light amount is preferably in the range of 5 mJ / cm 2 to 50,000 mJ / cm 2 and more preferably 10 mJ / cm2 to 20,000 mJ / cm 2 Within this range. If the irradiation energy is within this range, a sufficient number of growth active species can be generated from the photoinitiator.

[0088] The benzoylformamide derivative (D) of the present invention can be included as a photoinitiator in an energy ray curable composition for various uses. 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. If D is contained in an amount of 0.1% by mass or more, photopolymerization can be immediately started by irradiation with 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% by mass to 20% by mass, particularly preferably 1% by mass to 10% by mass, relative to the entire curable composition. When D contains an ethylenically unsaturated group, a cured product can be formed from D alone, and thus 100% by mass of D can be contained. Further, from the viewpoint of enabling the curable composition to be sufficiently cured and the physical properties of the obtained cured product to be good, D can be used in combination with a compound having one ethylenically unsaturated group in the molecule (hereinafter referred to as a monofunctional unsaturated compound (h1)) and / or a compound having two or more ethylenically unsaturated groups in the molecule (hereinafter referred to as a polyfunctional unsaturated compound (h2)) as another polymerizable compound (h). In this case, the content of D is more preferably 0.5% by mass to 90% by mass, particularly preferably 1% by mass to 70% by mass, relative to the entire curable composition.

[0089] The benzoylformamide derivative (D) of the present invention can be contained as a photosensitizer in an active energy ray curable composition. 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 in an amount of 0.1% by mass or more, D can be excited by irradiation with active energy rays, activating the photoinitiator in the curable composition, causing photopolymerization to start immediately, and enabling the curable composition to 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 anionionic 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, although it varies depending on the structure and molecular weight of D, the content of D in the curable composition is preferably 30% by mass or less. 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% by mass to 20% by mass, particularly preferably 1% by mass to 10% by mass, with respect to the entire curable composition. When D contains an ethylenically unsaturated group and / or a cyclic ether group, a cured product can be formed from D alone, and thus 100% by mass of D can be contained. Further, from the viewpoint of enabling the curable composition to be sufficiently cured and the physical properties of the obtained cured product to be 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 this case, the content of D is more preferably 0.5% by mass to 90% by mass, particularly preferably 1% by mass to 70% by mass, with respect to the entire curable composition.

[0090] The benzoylformamide derivative (D) of the present invention can be used separately as a photoinitiator and a photosensitizer, and further, Ds 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% by mass to 80% by mass, preferably 1% by mass to 75% by mass, more preferably 2% by mass to 50% by mass, and particularly preferably 3% by mass to 30% by mass.

[0091] The polymerizable 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% by mass to 99.9% by mass with respect to the entire curable composition. Further, from the viewpoint of being able to appropriately adjust the physical properties of the cured product, the content of h is preferably 10% by mass to 99.5% by mass, more preferably 30% by mass to 99% by mass.

[0092] 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 ethynyl group. These groups may be used alone or in combination of two or more. With respect to the whole curable composition, the content of h1 is preferably from 0% by mass to 90% by mass, more preferably from 5% by mass to 70% by mass, and particularly preferably from 10% by mass to 50% by mass. h1 generally has a low viscosity, and by containing h1, it is possible to expect the effects of lowering the viscosity of the curable composition and improving the workability.

[0093] Examples of the monofunctional unsaturated compound (h1) containing a (meth)acrylate group include: (meth)acrylic acid alkyl esters, (meth)acrylic acid hydroxyalkyl esters, (meth)acrylic acid alkyl carboxylic acids, (meth)acrylic acid alkyl sulfonic acids, (meth)acrylic acid alkyl phosphoric acids, alkoxy (hereinafter also referred to as alkoxy) alkylene glycol (meth)acrylates, alkoxy diethylene glycol (meth)acrylates, alkoxy triethylene glycol (meth)acrylates, alkoxy polyalkylene glycol (meth)acrylates, phenoxy alkylene glycol (meth)acrylates, phenoxy diethylene glycol (meth)acrylates, phenoxy triethylene glycol (meth)acrylates, phenoxy polyalkylene glycol (meth)acrylates, N-alkylamino (meth)acrylates, (meth)acrylic acid N-alkylaminoalkyl esters, (meth)acrylic acid N,N-dialkylaminoalkyl esters, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, dicyclopentyl (meth)acrylate, dicyclopentyloxyethyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenoxyethyl (meth)acrylate, borneol (meth)acrylate, isobornyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate, (meth)acrylate esters into which a cyclic structure such as N-(meth)acryloxyethylnorbornene carboxamide is introduced. The above alkyl group is a linear alkyl group having 1 to 18 carbon atoms, a branched alkyl group having 3 to 18 carbon atoms, or a cyclic alkyl group having 3 to 18 carbon atoms, and the alkylene group is an alkylene group having 1 to 4 carbon atoms.

[0094] Examples of the monofunctional unsaturated compound (h1) containing (meth)acrylamide group include: (meth)acrylamide, mono- or di-substituted (meth)acrylamide, N-(meth)acryloylmorpholine, diacetone (meth)acrylamide, etc. Further, examples of the mono- or di-substituted (meth)acrylamide include: N-alkyl (meth)acrylamide, N,N-dialkyl (meth)acrylamide, N-hydroxyalkyl (meth)acrylamide, N,N-di(hydroxyalkyl) (meth)acrylamide, N-hydroxyalkyl-N-(4-hydroxyphenyl) (meth)acrylamide, N-alkyl-N-hydroxyalkyl (meth)acrylamide, N-alkyl-N-(4-hydroxyphenyl) (meth)acrylamide, 4-hydroxyphenyl (meth)acrylamide, N,N-di(4-hydroxyphenyl) (meth)acrylamide, N-alkoxyalkyl (meth)acrylamide, N,N-di(alkoxyalkyl) (meth)acrylamide, N-alkyl-N-alkoxyalkyl (meth)acrylamide, N-sulfoalkyl acrylamide, N-alkylamino (meth)acrylamide, N-alkylaminoalkyl (meth)acrylamide, N,N-dialkylaminoalkyl (meth)acrylamide, etc. The above alkyl groups are straight-chain alkyl groups having 1 to 18 carbon atoms, branched-chain alkyl groups having 3 to 18 carbon atoms, or cyclic alkyl groups having 3 to 18 carbon atoms.

[0095] Examples of the monofunctional unsaturated compound (h1) containing vinyl group include: vinyl carboxylate having a carboxyl group with 1 to 18 carbon atoms, alkyl vinyl ether, 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 above alkyl groups are straight-chain alkyl groups having 1 to 18 carbon atoms, branched-chain alkyl groups having 3 to 18 carbon atoms, or cyclic alkyl groups having 3 to 18 carbon atoms.

[0096] Examples of the monofunctional unsaturated compound (h1) containing allyl group include: allyl carboxylate having a carboxyl group with 1 to 18 carbon atoms, alkyl allyl ethers, phenyl allyl ether, alkyl phenyl allyl ether, allylamine, mono- or dialkyl allylamine, etc. The above alkyl groups are straight-chain alkyl groups having 1 to 18 carbon atoms, branched-chain alkyl groups having 3 to 18 carbon atoms, or cyclic alkyl groups having 3 to 18 carbon atoms.

[0097] Examples of the monofunctional unsaturated compound (h1) containing a styryl group include styrene, α-alkylstyrene, α-methylstyrene dimer, o-alkylstyrene, m-alkylstyrene, p-alkylstyrene, p-styrenesulfonic acid, etc. The above alkyl group is a linear alkyl group having 1 to 18 carbon atoms, a branched alkyl group having 3 to 18 carbon atoms, or a cyclic alkyl group having 3 to 18 carbon atoms.

[0098] Examples of the polyfunctional unsaturated compound (h2) include compounds having two or more unsaturated groups such as (meth)acrylate group, (meth)acrylamide group, vinyl group, allyl group, styryl group, and ethynyl group. It may be a compound containing only one of these unsaturated groups, or may be a compound containing two or more of these unsaturated groups in combination. In addition, in order to obtain good curability, it is more preferably a compound in which the unsaturated group contains one or more (meth)acrylate groups or (meth)acrylamide groups. The content of h2 is preferably 0% by mass to 99% by mass, more preferably 1% by mass to 70% by mass, and particularly preferably 5% by mass to 50% based on the whole curable composition. By containing h2, the strength and hardness of the obtained cured product are high, and excellent durability can be expected.

[0099] Examples of the polyfunctional unsaturated compound (H2) include: allyl (meth)acrylate, allyloxyalkoxy (meth)acrylate, allyl (meth)acrylamide, allyloxyalkoxy (meth)acrylamide, vinyloxyalkoxy (meth)acrylate, diallylamine, alkyldiallylamine, dialkyldiallyl quaternary ammonium 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, di-trimethylolpropane tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tri(meth)acryloyloxyethoxytriol, glycerol polyglycidyl ether poly(meth)acrylate, isocyanuric acid ethoxylated tri(meth)acrylate, ethoxylated dipentaerythritol penta(meth)acrylate, ethoxylated dipentaerythritol hexa(meth)acrylate, ethoxylated pentaerythritol tri(meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, succinic acid modified pentaerythritol tri(meth)acrylate, etc. The above alkyl group is a linear alkyl group having 1 to 18 carbon atoms, a branched alkyl group having 3 to 18 carbon atoms, or a cyclic alkyl group having 3 to 18 carbon atoms, and the alkylene group is an alkylene group having 1 to 4 carbon atoms.

[0100] The number average molecular weight of the polyfunctional unsaturated compound (H2) is preferably 100 to 50,000. When the molecular weight is 100 or more, the cured product obtained has low curing shrinkage, so it is preferred. When the molecular weight is 50,000 or less, the viscosity of the curable composition is low and the operability is excellent, so it is preferred. From these viewpoints, the molecular weight of H2 is more preferably 200 to 20,000, and particularly preferably 300 to 15,000.

[0101] The cyclic ether compound (H3) is a compound having one or more cyclic ether groups in the molecule. The cyclic ether groups of H3 include epoxy groups, glycidyl groups, and oxetanyl groups. In the case of containing a plurality of these cyclic ether groups, only one kind may be contained, or two or more kinds may be contained in combination. Examples of the compound having one cyclic ether group as H3 include: alkyl glycidyl ethers, alkyl epoxides, aryl glycidyl ethers, epoxy cycloalkanes, alkyl oxetanes, glycidyl (meth)acrylate, glycidyl 4-hydroxybutyl (meth)acrylate, vinyl glycidyl ether. Examples of the compound having a plurality of cyclic ether groups as H3 include: alkylene glycol diglycidyl ethers, aryl diglycidyl ethers, trimethylolpropane triglycidyl ethers, (3,4-epoxycyclohexylmethyl) 3,4-epoxycyclohexanecarboxylate, alkylene bisoxetane. The above alkyl groups are linear alkyl groups having 1 to 18 carbon atoms, branched alkyl groups having 3 to 18 carbon atoms, cyclic alkyl groups having 3 to 18 carbon atoms, alkylene groups are linear alkylene groups having 1 to 18 carbon atoms, branched alkylene groups having 3 to 18 carbon atoms, cyclic alkylene groups having 3 to 18 carbon atoms, and aryl groups are aryl groups having 6 to 18 carbon atoms. These H3s can be used alone or in combination of multiple kinds.

[0102] The content of the cyclic ether compound (H3) relative to the whole curable composition is preferably 0% by mass to 99% by mass, more preferably 5% by mass to 90% by mass, and particularly preferably 10% by mass to 50% by mass. H3 generally has a low viscosity, and by containing H3, it is possible to expect the effects of lowering the viscosity of the curable composition and improving the workability.

[0103] The benzoylmethaneamide derivative (D) of the present invention has high photoinitiation in radical photopolymerization and can be suitably used as a photoinitiator for various purposes. In the case where higher photoinitiation is required, D can be used in combination with other photoinitiators. The photoinitiators that can be used in combination are not particularly limited. For example, examples include: benzoins such as benzoin and benzoin alkyl ethers; acetophenones such as 2-hydroxy-2-methyl-1-phenylpropan-1-one; acylphosphine oxides such as 2,4,6-trimethylbenzoyl diphenylphosphine oxide; benzoylformic acid esters such as methyl benzoylformate; aminobenzophenones such as 2-methyl-2-morpholino(4-methylthiophenyl)propan-1-one; oxime esters such as 1-(9,9-dimethyl-9H-fluoren-2-yl)-1,2-propanedione 2-(O-acetone oxime). The photoinitiator used in combination can be used in combination with D at an arbitrary ratio as needed, and can be used alone or in combination of multiple kinds.

[0104] The benzoylformamide derivative (D) can be used in a mixed polymerization system of photo-induced radical polymerization and thermal radical polymerization. The thermal polymerization initiator that can be used in combination with D is not particularly limited. For example, it can include: ketone peroxides such as methyl ethyl ketone peroxide; peroxyketals such as 1,1-bis(tert-hexylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(tert-hexylperoxy)cyclohexane, 1,1-bis(tert-butylperoxy)cyclohexane; hydroperoxides such as 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, p-menthane hydroperoxide; dialkyl peroxides such as dicumyl peroxide, di-tert-butyl peroxide; diacyl peroxides such as dilauroyl peroxide, benzoyl peroxide; peroxydicarbonates such as bis(4-tert-butylcyclohexyl) peroxydicarbonate, bis(2-ethylhexyl) peroxydicarbonate; peresters such as tert-butyl peroxy-2-ethylhexanoate, tert-hexyl peroxyisopropylmonocarbonate, tert-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); polymeric azo polymerization initiators containing polydimethylsiloxane units (manufactured by FUJIFILM Wako Pure Chemical Corporation, VPS-1001N), polymeric 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 any ratio as needed, and one kind can be used alone or multiple kinds can be used.

[0105] The benzoylformamide derivative (D) has a sufficient photosensitizing effect on photo-induced radical polymerization and can be suitably used as a photosensitizer for photo-induced radical polymerization in various applications. In cases where a further photosensitizing effect is required, it can be used in combination with other photosensitizers. The photosensitizer that can be used in combination with D is not particularly limited. For example, it can include: benzophenones, unsaturated ketones represented by anthracene derivatives; 1,2-diketone derivatives, benzoin derivatives, anthraquinone derivatives, thioxanthone derivatives, coumarin derivatives, thiols, disulfides, etc. represented by benzil and camphorquinone. These photosensitizers can be used in combination with D at any ratio as needed, and one kind can be used alone or multiple kinds can be used.

[0106] The benzoylformamide derivative (D) can be suitably used as a photosensitizer for photoionic polymerization for various purposes. When D is used for photoionic polymerization, the photoionic polymerization initiator is not particularly limited, and examples thereof include: 2-(9-oxoxanthen-2-yl)propanoic acid 1,5,7-triazabicyclo[4.4.0]dec-5-ene, and photocationic polymerization initiators such as 1,2-dicyclohexyl-4,4,5,5-tetramethylbiguanidinium n-butyltriphenylborate, and photoanionic polymerization initiators such as antimony-based and triarylsulfonium salt-based photoinitiators. In the photoanionic polymerization system or the photocationic polymerization system, the polymerization initiator of each polymerization system can be used alone or in combination of multiple kinds.

[0107] The benzoylformamide derivative (D) also has a sufficient photosensitizing effect on photoionic polymerization and can be used alone as a photosensitizer for photoionic polymerization. In the case where a further photosensitizing effect is required, it can be used in combination with other photosensitizers for photoionic polymerization. The photoionic polymerization initiator that can be used in combination with D is not particularly limited, and as long as it is a photosensitizer that can be used for photoradical polymerization, it can also be suitably used as a photosensitizer for photoionic polymerization. In addition, other photosensitizers can be used in combination with D at any ratio according to needs, and can be used alone or in combination of multiple kinds.

[0108] According to the usage method and purpose of the curable composition and the obtained cured product, the curable composition may further contain an organic solvent and water. In this case, the organic solvent and water can be removed in advance before the polymerization reaction (curing), or the polymerization reaction can be carried out in a state containing the organic solvent and water, and the organic solvent and water can 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, more preferably 50% by mass or less, based on the whole curable composition.

[0109] Examples of the 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, and methyl tert-butyl ether toluene; aromatic hydrocarbons such as xylene; aliphatic hydrocarbons such as hexane and cyclohexane; amides such as N,N-dimethylformamide, dimethylacetamide, and N,N-dimethylpropionamide; amide ethers such as 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 dichloromethane, chloroform, and dichloroethane; sulfoxides such as dimethyl sulfoxide; imidazolidinones such as 1,3-dimethyl-2-imidazolidinone. These organic solvents may be used alone or in combination of two or more.

[0110] The benzoylformamide derivative (D) of the present invention can be suitably used in: UV flexographic inks; UV offset inks; UV screen inks; UV inkjet inks; an active energy ray-curable nail cosmetic composition (gel nail); a UV curable adhesive; a UV curable adhesive; an active energy ray-curable sealant used in a sealing material or a sealant; an active energy ray-curable coating agent used in coatings or coating agents for automobiles, electrical appliances, furniture, etc.; an active energy ray-curable decorative sheet resin composition used in decorative sheets used in surface coatings of automobiles, electrical appliances, etc.; an active energy ray-curable self-healing material resin composition used in functional components, devices, etc. such as coating agents with self-healing properties, three-dimensional shaped objects, nail decoration materials, automotive exterior protection, decorative films, etc.; an active energy ray-curable elastomer composition for elastomers used in transparent adhesive sheets, cushioning materials, packings, anti-vibration materials, sound-absorbing materials, printing plates, sealing materials, abrasives, etc.; an active energy ray-curable three-dimensional shaping ink composition used in model materials or support materials for 3D printers; an active energy ray-curable vehicle coating agent composition such as an automotive coating; an active energy ray-curable composition used in various coating fields such as ship bottom coatings, antifogging materials, antifouling coatings, etc.; an active energy ray-curable composition used in the field of surface coating of medical devices; an active energy ray-curable dental material composition; an active energy ray-curable photosensitive composition; an active energy ray-curable hydrogel composition; an active energy ray-curable intraocular implant material composition, etc. In addition, the obtained hydrogel composition can also be suitably used as a superabsorbent resin, disposable diapers, soft contact lenses, etc. in the sanitary field; artificial organs, etc. in the medical field; soil conditioners, etc. in the civil / construction field; water retention materials, etc. in the agricultural field; impact-absorbing materials, etc. in various field materials.

[0111] [Examples]

[0112] Hereinafter, the present invention will be described in detail by way of examples. However, these examples are only illustrative examples for suitably explaining the present invention and do not limit the present invention at all. In addition, hereinafter, unless otherwise specified, "parts" and "%" are both based on mass.

[0113] Hereinafter, the devices and analysis conditions used for the analysis methods used in the examples and comparative examples of the present invention will be described.

[0114] (1) Fourier transform infrared spectroscopy (FT-IR (Fourier Transform-Infrared Spectroscopy) analysis)

[0115] The FT-IR analysis was carried out using the following device.

[0116] Nicolet iS50 (manufactured by Thermo Fisher Scientific Inc.)

[0117] (2) Liquid chromatography - mass spectrometry (LC - MS) analysis

[0118] The conditions for LC - MS analysis are as described below.

[0119] Column: XBride C18, 4.6 mm - 150 mm, 3.5 μm (manufactured by Nihon Waters Co., Ltd.)

[0120] Eluent conditions: water / methanol / 1% formic acid aqueous solution = 60 / 30 / 10

[0121] Detection wavelength: 258 nm

[0122] Column oven: 40 °C

[0123] (3) Nuclear magnetic resonance spectroscopy 1 1H - NMR (Nuclear Magnetic Resonance) analysis

[0124] 1 1H - NMR analysis was carried out using a 400 MHz device manufactured by JEOL Ltd., and the resonance frequency of the methyl group of tetramethylsilane was set to 0.0 ppm.

[0125] (4) Gel permeation chromatography (GPC) analysis

[0126] The conditions for GPC analysis are as described below.

[0127] Equipment: Prominence - I LC - 2030C (manufactured by Shimadzu Corporation)

[0128] Guard column: Shodex KF - G 1 piece (manufactured by Showa Denko K.K.)

[0129] Column: Shodex KF - 803 1 piece (manufactured by Showa Denko K.K.)

[0130] Column temperature: 40 °C

[0131] Mobile phase: tetrahydrofuran (THF; Tetrahydrofuran)

[0132] Flow rate: 0.5 mL / min

[0133] Standard sample: Polystyrene

[0134] (5) High Performance Liquid Chromatography (HPLC) analysis

[0135] The conditions for HPLC analysis are as described below.

[0136] Apparatus: Prominence-I LC-2030C (manufactured by Shimadzu Corporation)

[0137] Column: Mightysil RP-18GP, 4.6 mm - 250 mm, 5 μm (manufactured by Kanto Chemical Co., Inc.)

[0138] Eluent conditions: Methanol / 10 mM phosphoric acid aqueous solution = 50 / 50

[0139] Measurement wavelength: 258 nm

[0140] Column oven: 40 °C

[0141] The following shows various raw materials and solvents used in the examples and comparative examples.

[0142] (1) Benzoylformic acid compound (a1)

[0143] a1-1: Methyl benzoylformate

[0144] a1-2: Methyl 3,4,5-trimethoxybenzoylformate

[0145] a1-3: Methyl 4-methoxycarbonylbenzoylformate

[0146] a1-4: Methyl 4-acetoxybenzoylformate

[0147] a1-5: Methyl 4-dimethylaminobenzoylformate

[0148] a1-6: Ethyl 4-methylbenzoylformate

[0149] a1-7: Methyl 2-acetamidobenzoylformate

[0150] a1-8: Methyl 4-methoxybenzoylformate

[0151] a1-9: Methyl 3,5-dimethoxybenzoylformate

[0152] a1-10: Methyl 3-methoxybenzoylformate

[0153] a1-11: Ethyl 3-butoxybenzoylformate

[0154] a1-12: Methyl 4-bromobenzoylformate

[0155] (2) Amino compound (a2)

[0156] a2-1: (2S,3S,4R)-2-Amino-1,3,4-octadecanetriol

[0157] a2-2: Diethanolamine

[0158] a2-3: 3-Piperidinemethanol

[0159] a2-4: Dimethylamine (11% methanol solution, 2.0 mol / L)

[0160] a2-5: 8-Amino-1-octanol

[0161] a2-6: Aminoethanol

[0162] a2-7: 2-Amino-2-methyl-1-propanol

[0163] a2-8: 1,3-Diamino-2-propanol

[0164] a2-9: DL-2-Amino-1-butanol

[0165] a2-10: 4-Aminobenzyl alcohol

[0166] a2-11: 2-(2-Aminoethoxy)ethanol

[0167] a2-12: Tris(hydroxymethyl)aminomethane

[0168] a2-13: D-Glucosamine

[0169] a2-14: 3-Amino-1,2-propanediol

[0170] a2-15: 2-Amino-1,3-propanediol

[0171] a2-16: 2-Amino-2-ethyl-1,3-propanediol

[0172] (3) Isocyanate compound (b1)

[0173] b1-1: Isophorone diisocyanate

[0174] b1-2: Trimethylhexamethylene diisocyanate

[0175] 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 of isophorone diisocyanate)

[0176] b1-4: 1,3,5-tris(6-isocyanatohexan-1-yl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (isocyanurate form of hexamethylene diisocyanate)

[0177] b1-5: hexamethylene diisocyanate

[0178] b1-6: methylene bisphenyl isocyanate

[0179] b1-7: pentamethylene diisocyanate (STABiO PDI, manufactured by Mitsui Chemicals, Inc.)

[0180] b1-8: dicyclohexylmethane-4,4-diisocyanate

[0181] (4) Compound having a hydroxyl group (b2)

[0182] b2-1: polyethylene glycol (number average molecular weight 300)

[0183] b2-2: hydrogenated poly-1,2-butadiene having hydroxyl groups at both ends (number average molecular weight 1,000) (GI-1000, manufactured by Nippon Soda Co., Ltd.)

[0184] b2-3: ETERNAC0LL UH-50 (number average molecular weight 500) (manufactured by Ube Industries, Ltd.)

[0185] 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.)

[0186] b2-5: 1,4-butanediol

[0187] b2-6: isopropyl alcohol

[0188] b2-7: isostearyl alcohol

[0189] b2-8: ADEKA P0LYETHER BPX-2000 (manufactured by ADEKA Corporation)

[0190] b2-9: KURARAY P0LY0L P-1010 (number average molecular weight 1,000) (manufactured by KURARAY Co., Ltd.)

[0191] b2-10: UNI0L TG330 (polyoxypropylene glycerol ether, molecular weight 330, manufactured by NOF Corporation)

[0192] b2-11: polypropylene glycol (number average molecular weight 1,000)

[0193] b2-12: KURARAY POLYOL P-6010 (number average molecular weight 6,000) (manufactured by Kuraray Co., Ltd.)

[0194] b2-13: Polytetramethylene glycol (number average molecular weight 650) (BioPTMG650, manufactured by Mitsubishi Chemical Corporation)

[0195] (5) Compound (b3) having an ethylenically unsaturated group and a reactive group

[0196] b3-1: 2-Acryloyloxyethyl isocyanate

[0197] b3-2: N-(2-Hydroxyethyl)acrylamide (registered trademarks "Kohshylmer", "HEAA", manufactured by KJ Chemicals Co., Ltd.)

[0198] b3-3: Acryloyl chloride

[0199] b3-4: Allyl chloride

[0200] b3-5: Acrylonitrile

[0201] b3-6: Unsaturated polyester diol (a polyester composed of 1,5-pentanediol / maleic acid / adipic acid = 4 / 1 / 2 (molar ratio))

[0202] b3-7: 2-Hydroxyethyl maleimide

[0203] b3-8: 2-Hydroxyethyl acrylate

[0204] b3-9: N-(Hydroxymethyl)acrylamide

[0205] b3-10: 4-Hydroxybutyl acrylate

[0206] b3-11: Pentaerythritol triacrylate

[0207] b3-12: 2-Hydroxyethyl methacrylate

[0208] b3-13: N-(2-Hydroxyethyl)methacrylamide

[0209] b3-14: 4-Hydroxybutyl vinyl ether

[0210] b3-15: Oleyl alcohol

[0211] b3-16: Polypropylene glycol (6) monoacrylate

[0212] b3-17: Dipentaerythritol pentaacrylate

[0213] (6) Compound (b4) having a cyclic ether group and a reactive group

[0214] b4-1: Epichlorohydrin

[0215] b4-2: 7-Oxabicyclo[4.1.0]heptan-3-methanol

[0216] b4-3: 2-Hydroxyethyl glycidyl ester

[0217] (7) Solvent (c)

[0218] c-1: Toluene

[0219] c-2: 1,2-Dichloroethane

[0220] c-3: Ethyl acetate

[0221] c-4: 4-Methyltetrahydrofuran

[0222] c-5: 3-Methoxy-N,N-dimethylpropanamide (registered trademarks “Kohshylvent”, “KJCMPA”, manufactured by KJ Chemicals Co., Ltd.)

[0223] The monofunctional unsaturated compound (h1), polyfunctional unsaturated compound (h2), cyclic ether-containing compound (h3), photoinitiator (E), photosensitizer (I), thermal initiator (J), and other additives (k) used in the active energy ray curable compositions of the examples and comparative examples are shown below.

[0224] (8) Polymerizable compound (h)

[0225] (8-1) Monofunctional unsaturated compound (h1)

[0226] h1-1: N-Acryloylmorpholine (registered trademarks “Kohshylmer”, “ACMO”, manufactured by KJ Chemicals Co., Ltd.)

[0227] h1-2: Isobornyl acrylate

[0228] h1-3: N,N-Diethylacrylamide (registered trademarks “Kohshylmer”, “DEAA”, manufactured by KJ Chemicals Co., Ltd.)

[0229] h1-4: 4-Hydroxybutyl acrylate

[0230] h1-5: Methyl 3-acrylaminopropionate

[0231] h1-6: N-acryloyloxyethyl norbornene carboxamide (registered trademark "Kohshylmer", manufactured by KJ Chemicals Co., Ltd.)

[0232] h1-7: N-octylacrylamide (registered trademark "Kohshylmer", manufactured by KJ Chemicals Co., Ltd.)

[0233] h1-8: N-(2-hydroxyethyl)acrylamide (registered trademarks "Kohshylmer", "HEAA", manufactured by KJ Chemicals Co., Ltd.)

[0234] h1-9: tert-butylcyclohexyl acrylate (registered trademark "Kohshylmer", manufactured by KJ Chemicals Co., Ltd.)

[0235] h1-10: tetrahydrofurfuryl acrylate

[0236] h1-11: N-vinylpyrrolidone

[0237] h1-12: N-oleylacrylamide (registered trademark "Kohshylmer", manufactured by KJ Chemicals Co., Ltd.)

[0238] h1-13: diacetoneacrylamide (registered trademark "Kohshylmer", manufactured by KJ Chemicals Co., Ltd.)

[0239] h1-14: N,N-dimethylacrylamide (registered trademarks "Kohshylmer", "DMAA", manufactured by KJ Chemicals Co., Ltd.)

[0240] h1-15: 2-hydroxyethyl methacrylate

[0241] h1-16: phenoxyethyl acrylate

[0242] h1-17: lauryl acrylate

[0243] h1-18: isobornyl methacrylate

[0244] h1-19: 2-methacryloyloxyethyl acid phosphate

[0245] (8-2) Polyfunctional unsaturated compound (h2)

[0246] h2-1: hexanediol diacrylate

[0247] h2-2: dipentaerythritol hexaacrylate

[0248] h2-3: Quick Cure 8100 (Registered trademark “Quick Cure”, manufactured by KJ Chemicals Co., Ltd.)

[0249] h2-4: Quick Cure 7100 (Registered trademark “Quick Cure”, manufactured by KJ Chemicals Co., Ltd.)

[0250] h2-5: Polyethylene glycol (14) diacrylate

[0251] h2-6: Urethane diacrylate (Violet UV3000, manufactured by Mitsubishi Chemical Corporation)

[0252] h2-7: Trimethylolpropane triacrylate

[0253] h2-8: Pentaerythritol triacrylate

[0254] h2-9: Quick Cure 7300 (Registered trademark “Quick Cure”, manufactured by KJ Chemicals Co., Ltd.)

[0255] h2-10: Dimethylol-tricyclodecane diacrylate

[0256] h2-11: Urethane diacrylate (Violet UV6630, manufactured by Mitsubishi Chemical Corporation)

[0257] h2-12: Bisphenol A diacrylate with polyethylene glycol (20) introduced

[0258] h2-13: 2-(2-Vinyloxyethoxy)ethyl acrylate

[0259] h2-14: Diethylene glycol divinyl ether

[0260] h2-15: Bisphenol A epoxy acrylate oligomer (Miramer PE-210, manufactured by MIW0N Co., Ltd.)

[0261] h2-16: Bisphenol A diacrylate with polyethylene glycol (10) introduced

[0262] h2-17: 2,4-Dimethyl-1,6-hexanediyl bis[2-(methacryloyloxy)ethyl carbamate]

[0263] h2-18: Ethylene bisacrylamide

[0264] h2-19: Triethylene glycol dimethacrylate

[0265] (9) Containing cyclic ether compound (h3)

[0266] h3-1: 2-Ethylhexyl glycidyl ether

[0267] h3-2: Bisphenol A diglycidyl ether

[0268] h3-3: 1,6-Hexanediol diglycidyl ether

[0269] h3-4: Trimethylolpropane triglycidyl ether

[0270] h3-5: Butyl glycidyl ether

[0271] h3-6: 4-Hydroxybutyl acrylate glycidyl ether

[0272] (10) Photoinitiator (E)

[0273] E-1: Oligomer of 2-hydroxy-1-(4-isopropenylphenyl)-2-methylpropan-1-one (ESACURE KIP 150, manufactured by IGM Resin B.V.)

[0274] E-2: Methyl benzoylformate (Omnirad MBF, manufactured by IGM Resin B.V.)

[0275] E-3: 2,4,6-Trimethylbenzoyl diphenylphosphine oxide (Omnirad TPO, manufactured by IGM Resin B.V.)

[0276] E-4: Kohshylex-I3003 (registered trademark "Kohshylex", manufactured by KJ Chemicals Co., Ltd.)

[0277] E-5: 1-Hydroxycyclohexyl phenyl ketone (Omnirad 184, manufactured by IGM Resin B.V.)

[0278] E-6: 2-Hydroxy-2-methylpropiophenone (Omnirad1173, manufactured by IGM Resin B.V.)

[0279] E-7: 1-[4-(2-Hydroxyethyl)-phenyl]-2-hydroxy-methylpropanone (Omnirad 2959, manufactured by IGM ResinB.V.)

[0280] E-8: Benzophenone

[0281] E-9: α-[(4-Benzoylphenoxy)acetyl]-ω-{[(4-benzoylphenoxy)acetyl]oxy}poly(oxybutane-1,4-diyl) (Omnipol BP, manufactured by IGM Resin B.V.)

[0282] E-10: 2-(9-oxoxanthen-2-yl)propanoic acid 1,5,7-triazabicyclo[4.4.0]dec-5-ene

[0283] E-11: 1,2-dicyclohexyl-4,4,5,5-tetramethylbiguanidinium n-butyltriphenylborate

[0284] (11) Photosensitizer (I)

[0285] I-1: Poly(ethylene glycol) bis(p-dimethylaminobenzoate) (manufactured by Omnipol ASA, IGM Resin B.V.)

[0286] I-2: Bis N,N-[2-(4-dimethylaminobenzoyl)oxyethylene-1-yl]methylamine (manufactured by Esacure A198, IGM Resin B.V.)

[0287] I-3: Isopropylthioxanthone

[0288] I-4: 2-ethylanthraquinone

[0289] I-5: Polytetramethylene glycol (3) carboxymethoxythioxanthone diester (manufactured by Omnipol TX, IGM Resin B.V.)

[0290] (12) Thermal polymerization initiator (J)

[0291] J-1: Azobisisobutyronitrile

[0292] (13) Other additives (k)

[0293] k-1: Pentaerythritol tetrakis(3-mercaptobutyrate)

[0294] k-2: Methyl-5-norbornene-2,3-dicarboxylic anhydride

[0295] k-3: BYK JET9151 (a pigment dispersant, a maleimide-styrene copolymer with an ammonium salt structure, manufactured by BYK Chemie)

[0296] k-4: Carbon black dispersion (manufactured by Mitsubishi Chemical Corporation)

[0297] k-5: Pigment Yellow 155

[0298] k-6: VALIFAST BLUE1613 (manufactured by 0RIENT CHEMICAL INDUSTRIES Co., LTD.)

[0299] k-7: BYK-331 (Leveling agent, polyether-modified polydimethylsiloxane, manufactured by BYK Chemie)

[0300] k-8: PETROTAC 100V (manufactured by Tosoh Corporation)

[0301] k-9: Trimethylsilyl surface-modified silica (AEROSIL RX200, manufactured by Nippon AEROSIL Co., Ltd.)

[0302] k-10: Hydrogenated rosin (non-polymeric polymer, Tackifier KE-359, manufactured by Arakawa Chemical Industries)

[0303] k-11: Reolosi 1QS-30 (manufactured by Tokuyama Corporation)

[0304] k-12: Inorganic filler (titanium oxide)

[0305] k-13: Methacrylic acid / methyl methacrylate / styrene copolymer adhesive

[0306] k-14: Polyvinyl alcohol JC-25 (manufactured by JAPAN VAM&POVAL Co., Ltd.)

[0307] k-15: ELEMINOL JS-20 (manufactured by Sanyo Chemical Industries, Ltd.)

[0308] Synthesis of benzoylformamide derivative (D-1) in Example 1

[0309] Add 197.0 g (1.20 moles) of methyl benzoylformate (a1-1), 317.5 g (1.00 mole) of (2S,3S,4R)-2-amino-1,3,4-octadecanetriol (a2-1), 500 g of toluene (c-1) as a solvent, and 1.0 g (0.01 mole) of triethylamine (TEA: Triethylamine) as a catalyst to a 1,000 mL flask equipped with a reflux condenser, a stirrer, a thermometer, and a dropping funnel, and heat to 70 °C while stirring. After reacting at 70 °C for 8 hours, unreacted raw materials, the solvent, by-produced methanol, and the catalyst were distilled off under reduced pressure to obtain the benzoylformamide derivative (D-1) as a pale yellow solid (yield 85%). The identification of D-1 was carried out by 1 1H-NMR analysis, and the chemical shift values of representative protons are shown in Table 1-1. By liquid chromatography-mass spectrometry (LC-MS analysis), the molecular weight of the product was 450 (the molecular ion peak of the mass spectrum was 451). According to 1As a result of H-NMR and LC-MS analyses, it was confirmed that the product was the benzoylformamide derivative (D-1) shown in Table 1-1.

[0310] Synthesis of benzoylformamide derivatives (D-2), benzoylformamide derivatives (D-3), benzoylformamide derivatives (D-5) to benzoylformamide derivatives (D-20) in Example 2, Example 3, Example 5 to Example 20

[0311] Reactions were carried out under the same conditions as in Example 1 according to the raw materials and addition ratios shown in Table 1-1 and Table 1-2 to obtain benzoylformamide derivatives (D-2), benzoylformamide derivatives (D-3), benzoylformamide derivatives (D-5) to benzoylformamide derivatives (D-20). The identification of the obtained benzoylformamide (D) was likewise carried out by 1 H-NMR analysis and LC-MS analysis, and the chemical shift values of representative protons, and the molecular weights and yields of the products are shown in Table 1-1 and Table 1-2. According to 1 As a result of H-NMR and LC-MS analyses, it was confirmed that the products were the benzoylformamide derivatives (D-2), benzoylformamide derivatives (D-3), benzoylformamide derivatives (D-5) to benzoylformamide derivatives (D-20) shown in Table 1-1 and Table 1-2.

[0312] Synthesis of benzoylformamide derivative (D-4) in Example 4

[0313] 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 benzoylformamide derivative (D-4) as a pale yellow solid (yield 75%). The identification of D-4 was carried out by 1 H-NMR and LC-MS analyses, and the respective analysis data and the chemical formula of D-4 are shown in Table 1-1.

[0314] Synthesis of benzoylformamide derivative (D-21) in Example 21

[0315] 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 ADEKA POLYETHER BPX-2000 (b2-8) 362 g in place of solvent (c) were added, and the reaction was carried out under the same conditions as in Example 1. Then, nitrogen was passed at 100 cm at 25 °C 3A flow rate of / minute was introduced for 10 minutes (foaming) to remove unreacted raw materials and by-produced methanol, and a solution of benzoylamidomethylamide derivative (D-21) in b2-8 (yield 84%) was obtained. The identification of D-21 was similarly carried out by 1 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. In addition, it was confirmed that the obtained solution was a mixture of D-21 and b2-8 with a mass ratio of 1 / 1.

[0316] Example 22 Synthesis of benzoylamidomethylamide derivative (D-22)

[0317] To a 300 mL flask equipped with a reflux condenser, stirrer, thermometer, and dropping funnel, 45.7 g of the benzoylamidomethylamide 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) as a catalyst was added to the mixture, and the reaction was carried out with stirring at 70 °C for 4 hours. 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 the carbamate group and the benzoylamidomethyl group (disubstituted) derived from D-2 was confirmed by FT-IR analysis of the product. By 1 1H-NMR analysis, the presence of the acrylate group (5.85 ppm, 6.20 ppm, 6.45 ppm) was confirmed. Furthermore, by LC-MS analysis, the molecular weight of the product was confirmed to be 520, and the product was confirmed to be the benzoylamidomethylamide derivative (D-22) shown in Table 2-1. In Table 2-1, the chemical formula, molecular weight, and average number of benzoylamidomethyl groups per molecule of D-22, the number of atoms directly bonded between the nitrogen atom of the benzoylamidomethyl group and the nearest nitrogen atom of the carbamate group, and the average number ratio of carbamate groups and benzoylamidomethyl groups per molecule are shown.

[0318] Example 23 Synthesis of benzoylamidomethylamide derivative (D-23)

[0319] Except for not using a reaction solvent, the reaction of 50.0 g of benzoylamidomethylamide 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 dibutyltin dilaurate as a catalyst in the same manner as in Example 22 to obtain a pale yellow viscous solid product (yield 96%). The presence of the carbamate group and the benzoylamidomethyl group (disubstituted) derived from D-3 was confirmed by FT-IR analysis of the product. By 1The presence of acrylamide groups (5.60 ppm, 6.10 ppm, 6.50 ppm) was confirmed by 1H-NMR analysis. Furthermore, the molecular weight of the product was confirmed to be 675 by LC-MS analysis, and the product was confirmed to be 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.

[0320] Synthesis of Benzoylformamide Derivative (D-24) in Example 24

[0321] 74.7 g of the benzoylformamide derivative (D-5) synthesized in Example 5 and 100 g of 1,2-dichloroethane (c-2) were added to a 300 mL flask equipped with a reflux condenser, a stirrer, a thermometer, and a dropping funnel and mixed. The mixture was cooled to -10°C, and while maintaining the temperature at -10°C to 0°C, 25.3 g of acryloyl chloride (b3-3) was added dropwise to carry out the reaction. Then, extraction was carried out using 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 the benzoylformamide group (monosubstituted) derived from D-5 was confirmed by FT-IR analysis of the product, and the presence of the acrylate group was confirmed by 1 1H-NMR analysis. Furthermore, the molecular weight of the product was confirmed to be 331 by LC-MS analysis. The chemical formula and other data of product D-24 are summarized in Table 2-1.

[0322] Synthesis of Benzoylformamide Derivative (D-25) in Example 25

[0323] 6.0 g of sodium hydride and 50 g of 4-methyltetrahydrofuran (c-4) were added to a 500 mL flask equipped with a reflux condenser, a stirrer, a thermometer, and a dropping funnel. 63.6 g of the benzoylformamide derivative (D-18) was dissolved in 50 g of c-4 and added to the dropping funnel, and it was added dropwise over 30 minutes while confirming the amount of hydrogen gas generated. After the addition was completed, 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 inactivate the remaining sodium hydride, c-4 was separated, and further extraction was carried out 3 times using saturated brine. The extract was concentrated using an evaporator, purified by silica gel column chromatography, and then the solvent was removed under reduced pressure to obtain a pale yellow viscous liquid product (yield 43%). The presence of the benzoylformamide group (monosubstituted) derived from D-18 was confirmed by FT-IR analysis of the product. The presence of the allyl ether group (5.00 ppm, 5.05 ppm, 5.85 ppm, 3.85 ppm) was confirmed by 1 1H-NMR analysis. In addition, the molecular weight of the product was confirmed to be 347 by LC-MS analysis. The chemical formula and other data of D-25 are summarized in Table 2-1.

[0324] Synthesis of Benzoylformamide Derivative (D-26) in Example 26

[0325] 40.4 g of trifluoromethanesulfonic acid was added to a 500 mL flask equipped with a reflux condenser, a stirrer, a thermometer, and a dropping funnel. 4.8 g of ion-exchanged water was added while cooling 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 the reaction was completed, extraction was performed twice with ion-exchanged water, the organic layer was concentrated, and purification was carried out by silica gel column chromatography. Furthermore, the solvent was removed under reduced pressure to obtain a pale yellow viscous liquid product (yield 38%). The presence of the benzoylformamide group (monosubstituted) derived from D-9 was confirmed by FT-IR analysis of the product, and the presence of the acrylamide group and two benzoylformamide groups was confirmed by 1 1H-NMR analysis. Furthermore, the molecular weight of the product was confirmed to be 407 by LC-MS analysis. The chemical formula and other data of D-26 are summarized in Table 2-1.

[0326] Synthesis of Benzoylformamide Derivatives (D-27), Benzoylformamide Derivative (D-28), Benzoylformamide Derivative (D-30), Benzoylformamide Derivative (D-32), Benzoylformamide Derivatives (D-36) to Benzoylformamide Derivative (D-39) in Example 27, Example 28, Example 30, Example 32, Example 36 to Example 39

[0327] 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. The chemical formula and other data of the product are summarized in Tables 2-1 to 2-3. Specifically, the presence of the maleimide group (7.05 ppm), acrylate group (5.85 ppm, 6.20 ppm, 6.45 ppm), and acrylamide group (5.60 ppm, 6.10 ppm, 6.50 ppm) was confirmed by 1 1H-NMR analysis.

[0328] Synthesis of Benzoylformamide Derivative (D-29) in Example 29

[0329] Using the same reaction apparatus as in Example 23, 18.8 g of benzoylamine derivative (D-7), 23.5 g of trimethylhexamethylene diisocyanate (b1-2), 57.7 g of unsaturated polyester diol (b3-6), and 0.05 g of zirconium tetrakis acetylacetonate as a catalyst were mixed and reacted with stirring at 60°C for 5 hours. The disappearance of the isocyanate group was confirmed by FT-IR analysis of the reaction solution to obtain a pale yellow viscous liquid product (yield 96%). The presence of the carbamate group and the benzoylamine group was confirmed by FT-IR analysis of the product, and the presence of the maleate group (6.30 ppm) was confirmed by 1 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 benzoylamine derivative (D-29) confirmed from these results are shown in Table 2-1.

[0330] Synthesis of benzoylamine derivatives (D-31), benzoylamine derivatives (D-34), benzoylamine derivatives (D-35), benzoylamine derivatives (D-40) to benzoylamine derivatives (D-46), benzoylamine derivatives (D-48) to benzoylamine derivatives (D-54) in Examples 31, 34, 35, 40 to 46, 48 to 54

[0331] Using the raw materials shown in Tables 2-2 to 2-6, the benzoylamine derivative (D) was synthesized in the same manner as in Example 23. The presence of the carbamate group and the benzoylamine group was confirmed by FT-IR analysis, and by 11H-NMR analysis confirmed the presence of acrylate groups (5.85 ppm, 6.20 ppm, 6.45 ppm), methacrylate groups (5.65 ppm, 6.20 ppm), acrylamide groups (5.60 ppm, 6.10 ppm, 6.50 ppm), methacrylamide groups (5.60 ppm, 6.20 ppm), vinyl ether groups (4.75 ppm, 4.80 ppm, 6.75 ppm), and various unsaturated groups. 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), benzoylformamide derivatives (D-34), benzoylformamide derivatives (D-35), benzoylformamide derivatives (D-40) to benzoylformamide derivatives (D-46), benzoylformamide derivatives (D-48) to benzoylformamide derivatives (D-54) are summarized in Tables 2-2 to 2-6. In addition, 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.

[0332] Synthesis of benzoylformamide derivative (D-33) in Example 33

[0333] Using the raw materials shown in Table 2-2, in the same manner as in Example 22, 39.6 g of benzoylformamide derivative (D-10), 39.8 g of isophorone diisocyanate (b1-1), 20.6 g of N-(hydroxymethyl)acrylamide (b3-9), 100.0 g of polymerizable compound N-acrylylmorpholine (h1-1) instead of solvent (c), and 0.02 g of bismuth tris(2-ethylhexanoate) as a catalyst were mixed and reacted with stirring at 60 °C for 6 hours. The disappearance of isocyanate groups was confirmed by FT-IR analysis of the reaction solution, and a pale yellow liquid product (yield 99%) was obtained. The presence of urethane groups and benzoylformamide groups was confirmed by FT-IR analysis of the product, and the presence of acrylamide groups (5.60 ppm, 6.10 ppm, 6.50 ppm) derived from b3-9 was confirmed by 1 1H-NMR analysis. In addition, the molecular weight of D-33 was confirmed to be 588 by LC-MS analysis, and an h1-1 solution (50% by mass) of D-33 was obtained. These analysis results are shown in Table 2-2.

[0334] Synthesis of benzoylformamide derivative (D-47) in Example 47

[0335] 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-(2-hydroxyethyl)acrylamide (b3-2), 4.0 g of oleyl alcohol (b3-15), and 0.01 g of dibutyltin dilaurate as a catalyst were mixed and reacted with stirring at 60 °C 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 (yield 95%) was obtained. The presence of the carbamate group and the benzoylformamide group was confirmed by FT-IR analysis of the product, and the presence of the acrylamide group derived from b3-2 (5.60 ppm, 6.10 ppm, 6.50 ppm) and the unsaturated group of the oleyl group derived from b3-15 (5.35 ppm) was confirmed by 1 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.

[0336] Example 55 Synthesis of benzoylformamide derivative (D-55)

[0337] 67.6 g of benzoylformamide derivative (D-6) and 50.0 g of 4-methyltetrahydrofuran (c-4) were added to a 300 mL flask equipped with a reflux condenser, a stirrer, a thermometer, and a dropping funnel and mixed, and then 21.6 g of epichlorohydrin (b4-1) was added. After adding 0.5 g of boron trifluoride diethyl ether while maintaining 20 °C, 10.8 g of b4-1 was further added dropwise over 1 hour, and after the addition was completed, the reaction was carried out for another 2 hours. 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 the benzoylformamide group was confirmed by FT-IR analysis of the product, and the presence of the glycidyl group (3.00 ppm, 3.85 ppm) was confirmed by 1 1H-NMR analysis. Furthermore, the molecular weight of the product was confirmed to be 249 by LC-MS analysis. From these results, it was confirmed that the product was the benzoylformamide derivative (D-55) shown in Table 2-6.

[0338] Examples 56 to 58 Synthesis of benzoylformamide derivatives (D-56) to benzoylformamide derivatives (D-58)

[0339] Using the raw materials shown in Table 2-6, the synthesis of benzoylformamide derivative (D) was carried out in the same manner as in Example 23. The presence of the carbamate group and the benzoylformamide group was confirmed by FT-IR analysis, and by 1The presence of cyclic ethers and unsaturated groups was confirmed by 1H-NMR analysis. Specifically, by 1 1H-NMR analysis, 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. 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 benzoylformamide derivatives (D-56) to benzoylformamide derivatives (D-58) are summarized in Table 2-6.

[0340] [Table 1-1]

[0341]

[0342]

[0343] [Table 1-2]

[0344]

[0345] [Table 2-1]

[0346]

[0347]

[0348] (*1) Average number of benzoylformamide groups introduced per molecule.

[0349] (*2) Number of atoms directly bonded between the nitrogen atom of the benzoylformamide group and the nitrogen atom of the nearest carbamate group.

[0350] [Table 2-2]

[0351]

[0352]

[0353] (*1) Average number of benzoylformamide groups introduced per molecule.

[0354] (*2) Number of atoms directly bonded between the nitrogen atom of the benzoylformamide group and the nitrogen atom of the nearest carbamate group.

[0355] [Table 2-3]

[0356]

[0357]

[0358] (*1) Average number of benzoylformamido groups introduced per molecule.

[0359] (*2) Number of atoms directly bonded between the nitrogen atom of the benzoylformamido group and the nitrogen atom of the nearest carbamate group.

[0360] [Table 2-4]

[0361]

[0362]

[0363] (*1) Average number of benzoylformamido groups introduced per molecule.

[0364] (*2) Number of atoms directly bonded between the nitrogen atom of the benzoylformamido group and the nitrogen atom of the nearest carbamate group.

[0365] [Table 2-5]

[0366]

[0367]

[0368] (*1) Average number of benzoylformamido groups introduced per molecule.

[0369] (*2) Number of atoms directly bonded between the nitrogen atom of the benzoylformamido group and the nitrogen atom of the nearest carbamate group.

[0370] [Table 2-6]

[0371]

[0372]

[0373] (*1) Average number of benzoylformamido groups introduced per molecule.

[0374] (*2) Number of atoms directly bonded between the nitrogen atom of the benzoylformamido group and the nitrogen atom of the nearest carbamate group.

[0375] Examples 59 to 100 and Comparative Examples 1 to 3 (Preparation and Evaluation of Actinic Energy Ray-Curable Compositions)

[0376] Using the benzoylformamide derivatives (D-1) to benzoylformamide derivatives (D-54) synthesized as examples and the commercially available photoinitiators (E-1) to photoinitiators (E-3) as comparative examples, the monofunctional unsaturated compound (h1), the polyfunctional unsaturated compound (h2), the photosensitizer (I), and other components (k) were metered in the proportions shown in Table 3-1 and Table 3-2, and mixed at 25°C for 30 minutes to obtain an active energy ray curable composition (hereinafter simply referred to as the curable composition). The miscibility of the obtained curable composition and the curability with respect to light of different wavelengths were evaluated. In addition, a photocured product of the curable composition was prepared, and the low molecular weight component content derived from the photoinitiator in the cured product, the light yellowing resistance, and the durability of the cured product were evaluated by the following methods, and the evaluation results are shown in Table 3-1 and Table 3-2.

[0377] [Miscibility]

[0378] The state of the curable composition was visually observed, and the miscibility was evaluated in four grades.

[0379] ++: High transparency, and no turbidity or phase separation was confirmed at all.

[0380] +: High transparency, but slight turbidity was slightly visible.

[0381] ±: No phase separation was confirmed, but turbidity was confirmed.

[0382] -: Turbidity and phase separation were confirmed.

[0383] [Curability]

[0384] Using a bar coater, the curable composition was coated on a polyethylene terephthalate film (C0SM0SHINE A-4100, corona-treated surface, thickness 100 μm, manufactured by Toyobo Co., Ltd.) (hereinafter referred to as PET (polyethylene terephthalate) film) so that the film thickness became 20 μm. The coated film was irradiated with light of different wavelengths to cure the film, and the cumulative light amount until the viscosity disappeared when touching the cured product was determined, and the curability was evaluated in four grades. The following three types of lamps were used for ultraviolet irradiation. In addition, the lower the cumulative light amount required until the viscosity disappears, the higher the curability.

[0385] 1) High-pressure mercury lamp: wavelength 200 nm to 450 nm, illuminance 100 mW / cm 2 .

[0386] 2) UV-LED lamp: wavelength 385 nm, illuminance 100 mW / cm 2 .

[0387] 3) UV-LED lamp: wavelength 405 nm, illuminance 100 mW / cm 2 .

[0388] ++: Cumulative light quantity is less than 500 mJ / cm 2 when the viscosity disappears.

[0389] +: Cumulative light quantity is 500 mJ / cm 2 or more and less than 1,000 mJ / cm 2 when the viscosity disappears.

[0390] ±: Cumulative light quantity is 1,000 mJ / cm 2 or more and less than 5,000 mJ / cm 2 when the viscosity disappears.

[0391] -: Even when the cumulative light quantity is 5,000 mJ / cm 2 the viscosity remains.

[0392] [Low molecular weight component content]

[0393] The curable composition was coated on a polyester-based heavy release film (E7001, thickness 75 μm, manufactured by Toyobo Co., Ltd.) (hereinafter referred to as the heavy release film), and using a tabletop roll laminator (RSL-382S manufactured by Royal Sovereign), without entraining air bubbles and with a film thickness of 20 μm, it was laminated with a polyester-based light release film (E7002, thickness 50 μm, manufactured by Toyobo Co., Ltd.) (hereinafter referred to as the light release film), and ultraviolet rays were irradiated (high-pressure mercury lamp, illuminance 100 mW / cm 2 , cumulative light quantity 5,000 mJ / cm 2 ). Then, the light release film was peeled off, three test pieces with a size of 5 cm 2 were cut out, dried at 90 °C for 2 minutes, weighed, and set as the mass of the cured film before extraction. In a non-ultraviolet-transmissive brown glass bottle, 25 g of acetone and the weighed cured film were placed, the glass bottle was sealed, and the glass bottle was rotated at 30 °C for 48 hours to extract the soluble components in the cured film. The extracted solution was filtered through a 0.45 μm filter, subjected to HPLC analysis, the low molecular weight components were quantified based on the calibration curve, and the content of the low molecular weight components was calculated by the following formula and evaluated as follows.

[0394] Low molecular weight component content (%) = (mass of the extracted low molecular weight components / mass of the cured film before extraction) × 100%

[0395] ++: The content of the low molecular weight components is 1.0% or less.

[0396] +: The content rate of the low molecular weight component is more than 1.0% to 2.0% or less.

[0397] ±: The content rate of the low molecular weight component is more than 2.0% to 4.0% or less.

[0398] -: The content rate of the low molecular weight component is more than 4.0%.

[0399] [Lightfast yellowing property]

[0400] Adhere the heavy release film closely to a horizontally set glass plate. Set a silicone spacer (hereinafter, silicone is used when the material is not specified) with an internal volume of 10 mm × 10 mm × 0.5 mm on the heavy release film, and fill the spacer with the curable composition. Cover the liquid surface of the spacer with the light release film in a manner that does not entrap air bubbles, and irradiate ultraviolet rays (wavelength 405 nm, illuminance 100 mW / cm 2 , cumulative light quantity 20,000 mJ / cm 2 ) using a UV-LED lamp. Then, peel off the light release film, take out the cured product from the spacer, and observe it visually. Evaluate the lightfast yellowing property according to the following criteria.

[0401] ++: Yellowing is not confirmed at all.

[0402] +: Yellowing is extremely slightly confirmed.

[0403] ±: Yellowing is confirmed.

[0404] -: Obvious yellowing is confirmed.

[0405] [Durability]

[0406] Except for changing the cumulative light quantity to 5,000 mJ / cm 2 , produce a cured product of the curable composition in the same manner as the evaluation of the lightfast yellowing property. Then, leave it standing in a thermo-hygrostat at a temperature of 40°C and a relative humidity of 50% for 168 hours, observe visually whether there is exudation on the surface of the cured product, and evaluate the durability according to the following criteria.

[0407] ++: Exudation is not confirmed at all.

[0408] +: Exudation is extremely slightly confirmed.

[0409] ±: Exudation is slightly confirmed.

[0410] -: Exudation is severely confirmed.

[0411] [Table 3-1]

[0412]

[0413] [Table 3-2]

[0414]

[0415] It can be clearly seen from the evaluation results in Table 3-1 and Table 3-2 that the curable compositions of each example using the benzoylformamide derivative (D) of the present invention have good miscibility, and have high curability not only for high-pressure mercury lamps but also for the light rays of 385 nm and 405 nm of UV-LED lamps. The content of low-molecular-weight components in the cured products obtained in the examples is low, the safety is high, and the light yellowing resistance and durability are excellent. In addition, D-20 (Example 66) having a monosubstituted benzoylformamide group shows higher curability than D-3 (Example 60) having a disubstituted benzoylformamide group. D-40 (Example 86) containing a urethane group shows higher miscibility and curability than D-24 (Example 70) not containing a urethane group. Among Ds in which the number of atoms directly bonded between the nitrogen atom of the benzoylformamide group and the nearest nitrogen atom of the urethane group is 10 (D-30 of Example 76), 7 (D-36 of Example 82), and 4 (D-40 of Example 86), Ds with 7 and 4 atoms show higher curability than D with 10 atoms, and D with 4 atoms shows the highest curability. D-42 (Example 88) and D-43 (Example 89) in which the benzene ring of the benzoylformamide group has a methoxy group show higher curability than D-44 (Example 90) without a methoxy group. In addition, 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 show good miscibility. 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 show good miscibility despite having a high molecular weight. The content of low-molecular-weight components in the cured products obtained in these examples is low, and the light yellowing resistance and durability of the cured products are both high. On the other hand, in Comparative Example 1 using Esacure KIP 150 (E-1) as a photoinitiator, the curability for the light ray of wavelength 405 nm is low, the residual components (unpolymerized) of the polymerizable compound (h) and the decomposition products generated by the intramolecular cleavage of E-1 both remain in the cured product, and the content of low-molecular-weight components in the cured product is high.In Comparative Example 2 using methyl benzoylformate (E-2) and Comparative Example 3 using 2,4,6-trimethylbenzoyldiphenylphosphine oxide (E-3), although they can be cured by light at 405 nm, since E-2 with a molecular weight of 164 itself is a low-molecular-weight component and E-3 is an intramolecular cleavage type photoinitiator for polymerization, the content rates of low-molecular-weight components in the cured products of Comparative Example 2 and Comparative Example 3 are both high. In addition, the light fast yellowing resistance and durability of the cured products in Comparative Examples 1 to 3 are both low.

[0416] Examples 101 to 137 and Comparative Examples 4 to 10 (Preparation and Evaluation of Photo-Radical Polymerization Type Active Energy Ray Curable Compositions)

[0417] Using the benzamide derivatives (D-2) to benzamide derivatives (D-57) obtained in each example and commercially available photosensitizers (I-3) and photosensitizer (I-4) as comparative examples, a monofunctional unsaturated compound (h1), a polyfunctional unsaturated compound (h2), and a radical photoinitiator (E) were metered according to the compositions shown in Table 4-1 and Table 4-2, and mixed at 25 °C for 30 minutes to prepare a photo-radical polymerization type active energy ray curable composition (hereinafter also referred to as a radical type curable composition). The compatibility of the obtained radical type curable composition and the curability for light of different wavelengths, the light fast yellowing resistance and durability of the obtained cured product were evaluated by the same method as the evaluation of the above curable composition, and the evaluation results are shown in Table 4-1 and Table 4-2. The higher the curability of the curable composition, the higher the photosensitivity (sensitivity) of D.

[0418] [Table 4-1]

[0419]

[0420] [Table 4-2]

[0421]

[0422] (*3) No cured product was obtained and the evaluation was not carried out.

[0423] Examples 138 to 143 and Comparative Examples 11 to 15 (Preparation and Evaluation of Photo-Ionic Polymerization Type Active Energy Ray Curable Compositions)

[0424] Using the benzoylformamide derivatives (D) obtained in each of the examples and commercially available photosensitizers (I-3) to (I-5), in accordance with the composition shown in Table 5, measure the cyclic ether compound (h3) and the photoionic polymerization initiator (E-10) or the photoionic polymerization initiator (E-11), and other additives (k), and mix them at 25°C for 30 minutes to prepare a photoionic polymerization-based active energy ray-curable composition (hereinafter also referred to as an ionic curable composition). Evaluate the miscibility of the obtained ionic curable composition, the curability with respect to light of different wavelengths, the light yellowing resistance and durability of the obtained cured product by the following methods, and show the evaluation results in Table 5. The higher the curability of the curable composition, the higher the photosensitivity of D.

[0425] [Miscibility]

[0426] Evaluate the miscibility of the photoionic polymerization-based active energy ray-curable composition in accordance with the same method and evaluation criteria as those for evaluating the miscibility of the above-mentioned free radical polymerization-based curable composition.

[0427] [Curability]

[0428] Similar to the evaluation of the curability of the above-mentioned free radical polymerization-based curable composition, prepare a coating film with a film thickness of 20 μm on a PET film, and irradiate active energy rays under the following conditions using various light sources of 4) to 6) below. Then, leave it standing in a constant temperature machine at 70°C for 1 hour to obtain a film-shaped cured product. Calculate the cumulative light amount at which the stickiness disappears when touching the surface of the obtained cured product, and evaluate the curability according to the following criteria. The lower the cumulative light amount required until the stickiness disappears, the higher the curability.

[0429] 4) High-pressure mercury lamp: wavelength 200 nm to 450 nm, illuminance 500 mW / cm 2 .

[0430] 5) UV-LED lamp: wavelength 385 nm, illuminance 500 mW / cm 2 .

[0431] 6) UV-LED lamp: wavelength 405 nm, illuminance 500 mW / cm 2 .

[0432] ++: The stickiness disappears when the cumulative light amount does not reach 5,000 mJ / cm 2

[0433] +: The stickiness disappears when the cumulative light amount is irradiated to 10,000 mJ / cm 2

[0434] ±: The stickiness disappears when the cumulative light amount is irradiated to 50,000 mJ / cm 2

[0435] -: Even when the cumulative light quantity irradiated is 50,000 mJ / cm 2 And the viscosity remains.

[0436] [Lightfast yellowing resistance]

[0437] Except for changing the curing conditions to the following, a photoionization-based cured product is produced in the same manner as the curing property evaluation of the above photoionization polymerization-based curable composition. The lightfast yellowing resistance of the obtained cured product is evaluated in the same manner as the lightfast yellowing resistance evaluation of the above photoradical polymerization-based cured product.

[0438] Curing conditions: UV-LED lamp: Irradiation is carried out under the conditions of a wavelength of 405 nm, an illuminance of 1,000 mW / cm 2 and a cumulative light quantity of 100,000 mJ / cm 2 , and then left standing at 70 °C for 1 hour.

[0439] [Durability]

[0440] Except for changing the curing conditions to irradiate a cumulative light quantity of 50,000 mJ / cm 2 otherwise, a cured product is produced in the same manner as the above photoionization polymerization-based curable composition. The durability of the obtained cured product is evaluated in the same manner as the lightfast yellowing resistance evaluation of the above photoionization polymerization-based curable composition.

[0441] [Table 5]

[0442]

[0443] (*3) A cured product was not obtained, and the evaluation was not carried out.

[0444] Examples 144 to 151 and Comparative Examples 16 to 18 (Preparation of a photo-mixed polymerization-based active energy ray curable composition and evaluation of a photosensitizer)

[0445] Using the benzoylmethanamide derivative (D) synthesized in the examples and the commercially available photosensitizers (I-3), photosensitizer (I-5), and commercially available photoinitiator (E-5) as comparative examples, the unsaturated compound (h1), unsaturated compound (h2), cyclic ether compound (h3), and photoionization polymerization initiator (E-10) or photoionization polymerization initiator (E-11), other additives (k) are metered according to the ratios shown in Table 6, and a photo-mixed polymerization-based active energy ray curable composition and a cured product are obtained by the same method as the evaluation of the photosensitizer of the above photoionization polymerization system. By the same method as the evaluation of the photosensitizer of the above photoionization polymerization system, the miscibility and curability of the curable composition, the lightfast yellowing resistance and durability of the cured product are evaluated, and the results are shown in Table 6. The higher the curability of the curable composition, the higher the photosensitivity of D.

[0446] [Table 6]

[0447]

[0448] (*3) No cured product was obtained and evaluation was not carried out.

[0449] It can be clearly seen from the results of Table 4-1, Table 4-2, Table 5, and Table 6 that the curable compositions of each example using benzoylamine derivative (D) as a photosensitizer show good miscibility. D shows photosensitivity to continuous light of a wide range of wavelengths of a high-pressure mercury lamp and to light of wavelengths 385 nm and 405 nm of a UV-LED lamp, and the curable composition containing D shows high curability. It was confirmed that D has high photosensitivity even when used in combination with any one or more of general photo radical polymerization initiators, general photoionic photo polymerization initiators, or photo radical polymerization initiator D. The photo radical-based, photoionic-based, and photo hybrid-based curable compositions all have high curability, and curable products with good light fast yellowing resistance and durability can be obtained. In addition, 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 have a very high photosensitizing effect on light of wavelengths 385 nm and 405 nm, and it was clarified that by containing an electron-donating methoxy group, the absorption wavelength of D shifts to the long wavelength side. D-55 to D-58 (Examples 140 to 143) having a cyclic epoxy group show photosensitivity to a photoionic polymerization initiator, and at the same time are incorporated into the cured product by photoionic polymerization, and the curable composition has high curability, and a curable product with high durability can be obtained. In Examples 144, 145, and 147 to 151, a photo hybrid polymerization system of photoionic polymerization initiation and photo radical polymerization and photoionic polymerization of D was used in combination. In these examples, the curable composition also has high curability, and the obtained curable product has good light fast yellowing resistance and durability. That is, it was confirmed that D has an effect both as a photo radical polymerization initiator and as a photosensitizer for photoionic polymerization. On the other hand, in Comparative Examples 4 to 8, Comparative Example 11, and Comparative Example 16 where no photosensitizer was used, 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 isopropyl thioxanthone (I-3) and 2-ethyl anthraquinone (I-4) as photosensitizers, the curable composition has good curability, but the obtained curable product has low light fast yellowing resistance and durability. In the ionic and hybrid comparative examples, the same results as those of the radical system were also confirmed. In Comparative Examples 15 and 18 using high molecular weight thioxanthone (I-5), the photosensitivity is lower than that in the case of using low molecular weight I-3, the curability of the curable composition is lower, the obtained curable product shows yellowing, and the durability of the curable product is lower.

[0450] Examples 152 to 161 and Comparative Examples 19 to 21 (Active Energy Ray-Curable Ink Composition and Its Evaluation)

[0451] According to the ratios (in terms of solid components) described in Table 7, measure the benzoylamide 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), and mix them at 25 °C for 30 minutes to obtain an active energy ray-curable ink composition (hereinafter also referred to as the ink composition). Evaluate the viscosity and curability of the ink composition by the following methods. In addition, perform inkjet printing using the ink composition, and evaluate the ink ejection stability, adhesion resistance of the printed matter, clarity, and bleeding resistance as printing suitability by the following methods. Furthermore, use the ink composition to prepare a cured product for evaluating the low molecular weight component content rate, and evaluate the low molecular weight component content rate in the cured product of the ink composition by the same method as the evaluation of the low molecular weight component content rate in the cured product of the above curable composition. Show these evaluation results in Table 7.

[0452] [Viscosity]

[0453] According to ISO 2884-1, measure the viscosity of the ink composition using a cone-plate viscometer (manufactured by Toki Sangyo Co., Ltd., RE550 type viscometer). Evaluate the viscosity of the ink composition for inkjet printing in the following four grades.

[0454] ++: Viscosity is 5 mPa·s or more and less than 50 mPa·s.

[0455] +: Viscosity is 50 mPa·s or more and less than 100 mPa·s.

[0456] ±: Viscosity is 100 mPa·s or more and less than 200 mPa·s.

[0457] -: Viscosity is 200 mPa·s or more.

[0458] [Method for Producing Printed Matter by Ultraviolet Irradiation]

[0459] Using a bar coater, form a coating film with a thickness of 20 μm of the ink composition on a PET film, and cure it by ultraviolet irradiation (UV-LED lamp: wavelength 395 nm, illuminance 1,000 mW / cm 2 ) to produce a printed matter.

[0460] [Curability]

[0461] When producing a printed matter, the cumulative light amount until the ink composition is completely cured (non-sticky state) is measured, and the curability of the ink composition is evaluated according to the following criteria.

[0462] ++: The cumulative light amount is less than 1,000 mJ / cm 2 and it is completely cured at this time.

[0463] +: The cumulative light amount is 1,000 mJ / cm or more and less than 2,000 mJ / cm 2 and it is completely cured at this time. 2

[0464] ±: The cumulative light amount is 2,000 mJ / cm or more and less than 5,000 mJ / cm 2 and it is completely cured at this time. 2

[0465] -: The cumulative light amount required until complete curing is 5,000 mJ / cm 2 or more.

[0466] [Printing suitability]

[0467] The obtained ink composition is filled into an inkjet printer (manufactured by Fujifilm Corporation, LuxelJetUV350GTW), and coated paper is used to print a solid image, and the ejection stability of the ink as printing suitability is evaluated.

[0468] [Ejection stability]

[0469] The printing state of the printed matter is visually observed, and the ejection stability is evaluated according to the following criteria.

[0470] ++: Printing is good without ink leakage.

[0471] +: There is slightly ink leakage.

[0472] -: There is extensive ink leakage.

[0473] [Anti-blocking property]

[0474] The printed matter is left standing for 5 minutes in an environment of room temperature 23°C and relative humidity 50%, and offset paper is overlapped on the printing surface, and a load of 1 kg / cm 2 is applied for 1 minute, and the degree of ink transfer to the paper is visually observed, and the anti-blocking property is evaluated according to the following criteria.

[0475] ++: The ink is dry and there is no ink transfer to the paper at all.

[0476] +: The ink is dry and there is slightly ink transfer to the paper.

[0477] ±: The ink is substantially dry and there is ink transfer to the paper. ​​

[0478] -: The ink is hardly dried and there is much transfer to the paper.

[0479] [Clarity]

[0480] Visually observe the image clarity of the printed matter obtained from the ink composition formulated with pigments, and evaluate the clarity according to the following criteria.

[0481] ++: No ink bleeding is seen at all and the image is clear.

[0482] +: There is almost no ink bleeding and the image is good.

[0483] -: Ink bleeding is visible.

[0484] [Bleeding resistance]

[0485] Leave 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 bleeding resistance according to the following criteria.

[0486] ++: No bleeding is confirmed at all.

[0487] +: Slight bleeding is confirmed.

[0488] -: Severe bleeding is confirmed.

[0489] It can be clearly seen from the results in Table 7 that the ink compositions of the examples have high curability, there are no low molecular weight components in the obtained cured films (printed matters), the cured films have good drying properties, little bleeding, and high-durability printed matters can be produced. On the other hand, the ink composition of Comparative Example 19 has low curability. In Comparative Examples 20 and 21, although curing can be achieved, there are many low molecular weight components in the printed matters, and the cured films have poor anti-tackiness, bleeding resistance, and the clarity of the printed matters is poor. In addition, in Comparative Example 20 using Esacure KIP 150 (E-1), the ejection stability of the ink is low and the printing suitability is low. In addition, in the examples formulated with pigments, clear printed matters can be obtained. It is considered that this is because the pigments are uniformly dispersed or dissolved in the ink compositions of the examples. Furthermore, the ink compositions of the examples have low viscosities, high ejection stabilities, and are suitable for inkjet printing.

[0490] [Table 7]

[0491]

[0492] (*4) Does not contain pigments or dyes and evaluation was not performed.

[0493] Examples 162 to 170 and Comparative Examples 22 and 23 (Preparation and evaluation of an active energy ray curable adhesive composition)

[0494] According to the ratios (in terms of solid component conversion) described in Table 8, benzoylformamide derivative (D), curable composition (F) containing D, commercially available photoinitiator (E), monofunctional unsaturated compound (h1), polyfunctional unsaturated compound (h2), and other components (k) were metered 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). Using the adhesive composition, an adhesive sheet having an adhesive layer was produced by the following method, and the curability and adhesiveness (adhesive strength) to various substrates of the adhesive composition were evaluated. The low molecular weight component content, transparency, exudation resistance, secondary processability, and light yellowing resistance of the obtained adhesive layer (cured product of the adhesive composition) were evaluated by the same method as the evaluation of the above curable composition. These evaluation results are shown in Table 8.

[0495] [Curability]

[0496] A heavy release film was closely attached to a horizontally placed glass plate, and a spacer with a thickness of 1 mm and an inner size of 60 mm × 100 mm was set. The prepared adhesive compositions of the examples and comparative examples were filled inside the spacer. A light release film was overlapped on the filled composition, and irradiated with a UV-LED lamp having a wavelength of 405 nm and an illuminance of 100 mW / cm 2 such that the cumulative light amount became 1,000 mJ / cm 2 to cure the adhesive composition. Then, the light release film was peeled off to obtain an adhesive sheet composed of the cured product (adhesive layer) of the adhesive composition and the heavy release film. The curability of the adhesive composition was evaluated by touching the adhesive layer and according to the following criteria.

[0497] ++: A cured product maintaining its shape was obtained, and there was no liquid attachment at all.

[0498] +: A cured product maintaining its shape was obtained, and there was a slight liquid attachment.

[0499] ±: A cured product maintaining its shape was obtained, and there was liquid attachment.

[0500] -: Curing was insufficient, and a cured product maintaining its shape could not be obtained.

[0501] [Low molecular weight component content]

[0502] The low molecular weight component content of the obtained adhesive 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.

[0503] [Transparency]

[0504] Under the 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 a haze meter (manufactured by Nippon Denshoku Industries Co., Ltd., NDH-8000) was used to measure the total light transmittance of the glass substrate and the adhesive layer according to ISO 14782. Then, the transmittance of the glass substrate was measured in the same way, and the transmittance of the adhesive layer itself was calculated by subtracting the transmittance of the glass substrate 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.

[0505] ++: The transmittance is 90% or more.

[0506] +: The transmittance is 85% or more but less than 90%.

[0507] ±: The transmittance is 50% or more but less than 85%.

[0508] -: The transmittance is less than 50%.

[0509] [Exudation resistance]

[0510] The obtained adhesive sheet was left standing in a thermo-hygrostat at a temperature of 40°C and a relative humidity of 50% for 168 hours. Then, it was placed in an environment of a temperature of 23°C and a relative humidity of 50% for 30 minutes, and the exudation resistance of the adhesive layer was evaluated by touching the adhesive layer on the surface of the adhesive sheet according to the following criteria.

[0511] ++: There is no liquid attachment at all, and exudation is not confirmed at all.

[0512] +: There is a very slight liquid attachment, and exudation is very slightly confirmed.

[0513] ±: There is a slight liquid attachment, and exudation is slightly confirmed.

[0514] -: There is a liquid attachment, and exudation is confirmed.

[0515] [Adhesive force]

[0516] Under the environment of a temperature of 23°C and a relative humidity of 50%, the adhesive layer was transferred from the obtained adhesive sheet to the film or plate of the following base material, and a pressing roller with a weight of 2 Kg was used to make two round trips for pressure adhesion, and then it was left standing in the same environment for 30 minutes. Then, a tensile testing machine (manufactured by ORIENTEC Co., Ltd., Tensilon RTA-100, hereinafter also referred to as a universal testing machine) was used to measure the 180° peel strength (N / 25 mm) (peel speed: 300 mm / minute) according to ISO 29862, and the adhesive force was evaluated according to the following criteria.

[0517] PET2: Polyethylene terephthalate film (COSM0SHINE A4160, corona-treated, manufactured by Toyobo Co., Ltd.)

[0518] PC (polycarbonate): Polycarbonate (sheet) (PC1600, manufactured by CITAKIR0N Co., Ltd.)

[0519] GL (glass): Glass (sheet) (EAGLE XG, manufactured by Corning Inc.)

[0520] ++: The peel strength is 20 (N / 25mm) or more.

[0521] +: The peel strength is 10 (N / 25mm) or more and less than 20 (N / 25mm).

[0522] ±: The peel strength is 5 (N / 25mm) or more and less than 10 (N / 25mm).

[0523] -: The peel strength is less than 5 (N / 25mm).

[0524] [Secondary processability]

[0525] Similar to the evaluation of the adhesive strength, transfer the adhesive layer to a film or sheet of a different substrate, perform pressure adhesion, and leave it standing in a constant temperature bath at 80°C for 24 hours. Then, place it in an environment with a temperature of 23°C and a relative humidity of 50% for 30 minutes, peel off the adhesive layer, visually observe the remaining state of the adhesive layer (paste) on the substrate surface, and evaluate the secondary processability of the adhesive layer according to the following criteria.

[0526] ++: No paste residue.

[0527] +: There is a very slight paste residue.

[0528] ±: There is a slight paste residue.

[0529] -: There is paste residue.

[0530] [Durability]

[0531] Transfer the adhesive layer of the adhesive sheet to a glass substrate, and leave it standing in a thermo-hygrostat with a temperature of 85°C and a relative humidity of 85% for 100 hours. Then, place it in an environment with a temperature of 23°C and a relative humidity of 50% for 30 minutes, visually observe the state of the adhesive layer, and evaluate the durability according to the following criteria.

[0532] ++: The adhesive layer is transparent and there are no bulges or bubbles.

[0533] +: The adhesive layer is slightly blurred, but there are no bulges or bubbles.

[0534] -: The adhesive layer is blurred or there are bulges or bubbles.

[0535] [Table 8]

[0536]

[0537] As is clearly seen from the results in Table 8, the adhesive composition of the example has high curability, and the adhesive layer obtained by curing the adhesive composition has high transparency and high adhesiveness (adhesive strength) to various substrates. In addition, the content of low molecular weight components in the cured product (adhesive layer) obtained in the example is low, and the exudation resistance, durability, and light yellowing resistance are high. Also, the secondary processability when peeling the cured product from the substrate is good. On the other hand, the curability of the adhesive composition of the comparative example is low, the content of low molecular weight components in the obtained cured product is high, the adhesive strength of the adhesive layer is low, and the exudation resistance, durability, light yellowing resistance, and secondary processability are all low.

[0538] Examples 171 to 177 and Comparative Examples 24 and 25 (Preparation and Evaluation of Actinic Energy Ray Curable Adhesive Composition)

[0539] According to the ratios (in terms of solid components) described in Table 9, benzoylformamide derivative (D), curable composition (F) containing D, commercially available photoinitiator (E), monofunctional unsaturated compound (h1), polyfunctional unsaturated compound (h2), and other components (k) were measured and mixed at 25°C for 30 minutes to prepare an actinic energy ray curable adhesive composition (hereinafter also referred to as the adhesive composition). The curability of the adhesive composition and the content of low molecular weight components in the obtained cured product were evaluated. In addition, various substrates were adhered using the adhesive composition to produce a laminate, and the adhesive strength and durability of the laminate were evaluated. These evaluation results are shown in Table 9.

[0540] [Curability]

[0541] A PET film was closely attached to a horizontally placed 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 overlapped. 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, and the presence or absence of stickiness on the surface of the cured film was confirmed. Based on the cumulative light amount required until the stickiness disappeared, the curability of the adhesive composition was evaluated according to the following criteria.

[0542] ++: The stickiness disappeared when the cumulative light amount was less than 500 mJ / cm 2 .

[0543] +: The stickiness disappeared when the cumulative light amount was 500 mJ / cm 2 or more and less than 1,000 mJ / cm 2 .

[0544] ±: The cumulative light amount is 1,000 mJ / cm 2 or more and less than 5,000 mJ / cm 2 and the viscosity disappears.

[0545] -: Even when the cumulative light amount is 5,000 mJ / cm 2 the viscosity remains.

[0546] [Laminated body production]

[0547] Apply the adhesive composition to various film-like or plate-like base materials (substrates) shown below, and use a tabletop roll laminator (RSL-382S) to laminate with a PET film in such a way that no bubbles are trapped and the adhesive layer has a thickness of 20 μm, and irradiate with ultraviolet light (wavelength 405 nm, illuminance 50 mW / cm 2 using a UV-LED lamp with a cumulative light amount of: 2,000 mJ / cm 2 ) to produce a laminated body.

[0548] Base material (substrate)

[0549] PET3: Polyethylene terephthalate film (COSMOSHINE E5100, corona-treated, manufactured by Toyobo Co., Ltd.)

[0550] polymethyl methacrylate): Polymethyl methacrylate (plate) (Comoglas P, manufactured by Kuraray Co., Ltd.)

[0551] PC: Polycarbonate (plate) (PC1600, manufactured by CI TAKIR0N Co., Ltd.)

[0552] [Adhesive strength]

[0553] Use a universal testing machine to measure the 180° peel strength (N / 25 mm) of the laminated body according to IS029862 (peel speed 300 mm / minute), and evaluate the adhesive strength based on the following criteria.

[0554] ++: The peel strength is 20 (N / 25 mm) or more.

[0555] +: The peel strength is 10 (N / 25 mm) or more and less than 20 (N / 25 mm).

[0556] ±: The peel strength is 5 (N / 25 mm) or more and less than 10 (N / 25 mm).

[0557] -: The peel strength is less than 5 (N / 25 mm).

[0558] [Durability]

[0559] Similar to the evaluation of the curability of the adhesive composition, a cured product (adhesive layer) was formed on a glass substrate (cumulative light quantity: 2,000 mJ / cm 2 ), and it was left standing in a thermo-hygrostat at a temperature of 85°C and a relative humidity of 85% for 100 hours. Then, it was placed in an environment at a temperature of 23°C and a relative humidity of 50% for 30 minutes, and the state of the laminate was visually observed, and the durability was evaluated according to the following criteria.

[0560] ++: The laminate is transparent and there is no peeling or bubbles.

[0561] +: The laminate has a very slight haze, but there is no peeling or bubbles.

[0562] ±: The laminate has a slight haze or peeling or bubbles.

[0563] -: The laminate has a very severe haze or peeling or bubbles.

[0564] [Low molecular weight component content rate]

[0565] Similar to the evaluation of the curability of the adhesive composition, a cured product (adhesive layer) was formed on a PET film (UV-LED with a wavelength of 405 nm and an illuminance of 50 mW / cm 2 , cumulative light quantity: 2,000 mJ / cm 2 ). The obtained PET film with an adhesive layer was cut into test pieces with a size of 5 cm 2 , and the low molecular weight component content rate in the adhesive layer was evaluated in the same manner as the evaluation of the low molecular weight component content rate in the cured product of the above curable composition.

[0566] [Table 9]

[0567]

[0568] It can be clearly seen from the results in Table 9 that the adhesive compositions of the examples have high curability, and the laminates (adherends) obtained by curing these adhesive compositions have high adhesive strength to the same and different substrates. In addition, the content rate of the low molecular weight components in the cured product (adhesive layer) is low, and the durability of the laminate is good. Such adhesive compositions exhibit characteristics suitable as adhesives. On the other hand, the adhesive compositions of the comparative examples have low curability, a large amount of low molecular weight components remain in the adhesive layer, and both the adhesive strength and durability of the adherends are low.

[0569] Examples 178 to 184 and Comparative Examples 26 and 27 (Preparation and Evaluation of Actinic Energy Ray Curable Sealant Compositions)

[0570] According to the ratios described in Table 10 (in terms of solid component conversion), benzoylformamide derivative (D), a commercially available photoinitiator (E), monofunctional unsaturated compound (h1), polyfunctional unsaturated compound (h2), and other components (k) were metered and mixed at 25°C for 30 minutes to prepare an active energy ray-curable sealant composition (hereinafter also referred to as the sealant composition). A cured product of the sealant composition was made, and the curability of the sealant composition, the transparency of the obtained cured product, the resistance to humidity and heat yellowing, water resistance, outgassing resistance, heat cycle resistance, and corrosion resistance were evaluated. In addition, the content rate of low molecular weight components in the cured product of the sealant composition was evaluated in the same manner as the cured product of the above curable composition. These evaluation results are shown in Table 10.

[0571] [Production of Cured Product of Sealant Composition]

[0572] A spacer (30 mm × 15 mm × 3 mm) was placed 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 (UV-LED lamp with a wavelength of 405 nm and an illuminance of 500 mW / cm 2 , cumulative light amount: 1,000 mJ / cm 2 ) were irradiated to obtain a cured product of the sealant composition.

[0573] [Curability]

[0574] The cured product was evaluated according to the following criteria to evaluate the curability.

[0575] ++: A cured product that maintains its shape is obtained, and there is no stickiness when touching the cured product.

[0576] +: A cured product that maintains its shape is obtained, and there is stickiness when touching the cured product.

[0577] ±: A cured product that maintains its shape is obtained, but there is a liquid attachment when touching the cured product.

[0578] -: Curing is insufficient, and a cured product that maintains its shape is not obtained.

[0579] [Transparency]

[0580] After leaving the cured product to stand for 24 hours in an environment at a temperature of 23°C and a relative humidity of 50%, the transmittance of the cured product was measured with the same haze meter as above, and the transparency was evaluated according to the following criteria.

[0581] ++: The transmittance is 90% or more.

[0582] +: The transmittance is 85% or more and less than 90%.

[0583] ±: Transmittance is 50% or more but less than 85%.

[0584] -: Transmittance is less than 50%.

[0585] [Moisture and Heat Resistance and Yellowing Resistance]

[0586] In an environment with a temperature of 23°C and a relative humidity of 50%, after leaving the cured product standing for 24 hours, measure the transmission spectrum of the cured product using a dedicated transmission color measuring machine (manufactured by Nippon Denshoku Industries Co., Ltd., TZ-6000), and set it as the initial b value. Then, leave the cured product standing 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 moisture and heat resistance and yellowing resistance. Leave the cured product after the test standing in an environment with a temperature of 23°C and a relative humidity of 50% for 24 hours, conduct a transmission color measurement, and set it as the b value after moisture and heat treatment. The difference between the b value after moisture and heat treatment and the initial b value is set as the change value Δb (Δb = b value after moisture and heat treatment - initial b value). Evaluate the moisture and heat resistance and yellowing resistance of the cured product according to the following criteria.

[0587] ++: Both the initial b value and the b value after moisture and heat treatment are 0.2 or less, and Δb is 0.1 or less.

[0588] +: Any one of the initial b value and the b value after moisture and heat treatment exceeds 0.2, but both are 0.5 or less, and Δb is 0.2 or less.

[0589] ±: Any one of the initial b value and the b value after moisture and heat treatment exceeds 0.5, but both are 1.0 or less, and Δb is 0.3 or less.

[0590] -: Any one of the initial b value and the b value after moisture and heat treatment exceeds 1.0, or Δb exceeds 0.3.

[0591] [Water Resistance]

[0592] Cut 1 g from the cured product and use it as a test piece. Leave it standing in a thermo-hygrostat at a temperature of 85°C and a relative humidity of 95%. After leaving it standing for 48 hours, measure the weight of the test piece again. Calculate the water absorption rate using the following formula and evaluate the water resistance according to the following criteria. The lower the water absorption rate, the higher the water resistance of the cured product.

[0593] Water absorption rate (%) = (weight after water absorption - weight before water absorption) / weight before water absorption × 100%

[0594] ++: Water absorption rate is less than 1.0%.

[0595] +: Water absorption rate is 1.0% or more but less than 2.0%.

[0596] ±: Water absorption rate is 2.0% or more but less than 3.0%.

[0597] -: Water absorption rate is 3.0% or more.

[0598] [Gas release resistance]

[0599] Cut 1 g from the self-cured product and leave it statically as a test piece in a constant temperature bath set at 100 °C. Pass a dry nitrogen gas stream through it for 24 hours, and then measure the weight of the test piece again. Calculate the gas release rate using the following formula and evaluate the gas release resistance according to the following criteria. The lower the gas release rate, the higher the gas release resistance.

[0600] Gas release rate (%) = (Weight after test - Weight before test) / Weight before test × 100%

[0601] ++: The gas release rate is less than 0.1%.

[0602] +: The gas release rate is 0.1% or more and less than 0.2%.

[0603] ±: The gas release rate is 0.2% or more and less than 0.3%.

[0604] -: The gas release rate is 0.3% or more.

[0605] [Heat resistance to cyclic change]

[0606] After leaving it at -40 °C for 30 minutes and then at 100 °C for 30 minutes, set the above treatment as 1 heat cycle, and repeat the treatment of the cured product for 100 cycles. Then, visually observe the cured product and evaluate the heat resistance to cyclic change according to the following criteria.

[0607] ++: No change is observed at all.

[0608] +: Generation of bubbles is slightly visible, but generation of blurring and cracking is not observed.

[0609] ±: Generation of a little bubbles or cracking is visible, and it is slightly blurred.

[0610] -: Bubbles or cracking are generated on the entire surface, and it is in a semi-transparent state.

[0611] [Corrosion resistance]

[0612] After the above-mentioned damp heat yellowing resistance test, visually observe the surface of the copper foil and evaluate the corrosion resistance of the cured product according to the following criteria. The lower the corrosion of the copper foil, the lower the metal corrosion of the cured product and the higher the corrosion resistance of the cured product.

[0613] ++: Corrosion of the copper foil in the cured product is present.

[0614] +: Corrosion of the copper foil in the cured product is slightly present.

[0615] ±: Corrosion of the copper foil in the cured product is slightly present.

[0616] -: Significant corrosion of the copper foil in the cured product is present.

[0617] [Table 10]

[0618]

[0619] It can be clearly seen from the results in Table 10 that the sealant composition of the example has high curability, the content of low-molecular-weight components in the obtained cured product (sealant) is low, the cured product has high transparency, heat and humidity resistance to yellowing, and water resistance, and there is little generation of outgassing. In addition, the heat cycle resistance and corrosion resistance are good. On the other hand, the curability of the sealant composition of the comparative example is low, there is a lot of residual low-molecular-weight components in the sealant, and the sealant cannot meet any two or more physical properties among transparency, heat and humidity resistance to yellowing, water resistance, outgassing resistance, heat cycle resistance and corrosion resistance.

[0620] Examples 185 to 192 and Comparative Examples 28 and 29 (Preparation and Evaluation of Actinic Energy Ray Curable Coating Agent Composition)

[0621] According to the ratios (in terms of solid component conversion) described in Table 11, the 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 actinic energy ray curable coating agent composition (hereinafter also referred to as the coating agent composition). Using the coating agent composition, a coating was made by the following method, and the curability of the coating agent composition, the adhesion of the obtained coating, light yellowing resistance, bend resistance, chemical resistance, damage resistance, durability, and the content of low-molecular-weight components were evaluated, and the results are shown in Table 11.

[0622] [Curability]

[0623] The curability of the coating agent composition was evaluated according to the same method and evaluation criteria as the above adhesive composition.

[0624] [Coating Production]

[0625] A PET film was closely attached 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 using a bar coater, and under a nitrogen atmosphere, ultraviolet irradiation with a wavelength of 385 nm UV-LED lamp and an illuminance of 500 mW / cm 2 , and a cumulative light amount of 2,000 mJ / cm 2 was performed to produce a coating on the PET film.

[0626] [Adhesion Evaluation]

[0627] According to the cross-cut method described in ISO 2409, slits are cut on the surface of the coating using a cutting knife to make 100 squares of 1 mm × 1 mm, which are designated as test pieces. After attaching a commercially available transparent tape to the test pieces and then peeling it off, the number of squares remaining on the test pieces is counted, and the adhesion is evaluated according to the following criteria.

[0628] ++: 100 squares remain.

[0629] +: 90 or more and 99 or less squares remain.

[0630] -: The number of remaining squares is 89 or less.

[0631] [Lightfast yellowing resistance]

[0632] Similarly to the evaluation of the lightfast yellowing resistance of the cured product of the above curable composition, using a UV-LED (wavelength 405 nm, illuminance 100 mW / cm 2 , cumulative light quantity 20,000 mJ / cm 2 ), ultraviolet rays are irradiated onto the coating to evaluate the lightfast yellowing resistance of the coating.

[0633] [Flexural resistance]

[0634] According to the cylindrical mandrel method described in IS0 1519, with the coating on the outside, it is bent while one side is in contact with a mandrel (10 mm φ). Then, the coating is visually observed, and the flexural resistance is evaluated according to the following criteria.

[0635] ++: There is no whitening or cracking at the bent part.

[0636] +: A part of the bent part turns white.

[0637] ±: A part of the bent part cracks.

[0638] -: The bent part cracks.

[0639] [Chemical resistance]

[0640] Using the prepared coating, oleic acid is coated on the surface of the coating to be about 1 cm in diameter. After maintaining it at 23 °C for 1 hour, it is rinsed with a neutral detergent, and the surface state is visually observed to evaluate the chemical resistance according to the following criteria.

[0641] ++: No trace of oleic acid is seen at all.

[0642] +: A very thin whitening trace is slightly visible in the part coated with oleic acid.

[0643] ±: The part coated with oleic acid turns white, and swelling is visible on the surface.

[0644] -: The part coated with oleic acid is sticky and surface peeling can be seen.

[0645] [Damage resistance]

[0646] Under the environment of room temperature 23°C and humidity 50%, use steel wool (#0000, load 100 g) to grind back and forth 10 times on the surface of the coating, visually observe the coating surface, and evaluate the damage resistance according to the following criteria.

[0647] ++: No damage to the coating is confirmed.

[0648] +: Slightly fine damage is confirmed in a part of the coating.

[0649] ±: Strip-shaped damage is confirmed on the whole coating.

[0650] -: Peeling of the coating is confirmed.

[0651] [Durability]

[0652] Evaluate the durability of the coating by the same method as the durability evaluation of the cured product of the above adhesive composition.

[0653] [Low molecular weight component content]

[0654] Except that the light source is a UV-LED lamp with a wavelength of 385 nm and an illuminance of 1,000 mW / cm 2 and the cumulative light amount is set to 10,000 mJ / cm 2 Evaluate the low molecular weight component content of the coating by the same method as the evaluation of the low molecular weight component content in the cured product of the above curable composition.

[0655] [Table 11]

[0656]

[0657] It can be clearly seen from the results in Table 11 that the coating agent compositions of the examples have high curability for long-wavelength light, and the obtained cured products (coatings) have good adhesion, light yellowing resistance, bending resistance, chemical resistance and durability. The characteristics of such coating agent compositions are suitable for vehicle applications, indoor and outdoor coating agents, and coating agents for decoration. On the other hand, the coating agent compositions of the comparative examples have low curability for long-wavelength light, a large amount of low molecular weight components remain in the obtained coatings, and various physical properties of the coatings are low.

[0658] Examples 193 to 202 and Comparative Examples 30 and 31 (Preparation and Evaluation of Ink Composition for Stereolithography with Actinic Energy Ray Curing)

[0659] Based on the ratios described in Table 12 (in terms of solid content conversion), measure benzoylformamide derivative (D), curable composition (F) containing D, commercially available photoinitiator (E), monofunctional unsaturated compound (h1), and polyfunctional unsaturated compound (h2), and mix them at 25°C for 30 minutes to prepare an active energy ray curable three-dimensional shaping ink composition (hereinafter also referred to as three-dimensional shaping ink composition). Evaluate the viscosity and curability of the three-dimensional shaping ink composition. Fabricate a three-dimensional shaped object by the following shaping method, and evaluate the resistance to curing shrinkage and the content rate of low molecular weight components in the shaped object. Evaluate the strength, heat resistance, shaping accuracy, light yellowing resistance, and bleeding resistance of the obtained shaped object. Show these evaluation results in Table 12.

[0660] [Viscosity]

[0661] According to ISO 2884-1, measure the viscosity of the three-dimensional shaping ink composition using a cone plate viscometer (RE550 viscometer) and evaluate it according to the following criteria.

[0662] ++: Viscosity is 5 mPa·s or more and less than 500 mPa·s.

[0663] +: Viscosity is 500 mPa·s or more and less than 2,000 mPa·s.

[0664] -: Viscosity is 2,000 mPa·s or more.

[0665] [Curability]

[0666] Except that the light source is a UV-LED lamp with a wavelength of 405 nm and an illuminance of 5 mW / cm 2 , evaluate the curability of the three-dimensional shaping ink composition by the same method as the above curable composition.

[0667] [Fabrication of Shaped Object]

[0668] Attach a heavy release film closely to a horizontally placed glass plate, and set a spacer with an internal size of 6 mm × 60 mm × 60 mm on the heavy release film. Fill the spacer with the three-dimensional shaping ink composition of each example and comparative example in such a way as to form a layer with a thickness of 0.3 mm. After standing in a constant temperature machine at 60°C for 1 minute, irradiate ultraviolet rays (wavelength 405 nm, illuminance 5 mW / cm 2 , cumulative light quantity 100 mJ / cm 2) and solidify it. Similarly, a three-dimensional modeling ink composition (thickness: 0.3 mm) is filled on the solidified film (the first layer) in the spacer and solidified. The same operation is repeated to obtain a total of 20 layers of solidified products (6 mm × 60 mm × 60 mm). The solidified products are irradiated with ultraviolet rays (wavelength: 405 nm, illuminance: 100 mW / cm 2 , cumulative light quantity: 2,000 mJ / cm 2 ) using a UV-LED lamp to obtain the shaped article after post-curing treatment.

[0669] [Low molecular weight component content]

[0670] A test piece with a thickness of 0.5 m is cut from the shaped article and weighed 0.5 g. The low molecular weight component content in the shaped article is evaluated by the same method as the evaluation of the low molecular weight component content of the solidified product of the above curable composition.

[0671] [Curing shrinkage resistance]

[0672] The density of the three-dimensional modeling ink composition is measured using a Gay-Lussac type specific gravity bottle according to ISO 758. The density of the shaped article is measured using an electronic densitometer (MDS-300 manufactured by Alfa Mirage Co., Ltd.) according to ISO 1183-1. The curing shrinkage rate is calculated from the density of the three-dimensional modeling ink composition and the density of the shaped article by the following formula, and the curing shrinkage resistance of the three-dimensional modeling ink composition is evaluated according to the following criteria. The lower the curing shrinkage rate, the higher the curing shrinkage resistance.

[0673] Curing shrinkage rate (%) = (Ds - Dl) / D1 × 100%

[0674] (In the formula, Ds is the density of the shaped article, and D1 is the density of the three-dimensional modeling ink composition.)

[0675] ++: The curing shrinkage rate is less than 6%.

[0676] +: The curing shrinkage rate is 6% or more and less than 7%.

[0677] ±: The curing shrinkage rate is 7% or more and less than 8%.

[0678] -: The curing shrinkage rate is 8% or more.

[0679] [Strength]

[0680] According to ISO 48, the Shore D hardness of the shaped article is measured, and the strength of the three-dimensional shaped article is evaluated according to the following criteria.

[0681] ++: The Shore D hardness is 60 or more.

[0682] +: Shore D hardness is 40 or more and less than 60.

[0683] -: Shore D hardness is less than 40.

[0684] [Heat resistance]

[0685] The glass transition temperature (Tg) of the shaped article was measured by 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.

[0686] ++: Tg is 60 °C or more.

[0687] +: Tg is 40 °C or more and less than 60 °C.

[0688] -: Tg is less than 40 °C.

[0689] [Shaping accuracy]

[0690] The side surface of the shaped article was visually observed, and in addition, the height of the shaped article was measured. Combining these results, the shaping accuracy was evaluated according to the following criteria.

[0691] ++: The height is 6 mm ± less than 0.1 mm, and there are no irregularities on the side surface.

[0692] +: The height is 6 mm ± 0.1 mm or more and less than ±0.2 mm, or there are slight irregularities on the side surface.

[0693] ±: The height is 6 mm ± 0.2 mm or more and less than ±0.3 mm, or there are some irregularities on the side surface.

[0694] -: The height is 6 mm ± 0.3 mm or more, or there are obvious irregularities on the side surface.

[0695] [Lightfast yellowing resistance]

[0696] The shaped article was further irradiated with ultraviolet rays (UV-LED lamp, wavelength 405 nm, 100 mW / cm 2 , cumulative light amount 20,000 mJ / cm 2 ), and the lightfast yellowing resistance of the shaped article was evaluated in the same manner as the lightfast yellowing resistance of the cured product of the above curable composition.

[0697] [Exudation resistance]

[0698] After 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, the side surface of the shaped article was visually observed, and the exudation resistance of the shaped article was evaluated in the same manner as the exudation resistance of the cured film of the ink composition.

[0699] [Table 12]

[0700]

[0701] As is clearly shown in Table 12, the ink composition for three-dimensional shaping of the examples has high curability for long-wavelength light, low shrinkage during curing, and high shaping accuracy of the obtained shaped article. In addition, the strength and heat resistance of the shaped article obtained in the examples are both high, and the exudation resistance and light yellowing resistance are good. On the other hand, the ink composition for three-dimensional shaping of the comparative examples has low curability and low shaping accuracy of the obtained shaped article. The shaped article of the comparative example contains a large amount of low-molecular-weight components and fails to meet the strength, heat resistance, light yellowing resistance of the shaped article, and the exudation resistance is particularly low.

[0702] Examples 203 to 208 and Comparative Examples 32 and 33 (Preparation and Evaluation of Actinic Energy Ray-Curable Nail Cosmetic Composition)

[0703] According to the ratios (in terms of solid components) described in Table 13, benzoylformamide derivative (D), commercially available photoinitiator (E), monofunctional unsaturated compound (h1), polyfunctional unsaturated compound (h2), photosensitizer (I), and other components (k) were metered and mixed at 25 °C for 30 minutes to prepare an actinic energy ray-curable nail cosmetic composition (hereinafter also referred to as nail cosmetic composition). The curability, adhesion to nylon substrate, surface hardness, surface glossiness, light yellowing resistance, and low-molecular-weight component content in the cured film of the nail cosmetic composition were evaluated, and the results are shown in Table 13.

[0704] [Curability]

[0705] Using a separator, the nail cosmetic composition was coated on a test piece of nylon 6 (manufactured by Toray Plastic Seiko Co., Ltd., SHT-N6 (NC)) so that the film thickness became 100 μm. Ultraviolet irradiation was performed with a UV-LED lamp for nail art (manufactured by BEAUTY NAILER, wavelength 405 nm, output 48 W) to produce a cured film. The time when the stickiness 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 stickiness disappeared, the higher the curability.

[0706] ++: The stickiness disappeared in less than 1 minute.

[0707] +: The stickiness disappeared in more than 1 minute and less than 3 minutes.

[0708] ±: The stickiness disappeared in more than 3 minutes and less than 10 minutes.

[0709] -: The stickiness did not disappear even after more than 10 minutes.

[0710] [Adhesion]

[0711] Using the composition for nail cosmetics, it is coated on a nylon substrate in the same manner as in the evaluation of curability, and a curing film is produced by irradiating with a UV-LED lamp for nail art for 3 minutes. According to ISO 2409, the adhesion of the obtained curing film is evaluated in the same manner as the evaluation of the coating adhesion of the coating agent composition.

[0712] [Surface hardness]

[0713] A curing film is produced in the same manner as in the adhesion evaluation. A load of 750 g is pressed against the surface of the film at an angle of 45° using a pencil with a hardness of HB for scribing, and the change in the film surface is visually confirmed. The surface hardness is evaluated according to the following criteria. The less damage and peeling occur on the film surface, the higher the surface hardness.

[0714] + : No damage or peeling occurred.

[0715] ± : No peeling occurred, but damage occurred.

[0716] - : Peeling occurred.

[0717] [Surface glossiness]

[0718] A curing film is produced in the same manner as in 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 is visually observed, and the surface glossiness of the curing film is evaluated according to the following criteria.

[0719] + : Glossy.

[0720] ± : Reflection of light can be confirmed, but blurred areas are visible.

[0721] - : Reflection of light cannot be confirmed, no gloss.

[0722] [Low molecular weight component content]

[0723] A curing film is produced in the same manner as in the adhesion evaluation. Using a test piece of nylon 6 with the obtained curing film, the low molecular weight component content in the curing film is evaluated in the same manner as the evaluation of the low molecular weight component content of the cured product (adhesive layer) of the adhesive composition.

[0724] [Lightfast yellowing resistance]

[0725] A curing film is produced in the same manner as in the adhesion evaluation and placed in a xenon fade tester, and irradiated with ultraviolet rays with an intensity of 70 μW / cm 2 for 120 hours. Then, the discoloration of the curing film is visually observed, and the lightfast yellowing resistance is evaluated according to the following criteria.

[0726] ++ : No yellowing is confirmed at all.

[0727] +: Slight yellowing is confirmed.

[0728] ±: Yellowing is confirmed.

[0729] -: Obvious yellowing is confirmed.

[0730] [Table 13]

[0731]

[0732] It can be clearly seen from the results of Table 13 that the nail cosmetic composition of the examples has high curability for the UV lamp for light-cured nails, and the obtained cured film has high adhesion to a nylon substrate (a material having multiple amide bonds like nails whose main component is protein). It can be known that such a nail cosmetic composition can be suitably used as a light-cured nail for a base gel directly coated on nails. In addition, the content rate of low-molecular-weight components in the cured film is low, and safety can be ensured. The surface glossiness, surface hardness, and light yellowing resistance of the cured film are good, and it can be suitably used as a light-cured nail for a top coat. On the other hand, the curability of the nail cosmetic composition of the comparative examples is low, a large amount of low-molecular-weight components are contained in the obtained cured film, and the adhesion, surface hardness, surface glossiness, and light yellowing resistance of the cured film are low.

[0733] Examples 209 to 214 and Comparative Examples 34 to 36 (Preparation and Evaluation of Actinic Energy Ray-Curable Dental Material Compositions)

[0734] According to the ratios (in terms of solid components) described in Table 14, a benzoylformamide derivative (D), a commercially available photoinitiator (E), a monofunctional unsaturated compound (h1), a polyfunctional unsaturated compound (h2), and other components (k) are measured 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 are evaluated. The dental material composition is cured to obtain a cured product. The content rate of low-molecular-weight components, hardness, surface smoothness, and flexural strength in the cured product are evaluated, and the results are shown in Table 14.

[0735] [Solubility (Dispersibility)]

[0736] The state of the dental material composition is visually observed, and the solubility (dispersibility) is evaluated according to the following criteria.

[0737] +: The obtained composition is in a uniform state.

[0738] ±: A slightly non-uniform state can be seen in the obtained composition.

[0739] -: The obtained composition is in a non-uniform state.

[0740] [Storage Stability]

[0741] Add the dental material composition into a light-shielding helical tube, cover the lid, and store it under two conditions: 40 °C for 1 month and 80 °C for 2 weeks. Confirm the dissolution or dispersion state of the composition after storage, and evaluate the storage stability according to the following criteria.

[0742] +: There is no change in the state after storage under both conditions of 40 °C for 1 month and 80 °C for 2 weeks.

[0743] ±: A change in the state after storage is confirmed under either condition of 40 °C for 1 month or 80 °C for 2 weeks.

[0744] -: Changes in the state after storage are confirmed under both conditions of 40 °C for 1 month and 80 °C for 2 weeks.

[0745] [Curing Property]

[0746] Fill the dental material composition into a polytetrafluoroethylene mold (20 mm × 20 mm × 10 mm) with a 6-mm-diameter hole in the center, and crimp it with a polypropylene film. Irradiate it with ultraviolet light (wavelength 405 nm, illuminance 50 mW / cm 2 ) for 30 seconds, peel off the polypropylene film, and touch the cured body by hand. Evaluate the curing property according to the following criteria.

[0747] ++: Completely non-greasy.

[0748] +: Slightly greasy, but no fingerprint remains on the surface.

[0749] ±: Greasy, and fingerprint remains on the surface.

[0750] -: Seriously greasy, and the surface sticks to the fingers.

[0751] [Low-Molecular-Weight Component Content]

[0752] Use the cured product obtained in the curing property evaluation to evaluate the low-molecular-weight component content of the cured product of the dental material composition in the same way as the evaluation of the low-molecular-weight component content of the curable composition.

[0753] [Hardness]

[0754] Polish and grind the surface of the cured product obtained in the curing property evaluation, and measure the Knoop hardness with a microhardness tester (manufactured by Matsuzawa Seiki Co., Ltd., DMH-2) under the conditions of a temperature of 23 °C, a load of 100 gf, and a load application time of 20 seconds. Evaluate the hardness according to the following criteria.

[0755] ++: Knoop hardness is 200 KHN or more.

[0756] +: Knoop hardness is 70 KHN or more and less than 200 KHN.

[0757] -: Knoop hardness is less than 70 KHN.

[0758] [Surface smoothness]

[0759] Visually observe the surface of the cured product obtained in the curability evaluation, and evaluate the surface smoothness according to the following criteria.

[0760] ++: The surface is smooth and shiny.

[0761] +: The surface is generally smooth and slightly blurred or uneven can be seen.

[0762] ±: The surface is overall blurred, and a little unevenness or granular matter is confirmed.

[0763] -: The surface is overall blurred and covered with granular matter.

[0764] [Flexural strength]

[0765] Adhere the heavy release film closely to a horizontally placed glass plate, place a polytetrafluoroethylene spacer (2 mm × 2 mm × 25 mm) on the heavy release film, and fill the dental material composition. Cover the liquid surface of the spacer with the light release film in a way that no air bubbles are entrained, and irradiate ultraviolet rays (wavelength 405 nm, illuminance 50 mW / cm 2 , cumulative light quantity 1,500 mJ / cm 2 ) using a UV-LED lamp. Then, peel off the double-sided release film, take out the cured product from the spacer to obtain a test piece. After immersing the test piece in water at 37 °C for 24 hours, conduct a flexural test using a universal testing machine. The test conditions are based on ISO 4049, the distance between the fulcrums is 20 mm, and the crosshead speed is 1 mm / minute. Evaluate the flexural strength according to the following criteria.

[0766] ++: Flexural strength is 100 MPa or more.

[0767] +: Flexural strength is 90 MPa or more and less than 100 MPa.

[0768] ±: Flexural strength is 80 MPa or more and less than 90 MPa.

[0769] -: Flexural strength is less than 80 MPa.

[0770] [Table 14]

[0771]

[0772] As is clearly seen from the results in Table 14, the dental material composition of the examples has high solubility or dispersibility, high curability and high storage stability. The content rate of low-molecular-weight components in the obtained cured product is low, and the safety as a dental material is excellent. In addition, both the hardness and flexural strength of the cured product are high, and the surface smoothness is good. On the other hand, the curability of the dental material composition of the comparative examples is low, and both the solubility and storage stability are insufficient. In addition, the content rate of low-molecular-weight components in the cured product is high, and there are concerns about safety. The surface smoothness, hardness and flexural strength of the cured product are low. The dental material composition of the present invention can be suitably used as a dental restoration material (crown composite resin, caries cavity filling composite resin, post composite resin, filling and restoration composite resin), denture base resin, adhesive resin, adhesive material (resin cement, resin-added glass ionomer cement), dental bonding material (orthodontic bonding material, cavity coating bonding material), denture base relining material, impression material, dental temporary sealing material, dental fissure sealing material, CAD / CAM (Computer Aided Design-Computer Aided Manufacture) resin sealant, temporary crown, artificial tooth material.

[0773] Examples 215 to 220 and Comparative Examples 37 and 38 (Preparation and Evaluation of Actinic Energy Ray-Curable Photosensitive Compositions)

[0774] According to the ratios (in terms of solid components) described in Table 15, a benzoylformamide derivative (D), a commercially available photoinitiator (E), a monofunctional unsaturated compound (h1), a polyfunctional unsaturated compound (h2), a thermal 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 the photosensitive composition). Using the photosensitive composition, a photosensitive resin was produced by the following method, and the sensitivity (curability) and storage stability of the obtained photosensitive resin were evaluated. In addition, a pattern cured product was produced from the photosensitive composition, and the pattern formability of the obtained cured product and the content rate of low-molecular-weight components in the cured product were evaluated. These results are shown in Table 15.

[0775] [Production of Photosensitive Resin]

[0776] Using the photosensitive compositions of the examples and comparative examples, coating was carried out by a spin coater so that the film thickness became 15 μm, and drying was carried out in an oven for 3 minutes. Then, ultraviolet rays were irradiated for 3 minutes (wavelength 405 nm, illuminance 0.5 mW / cm 2 , cumulative light amount 90 mJ / cm 2) to obtain a photosensitive resin (cured product). Drying of the photosensitive composition not containing the thermal polymerization initiator (J) is carried out at 80 °C. Drying of the photosensitive composition containing the thermal polymerization initiator (J) is carried out at 40 °C, and after irradiation with ultraviolet rays, heat treatment is carried out in an oven at 130 °C for 30 minutes.

[0777] [Sensitivity]

[0778] Touch the photosensitive resin with a finger and evaluate the sensitivity according to the following criteria.

[0779] ++: Completely non-greasy.

[0780] +: Slightly greasy, but no fingerprint remains on the surface.

[0781] ±: Greasy, fingerprint remains on the surface.

[0782] -: Seriously greasy, the surface adheres to the finger.

[0783] [Storage stability]

[0784] Leave the photosensitive resin in a thermo-hygrostat at a temperature of 40 °C and a relative humidity of 50% for 168 hours, visually observe the surface of the photosensitive resin, and evaluate the storage stability according to the following criteria. The less exudation, the higher the storage stability.

[0785] ++: No exudation is confirmed at all.

[0786] +: Slight exudation is confirmed.

[0787] -: Serious exudation is confirmed.

[0788] [Low molecular weight component content]

[0789] Cut 3 test pieces with a size of 5 cm from the photosensitive resin 2 , and dry them at 130 °C for 30 minutes. Then, evaluate the low molecular weight component content of the photosensitive resin (cured product of the photosensitive composition) in the same manner as the evaluation of the low molecular weight component content of the cured product of the curable composition.

[0790] [Manufacture of pattern cured product]

[0791] Using a negative photomask (pattern mask), cure the photosensitive compositions of the examples and comparative examples in the same manner as the manufacture of the photosensitive resin. Then, remove the negative photomask from the cured product, and remove the unexposed portion with cyclopentanone to obtain a pattern cured product.

[0792] [Pattern formability]

[0793] Evaluate the pattern formability of the pattern cured product according to the following criteria.

[0794] ++: There are no strains in the pattern and no defects in the edge part.

[0795] +: There is no strain in the pattern, and there are slightly defects in the edge part.

[0796] ±: There is slightly strain in the pattern, and there are defects in the edge part.

[0797] -: There are strains in the pattern and defects in the edge part.

[0798] [Table 15]

[0799]

[0800] It can be clearly seen from the results in Table 15 that the photosensitive composition of the examples has high curability (sensitivity), the cured product (photosensitive resin) obtained by curing the photosensitive composition has high storage stability, and the content of low-molecular-weight components is low. In addition, the pattern cured product of the examples obtained by using a pattern mask has excellent pattern formability. On the other hand, the photosensitive composition of the comparative examples has low sensitivity, the content of low-molecular-weight components in the cured product obtained from the photosensitive composition is high, and the storage stability is low. In addition, the pattern formability of the pattern cured product of the comparative examples obtained by using a pattern mask is poor.

[0801] Examples 221 to 227 and Comparative Examples 39 and 40 (Preparation and Evaluation of Actinic Energy Ray-Curable Hydrogel Composition)

[0802] According to the ratios (in terms of solid components) described in Table 16, measure benzoylformamide derivative (D), commercially available photoinitiator (E), monofunctional unsaturated compound (h1), polyfunctional unsaturated compound (h2), ion-exchanged water and other components (k), and mix them at 25 °C for 30 minutes to prepare an actinic energy ray-curable hydrogel composition (hereinafter also referred to as the hydrogel composition). Evaluate the miscibility and curability of the hydrogel composition. In addition, evaluate the appearance and the content of low-molecular-weight components of the obtained cured product (hydrogel), and show the results in Table 16.

[0803] [Miscibility]

[0804] Evaluate the prepared hydrogel composition according to the same method and evaluation criteria as the miscibility evaluation of the above-mentioned actinic energy ray-curable composition.

[0805] [Curability]

[0806] Use a bar coater to coat the hydrogel composition on a PET film so that the film thickness becomes 20 μm. Irradiate ultraviolet rays under the following conditions 7) to 9) to cure the coating film, touch the cured product and evaluate the curability according to the following criteria.

[0807] 7) High-pressure mercury lamp: wavelength 200 nm to 450 nm, illuminance 100 mW / cm 2 , 1,000 mJ / cm 2 .

[0808] 8) UV-LED lamp: wavelength 385 nm, illuminance 100 mW / cm 2 , 1,000 mJ / cm 2 .

[0809] 9) UV-LED lamp: wavelength 405 nm, illuminance 100 mW / cm 2 , 1,000 mJ / cm 2 .

[0810] ++: The whole forms a gel and is in a slightly hard state.

[0811] +: The whole forms a gel and is in a slightly soft state.

[0812] ±: Gel is formed locally.

[0813] -: No gel is formed.

[0814] [Appearance of cured product]

[0815] Observe the appearance of the cured product obtained in the curability evaluation under ultraviolet irradiation condition 9) visually, and evaluate it according to the following criteria.

[0816] +: No turbidity and phase separation.

[0817] ±: No phase separation, but turbidity.

[0818] -: Turbidity and phase separation.

[0819] [Content rate of low-molecular-weight components]

[0820] Use the cured product obtained in the curability evaluation under ultraviolet irradiation condition 9), and evaluate the content rate of low-molecular-weight components (excluding water) of the cured product (hydrogel) in the same way as the evaluation of the content rate of low-molecular-weight components of the above curable composition cured product.

[0821] [Table 16]

[0822]

[0823] (*3) No cured product was obtained, and the evaluation was not carried out.

[0824] As is clearly shown by the results in Table 16, the hydrogel compositions of the examples contain water-soluble or hydrophilic morpholino acrylate (h1-1), N-(2-hydroxyethyl) acrylamide (h1-7), or N-vinylpyrrolidone (h1-11) and water, showing good miscibility and being in an aqueous solution state. The hydrogel compositions of the examples have high curability, and the cured product obtained by curing the hydrogel composition forms a gel (hydrogel) as a whole. In addition, the cured product (hydrogel) has a low content rate of low-molecular-weight components and high safety. Such a hydrogel can be suitably used as a sanitary material or a medical material. On the other hand, the hydrogel compositions of the comparative examples have low miscibility and curability, and even when irradiated with ultraviolet rays, a uniform hydrogel cannot be formed, and the content rate of low-molecular-weight components cannot be evaluated. In addition, in the comparative examples where a hydrogel is locally formed, the content rate of low-molecular-weight components in the hydrogel is high.

[0825] Examples 228 to 234 and Comparative Examples 41 and 42 (Preparation and Evaluation of Actinic Energy Ray-Curable Aqueous Compositions)

[0826] According to the ratios (in terms of solid components) described in Table 17, a benzoylformamide 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. In addition, 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.

[0827] [Dispersibility]

[0828] 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.

[0829] +: The aqueous composition is a stable and uniform emulsion.

[0830] ±: The aqueous composition is locally coagulated and is a non-uniform emulsion.

[0831] -: Phase separation occurs in the aqueous composition.

[0832] [Curability]

[0833] A coating film of the aqueous composition was prepared by the same method as the curability evaluation of the above-mentioned curable composition, dried at 80°C for 5 minutes, and then irradiated with ultraviolet rays to evaluate the curability.

[0834] [Appearance of Cured Product]

[0835] Visually observe the cured product obtained in the curability evaluation under ultraviolet irradiation condition 3), and evaluate the appearance of the cured product according to the following criteria.

[0836] +: The cured product has no turbidity or phase separation.

[0837] ±: The cured product has turbidity.

[0838] -: The cured product undergoes phase separation.

[0839] [Low molecular weight component content rate]

[0840] Use the cured product obtained in the curability evaluation under ultraviolet irradiation condition 3) to evaluate the low molecular weight component content rate of the aqueous composition cured product in the same manner as the evaluation of the low molecular weight component content rate of the above curable composition.

[0841] [Table 17]

[0842]

[0843] (*3) No cured product was obtained, and the evaluation was not carried out.

[0844] It can be clearly seen from the results in Table 17 that the aqueous composition of the example has good dispersibility, can maintain a good emulsion state, and has high curability even when using long-wavelength light. The content rate of the low molecular weight component in the obtained cured product is low. On the other hand, the aqueous composition of the comparative example has low dispersibility and curability, and a large amount of low molecular weight components are contained in the obtained cured product.

[0845] The present invention includes the following contents.

[0846] (1) A benzoylamine derivative having a benzoylamino group represented by the general formula (1).

[0847]

[0848] In the formula, Q 1 to Q 3 independently represent a hydrogen atom, a substituent represented by formula (Chemical formula 2) to formula (Chemical formula 8), a halogen group, or a nitrile group, and are bonded to any position from the 2nd to the 6th position.

[0849]

[0850] R 1 to R 10 each independently represent a hydrogen atom, a straight-chain alkyl group having 1 to 18 carbon atoms, a straight-chain alkenyl group having 2 to 18 carbon atoms, a branched-chain alkyl group having 3 to 18 carbon atoms, a branched-chain 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;

[0851] * is the bonding position.

[0852] (2) The benzoylformamide derivative as described in (1) above, wherein the benzoylformamide derivative is at least one compound represented by any one of the general formulas (2) to (4).

[0853]

[0854] In the formula, Q 1 to Q 3 has the same definition as described in the general formula (1);

[0855] B 1 represents a hydrogen atom, 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 carbamate group, a thiocarbamate group, a urea group, a siloxanyl group, an amide group, an imide group, an ethylenically unsaturated group or a benzoylformamide group;

[0856] 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 carbamate group, a thiocarbamate group, a urea group, an amide group, an imide group, a siloxanyl group, an ethylenically unsaturated group or a benzoylformamide group.

[0857]

[0858] In the formula, Q 1 to Q 3 has the same definition as described in the general formula (1);

[0859] 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 carbamate group, a thiocarbamate group, an isocyanurate group, a urethane group, a urea group, a siloxanyl group, an amide group or an imide group;

[0860] R 11 represents a hydrogen atom, a straight-chain alkyl group having 1 to 18 carbon atoms, a straight-chain alkenyl group having 2 to 18 carbon atoms, a branched-chain alkyl group having 3 to 18 carbon atoms, a branched-chain 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 aryl group having 6 to 8 carbon atoms;

[0861] R 12Represents 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 are substituted with an oxygen atom, a nitrogen atom, a sulfur atom, a hydroxyl group, a thiol group, or an amino group;

[0862] m represents an integer from 1 to 10.

[0863]

[0864] In the formula, Q 1 to Q 3 are the same as defined in the general formula (1);

[0865] A 1 represents a divalent organic group that may have an ether group, a thioether group, an ester group, a carbonate group, a carbamate group, a thiocarbamate group, a urea group, a siloxane group, an amide group, or an imide group;

[0866] B 4 and B 5 independently represent a monovalent organic group that may have an ethylenically unsaturated group, an ether group, a thioether group, an ester group, a carbonate group, a carbamate group, a thiocarbamate group, an isocyanurate group, a urethane group, a urea group, a siloxane group, an amide group, or an imide group, and one or both of B 4 and B 5 contain one or more ethylenically unsaturated bonds;

[0867] 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;

[0868] R 14 represents a linear saturated trivalent hydrocarbon group having 1 to 8 carbon atoms, a linear unsaturated trivalent hydrocarbon group having 2 to 8 carbon atoms, a branched saturated or unsaturated trivalent hydrocarbon group having 3 to 8 carbon atoms, an alicyclic saturated or unsaturated trivalent hydrocarbon group having 3 to 8 carbon atoms, a trivalent aromatic hydrocarbon group having 6 to 8 carbon atoms, or a trivalent organic group in which any one or more atoms of these hydrocarbon groups are substituted with an oxygen atom, a nitrogen atom, a sulfur atom, a hydroxyl group, a thiol group, or an amino group;

[0869] R 15A divalent organic group in which a straight-chain saturated divalent hydrocarbon group having 1 to 18 carbon atoms, a straight-chain unsaturated divalent hydrocarbon group having 2 to 18 carbon atoms, a branched-chain saturated or unsaturated divalent hydrocarbon group having 3 to 8 carbon atoms, a cycloaliphatic saturated or unsaturated divalent hydrocarbon group having 3 to 8 carbon atoms, a divalent aromatic hydrocarbon group having 6 to 8 carbon atoms, or any one or more atoms of these hydrocarbon groups are substituted with an oxygen atom, a nitrogen atom, a sulfur atom, a hydroxyl group, a mercapto group, or an amino group;

[0870] n represents an integer from 1 to 100.

[0871] (3) The benzoylformamide derivative as described in (1) or (2) above, wherein Q of the benzoylformamide group represented by the general formula (1) 1 to Q 3 are each independently a hydrogen atom, a substituent represented by the formula (Chemical Formula 3), or a substituent represented by the formula (Chemical Formula 6).

[0872] (4) The benzoylformamide derivative as described in any one of (1) to (3) above, which has one or more ethylenically unsaturated bonds in the molecule, and the ethylenically unsaturated bonds are included in 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.

[0873] (5) The benzoylformamide derivative as described in any one of (2) to (4) above, wherein the ethylenically unsaturated bonds are included in an acrylate group or an acrylamide group.

[0874] (6) The benzoylformamide derivative as described in any one of (2) to (5) above, which has one or more carbamate groups in the molecule, and the number of atoms directly bonded between the nitrogen atom of the benzoylformamide group and the nitrogen atom of the nearest carbamate group is 3 to 20.

[0875] (7) The benzoylformamide derivative as described in any one of (2) to (6) above, which has one or more carbamate groups in the molecule, and the number of atoms directly bonded between the nitrogen atom of the benzoylformamide group and the nitrogen atom of the nearest carbamate group is 4 to 10.

[0876] (8) The benzoylformamide derivative as described in any one of (2) to (7) above, wherein m of the benzoylformamide derivative represented by the general formula (3) is an integer from 1 to 4.

[0877] (9) The benzoylformamide derivative as described in any one of (2) to (8) above, wherein n of the benzoylformamide derivative represented by the general formula (4) is an integer from 2 to 50.

[0878] (10) The benzoylformamide derivative according to any one of (2) to (9) above, wherein the ratio of the total number of carbamate groups to the total number of benzoylformamide groups in the benzoylformamide derivative represented by the general formula (3) is 0.5 to 10.0.

[0879] (11) The benzoylformamide derivative according to any one of (2) to (10) above, wherein the ratio of the total number of carbamate groups to the total number of benzoylformamide groups in the benzoylformamide derivative represented by the general formula (4) is 2.0 to 15.0.

[0880] (12) The benzoylformamide derivative according to any one of (1) to (11) above, which is a photoinitiator.

[0881] (13) A photoinitiator according to (12) above, wherein the benzoylformamide group represented by the general formula (1) is represented by a benzoylformic acid monosubstituted amide.

[0882] (14) The benzoylformamide derivative according to any one of (1) to (11) above, which is a photosensitizer for free radical photopolymerization and / or a photosensitizer for ionic photopolymerization.

[0883] (15) An actinic energy ray curable composition containing the benzoylformamide derivative according to any one of (1) to (12) and (14) above.

[0884] (16) An actinic energy ray curable ink composition containing the benzoylformamide derivative according to any one of (1) to (12) and (14) above.

[0885] (17) An actinic energy ray curable adhesive composition containing the benzoylformamide derivative according to any one of (1) to (12) and (14) above.

[0886] (18) An actinic energy ray curable bonding agent composition containing the benzoylformamide derivative according to any one of (1) to (12) and (14) above.

[0887] (19) An actinic energy ray curable sealant composition containing the benzoylformamide derivative according to any one of (1) to (12) and (14) above.

[0888] (20) An actinic energy ray curable photosensitive composition containing the benzoylformamide derivative according to any one of (1) to (12) and (14) above.

[0889] (21) A photo-curable nail cosmetic composition containing a benzoylformamide derivative as described in any one of (1) to (12) and (14) above.

[0890] (22) A photo-curable dental material composition containing a benzoylformamide derivative as described in any one of (1) to (12) and (14) above.

[0891] (23) A photo-curable coating agent composition containing a benzoylformamide derivative as described in any one of (1) to (12) and (14) above.

[0892] (24) A photo-curable aqueous composition containing a benzoylformamide derivative as described in any one of (1) to (12) and (14) above.

[0893] (25) A photo-curable inkjet ink composition containing a benzoylformamide derivative as described in any one of (1) to (12) and (14) above.

[0894] (26) A photo-curable elastomer composition containing a benzoylformamide derivative as described in any one of (1) to (12) and (14) above.

[0895] (27) A photo-curable resin composition for decorative sheets containing a benzoylformamide derivative as described in any one of (1) to (12) and (14) above.

[0896] (28) A photo-curable architectural coating composition containing a benzoylformamide derivative as described in any one of (1) to (12) and (14) above.

[0897] (29) A photo-curable coating agent composition for the surface of medical devices containing a benzoylformamide derivative as described in any one of (1) to (12) and (14) above.

[0898] (30) A photo-curable ink composition for three-dimensional modeling containing a benzoylformamide derivative as described in any one of (1) to (12) and (14) above.

[0899] (31) A photo-curable flexographic ink composition containing a benzoylformamide derivative as described in any one of (1) to (12) and (14) above.

[0900] (32) A photo-curable offset ink composition containing a benzoylformamide derivative as described in any one of (1) to (12) and (14) above.

[0901] (33) A curable active energy ray screen printing ink composition containing a benzoylformamide derivative as described in any one of the above (1) to (12) and (14).

[0902] (34) A resin composition for a curable active energy ray self-healing material containing a benzoylformamide derivative as described in any one of the above (1) to (12) and (14).

[0903] [Industrial Applicability]

[0904] As described above, the benzoylformamide derivative (D) of the present invention exhibits high curability for ultraviolet rays of various wavelengths including long-wavelength ultraviolet rays having a wavelength of 360 nm to 420 nm. In particular, even when using UV-LED lamps of 385 nm, 395 nm, and 405 nm, it exhibits high photo-polymerization initiation property, photosensitivity, and curability. In addition, by containing a urethane group and an ethylenically unsaturated group in the molecule, these various properties and effects of D are further enhanced. In particular, the cured product obtained by containing D having an ethylenically unsaturated group has extremely few low-molecular-weight components, high safety and high adhesion to various materials, and also has good physical properties such as surface hardness, light yellowing resistance, durability, and transparency. The benzoylformamide derivative (D) of the present invention can be suitably used as a curable active energy ray ink composition, a curable active energy ray inkjet ink composition, a curable active energy ray flexographic ink composition, a curable active energy ray offset ink composition, a curable active energy ray screen printing ink composition, a curable active energy ray nail cosmetic composition, a curable active energy ray adhesive composition, a curable active energy ray adhesive composition, a curable active energy ray sealant composition, a curable active energy ray coating agent composition, a curable active energy ray resin composition for decorative sheets, a curable active energy ray elastomer composition, a curable active energy ray three-dimensional modeling ink composition, a curable active energy ray vehicle coating agent composition, a curable active energy ray resin composition for self-healing materials, a curable active energy ray architectural coating composition, a ship bottom coating, an antifogging material, an antifouling coating, and other curable active energy ray compositions used in various coating fields, a curable active energy ray composition used in the field of coating the surface of medical devices, a curable active energy ray dental material composition, a curable active energy ray photosensitive composition, a curable active energy ray hydrogel composition, and a curable active energy ray aqueous dispersion composition. In addition, the obtained hydrogel composition and aqueous composition can also be suitably used as materials in various fields such as high water-absorbing resins, sanitary napkins, soft contact lenses, etc. in the hygiene field; coating the surface of medical devices and artificial organs, etc. in the medical field; soil conditioners, etc. in the civil / construction field; water retention materials, etc. in the agricultural field; impact-absorbing materials, etc.

Claims

1. A benzoylformamide derivative having a benzoylformamido group represented by the general formula (1): Q 1 to Q 3 each independently represents a hydrogen atom, a substituent represented by Formula (2) to Formula (8), a halogen group, or a nitrile group, and is bonded to any one of the second to sixth positions; R 1 to R 10 each independently represents a hydrogen atom, a straight-chain alkyl group having 1 to 18 carbon atoms, a straight-chain alkenyl group having 2 to 18 carbon atoms, a branched-chain alkyl group having 3 to 18 carbon atoms, a branched-chain 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); wherein, Q 1 to Q 3 are the same as defined in General Formula (1); B 1 represents a hydrogen atom or 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 carbamate group, a thiocarbamate group, a urea group, a siloxane group, an amide group, an imide group, an ethylenically unsaturated group or a benzoylmethanamide 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 carbamate group, a thiocarbamate group, a urea group, an amide group, an imide group, a siloxane group, an ethylenically unsaturated group or a benzoylmethanamide group; Wherein, Q 1 to Q 3 are the same as defined in General Formula (1); B 3 represents an m-valent organic group that 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, a urethane group, a siloxane group, an amide group or an imide group; R 11 represents a hydrogen atom, a straight-chain alkyl group having 1 to 18 carbon atoms, a straight-chain alkenyl group having 2 to 18 carbon atoms, a branched-chain alkyl group having 3 to 18 carbon atoms, a branched-chain 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 mercapto group, or an amino group; m represents an integer of 1 to 10; Wherein, Q 1 to Q 3 are the same as defined in the 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 thiocarbamate group, a urea group, a siloxane group, an amide group or an imide group; B 4 and B 5 each independently represent a monovalent 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, a urethane group, a siloxane group, an amide group or an imide group, and one or both of B 4 and B 5 contain 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 linear saturated trivalent hydrocarbon group having 1 to 8 carbon atoms, a linear unsaturated trivalent hydrocarbon group having 2 to 8 carbon atoms, a branched saturated or unsaturated trivalent hydrocarbon group having 3 to 8 carbon atoms, an alicyclic saturated or unsaturated trivalent hydrocarbon group having 3 to 8 carbon atoms, a trivalent aromatic hydrocarbon group having 6 to 8 carbon atoms, or a trivalent organic group in which any one or more 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 mercapto group, or an amino group; R 坫 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 8 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 mercapto group, or an amino 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 bonds are included in 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.

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 bonded between the nitrogen atom of the benzoylformamido 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 free radical photopolymerization and / or a photosensitizer for ionic photopolymerization.

7. A radiation curable composition containing the benzoylformamide derivative according to any one of claims 1 to 6.

8. A radiation curable ink composition containing the benzoylformamide derivative according to any one of claims 1 to 6.

9. A radiation curable adhesive composition containing the benzoylformamide derivative according to any one of claims 1 to 6.

10. A radiation curable bonding agent composition containing the benzoylformamide derivative according to any one of claims 1 to 6.

11. A radiation curable sealant composition containing the benzoylformamide derivative according to any one of claims 1 to 6.

12. A radiation curable photosensitive composition containing the benzoylformamide derivative according to any one of claims 1 to 6.

13. A radiation curable nail cosmetic composition containing the benzoylformamide derivative according to any one of claims 1 to 6.

14. A radiation curable dental material composition containing the benzoylformamide derivative according to any one of claims 1 to 6.

15. A radiation curable coating agent composition containing the benzoylformamide derivative according to any one of claims 1 to 6.

16. A radiation curable aqueous composition containing the benzoylformamide derivative according to any one of claims 1 to 6.

Images