Compounds, methods for producing compounds, polymerizable compositions, coating agents, adhesives, cured products, and methods for producing cured products.

Abstract

To provide a novel compound and the like. 【Solution means】A compound represented by the following formula (1). JPEG2026055027000017.jpg4562 In formula (1), R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , and R 10 each independently represents a hydrogen atom or a substituent, and R 11 represents a residue of an oligomer or polymer having a number average molecular weight of 200 to 1,000,000.

Description

[Technical Field]

[0001] This disclosure relates to compounds, methods for producing compounds, polymerizable compositions, coating agents, adhesives, cured products, and methods for producing cured products. [Background technology]

[0002] Conventionally, high-pressure mercury lamps and electrodeless lamps have been the main light sources used to cure polymerizable compounds. For example, Patent Document 1 describes using a mercury lamp to irradiate ultraviolet light in order to cure a polymerizable composition. However, in recent years, due to growing environmental awareness, energy-saving and long-lasting light-emitting diodes (LEDs) have come into use.

[0003] For example, Patent Document 2 describes curing a polymerizable composition using a photopolymerization initiator that reacts to LED irradiation. However, some of the compounds having an acylphosphine skeleton used here are toxic, and there are concerns that their use may be restricted in the future. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2007-224084 [Patent Document 2] International Publication No. 2010 / 008077 [Overview of the project] [Problems that the invention aims to solve]

[0005] The object of one embodiment of this disclosure is to provide a novel compound that reacts to long-wavelength light such as LEDs and yields a low-toxicity photopolymerization initiator, as well as a method for producing the compound. The object of other embodiments of this disclosure is to provide polymerizable compositions, coatings, and adhesives containing the above-mentioned compounds. An object of other embodiments of the present disclosure is to provide a cured product of the above polymerizable composition and a method for producing the cured product. **Means for Solving the Problems**

[0006] The present disclosure includes the following aspects. <1> A compound represented by the following formula (1). **Chemical Formula** In formula (1), R , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , and R 10 each independently represents a hydrogen atom or a substituent, R 11 represents a residue of an oligomer or polymer having a number average molecular weight of 200 to 1,000,000. <2> R 11 is the compound according to <1>, which is a residue of an oligomer or polymer containing a structural unit derived from a first radically polymerizable compound. <3> The first radically polymerizable compound is the compound according to <2>, which includes a compound having a (meth)acryloyl group. <4> The first radically polymerizable compound is the compound according to <2>, which includes a compound having a (meth)acryloyl group and a radical generating group. <5> <​​​​ [ka] JPEG2026055027000003.jpg5279 In equations (1) and (2), R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 12 , R 13 , R 14 , R 15 , and R 16 Each of these independently represents a hydrogen atom or a substituent. R 11 This represents a residue obtained by removing one hydrogen atom from an oligomer or polymer with a number-average molecular weight of 200 to 1,000,000. <7> Polymerization initiator, <1> ~ <5> A compound listed in any one of the following. <8> <6> A polymerizable composition comprising the polymerization initiator described in [reference] and a second radical polymerizable compound. <9> <8> A coating agent comprising the polymerizable composition described above. <10> <8> An adhesive comprising the polymerizable composition described above. <11> <8> A cured product of the polymerizable composition described above. <12> On the substrate, <8> A step of providing the polymerizable composition described above, A method for producing a cured product, comprising the step of irradiating a polymerizable composition with active energy rays. [Effects of the Invention]

[0007] According to one embodiment of the present disclosure, a novel compound is provided that reacts to long-wavelength light such as LEDs and yields a low-toxicity photopolymerization initiator, as well as a method for producing the compound. Other embodiments of the present disclosure provide polymerizable compositions, coatings, and adhesives containing the above-mentioned compounds. Other embodiments of the present disclosure provide a cured product of the polymerizable composition and a method for producing the cured product. [Brief explanation of the drawing]

[0008] [Figure 1] Figure 1 shows the results of quantifying the reaction rate of bis(2,4,6-trimethylbenzoyl)phosphine oxide (hereinafter abbreviated as "BAPO") by liquid chromatography. [Figure 2] Figure 2 shows the polymerization rate of methyl acrylate calculated using gas chromatography. [Figure 3] Figure 3 shows the change in the UV-visible spectrum of the reaction solution over time with light irradiation. [Figure 4] Figure 4 shows the 1H NMR spectrum of a mixture containing polymerization initiator 1. [Figure 5] Figure 5 shows the relationship between light irradiation time and the polymerization rate of n-butyl acrylate. [Figure 6] Figure 6 shows the results of sampling polymerization solutions with varying light irradiation times, diluting them 100 times (by volume) with butyl acetate, and measuring the UV-visible spectrum. [Figure 7] Figure 7 shows the changes in GPC before and after light irradiation in Example 1-1. [Figure 8] Figure 8 shows the changes in GPC before and after light irradiation in Example 1-2. [Figure 9] Figure 9 shows the measurement results of the MALDI-TOF mass spectrum of the obtained polymer. [Figure 10] Figure 10 shows the results of quantifying the reaction rate of BAPO using liquid chromatography. [Figure 11] Figure 11 shows the polymerization rate of isobornyl acrylate calculated using gas chromatography. [Figure 12] Figure 12 shows the change in the UV-visible spectrum of the reaction solution over time with light irradiation. [Modes for carrying out the invention]

[0009] In this specification, a numerical range indicated using "~" means a range that includes the numbers before and after "~" as the minimum and maximum values, respectively. In the numerical ranges described stepwise in this specification, the upper or lower limit stated in one numerical range may be replaced with the upper or lower limit of another numerical range described stepwise. Furthermore, in the numerical ranges described in this specification, the upper or lower limit stated in one numerical range may be replaced with the values ​​shown in the examples.

[0010] In this specification, the amount of each component in a composition means the total amount of multiple substances present in the composition, unless otherwise specified, if there are multiple substances corresponding to each component in the composition. In this specification, a combination of two or more preferred embodiments is a more preferred embodiment. In this specification, the term "process" includes not only independent processes but also processes that cannot be clearly distinguished from other processes, provided that the intended purpose of the process is achieved.

[0011] In this specification, "(meth)acrylate" is a concept that encompasses both acrylate and methacrylate. Similarly, "(meth)acrylic" is a concept that encompasses both acrylic and methacrylic.

[0012] [Compound] The compounds of this disclosure are represented by the following formula (1). [ka]

[0013] In formula (1), R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , and R 10 Each of these independently represents a hydrogen atom or a substituent, R 11 This represents a residue of an oligomer or polymer with a number-average molecular weight of 200 to 1,000,000.

[0014] The compounds disclosed herein are novel compounds (preferably (photo)polymerization initiators) that generate radicals with high sensitivity to light sources emitting long-wavelength light.

[0015] In the compounds disclosed herein, R 11 Its structure can be designed to suit the purpose and is applicable to various applications.

[0016] [R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , and R 10 ] In formula (1), R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , and R 10 Examples of substituents represented by include halogen atoms, hydroxyl groups, carboxyl groups, amide groups, alkyl groups, aryl groups, alkoxy groups, and aryloxy groups. The alkyl groups, aryl groups, alkoxy groups, and aryloxy groups may have further substituents. The alkyl group may be a linear alkyl group, a branched alkyl group, or a cyclic alkyl group. In particular, the alkyl group is preferably a methyl group.

[0017] Specifically, from the viewpoint of ease of manufacture, the compounds of this disclosure are preferably represented by the following formula (1A). R in formula (1A) 11 R in equation (1) 11 It is the same as this.

[0018] [ka]

[0019] [R 11 ] In equations (1) and (1A), R 11 This represents a residue of an oligomer or polymer with a number-average molecular weight of 200 to 1,000,000.

[0020] R 11 The number-average molecular weight of the residues of the oligomer or polymer represented by is preferably 200 to 1,000,000, and more preferably 250 to 10,000. In this disclosure, the number-average molecular weight is measured using gel permeation chromatography (GPC) on a polystyrene basis under the following conditions.

[0021] Column: Tosoh Corporation "TSKgel SuperMultiporeHZ-M 4.6mm ID × 15cm × 3 tubes, Substrate: Styrene-divinylbenzene copolymer, Particle size: 4μm, Exclusion limit molecular weight: 2,000,000 (polystyrene equivalent), Theoretical plate count: 16,000 or more, Molecular weight fractionation range: 500~1,000,000" Solvent: tetrahydrofuran Temperature: 40℃ Detector: RI Flow rate: 350μL / min

[0022] In the compound relating to this disclosure, a substituted carbonylphenyl group and a substituted phenyl group are bonded to the phosphorus atom of the -P=O group in formula (1), and further, residues of an oligomer or polymer with a number average molecular weight of 200 to 1,000,000 are bonded, resulting in high sensitivity to light sources that emit long wavelength light. Therefore, R 11 The structure of the residues of the oligomer or polymer represented by is not particularly limited.

[0023] From the perspective of high productivity and low environmental impact, R 11 It is preferable that this is a residue of an oligomer or polymer containing a structural unit derived from a first radical polymerizable compound.

[0024] "Structural units derived from a first radical polymerizable compound" simply means that the structure possessed by the first radical polymerizable compound is present, and it is not necessary whether or not it actually originated from that compound. The first radical polymerizable compound may be one type or two or more types.

[0025] In this disclosure, "radical polymerizable compound" means a compound having a radical polymerizable group.

[0026] In this disclosure, the "radical polymerizable group" is preferably a photopolymerizable group, and more preferably a photoradical polymerizable group. Examples of photoradical polymerizable groups include (meth)acryloyl groups, allyl groups, styryl groups, and vinyl groups.

[0027] Furthermore, the first radical polymerizable compound may have only one radical polymerizable group, or it may have two or more. In other words, the first radical polymerizable compound may be a monofunctional polymerizable compound, or it may be a polyfunctional polymerizable compound.

[0028] Examples of monofunctional polymerizable compounds include monofunctional (meth)acrylates, monofunctional (meth)acrylamides, monofunctional (meth)allyl compounds, monofunctional aromatic vinyl compounds, monofunctional vinyl ethers, and monofunctional N-vinyl compounds.

[0029] Examples of monofunctional (meth)acrylates include alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, lauryl (meth)acrylate, and stearyl (meth)acrylate; Mono(meth)acrylates of polyols such as trimethylolpropane mono(meth)acrylate, glycerin mono(meth)acrylate, pentaerythritol mono(meth)acrylate, ditrimethylolpropane mono(meth)acrylate, and dipentaerythritol mono(meth)acrylate: Monofunctional (meth)acrylates having an alicyclic structure, such as cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, tert-butylcyclohexyl (meth)acrylate, tricyclodecanemethylol (meth)acrylate, and dicyclopentenyloxyethyl (meth)acrylate; Phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, o-phenylphenol (meth)acrylate, (meth)acrylate of alkylene oxide adducts of phenols, (meth)acrylate of alkylene oxide adducts of alkylphenols, (meth)acrylate of alkylene oxide adducts of p-cumylphenol, (meth)acrylate of alkylene oxide adducts of o-phenylphenol, aromatic monofunctional (meth)acrylates such as 4-(meth)acryloyloxybenzophenone; Alkyl carbitol (meth)acrylates such as ethyl carbitol (meth)acrylate, butyl carbitol (meth)acrylate, and 2-ethylhexyl carbitol (meth)acrylate; Monofunctional (meth)acrylates having hydroxyl groups, such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxy (meth)acrylate, and 2-hydroxy-3-phenoxypropyl (meth)acrylate; (Meth)acrylic acid, Michael addition dimers of acrylic acid, ω-carboxy-polycaprolactone mono(meth)acrylate, monohydroxyethyl phthalate (meth)acrylate, and other monofunctional (meth)acrylates having a carboxyl group; Monofunctional (meth)acrylates having cyclic ether groups, such as glycidyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl (meth)acrylate, cyclohexanespiro-2-(1,3-dioxolan-4-yl)methyl (meth)acrylate, and 3-ethyl-3-oxetanylmethyl (meth)acrylate; Examples include monofunctional (meth)acrylates having heterocyclic rings, such as (meth)acryloylmorpholine, N-(2-(meth)acryloxyethyl)hexahydrophthalimide, and N-(2-(meth)acryloxyethyl)tetrahydrophthalimide.

[0030] Examples of monofunctional (meth)acrylamides include N-methyl(meth)acrylamide, Nn-propyl(meth)acrylamide, N-isopropyl(meth)acrylamide, Nn-butyl(meth)acrylamide, N-sec-butyl(meth)acrylamide, Nt-butyl(meth)acrylamide, Nn-hexyl(meth)acrylamide, and other N-alkyl(meth)acrylamides; N-hydroxyalkyl(meth)acrylamides such as N-hydroxyethyl(meth)acrylamide; and Examples of N,N-dialkyl(meth)acrylamides include N,N-dimethylaminoethyl(meth)acrylamide, N,N-dimethylaminopropyl(meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N,N-di-n-propyl(meth)acrylamide, N,N-diisopropyl(meth)acrylamide, N,N-di-n-butyl(meth)acrylamide, and N,N-dihexyl(meth)acrylamide.

[0031] Examples of monofunctional (meth)allyl compounds include (meth)allyl alcohol, (meth)allyl chloride, (meth)allyl benzoate, and (meth)allyl benzoate esters.

[0032] Examples of monofunctional aromatic vinyl compounds include styrene, dimethylstyrene, trimethylstyrene, isopropylstyrene, chloromethylstyrene, methoxystyrene, acetoxystyrene, chlorostyrene, dichlorostyrene, bromostyrene, methyl vinylbenzoate, 3-methylstyrene, 4-methylstyrene, 3-ethylstyrene, 4-ethylstyrene, 3-propylstyrene, 4-propylstyrene, 3-butylstyrene, 4-butylstyrene, 3-hexylstyrene, 4-hexylstyrene, 3-octylstyrene, 4-octylstyrene, 3-(2-ethylhexyl)styrene, 4-(2-ethylhexyl)styrene, allylstyrene, isopropenylstyrene, butenylstyrene, octenylstyrene, 4-t-butoxycarbonylstyrene, and 4-t-butoxystyrene.

[0033] Examples of monofunctional vinyl ethers include methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, n-butyl vinyl ether, t-butyl vinyl ether, 2-ethylhexyl vinyl ether, n-nonyl vinyl ether, lauryl vinyl ether, cyclohexyl vinyl ether, cyclohexylmethyl vinyl ether, 4-methylcyclohexylmethyl vinyl ether, benzyl vinyl ether, dicyclopentenyl vinyl ether, 2-dicyclopentenoxyethyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, butoxyethyl vinyl ether, methoxyethoxyethyl vinyl ether, ethoxyethoxyethyl vinyl ether, methoxypolyethylene glycol vinyl ether, tetrahydrofurfuryl vinyl ether, 2-hydroxyethyl vinyl ether, 2-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 4-hydroxymethylcyclohexylmethyl vinyl ether, diethylene glycol monovinyl ether, polyethylene glycol vinyl ether, chloroethyl vinyl ether, chlorobutyl vinyl ether, chloroethoxyethyl vinyl ether, phenylethyl vinyl ether, and phenoxypolyethylene glycol vinyl ether.

[0034] Examples of monofunctional N-vinyl compounds include N-vinyl-ε-caprolactam and N-vinylpyrrolidone.

[0035] Examples of polyfunctional polymerizable compounds include polyfunctional (meth)acrylates and polyfunctional vinyl ethers. Examples of polyfunctional (meth)acrylates include compounds having two (meth)acryloyl groups (hereinafter referred to as "bifunctional (meth)acrylates") and compounds having three or more (meth)acryloyl groups (hereinafter referred to as "trifunctional or more (meth)acrylates").

[0036] Examples of difunctional (meth)acrylates include aliphatic di(meth)acrylates such as ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butanediol di(meth)acrylate, hexanediol di(meth)acrylate, and nonanediol di(meth)acrylate; Di(meth)acrylates having an alicyclic structure, such as tricyclodecanedimethylol di(meth)acrylate and 1,4-cyclohexanedimethanol di(meth)acrylate; Di(meth)acrylates of trivalent or higher polyols such as glycerin di(meth)acrylate, trimethylolpropane di(meth)acrylate, ditrimethylolpropane di(meth)acrylate, pentaerythritol di(meth)acrylate, and dipentaerythritol di(meth)acrylate; Di(meth)acrylates of alkylene oxide adducts of the above polyols; Di(meth)acrylates having an isocyanuric acid skeleton, such as di(meth)acrylates of ethylene oxide adducts of isocyanurate; Examples include di(meth)acrylates of bisphenol alkylene oxide adducts, such as di(meth)acrylates of alkylene oxide adducts of bisphenol A and di(meth)acrylates of alkylene oxide adducts of bisphenol F. Examples of alkylene oxides in alkylene oxide adducts include ethylene oxide, propylene oxide, tetramethylene oxide, and combinations of ethylene oxide and propylene oxide.

[0037] Specifically, examples of methacrylates with three or more functional properties include: Poly(meth)acrylates of polyols such as glycerin tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, diglycerin tri or tetra(meth)acrylate, pentaerythritol tri or tetra(meth)acrylate, ditrimethylolpropane tri or tetra(meth)acrylate, and dipentaerythritol tri, tetra, penta or hexa(meth)acrylate; Poly(meth)acrylates of alkylene oxide adducts of the above polyols; Examples include tri(meth)acrylates having an isocyanuric acid skeleton, such as tri(meth)acrylates, which are ethylene oxide adducts of isocyanurate. Examples of alkylene oxides in alkylene oxide adducts include ethylene oxide, propylene oxide, tetramethylene oxide, and combinations of ethylene oxide and propylene oxide.

[0038] Examples of polyfunctional polymerizable compounds include urethane (meth)acrylate, polyester (meth)acrylate, epoxy (meth)acrylate, and polyether (meth)acrylate.

[0039] Examples of urethane (meth)acrylates include reaction products of polyols, organic polyisocyanates, and hydroxyl group-containing (meth)acrylates (hereinafter referred to as "UA1"), and reaction products of organic polyisocyanates and hydroxyl group-containing (meth)acrylates (hereinafter referred to as "UA2"). The following describes UA1 and UA2.

[0040] UA1 is a reaction product of a polyol, an organic polyisocyanate, and a hydroxyl group-containing (meth)acrylate.

[0041] Diols are preferred as the polyols in UA1. Preferred diols include low molecular weight diols, diols having a polyester skeleton, diols having a polyether skeleton, and diols having a polycarbonate skeleton. Examples of low molecular weight diols include ethylene glycol, propylene glycol, cyclohexanedimethanol, neopentyl glycol, 3-methyl-1,5-pentanediol, and 1,6-hexanediol. Examples of diols having a polyester skeleton include esterification reaction products of a diol component such as the above-mentioned low molecular weight diol or polycaprolactone diol, and an acid component such as a dicarboxylic acid or its anhydride. Examples of dicarboxylic acids or their anhydrides include adipic acid, succinic acid, phthalic acid, tetrahydolphthalic acid, hexahydrophthalic acid, and terephthalic acid, as well as their anhydrides. Examples of polyether diols include polyethylene glycol, polypropylene glycol, and polyethylamine glycol. Examples of polycarbonate diols include the reaction products of the above-mentioned low molecular weight diols and / or bisphenols such as bisphenol A, ethylene carbonate, and dialkyl carbonates such as dibutyl carbonate.

[0042] Examples of organic polyisocyanates include aliphatic polyisocyanates without an alicyclic structure (hereinafter simply referred to as "aliphatic polyisocyanates"), aliphatic polyisocyanates with an alicyclic structure (hereinafter referred to as "alicyclic polyisocyanates"), polyisocyanates with heterocyclic structures, and aromatic polyisocyanates. Examples of aliphatic polyisocyanates include 1,6-hexamethylene diisocyanate, tetramethylene diisocyanate, trimethylhexamethylene diisocyanate, and lysine diisocyanate. Examples of alicyclic polyisocyanates include hydrogenated tolylene diisocyanate, hydrogenated 4,4'-diphenylmethane diisocyanate, hydrogenated xylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, isophorone diisocyanate, and isophorone diisocyanate trimers. Examples of polyisocyanates having heterocycles include 1,6-hexanediisocyanate trimers. Examples of aromatic diisocyanates include tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, paraphenylenedi diisocyanate, and 1,5-naphthalene diisocyanate.

[0043] As the hydroxyl group-containing (meth)acrylate, hydroxyl group-containing mono(meth)acrylate is preferred. Examples of hydroxyl group-containing mono(meth)acrylates include hydroxyalkyl(meth)acrylates such as 2-hydroxyethyl(meth)acrylate, 2-hydroxypropyl(meth)acrylate, hydroxybutyl(meth)acrylate, hydroxypentyl(meth)acrylate, hydroxyhexyl(meth)acrylate, and hydroxyoctyl(meth)acrylate.

[0044] UA2 is a compound known as a urethane adduct, which is a reaction product of an organic polyisocyanate and a hydroxyl group-containing (meth)acrylate.

[0045] In UA2, specific examples of organic polyisocyanates and hydroxyl group-containing (meth)acrylates are as described above.

[0046] In UA2, a compound having a hydroxyl group and two or more (meth)acryloyl groups (hereinafter referred to as "hydroxyl group-containing polyfunctional (meth)acrylate") can also be used as the hydroxyl group-containing (meth)acrylate. For UA2, it is preferable to use an organic polyisocyanate and a hydroxyl group-containing polyfunctional (meth)acrylate (hereinafter referred to as "UA2-1"). Examples of hydroxyl group-containing polyfunctional (meth)acrylates include trimethylolpropane di(meth)acrylate, pentaerythritol di or tri(meth)acrylate, ditrimethylolpropane di or tri(meth)acrylate, and dipentaerythritol di, tri, tetra or penta(meth)acrylate. In particular, hydroxyl group-containing polyfunctional (meth)acrylates are preferred if they have three or more (meth)acryloyl groups and one hydroxyl group. Specifically, examples include pentaerythritol tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, and dipentaerythritol penta(meth)acrylate.

[0047] In the production of UA2-1, the hydroxyl-containing polyfunctional (meth)acrylate raw material is usually a mixture containing hydroxyl-containing polyfunctional (meth)acrylate and polyfunctional (meth)acrylate without hydroxyl groups. However, UA2-1 can also be produced using such a mixture. Specifically, examples include mixtures of trimethylolpropanedi(meth)acrylate and trimethylolpropanetri(meth)acrylate, mixtures of ditrimethylolpropanetri(meth)acrylate and ditrimethylolpropanetetra(meth)acrylate, and mixtures of dipentaerythritolpenta(meth)acrylate and dipentaerythritolhexa(meth)acrylate.

[0048] Another preferred compound of UA2 is a reaction product of an organic polyisocyanate having three or more isocyanate groups and a hydroxyl group-containing mono(meth)acrylate (hereinafter referred to as "UA2-2"). Examples of hydroxyl group-containing mono(meth)acrylates in UA2-2 include compounds similar to those described above. Examples of organic polyisocyanates having three or more isocyanate groups include the hexamethylene diisocyanate trimer and isophorone diisocyanate trimer mentioned above. Preferred examples of UA2-2 include the addition reaction product of a hexamethylene diisocyanate trimer and hydroxybutyl acrylate.

[0049] Furthermore, as UA2, a compound having three or more (meth)acryloyl groups is more preferred, which is a reaction product of an organic polyisocyanate and a hydroxyl group-containing (meth)acrylate.

[0050] In UA-1, urethane (meth)acrylate is produced by an addition reaction between a polyol, an organic polyisocyanate, and a hydroxyl group-containing (meth)acrylate, while in UA-2, it is produced by an addition reaction between an organic polyisocyanate and a hydroxyl group-containing (meth)acrylate. This addition reaction can be carried out without a catalyst, but to ensure the reaction proceeds efficiently, a tin-based catalyst such as dibutyltin dilaurate or an amine-based catalyst such as triethylamine may be added.

[0051] Examples of polyester (meth)acrylates include dehydrated condensates of polyester diol and (meth)acrylic acid. Examples of polyester diols include reaction products of a diol with a dicarboxylic acid or its anhydride. Examples of diols include low molecular weight diols such as ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, butylene glycol, polybutylene glycol, tetramethylene glycol, hexamethylene glycol, neopentyl glycol, cyclohexanedimethanol, 3-methyl-1,5-pentanediol, and 1,6-hexanediol, as well as alkylene oxide adducts thereof. Examples of dicarboxylic acids or their anhydrides include orthophthalic acid, isophthalic acid, terephthalic acid, adipic acid, succinic acid, fumaric acid, maleic acid, hexahydrophthalic acid, tetrahydrophthalic acid, and trimellitic acid, as well as their anhydrides (excluding trans dicarboxylic acids).

[0052] Epoxy (meth)acrylates are compounds obtained by the addition reaction of (meth)acrylic acid to epoxy resin. Examples of epoxy resins include aromatic epoxy resins and aliphatic epoxy resins.

[0053] Examples of aromatic epoxy resins include resorcinol diglycidyl ether, hydroquinone diglycidyl ether; diglycidyl ethers of bisphenol A, bisphenol F, bisphenol S, bisphenol fluorene or its alkylene oxide adducts; novolac-type epoxy resins such as phenol novolac-type epoxy resins and cresol novolac-type epoxy resins; glycidyl phthalimide; and o-diglycidyl phthalate esters.

[0054] Examples of aliphatic epoxy resins include diglycidyl ethers of alkylene glycols such as ethylene glycol, propylene glycol, 1,4-butanediol, and 1,6-hexanediol; diglycidyl ethers of polyalkylene glycols such as polyethylene glycol and polypropylene glycol; diglycidyl ethers of neopentyl glycol, dibromo-neopentyl glycol, and their alkylene oxide adducts; diglycidyl ethers of hydrogenated bisphenol A and its alkylene oxide adducts; and diglycidyl esters of tetrahydrophthalate. In the above, ethylene oxide and propylene oxide are preferred as the alkylene oxide in the alkylene oxide adduct.

[0055] Examples of polyether (meth)acrylate oligomers include polyalkylene glycol (meth) diacrylate, such as polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, and polytetramethylene glycol di(meth)acrylate.

[0056] In particular, the polymerizable group in the first radical polymerizable compound is more preferably a (meth)acryloyl group from the viewpoint of polymerizability. In other words, the first radical polymerizable compound preferably contains a compound having a (meth)acryloyl group.

[0057] Furthermore, if the first radical polymerizable compound contains a polyfunctional polymerizable compound, the resulting polymer may become insoluble or infusible due to crosslinking polymerization of the polyfunctional polymerizable compound. For this reason, the first radical polymerizable compound is preferably a monofunctional polymerizable compound, and more preferably a monofunctional (meth)acrylate.

[0058] In particular, when the compounds of this disclosure are used as photoradical polymerization initiators for coating films, the tackiness of the coating film surface can be suppressed due to the high glass transition temperature. Therefore, it is preferable that the first radical polymerizable compound includes a monofunctional (meth)acrylate having an alicyclic structure.

[0059] Furthermore, when the compounds of this disclosure are used as photoradical polymerization initiators for coating films, it is preferable that the first radical polymerizable compound includes a monofunctional (meth)acrylate having a heterocycle, as this makes it easier to obtain coating films with high scratch resistance.

[0060] Furthermore, when polymerizing the second radical polymerizable compound, described later, under atmospheric conditions, it is preferable that the first radical polymerizable compound contains a monofunctional (meth)acrylate having a hydroxyl group, in order to reduce polymerization inhibition by oxygen and facilitate rapid curing.

[0061] Furthermore, when the polymerization of the second radical polymerizable compound, described later, is carried out under atmospheric conditions, it is preferable that the first radical polymerizable compound contains a monofunctional (meth)acrylate having a cyclic ether group, from the viewpoint of reducing polymerization inhibition by oxygen, facilitating rapid curing, and obtaining a coating film with excellent adhesion to various plastic substrates.

[0062] Furthermore, the first radical polymerizable compound preferably contains a compound having a (meth)acryloyl group and a radical generating group, and more preferably contains a monofunctional (meth)acrylate having a radical generating group. In this disclosure, a radical generating group means a group that generates radicals upon irradiation with light. Preferably, the radical generating group is a hydrogen abstraction type radical generating group. Examples of radical-generating groups include groups having a benzophenone structure, groups having a ketocoumarin structure, and groups having a thioxanthone structure.

[0063] In particular, when producing the compounds of this disclosure, it is preferable that the radical generating group is a group having a benzophenone structure, since the radical generating group remains unreacted and acts effectively as a radical generating group in the polymerization of the second radical polymerizable compound described later. That is, the first radical polymerizable compound preferably contains a compound having a (meth)acryloyl group and a benzophenone structure, and more preferably contains a monofunctional (meth)acrylate having a benzophenone structure.

[0064] Examples of compounds having a (meth)acryloyl group and a radical generating group include 4-(meth)acryloyloxybenzophenone, 2-(4-benzoylphenoxy)ethyl (meth)acrylate, 2-(meth)acryloyloxybenzophenone, and 3-(meth)acryloyloxybenzophenone.

[0065] When the first radical polymerizable compound includes a compound having a (meth)acryloyl group and a radical generating group, curing is accelerated when the compound of this disclosure is used as a polymerization initiator. Generally, thermal radical polymerization is used to introduce radical-generating groups into a polymer backbone. In contrast, by performing a radical polymerization reaction using light of a wavelength that does not generate radicals in the radical-generating groups, the radical-generating groups can be introduced into the compounds of this disclosure.

[0066] From the above viewpoint, the first radical polymerizable compound preferably contains a monofunctional (meth)acrylate having an alicyclic structure, more preferably contains a monofunctional (meth)acrylate having an alicyclic structure, a monofunctional (meth)acrylate having a heterocyclic structure, a monofunctional (meth)acrylate having a hydroxyl group, and a monofunctional (meth)acrylate having a cyclic ether group, and even more preferably contains a monofunctional (meth)acrylate having an alicyclic structure, a monofunctional (meth)acrylate having a heterocyclic structure, a monofunctional (meth)acrylate having a hydroxyl group, a monofunctional (meth)acrylate having a cyclic ether group, and a monofunctional (meth)acrylate having a radical generating group.

[0067] The compounds of this disclosure are suitably used as polymerization initiators. The compounds of this disclosure are useful as polymerization initiators because they have an acylphosphine oxide skeleton. Furthermore, because the compounds of this disclosure have oligomer or polymer residues with a number average molecular weight of 200 to 1,000,000, curing shrinkage of the cured product obtained by polymerization is suppressed. In addition, because the compounds of this disclosure have oligomer or polymer residues with a number average molecular weight of 200 to 1,000,000, the generation of by-products during polymerization is suppressed. Moreover, although polymerization in the atmosphere is generally susceptible to oxygen inhibition, polymerization is possible even with highly hydrophobic monomers when using the polymerization initiators of this disclosure.

[0068] The compounds of this disclosure can be produced by the production methods of this disclosure shown below, in which case the compound represented by formula (3) may be produced together with the compound represented by formula (1). In other words, a mixture of the compound represented by formula (1) and the compound represented by formula (3) can be used for polymerization.

[0069] [ka]

[0070] R in equation (3) 1 , R 2 , R 3 , R 4 , R 5and R 11 is R in formula (1) 1 R 2 R 3 R 4 R 5 and R 11 is the same as that

[0071] The compound represented by formula (3) is preferably a compound represented by the following formula (3A). The compound represented by formula (3A) may be produced together with the compound represented by formula (1A).

[0072]

Chemical formula

[0073] R in formula (3A) 11 is the same as R in formula (1) 11 is the same as that

[0074] [Method for producing compound] The compound (preferably a polymerization initiator) of the present disclosure is preferably obtained by irradiating a composition containing a compound represented by the following formula (2) and a first radically polymerizable compound with light having a wavelength including 420 nm to 450 nm to produce a compound represented by formula (1).

Chemical formula

[0075] In formula (1) and formula (2), R 1 R 2 R 3 R 4 R 5 R 6 R 7 R 8 R 9 R 10 R 12 R 13 R 14 R 15 and R<, 16Each independently represents a hydrogen atom or a substituent. R 11 represents a residue obtained by removing one hydrogen atom from an oligomer or polymer having a number average molecular weight of 200 to 1,000,000. R 11 is preferably a residue of an oligomer or polymer containing a structural unit derived from the first radically polymerizable compound.

[0076] Details of the compound represented by formula (1) and the first radically polymerizable compound are as described above. The first radically polymerizable compound may be only one kind or two or more kinds.

[0077] Since the compound represented by formula (2) has absorption in the wavelength region of 420 nm to 450 nm, radicals can be generated by irradiating light including wavelengths of 420 nm to 450 nm, and the first radically polymerizable compound can be polymerized.

[0078] In formula (2), R 1 , R 2 , R 3 [[ID=Elementary substances or compounds having a specific structure or function are described. For example, as the substituents represented by R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 12 , R 13 , R 14 , R 15 , R 16 , and R 1 , examples of the substituents include a halogen atom, a hydroxyl group, a carboxy group, an amide group, an alkyl group, an aryl group, an alkoxy group, and an aryloxy group. The alkyl group, aryl group, alkoxy group, and aryloxy group may further have a substituent. The alkyl group may be a linear alkyl group, a branched alkyl group, or a cyclic alkyl group. Among them, the alkyl group is preferably a methyl group.

[0079] Specifically, the compound represented by formula (2) is preferably bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide. Various substituents may be attached to the aromatic ring of the benzoyl group. Due to the attachment of the phenyl group to the phosphorus atom, the polymerization reaction proceeds when irradiated with light containing wavelengths of 420 nm to 450 nm.

[0080] In the method for producing the compound of the present disclosure, the composition containing the compound represented by formula (2) and the first radical polymerizable compound (hereinafter also referred to as the "raw material composition") may also contain other components other than the compound represented by formula (2) and the first radical polymerizable compound.

[0081] In the raw material composition, the content of the compound represented by formula (2) is preferably 0.1% to 90% by mass, and more preferably 2% to 65% by mass, relative to the total content of the compound represented by formula (2) and the first radical polymerizable compound. In the raw material composition, the content of the first radical polymerizable compound is preferably 40% to 99.9% by mass, and more preferably 35% to 98% by mass, based on the total content of the compound represented by formula (2) and the first radical polymerizable compound.

[0082] The other components are preferably organic solvents. When the raw material composition contains organic solvents, the resulting compound is easy to handle if it is a solid or a highly viscous liquid. In the raw material composition, the content of the organic solvent is preferably 10 to 6000 parts by weight, with the total content of the compound represented by formula (2) and the first radical polymerizable compound being 100 parts by weight. When the content of the organic solvent is within the above range, the polymerization reaction proceeds smoothly.

[0083] Examples of organic solvents include alcohols such as methanol, ethanol, and propanol; ethers such as tetrahydrofuran, ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, methyl carbitol, ethyl carbitol, methyl cellosolve, and ethyl cellosolve; ketones such as acetone and methyl ethyl ketone; and esters such as ethyl acetate and butyl acetate.

[0084] In the method for producing the compound of this disclosure, from the viewpoint of suppressing the generation of by-products, it is preferable that the radicals generated from the compound represented by formula (2) abstract hydrogen atoms from the organic solvent and suppress the progress of radical polymerization. Therefore, the organic solvent is preferably one with a low chain transfer constant and is preferably a ketone or ester. However, when a highly hydrophilic compound is used as the first radical polymerizable compound, the organic solvent may have a relatively high chain transfer constant and may be an alcohol, ether, ethylene glycol alkyl ether, diethylene glycol alkyl ether, aliphatic hydrocarbon, alicyclic hydrocarbon, aromatic hydrocarbon, water, etc.

[0085] The reaction mechanism in the method for producing the compounds of this disclosure will be described below.

[0086] According to the inventors' studies, monoacylphosphine oxide has an absorption edge around 410 nm and cannot be photodegraded by visible light in the long-wavelength region of 420 nm or higher. On the other hand, bisacylphosphine oxide can be photodegraded in one step by irradiation with visible light around 420 nm to 450 nm. Therefore, by irradiating a composition containing the compound represented by formula (2) and the first radical polymerizable compound with light containing wavelengths of 420 nm to 450 nm, photodegradation is stopped in one step. This yields a monoacylphosphine oxide having an oligomer or polymer residue containing a structural unit derived from the first radical polymerizable compound at one end. Compounds containing a benzoyl group and an oligomer or polymer residue containing a structural unit derived from the first radical polymerizable compound can also be obtained. The former corresponds to the compound represented by formula (1) and is useful as a polymerization initiator. The latter, although it does not function as a polymerization initiator, contains a structure similar to that of the compound represented by formula (1), and is therefore useful as a filler with excellent compatibility with the compound represented by formula (1). Therefore, it is preferable to produce the compound represented by formula (1) and then use it in the polymerization reaction as a polymerization initiator composition without removing the filler. By using the polymerization initiator composition, curing shrinkage is suppressed. Deformation of the component is suppressed and the adhesion to the substrate is improved.

[0087] In the method for producing the compound of this disclosure, it is preferable to irradiate with light containing wavelengths of 420 nm to 450 nm, and to irradiate with light having a central wavelength of 420 nm to 450 nm.

[0088] Examples of light sources include semiconductor light sources such as light-emitting diodes (LEDs) and laser light. Considering economic efficiency and space saving of equipment, the light source is preferably an LED with a central wavelength of 420 nm to 450 nm. Furthermore, if the LED emits broad light with a wide half-width and short-wavelength light is also irradiated, it is preferable to install a light-absorbing film or the like between the LED and the reaction vessel to create a bandpass filter. Blue light cut films are readily available. Alternatively, a bandpass filter may be created by coating a film or plate made of plastic such as polyethylene terephthalate resin (PET), polymethyl methacrylate resin (PMMA), polystyrene resin (PS), polymethyl methacrylate-styrene copolymer (MS), or polycarbonate resin (PC) with a reactive resin containing an ultraviolet / visible light absorber, and then curing it with heat, moisture, etc. The reactive resin may be a urethane resin, epoxy resin, etc. Examples of ultraviolet / visible light absorbers include BASF's Chinuvin 477 and Chinuvin 970.

[0089] The reaction vessel is not particularly limited as long as it is made of a material that transmits light including wavelengths of 420 nm to 450 nm, for example, glass and plastic. If the raw material composition contains an organic solvent, the reaction vessel is preferably made of glass. The inner diameter of the reaction vessel is preferably in the range of 0.1 mm to 10 cm. If the inner diameter is small, light will easily pass through, shortening the reaction time, but the yield will be low. On the other hand, if the inner diameter is large, the yield will increase, but light will not reach areas far from the light source, so it will be necessary to efficiently promote decomposition by stirring or other means.

[0090] The light source may be installed in only one direction relative to the reaction vessel, or it may be installed in multiple directions. In particular, when the inner diameter is large, it is preferable to install light sources at multiple positions to shorten the reaction time and improve productivity. The reaction method may be batch or continuous flow. An example of a continuous flow method is to continuously arrange the light sources in the direction in which the liquid flows and continuously flow the reaction liquid into the reaction vessel. Furthermore, if heat removal during polymerization is difficult, a separate transparent tube may be installed outside the reaction vessel and cooling water may be circulated through it, or the reaction vessel may be air-cooled from the outside with a fan.

[0091] The reaction time cannot be uniquely determined because it depends on the concentration of the compound represented by formula (2) and the first radical polymerizable compound, the intensity of the light source, and the number of light sources. However, from the viewpoint of energy conservation and low environmental impact, the irradiation time should preferably be as short as possible, preferably between 1 millisecond and 10 minutes. If the optical path length is long and the reaction takes time, the length of the reaction vessel can be increased, multiple light sources can be placed along the vessel, and the reaction solution can be continuously irradiated with light while flowing. In this case, even if the irradiation time is long, the decrease in productivity can be suppressed by flowing the reaction solution at high speed. The reaction vessel may be made, for example, 10 cm to 2 m long, and a bypass may be provided to allow the liquid to remain and circulate within the reaction vessel several times. Furthermore, the reaction vessel may be bent to allow light from the light source to be efficiently irradiated.

[0092] The reaction rate varies depending on factors such as optical path length, light intensity, light energy, and flow rate. In practical terms, the reaction rate of the compound represented by formula (2) is preferably 90% or higher, and more preferably 95% or higher. Furthermore, the reaction rate of the first radical polymerizable compound is preferably 70% to 100%. Furthermore, in the method for producing the compound of this disclosure, even if the first radical polymerizable compound remains unreacted, in the polymerization reaction using the second radical polymerizable compound described later, the unreacted first radical polymerizable compound can be considered as part of the second radical polymerizable compound. Therefore, if the reaction rate of the compound represented by formula (2) is high, the reaction rate of the first radical polymerizable compound may be less than 70%.

[0093] The reaction solution after the reaction is complete may or may not be purified, depending on the purpose.

[0094] [Polymerizable composition] The polymerizable composition of this disclosure preferably comprises the polymerization initiator of this disclosure and a second radical polymerizable compound.

[0095] The second radical polymerizable compound may be the same as or different from the first radical polymerizable compound. The second radical polymerizable compound may be one type or two or more types.

[0096] By using the polymerizable composition of this disclosure, a polymer containing structural units derived from a second radical polymerizable compound can be obtained.

[0097] Specifically, polymers containing structural units derived from the second radical polymerizable compound are obtained, namely the compound represented by formula (4) and the compound represented by formula (5) below.

[0098] [ka] JPEG2026055027000011.jpg3343

[0099] R in equations (4) and (5) 1 , R 2 , R 3 , R 4 , R 5 , and R 11 R in equation (1) 1 , R 2 , R 3 , R 4 , R 5 , and R 11 It is the same as this. R 21 This is a polymer residue containing a structural unit derived from a second radical polymerizable compound. "Structural units derived from a second radical polymerizable compound" simply means that the structure possessed by the second radical polymerizable compound is present, and it is not necessary whether or not it actually originated from that compound.

[0100] Specific examples of second radical polymerizable compounds are the same as those for the first radical polymerizable compounds described above.

[0101] In particular, from the viewpoint of polymerizability, the polymerizable group in the second radical polymerizable compound is more preferably a (meth)acryloyl group. In other words, the second radical polymerizable compound preferably contains a compound having a (meth)acryloyl group.

[0102] In particular, from the viewpoint of obtaining a film with good surface hardness, the second radical polymerizable compound is preferably a polyfunctional polymerizable compound, more preferably a polyfunctional (meth)acrylate, and even more preferably a trifunctional or more (meth)acrylate.

[0103] Specifically, second radical polymerizable compounds include poly(meth)acrylates of polyols such as glycerin tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, diglycerin tri or tetra(meth)acrylate, pentaerythritol tri or tetra(meth)acrylate, ditrimethylolpropane tri or tetra(meth)acrylate, and dipentaerythritol tri, tetra, penta or hexa(meth)acrylate; Poly(meth)acrylates, which are alkylene oxide adducts of the above polyols, are preferred.

[0104] Furthermore, in terms of the excellent flexibility of the cured product, the second radical polymerizable compound is preferably a tri or tetra(meth)acrylate of an alkylene oxide adduct of diglycerin, and more preferably a tetra(meth)acrylate of an alkylene oxide adduct of diglycerin. The second radical polymerizable compound may also include mono, di, and tri(meth)acrylates of alkylene oxide adducts of diglycerin.

[0105] Examples of alkylene oxides in alkylene oxide adducts include ethylene oxide, propylene oxide, tetramethylene oxide, and combinations of ethylene oxide and propylene oxide. Ethylene oxide is preferred as the alkylene oxide. The number of moles of alkylene oxide adduct added is preferably 2 to 10 moles, and more preferably 4 to 8 moles.

[0106] In particular, the second radical polymerizable compound is preferably a combination of a poly(meth)acrylate of a polyol and a poly(meth)acrylate of an alkylene oxide adduct of a polyol. The mass ratio of the poly(meth)acrylate of the polyol to the poly(meth)acrylate of the alkylene oxide adduct of the polyol is preferably 5:95 to 55:45, and more preferably 5:95 to 50:50. When the proportion of poly(meth)acrylate in the polyol is 5% by mass or more, the cured product exhibits excellent scratch resistance (steel wool resistance). When the proportion of poly(meth)acrylate in the polyol is 55% by mass or less, the cured product exhibits excellent flexibility and curlability.

[0107] Examples of polyfunctional (meth)acrylates include, in addition to the compounds mentioned above, polyfunctional polymers, polyfunctional vinyl compounds, and polyfunctional allyl compounds.

[0108] [Application] The polymerizable compositions of this disclosure are applicable to coatings, inks, adhesives, and the like. When applying a polymerizable composition to a coating agent, ink, adhesive, etc., conventionally known additives may be added to the polymerizable composition. Examples of additives include UV absorbers, antioxidants, and light stabilizers such as hindered amines; as well as polymer fillers and inorganic fillers such as silica. When applied to ink, colorants such as pigments may be added.

[0109] [Method for manufacturing hardened products] A method for producing a cured product according to the present disclosure includes, for example, the steps of applying the polymerizable composition according to the present disclosure onto a substrate, and irradiating the applied polymerizable composition with active energy rays.

[0110] Examples of substrates include glass, ceramics, concrete, metal, resin, wood, paper, fabric, and leather.

[0111] Methods for imparting polymerizable compositions include known methods such as coating, inkjet, and immersion. Coating methods can be carried out using bar coaters, extrusion die coaters, air doctor coaters, blade coaters, rod coaters, knife coaters, squeeze coaters, reverse roll coaters, etc.

[0112] Examples of active energy rays include alpha rays, gamma rays, electron beams, X-rays, ultraviolet rays, visible light, and infrared light. Among these, the active energy ray is preferably visible light or ultraviolet light. Light sources for irradiating with active energy rays include ultraviolet lamps, halogen lamps, high-pressure mercury lamps, lasers, LEDs, and electron beam irradiation devices.

[0113] The wavelength of the active energy rays is preferably 200 to 600 nm, more preferably 300 to 450 nm, and even more preferably 350 to 420 nm. When curing with light exceeding a wavelength of 410 nm, it is preferable to add a thioxanthone compound such as 2,4-diethylthioxanthone or a photosensitizer such as Anthracure® UVS-581 manufactured by Air Water Performance Chemicals Inc. to the polymerizable composition. The illuminance of active energy rays is, for example, 50 mW / cm². 2 ~1000mW / cm 2 That is the case. The irradiation time for the active energy rays is, for example, 1 second to 5 minutes.

[0114] In the method for producing a cured product according to this disclosure, after applying the polymerizable composition onto a substrate, the applied polymerizable composition may be directly irradiated with active energy rays. Alternatively, in the method for producing a cured product according to this disclosure, after applying the polymerizable composition onto a substrate, a light-transmitting adherend may be placed on the substrate, and active energy rays may be irradiated through the adherend.

[0115] [Cured product] The cured product of the present disclosure is preferably a cured product of the polymerizable composition of the present disclosure. The cured product of the present disclosure can be manufactured, for example, using the method for manufacturing the cured product described above. [Examples]

[0116] The present disclosure will be explained in more detail below with reference to examples and comparative examples, but this disclosure is not limited thereto.

[0117] [Polymerization initiator 1] 2.1 g of bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (Omnirad380, manufactured by IGM Resins USA Inc., hereinafter also referred to as "BAPO") and 8.6 g of methyl acrylate (manufactured by Toagosei Co., Ltd.) were weighed into a 100 mL volumetric flask, and the flask was filled to the mark with butyl acetate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) to prepare the reaction solution. This was placed in a 3 cm diameter Schlenk tube, and dissolved oxygen was removed by freezing and degassing three times using liquid nitrogen. Next, while stirring at 400 rpm with a magnetic stirrer, an illuminance of 270 mW / cm was applied using an I-Graphics 425 nm LED (model: UVA 80×50-425), maintaining a distance of 2 cm between the light source and the Schlenk tube. 2 The solution containing polymerization initiator 1 was obtained by irradiating it with light for 60 seconds. The illuminance was estimated using a UV illuminometer C-9536-02 / H9958-02 manufactured by Hamamatsu Photonics K.K.

[0118] Figure 1 shows the results of quantifying the reaction rate of BAPO using liquid chromatography (HPLC system LC-20AD, manufactured by Shimadzu Corporation). Figure 2 shows the polymerization rate of methyl acrylate calculated using gas chromatography (GC column Zebron ZB-1 manufactured by Shimadzu Corporation (length 60 m, inner diameter 0.32 mm, film thickness 3.0 μm)). Figure 3 shows the change in the UV-visible spectrum of the reaction solution over time with light irradiation. Figure 3 shows the results of measurements taken using a Hitachi High-Technologies Corporation Spectrophotometer U-2910 with a path length of 1 cm after diluting the reaction solution 100 times (by volume) with acetonitrile. Figure 3 clearly shows that BAPO possesses atomic groups that can act as polymerization initiators, as it retains absorption in the visible light region even after decomposition.

[0119] 3.40 g of a solution containing polymerization initiator 1 was added to n-hexane in a volume ratio of 10, unreacted components and by-products were removed, and the mixture was vacuum-dried at 80°C for 24 hours to obtain a mixture containing 0.30 g of polymerization initiator 1. The mixture containing polymerization initiator 1 was subjected to gel permeation chromatography (Tosoh Corporation high-speed GPC instrument HLC-8320, columns: Tosoh Corporation TSKgelSuperMultipore HZ-M 4.6 mm ID × 15 cm × 3, substrate: styrene-·divinylbenzene copolymer, particle size: 4 μm, exclusion limit molecular weight: 2,000,000 (polystyrene equivalent), theoretical plate number: 16,000 or more, molecular weight fractionation range: 500~1,000,000). The molecular weight was calculated using the following method, and the number-average molecular weight was 1480, while the weight-average molecular weight was 2610. Figure 4 shows the mixture containing polymerization initiator 1. 1 This is a diagram showing the 1H NMR spectrum. Figure 4 shows the terminal structures of two compounds obtained by the decomposition of BAPO. The first is the compound corresponding to the peak shown in b) in Figure 4. This is the compound represented by formula (1A), where R 11 However, it was a residue of a homopolymer having a structural unit derived from methyl acrylate. The second is the compound corresponding to the peak shown in Figure 4a). This is the compound represented by formula (3A), where R 11 However, it was a residue of a homopolymer having a structural unit derived from methyl acrylate. The number of repeating units in the methyl acrylate was approximately 10. In other words, it was found that the mixture containing polymerization initiator 1 contains the compound represented by formula (1A) (i.e., polymerization initiator 1) and the compound represented by formula (3A).

[0120] <Example 1-1> Next, it was confirmed that the obtained polymerization initiator 1 was effective as a polymerization initiator. 0.06 g of the mixture containing the obtained polymerization initiator 1, 5.1 g of n-butyl acrylate (manufactured by Toagosei Co., Ltd.), and 3.7 g of butyl acetate were stirred at room temperature (25°C, the same applies below) for 30 minutes to obtain a homogeneous solution. This was placed in a Schlenk tube, and after freezing and degassing three times using liquid nitrogen, dissolved oxygen was removed. Then, while stirring at 400 rpm with a magnetic stirrer, a 385 nm LED (model: UVA 80×50-385) manufactured by I-Graphics was used, maintaining a distance of 2 cm between the light source and the Schlenk tube, and 360 mW / cm² was applied. 2 Light irradiation was performed using the following method. This value was estimated using a UV irradiance meter C-9536-02 / H9958-02 manufactured by Hamamatsu Photonics K.K. Figure 5 shows the relationship between light irradiation time and the polymerization rate of n-butyl acrylate. It was found that the mixture containing polymerization initiator 1 does not contain any other components that function as polymerization initiators, and that n-butyl acrylate polymerizes when irradiated with 385 nm light. Furthermore, the polymerization rate plateaus after about 20 seconds of irradiation, which is thought to be because the compound represented by formula (1A) is almost completely decomposed by light irradiation. Figure 6 shows the results of sampling polymerization solutions with varying light irradiation times, diluting them 100 times (by volume) with butyl acetate, and measuring the UV-visible spectrum. Figure 6 shows that as the light irradiation time increases, absorption around 365 nm disappears, indicating that the compound represented by formula (1A) is decomposing. Figure 7 shows the changes in GPC before and after photoirradiation in Example 1-1. After photoirradiation, a peak corresponding to high molecular weight polymers is observed, and the peak intensity of low molecular weight polymers decreases. From this, it is clear that polymerization initiator 1 is useful as a polymerization initiator.

[0121] <Examples 1-2> Next, 1.04 g of the mixture containing the obtained polymerization initiator 1, 3.22 g of n-butyl acrylate, and 18.08 g of butyl acetate were stirred at room temperature for 30 minutes to obtain a homogeneous solution. This was placed in a Schlenk tube, and after freezing and degassing three times using liquid nitrogen, dissolved oxygen was removed. Then, while stirring at 400 rpm with a magnetic stirrer, a 385 nm LED (model: UVA 80×50-385) manufactured by I-Graphics was used, maintaining a distance of 2 cm between the light source and the Schlenk tube, and 270 mW / cm² was applied. 2 Light irradiation was performed. In this polymerizable composition, the concentration of n-butyl acrylate is low, so the resulting polymer has a low molecular weight.

[0122] Figure 8 shows the changes in GPC before and after light irradiation in Example 1-2. As shown in Figure 8, it was found that a polymer with a lower average molecular weight than that of Example 1-1 was obtained. Figure 9 shows the measurement results of the MALDI-TOF mass spectrum of the obtained polymer (JMS-S3000SpiralTOF®, manufactured by JEOL Ltd.). Figure 9 shows that the obtained polymer contains the compound represented by formula (4) and the compound represented by formula (5). The compound represented by formula (5) was found to contain structural units derived from methyl acrylate and n-butyl acrylate, and it is clear that polymerization initiator 1 is useful as a polymerization initiator.

[0123] [Polymerization initiator 2] A solution containing polymerization initiator 2 was obtained in the same manner as polymerization initiator 1, except that 1.05 g of BAPO and 20.83 g of isobornyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., IBXA) were weighed into a 50 mL volumetric flask, and the flask was filled to the mark with butyl acetate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) to prepare the reaction solution. GPC analysis of the resulting polymerization initiator 2 revealed a number-average molecular weight of 4520 and a weight-average molecular weight of 24170.

[0124] Figure 10 shows the results of quantifying the reaction rate of BAPO using liquid chromatography (HPLC system LC-20AD, Shimadzu Corporation). Figure 11 shows the polymerization rate of isobornyl acrylate calculated using gas chromatography (Shimadzu Corporation, GC column Zebron ZB-1 (length 60m, inner diameter 0.32mm, film thickness 3.0μm)). It can be seen that BAPO and isobornyl acrylate have been quantitatively eliminated. Figure 12 shows the change in the UV-visible spectrum of the reaction solution over time with light irradiation. The spectrum in Figure 12 was obtained by diluting the reaction solution 100 times (by volume) with butyl acetate and measuring it using a Hitachi High-Tech Corporation Spectrophotometer U-2910 with an optical path length of 1 cm. Figure 12 clearly shows that BAPO still absorbs in the visible light region even after decomposition and possesses atomic groups that can act as polymerization initiators.

[0125] <Example 2-1> Next, the adhesive was prepared without purifying the solution containing polymerization initiator 2. Specifically, the solution containing the obtained polymerization initiator 2 was mixed with tricyclodecanedimethylol diacrylate (manufactured by Kyoeisha Chemical Co., Ltd., product name "Light Acrylate DCP-A", hereinafter also referred to as "DCPA") to the content (parts by mass) shown in Table 1 to prepare the adhesive. In Table 1, the content of polymerization initiator 2 is the content as solids. A polypropylene film (manufactured by Sun-Tox Co., Ltd., product name "Sun-Tox-OP", film thickness 60 μm) was coated with adhesive using a bar coater and dried in a 90°C dryer for 3 minutes to obtain a coating film from which butyl acetate had evaporated. A polypropylene film was then placed over this as a cover film and pressed with a roller to obtain a laminate with a 30 μm resin layer. This was then irradiated using a 365 nm-LED irradiation device HLDL-100X50U65 manufactured by CCS Corporation at an illuminance of 500 mW / cm². 2 The irradiation was performed for 30 seconds.

[0126] <Comparative Example 2-1> An adhesive was prepared by mixing DCPA, isobornyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., IBXA), and 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (manufactured by IGM Resins, product name "OMNIRAD TPO", hereinafter also referred to as "TPO") in the amounts (parts by mass) shown in Table 1. A laminate was obtained using the prepared adhesive in the same manner as in Example 2-1.

[0127] <Comparative Example 2-2> An adhesive was prepared by mixing DCPA, isobornyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., IBXA), and 1-hydroxycyclohexyl phenyl ketone (manufactured by IGM Resin, product name "OMNIRAD184") in the amounts (parts by mass) shown in Table 1. A laminate was obtained using the prepared adhesive in the same manner as in Example 2-1.

[0128] (Peel strength) The adhesive performance was evaluated by measuring the peel strength (test piece width 10 mm, peeling speed 50 mm / min) of the laminates obtained in Example 2-1, Comparative Example 2-1, and Comparative Example 2-2.

[0129] [Table 1]

[0130] As shown in Table 1, in Example 2-1, good results were obtained as an adhesive for plastic films by using the compound of this disclosure (polymerization initiator) containing structural units derived from isobornyl acrylate.

[0131] Generally, in active energy ray curing adhesives, when a large amount of polyfunctional polymerizable compounds are included, the stress generated at the interface between the substrate and the adhesive layer increases, and the adhesive strength tends to decrease. In Example 2-1, it was found that the adhesive strength was high despite the high content of the polyfunctional polymerizable compound.

[0132] [Polymerization initiator 3] A solution containing polymerization initiator 3 was obtained in the same manner as polymerization initiator 1, except that 2.10 g of BAPO, 13.33 g of isobornyl acrylate (IBXA, manufactured by Osaka Organic Chemical Industry Co., Ltd.), 9.86 g of acryloylmorpholine (ACMO®, manufactured by KJ Chemicals Co., Ltd.), 9.64 g of 4-hydroxybutyl acrylate (4-HBA, manufactured by Osaka Organic Chemical Industry Co., Ltd.), and 8.89 g of tetrahydrofurfuryl acrylate (Viscote #150, manufactured by Osaka Organic Chemical Industry Co., Ltd.) were weighed into a 100 mL volumetric flask, and the flask was filled to the mark with ethyl acetate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) (52.42 g of ethyl acetate) to prepare the reaction solution.

[0133] GPC analysis of the obtained polymerization initiator 3 solution revealed a number-average molecular weight of 6000 and a weight-average molecular weight of 38100. When the solution containing polymerization initiator 3 was added to 10 times (by volume) n-hexane, the precipitated polymer was recovered and GPC analysis was performed, revealing a number-average molecular weight of 6300 and a weight-average molecular weight of 40300.

[0134] [Polymerization initiator 4] A solution containing polymerization initiator 4 was obtained in the same manner as polymerization initiator 1, except that the reaction solution was prepared by weighing out 2.09 g of BAPO, 6.72 g of isobornyl acrylate (IBXA, manufactured by Osaka Organic Chemical Industry Co., Ltd.) as component (B), 3.36 g of acryloylmorpholine (ACMO®, manufactured by KJ Chemicals Co., Ltd.), 3.36 g of 4-hydroxybutyl acrylate (4-HBA, manufactured by Osaka Organic Chemical Industry Co., Ltd.), 3.02 g of tetrahydrofurfuryl acrylate (Viscote #150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), and 0.34 g of 4-methacryloyloxybenzophenone (MBP, manufactured by Shinryo Co., Ltd.) as component (C) and filling the flask to the mark with ethyl acetate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) (90.15 g of ethyl acetate).

[0135] GPC analysis of the obtained polymerization initiator 4 revealed a number-average molecular weight of 2200 and a weight-average molecular weight of 5900. When the solution containing polymerization initiator 4 was added to 10 times (by volume) n-hexane, the precipitated polymer was recovered and GPC analysis was performed, revealing a number-average molecular weight of 2400 and a weight-average molecular weight of 5300.

[0136] <Examples 3-1 to 3-4> Next, the coating solution was prepared without purifying the solution containing polymerization initiator 3 and the solution containing polymerization initiator 4. Specifically, a coating solution was prepared by mixing the obtained polymerization initiator 3 or a solution containing polymerization initiator 4 with a mixture of dipentaerythritol pentaacrylate and hexaacrylate (Toagosei Co., Ltd., Aronics M-402) and ethylene oxide modified diglycerin acrylate (Toagosei Co., Ltd., Aronics M-460) in the amounts (parts by mass) shown in Table 2. In Table 2, the content of polymerization initiator 3 and polymerization initiator 4 is the content as solids.

[0137] <Comparative Example 3-1> A coating solution was prepared by mixing a mixture of dipentaerythritol pentaacrylate and hexaacrylate (Toagosei Co., Ltd., Aronics M-402), acrylate of ethylene oxide-modified diglycerin (Toagosei Co., Ltd., Aronics M-460), and 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (IGM Resins, product name "OMNIRAD TPO") in the amounts (parts by mass) shown in Table 2.

[0138] <Comparative Example 3-2> A coating solution was prepared by mixing a mixture of dipentaerythritol pentaacrylate and hexaacrylate (Toagosei Co., Ltd., Aronics M-402), acrylate of ethylene oxide-modified diglycerin (Toagosei Co., Ltd., Aronics M-460), and 1-hydroxycyclohexyl-phenyl ketone (IGM Resins, product name "OMNIRAD184") in the amounts (parts by mass) shown in Table 2.

[0139] The coating solutions prepared in Examples 3-1 to 3-4, Comparative Example 3-1, and Comparative Example 3-2 were evaluated for their curability, curl, adhesion, and pencil hardness.

[0140] (curable) A coating solution was applied to a PET film (manufactured by Toyobo Co., Ltd., product name "Cosmoshine®" A4360, film thickness 50 μm) using a bar coater to achieve a cured film thickness of 5 μm. A 365 nm LED was used to measure the light intensity at 950 mW / cm². 2 The curing process was performed with an irradiation time of 5 seconds. The curability was evaluated based on the presence or absence of tack on the surface after curing. The evaluation criteria are as follows: A: There is no tuck. B: It has a tuck.

[0141] (curl) A coating solution was applied to a PET film (manufactured by Toyobo Co., Ltd., product name "Cosmoshine®" A4360, film thickness 50 μm) using a bar coater to achieve a cured film thickness of 30 μm. A 365 nm LED was used to measure the light intensity at 950 mW / cm². 2 Curing was performed with an irradiation time of 30 seconds. The substrate on which the cured film had formed was cut into 5cm x 5cm pieces, and the lift height at the four corners was measured. The lift height was taken as the average value of the four corners. In Comparative Examples 3-1 and 3-2, the deformation was so large that the lift height could not be measured, so it was indicated as "-".

[0142] (Adhesive) A cold-rolled steel sheet (compliant with JIS G3141:2017) treated with Bonderite N144 was coated with a coating solution using a bar coater to achieve a hardened film thickness of 30 μm. A 365 nm LED was used to measure the light intensity at 950 mW / cm². 2 The material was cured with an irradiation time of 30 seconds. The adhesion of the cured film was evaluated using the cross-cut method (JIS K5600-5-6). The numerical values ​​of the evaluation results are integers from 0 to 5, according to the judgment method specified in the JIS standard. A smaller number indicates better adhesion.

[0143] (Pencil hardness) A cured film was formed using the same method as for evaluating adhesion. The pencil hardness of the cured film was evaluated according to JIS K5600-5-4:1999.

[0144] [Table 2]

[0145] As shown in Table 2, in Examples 3-1 to 3-4, it was found that good curability could be obtained even for thin films by using the polymerization initiator of this disclosure. Furthermore, in Examples 3-1 to 3-4, it was found that curling was suppressed even when polyfunctional polymerizable compounds were cured. Furthermore, while Comparative Examples 3-1 and 3-2 showed no adhesion to the substrate at all, Examples 3-1 to 3-4 exhibited good adhesion. Generally, achieving both adhesion and pencil hardness is difficult. Higher pencil hardness tends to result in lower adhesion, and surface treatments such as applying a primer to the substrate beforehand are sometimes performed to ensure adhesion. In fact, in Comparative Examples 3-1 and 3-2, although the pencil hardness was high, the adhesion was extremely low and impractical. In contrast, in Examples 3-4, it was found that both adhesion and pencil hardness could be achieved.

[0146] In Examples 3-4, polymerization initiator 3 contains both an acylphosphine oxide structure and a benzophenone structure. The acylphosphine oxide structure functions as an α-cleavage type photopolymerization initiator, initiating polymerization, while the benzophenone structure functions as a hydrogen abstraction type photopolymerization initiator, contributing to an increase in the crosslinking density of the cured film. Because the residual strain is small when increasing the crosslinking density, it is thought that both adhesion and pencil hardness can be achieved. Furthermore, the inclusion of the benzophenone structure allows the by-product compound represented by formula (4) to also function as a polymerization initiator.

[0147] <Polymerization initiator 5A> Using an iGraphics 385nm LED (model: UVA 80×50-385), the illuminance was 360mW / cm². 2 A solution containing polymerization initiator 5A was obtained in the same manner as with polymerization initiator 1, except that it was irradiated with light for 60 seconds. GPC analysis of the solution containing polymerization initiator 5A revealed a number-average molecular weight of 1140 and a weight-average molecular weight of 2650. 100 mL of a solution containing polymerization initiator 5A was purified in the same manner as with polymerization initiator 1, and polymerization of n-butyl acrylate was attempted in the same manner as in Example 1-1. When irradiated with a 385nm LED for 60 seconds, polymerization did not occur at all. This is thought to be because BAPO was completely decomposed by the 385nm light when obtaining the solution containing polymerization initiator 5A.

[0148] <Polymerization initiator 6A> Illuminance 270mW / cm 2 A solution containing polymerization initiator 6A was obtained in the same manner as polymerization initiator 1, except that it was irradiated with light for 180 seconds. GPC analysis of the solution containing polymerization initiator 6A revealed a number-average molecular weight of 1200 and a weight-average molecular weight of 2540. 100 mL of a solution containing polymerization initiator 6A was purified in the same manner as with polymerization initiator 1, and polymerization of n-butyl acrylate was attempted in the same manner as in Example 1-1. Irradiated with a 385nm LED for 60 seconds, but polymerization did not occur at all. This is thought to be because the light irradiation time was too long when obtaining the solution containing polymerization initiator 6A, causing BAPO to completely decompose.

[0149] (Toxicity assessment) The toxicity of polymerization initiators 1 and 4 was evaluated. To assess toxicity, zebrafish embryos were exposed to the samples, and then the morphology of the zebrafish was observed. The presence or absence of toxicity was determined by the number of individuals showing abnormalities.

[0150] The conditions and methods for toxicity assessment are as follows: (1) Test organism: Zebrafish (Danio rerio) (2) Exposure conditions Duration: 5 to 120 hours after fertilization Method: Water stop type Test concentrations: polymerization initiator 1 0.005, 0.05, 0.50, 5.0 mg / L Polymerization initiator 4: 0.005, 0.05, 0.50, 5.0 mg / L Positive control group: 50 mg / L sodium valproate (VA) Test solution preparation method: Dimethyl sulfoxide (DMSO) solution at 200 times the concentration of each test concentration (set concentration) was diluted with test water to prepare the test solution. The test substance was handled under a yellow light. The VA aqueous solution was prepared by mixing VA and test water, stirring to dissolve, and adding DMSO to achieve a final concentration of 0.5% (volume / volume). (3) Environmental conditions Test water: Artificially prepared water (ISO 6341 - 1982) Test water temperature: 28 ± 1 °C Number of test organisms: 6 individuals per test section (1 individual per well) Volume of test solution: 24 mL (2 mL / well) Test container: 24 - well polystyrene plate Illumination: Exposure is carried out under dark conditions (performed under yellow light during test solution preparation, organism introduction, and observation of test organisms) Feeding: No feeding (4) Observation Observation of organisms: After 120 hours post - fertilization, anesthetic MS - 222 is added to a final concentration of 0.03%, and the morphology of the organisms is observed. Microscope: Inverted microscope CKX53 (Olympus) Observation items: Heart (abnormal heartbeat, abnormal heart size, abnormal heart chambers) Shape of the face (abnormal eye morphology, abnormal ear morphology, abnormal jaw morphology) Shape of the body (abnormal notochord morphology, abnormal tail morphology) Blood circulation (facial edema, abdominal edema (including around the heart), abnormal blood flow) Hatching (delayed hatching (unhatched at 72 hours post - fertilization: abnormal)) (5) Toxicity determination Toxicity score: If an abnormality is observed, a score of 10 is given for each item (maximum 120 points / individual). The average value of the total score in each test section is taken as the morphological abnormality score (MS), and the MS in the highest concentration section with a survival rate of 50% or more is taken as MS 50 and so on. Judgment criteria: MS 50 If it is 10 or more, it is judged as "positive (+)", and if it is less than 10, it is judged as "negative (-)". <L

[0151] Both polymerization initiator 1 and polymerization initiator 4 are negative, and no toxicity was observed in polymerization initiator 1 and polymerization initiator 4.

Industrial applicability

[0152] The compounds disclosed herein are useful as polymerization initiators for low-toxicity active-energy-ray-curable compositions. Block polymer mixtures, which normally can only be produced using living polymerization, can be easily manufactured using long-wavelength light sources such as LEDs. Furthermore, the compounds disclosed herein are applicable to adhesives, coatings, and the like.

Claims

1. A compound represented by the following formula (1). 【Chemistry 1】 In formula (1), R １ 、 R ２ 、 R ３ 、 R ４ 、 R ５ 、 R ６ 、 R ７ 、 R ８ 、 R ９ 、 and R １０ each independently represents a hydrogen atom or a substituent, R １１ This represents a residue of an oligomer or polymer with a number-average molecular weight of 200 to 1,000,000.

2. R １１ The compound according to claim 1, wherein is a residue of an oligomer or polymer containing a structural unit derived from a first radical polymerizable compound.

3. The compound according to claim 2, wherein the first radical polymerizable compound includes a compound having a (meth)acryloyl group.

4. The compound according to claim 2, wherein the first radical polymerizable compound includes a compound having a (meth)acryloyl group and a radical generating group.

5. The compound according to claim 2, wherein the first radical polymerizable compound includes a compound having a (meth)acryloyl group and a benzophenone structure.

6. A method for producing a compound, comprising irradiating a composition containing a compound represented by the following formula (2) and a first radical polymerizable compound with light containing wavelengths of 420 nm to 450 nm to produce a compound represented by formula (1). 【Chemistry 2】 【change】 In equations (1) and (2), R １ , R ２ , R ３ , R ４ , R ５ , R ６ , R ７ , R ８ , R ９ , R １０ , R １２ , R １３ , R １４ , R １５ , and R １６ Each of these independently represents a hydrogen atom or a substituent. R １１ This represents a residue obtained by removing one hydrogen atom from an oligomer or polymer with a number-average molecular weight of 200 to 1,000,000.

7. A compound according to any one of claims 1 to 5, which is a polymerization initiator.

8. A polymerizable composition comprising the compound described in claim 7 and a second radical polymerizable compound.

9. A coating agent comprising the polymerizable composition described in claim 8.

10. An adhesive comprising the polymerizable composition described in claim 8.

11. A cured product of the polymerizable composition according to claim 8.

12. A step of applying the polymerizable composition described in claim 8 onto a substrate, The process involves irradiating the polymerizable composition with active energy rays, A method for producing a cured product, including the following:

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