Compound, Method for Producing Compound, Polymerizable Composition, Coating Agent, Adhesive, Cured Product, and Method for Producing Cured Product

Abstract

To provide a novel compound and the like. 【Solution means】A compound represented by the following formula (1). JPEG0007683800000018.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] The present disclosure relates to a compound, a method for producing the compound, a polymerizable composition, a coating agent, an adhesive, a cured product, and a method for producing the cured product.

Background Art

[0002] Conventionally, high-pressure mercury lamps and electrodeless lamps have been the mainstream as light sources for curing polymerizable compounds. For example, Patent Document 1 describes performing ultraviolet irradiation using a mercury lamp to cure a polymerizable composition. However, in recent years, due to the increasing awareness of the environment, energy-saving and long-life light-emitting diodes (LEDs) have come to be used.

[0003] For example, Patent Document 2 describes curing a polymerizable composition using a photoinitiator that reacts by irradiation with an LED. However, some of the compounds having an acylphosphine skeleton used here are toxic, and there is a concern that their use will be restricted in the future.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0005] An object of an embodiment of the present disclosure is to provide a novel compound that reacts with light having a long wavelength such as an LED and gives a photoinitiator with low toxicity, and a method for producing the compound. Another object of an embodiment of the present disclosure is to provide a polymerizable composition, a coating agent, and an adhesive containing the above compound. 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 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 represents a residue of an oligomer or polymer having a number average molecular weight of 200 to 1,000,000. <2> R 11 is a residue of an oligomer or polymer containing a structural unit derived from a first radically polymerizable compound, the compound according to <1>. <3> The first radically polymerizable compound includes a compound having a (meth)acryloyl group, the compound according to <2>. <4> The first radically polymerizable compound includes a compound having a (meth)acryloyl group and a radical generating group, the compound according to <2>. <5> The first radically polymerizable compound includes a compound having a (meth)acryloyl group and a benzophenone structure, the compound according to <2>. <6> A compound represented by the following formula (2), and a method for producing a compound, which comprises irradiating a composition containing the first radically polymerizable compound with light having a wavelength in the range of 420 nm to 450 nm to produce the compound represented by formula (1). [Chemical formula] JPEG0007683800000003.jpg5279 In formulas (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 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. <7> The compound according to any one of <1> to <5>, which is a polymerization initiator. <8> A polymerizable composition comprising the polymerization initiator according to <6> and a second radically polymerizable compound. <9> A coating agent comprising the polymerizable composition according to <8>. <10> An adhesive comprising the polymerizable composition according to <8>. <11> A cured product of the polymerizable composition according to <8>. <12> A step of applying the polymerizable composition according to <8> onto a substrate, and A step of irradiating the applied polymerizable composition with active energy rays, and a method for producing a cured product. [Advantages of the Invention]

[0007] According to one embodiment of the present disclosure, a novel compound that reacts with long-wavelength light such as LED and provides a low-toxicity photoinitiator or the like, and a method for producing the compound are provided. According to another embodiment of the present disclosure, a polymerizable composition, a coating agent, and an adhesive containing the above compound are provided. According to another embodiment of the present disclosure, a cured product of the above polymerizable composition and a method for producing the cured product are provided.

Brief Description of the Drawings

[0008]

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Embodiments for Carrying Out the Invention

[0009] In this specification, the numerical range indicated using "~" means a range including the numerical values described before and after "~" as the minimum value and the maximum value, respectively. In the numerical ranges described stepwise in this specification, the upper limit value or the lower limit value described in a certain numerical range may be replaced with the upper limit value or the lower limit value of the numerical range of other stepwise descriptions. Also, in the numerical ranges described in this specification, the upper limit value or the lower limit value described in a certain numerical range may be replaced with the value shown in the examples.

[0010] In this specification, the amount of each component in the composition means the total amount of the plurality of substances present in the composition when there are a plurality of substances corresponding to each component in the composition, unless otherwise specified. In this specification, a combination of two or more preferred embodiments is a more preferred embodiment. In this specification, the term "step" includes not only an independent step but also, even when it cannot be clearly distinguished from other steps, as long as the intended purpose of the step is achieved.

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

[0012] [Compound] The compound of the present disclosure is represented by the following formula (1).

Chemical formula

[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 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.

[0014] The compound of the present disclosure is a compound that generates radicals with high sensitivity to a light source that emits long-wavelength light, and is a novel compound (preferably, a (photo)polymerization initiator).

[0015] In the compound of the present disclosure, the structure of R 11 can be designed according to 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), examples of the substituents represented by R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , and R 10 include, for example, 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.

[0017] Specifically, from the viewpoint of ease of production, the compound of the present disclosure is preferably represented by the following formula (1A). R in formula (1A) 11 is the same as R in formula (1) 11

[0018]

Chemical formula

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

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

[0021] Column: "TSKgel SuperMultipore HZ-M 4.6 mm ID × 15 cm × 3 columns, manufactured by Tosoh Corporation, base material: styrene-divinylbenzene copolymer, particle size: 4 μm, exclusion limit molecular weight: 2,000,000 (in terms of polystyrene), theoretical plate number: 16,000 or more, molecular weight fractionation range: 500 to 1,000,000" Solvent: Tetrahydrofuran Temperature: 40°C Detector: RI Flow rate: 350 μL / min

[0022] ​​In the compound according to the present disclosure, a carbonylphenyl group which may have a substituent and a phenyl group which may have a substituent are bonded to the phosphorus atom of the -P=O group in formula (1), and further, a residue of an oligomer or polymer having a number average molecular weight of 200 to 1,000,000 is bonded, whereby it is highly sensitive to a light source that emits light with a long wavelength. Therefore, R 11 The structure of the residue of the oligomer or polymer represented by is not particularly limited.

[0023] From the viewpoints of high productivity and low environmental impact, R 11 is preferably a residue of an oligomer or polymer containing a structural unit derived from a first radically polymerizable compound.

[0024] The "structural unit derived from a first radically polymerizable compound" means that the structure possessed by the first radically polymerizable compound may be present, and it does not matter whether it is actually derived from the compound. The first radically polymerizable compound may be only one kind, or may be two or more kinds.

[0025] In the present disclosure, the "radically polymerizable compound" means a compound having a radically polymerizable group.

[0026] In the present disclosure, the "radically polymerizable group" is preferably a photopolymerizable group, and more preferably a photo-radically polymerizable group. Examples of the photo-radically polymerizable group include (meth)acryloyl group, allyl group, styryl group, and vinyl group.

[0027] Also, the number of radically polymerizable groups possessed by the first radically polymerizable compound may be only one, or may be two or more. That is, the first radically polymerizable compound may be a monofunctional polymerizable compound or a polyfunctional polymerizable compound.

[0028] Examples of the monofunctional polymerizable compound include monofunctional (meth)acrylate, monofunctional (meth)acrylamide, monofunctional (meth)allyl compound, monofunctional aromatic vinyl compound, monofunctional vinyl ether, and monofunctional N-vinyl compound.

[0029] Examples of the monofunctional (meth)acrylate 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, mono(meth)acrylate of pentaerythritol, 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; aromatic monofunctional (meth)acrylates such as phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, o-phenylphenol (meth)acrylate, (meth)acrylate of an alkylene oxide adduct of phenol, (meth)acrylate of an alkylene oxide adduct of an alkylphenol, (meth)acrylate of an alkylene oxide adduct of p-cumylphenol, (meth)acrylate of an alkylene oxide adduct of o-phenylphenol, and 4-(meth)acryloyloxybenzophenone; Alkyl carbitol (meth) acrylates such as ethyl carbitol (meth) acrylate, butyl carbitol (meth) acrylate, 2-ethylhexyl carbitol (meth) acrylate; Mono-functional (meth) acrylates having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxy (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate; Mono-functional (meth) acrylates having a carboxy group such as (meth) acrylic acid, Michael addition type dimer of acrylic acid, ω-carboxy-polycaprolactone mono (meth) acrylate, mono-hydroxyethyl phthalate (meth) acrylate; Mono-functional (meth) acrylates having a cyclic ether group such as glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, (2-methyl-2-ethyl-1,3-dioxolan-4-yl) methyl (meth) acrylate, cyclohexane spiro-2-(1,3-dioxolan-4-yl) methyl (meth) acrylate, 3-ethyl-3-oxetanyl methyl (meth) acrylate; Examples of the mono-functional (meth) acrylate having a heterocyclic ring include (meth) acryloylmorpholine, N-(2-(meth)acryloxyethyl)hexahydrophthalimide, N-(2-(meth)acryloxyethyl)tetrahydrophthalimide.

[0030] Examples of the mono-functional (meth) acrylamide include N-alkyl (meth) acrylamides such as N-methyl (meth) acrylamide, N-n-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-n-butyl (meth) acrylamide, N-sec-butyl (meth) acrylamide, N-t-butyl (meth) acrylamide, N-n-hexyl (meth) acrylamide; 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, N,N-dihexyl (meth)acrylamide, and the like.

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

[0032] Examples of monofunctional aromatic vinyl compounds include styrene, dimethylstyrene, trimethylstyrene, isopropylstyrene, chloromethylstyrene, methoxystyrene, acetoxystyrene, chlorostyrene, dichlorostyrene, bromostyrene, methyl vinyl benzoate, 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 the monofunctional vinyl ether 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 the monofunctional N-vinyl compound include N-vinyl-ε-caprolactam and N-vinylpyrrolidone.

[0035] Examples of the polyfunctional polymerizable compound include polyfunctional (meth)acrylate and polyfunctional vinyl ether. Examples of the polyfunctional (meth)acrylate include a compound having two (meth)acryloyl groups (hereinafter referred to as "bifunctional (meth)acrylate") and a compound having three or more (meth)acryloyl groups (hereinafter referred to as "trifunctional or higher (meth)acrylate").

[0036] Examples of the bifunctional (meth)acrylate 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 tricyclodecane dimethylol di(meth)acrylate and 1,4-cyclohexanedimethanol di(meth)acrylate; di(meth)acrylates of polyols having a trivalent or higher valence 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)acrylate of ethylene oxide adduct of isocyanuric acid; Examples thereof include di(meth)acrylates of alkylene oxide adducts of bisphenol A and di(meth)acrylates of alkylene oxide adducts of bisphenol F. Examples of the alkylene oxide in the alkylene oxide adduct include ethylene oxide, propylene oxide, tetramethylene oxide, and combinations of ethylene oxide and propylene oxide.

[0037] Specific examples of the trifunctional or higher (meth)acrylate include poly(meth)acrylates of polyols such as glycerin tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, tri- or tetra(meth)acrylate of diglycerin, tri- or tetra(meth)acrylate of pentaerythritol, tri- or tetra(meth)acrylate of ditrimethylolpropane, and tri-, tetra-, penta- or hexa(meth)acrylate of dipentaerythritol; The poly(meth)acrylate of the alkylene oxide adduct of the above polyol; Examples thereof include tri(meth)acrylates having an isocyanuric acid skeleton such as tri(meth)acrylate of the ethylene oxide adduct of isocyanuric acid. Examples of the alkylene oxide in the alkylene oxide adduct include ethylene oxide, propylene oxide, tetramethylene oxide, and combinations of ethylene oxide and propylene oxide.

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

[0039] Examples of the urethane (meth)acrylate include the reaction product of a polyol, an organic polyisocyanate, and a hydroxyl group-containing (meth)acrylate (hereinafter referred to as "UA1"), and the reaction product of an organic polyisocyanate and a hydroxyl group-containing (meth)acrylate (hereinafter referred to as "UA2"). Hereinafter, UA1 and UA2 will be described.

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

[0041] As the polyol in UA1, a diol is preferred. As the diol, a low molecular weight diol, a diol having a polyester skeleton, a diol having a polyether skeleton, and a diol having a polycarbonate skeleton are preferred. Examples of the low molecular weight diol include ethylene glycol, propylene glycol, cyclohexanedimethanol, neopentyl glycol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, and the like. Examples of the diol 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 the dicarboxylic acid or its anhydride include adipic acid, succinic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, terephthalic acid, and their anhydrides. Examples of the polyether diol include polyethylene glycol, polypropylene glycol, and polytetramethylene glycol. Examples of the polycarbonate diol include reaction products of a diol component such as the above-mentioned low molecular weight diol or / and bisphenol such as bisphenol A, and a dialkyl carbonate such as ethylene carbonate and dibutyl carbonate.

[0042] Examples of the organic polyisocyanate include aliphatic polyisocyanates having no alicyclic structure (hereinafter simply referred to as "aliphatic polyisocyanates"), aliphatic polyisocyanates having an alicyclic structure (hereinafter referred to as "alicyclic polyisocyanates"), polyisocyanates having a heterocyclic ring, and aromatic polyisocyanates. Examples of the aliphatic polyisocyanate include 1,6-hexamethylene diisocyanate, tetramethylene diisocyanate, trimethylhexamethylene diisocyanate, and lysine diisocyanate. Examples of the alicyclic polyisocyanate include hydrogenated tolylene diisocyanate, hydrogenated 4,4'-diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, isophorone diisocyanate, and isophorone diisocyanate trimer. Examples of the polyisocyanate having a heterocyclic ring include 1,6-hexane diisocyanate trimer. Examples of the aromatic diisocyanate include tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, paraphenylene diisocyanate, and 1,5-naphthalene diisocyanate.

[0043] As the hydroxyl group-containing (meth)acrylate, a hydroxyl group-containing mono(meth)acrylate is preferred. Examples of the hydroxyl group-containing mono(meth)acrylate 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 reaction product of an organic polyisocyanate and a hydroxyl group-containing (meth)acrylate, and is a compound called a urethane adduct.

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

[0046] In UA2, as the hydroxyl group-containing (meth)acrylate, 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 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 the hydroxyl group-containing polyfunctional (meth)acrylate include trimethylolpropane di(meth)acrylate, di- or tri(meth)acrylate of pentaerythritol, di- or tri(meth)acrylate of ditrimethylolpropane, and di-, tri-, tetra-, or penta(meth)acrylate of dipentaerythritol. Among them, the hydroxyl group-containing polyfunctional (meth)acrylate preferably has three or more (meth)acryloyl groups and one hydroxyl group, and specific examples include pentaerythritol tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, and dipentaerythritol penta(meth)acrylate.

[0047] In the production of UA2-1, the raw material hydroxyl group-containing polyfunctional (meth)acrylate is usually a mixture containing a hydroxyl group-containing polyfunctional (meth)acrylate and a polyfunctional (meth)acrylate having no hydroxyl group. However, those produced using such a mixture can also be used as UA2-1. Specific examples include mixtures of trimethylolpropane di(meth)acrylate and trimethylolpropane tri(meth)acrylate, mixtures of ditrimethylolpropane tri(meth)acrylate and ditrimethylolpropane tetra(meth)acrylate, and mixtures of dipentaerythritol penta(meth)acrylate and dipentaerythritol hexa(meth)acrylate.

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

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

[0050] Urethane (meth)acrylate is produced by an addition reaction of a polyol, an organic polyisocyanate, and a hydroxyl group-containing (meth)acrylate in UA-1, and by an addition reaction of an organic polyisocyanate and a hydroxyl group-containing (meth)acrylate in UA-2. This addition reaction can occur even without a catalyst, but in order to promote the reaction 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)acrylate include dehydration condensates of polyester diol and (meth)acrylic acid. Here, examples of polyester diol include reaction products of diol and dicarboxylic acid or its anhydride. Examples of diol 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, 1,6-hexanediol, and alkylene oxide adducts thereof. Examples of dicarboxylic acid or its anhydride include dicarboxylic acids such as orthophthalic acid, isophthalic acid, terephthalic acid, adipic acid, succinic acid, fumaric acid, maleic acid, hexahydrophthalic acid, tetrahydrophthalic acid, and trimellitic acid, and anhydrides thereof (excluding trans-form dicarboxylic acids).

[0052] Epoxy (meth)acrylate is a compound obtained by adding (meth)acrylic acid to an epoxy resin. Examples of epoxy resin include aromatic epoxy resin and aliphatic epoxy resin.

[0053] Specific examples of the aromatic epoxy resin include resorcinol diglycidyl ether, hydroquinone diglycidyl ether; diglycidyl ethers of bisphenol A, bisphenol F, bisphenol S, bisphenol fluorene or their alkylene oxide adducts; novolak type epoxy resins such as phenol novolak type epoxy resin and cresol novolak type epoxy resin; glycidyl phthalimide; o-phthalic acid diglycidyl ester, and the like.

[0054] Specific examples of the aliphatic epoxy resin 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, dibromoneopentyl glycol and their alkylene oxide adducts; diglycidyl ethers of hydrogenated bisphenol A and its alkylene oxide adducts; tetrahydrophthalic acid diglycidyl ester, and the like. In the above, as the alkylene oxide of the alkylene oxide adduct, ethylene oxide, propylene oxide and the like are preferable.

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

[0056] Among them, from the viewpoint of polymerizability, the polymerizable group in the first radically polymerizable compound is more preferably a (meth) acryloyl group. That is, the first radically polymerizable compound preferably contains a compound having a (meth) acryloyl group.

[0057] In addition, when the first radically polymerizable compound contains a polyfunctional polymerizable compound, the resulting polymer may become insoluble and infusible due to crosslinking polymerization of the polyfunctional polymerizable compound. Therefore, the first radically polymerizable compound is preferably a monofunctional polymerizable compound, and more preferably a monofunctional (meth)acrylate.

[0058] In particular, when the compound of the present disclosure is used as a photo radical polymerization initiator for a coating film, since the tackiness of the coating film surface can be suppressed by a high glass transition temperature, the first radically polymerizable compound preferably contains a monofunctional (meth)acrylate having an alicyclic structure.

[0059] In addition, when the compound of the present disclosure is used as a photo radical polymerization initiator for a coating film, since a coating film with high scratch resistance is easily obtained, the first radically polymerizable compound preferably contains a monofunctional (meth)acrylate having a heterocyclic ring.

[0060] In addition, when the polymerization of the second radically polymerizable compound described later is carried out in the atmosphere, from the viewpoint of reducing polymerization inhibition by oxygen and easily achieving rapid curing, the first radically polymerizable compound preferably contains a monofunctional (meth)acrylate having a hydroxyl group.

[0061] In addition, when the polymerization of the second radically polymerizable compound described later is carried out in the atmosphere, from the viewpoint of reducing polymerization inhibition by oxygen, easily achieving rapid curing, and obtaining a coating film excellent in adhesion to various plastic substrates, the first radically polymerizable compound preferably contains a monofunctional (meth)acrylate having a cyclic ether group.

[0062] In addition, the first radically 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 the present disclosure, the radical generating group means a group having an action of generating radicals by irradiation with light. The radical generating group is preferably a hydrogen abstraction type radical generating group. Examples of the radical - generating group include a group having a benzophenone structure, a group having a ketocoumarin structure, and a group having a thioxanthone structure.

[0063] Among them, in producing the compound of the present disclosure, since the radical - generating group remains without reacting and effectively acts as a radical - generating group in the polymerization of the second radical - polymerizable compound described later, the radical - generating group is preferably a group having a benzophenone structure. 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 the compound 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 contains a compound having a (meth)acryloyl group and a radical - generating group, curing is promoted when the compound of the present disclosure is used as a polymerization initiator. In general, thermal radical polymerization is used to introduce a radical - generating group into a polymer skeleton. In contrast, the radical - generating group of the present disclosure can be introduced by performing a radical polymerization reaction using light having a wavelength at which the radical - generating group does not generate radicals.

[0066] From the above viewpoints, the first radically polymerizable compound preferably includes a monofunctional (meth)acrylate having an alicyclic structure, more preferably includes a monofunctional (meth)acrylate having an alicyclic structure, a monofunctional (meth)acrylate having a heterocyclic ring, a monofunctional (meth)acrylate having a hydroxyl group, and a monofunctional (meth)acrylate having a cyclic ether group, and even more preferably includes a monofunctional (meth)acrylate having an alicyclic structure, a monofunctional (meth)acrylate having a heterocyclic ring, 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 the present disclosure are suitably used as polymerization initiators. Since the compounds of the present disclosure have an acylphosphine oxide skeleton, they are useful as polymerization initiators. In addition, since the compounds of the present disclosure have residues of oligomers or polymers having a number average molecular weight of 200 to 1,000,000, the curing shrinkage of the cured product obtained by polymerization is suppressed. In addition, since the compounds of the present disclosure have residues of oligomers or polymers having a number average molecular weight of 200 to 1,000,000, the generation of by-products due to polymerization is suppressed. Also, generally, polymerization in the atmosphere is easily affected by oxygen inhibition, but if the polymerization initiator of the present disclosure is used, even a highly hydrophobic monomer can be polymerized.

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

[0069]

Chemical formula

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

[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

[0074] [Method for producing compound] The compound (preferably a polymerization initiator) of the present disclosure is preferably obtained by a method of irradiating a composition containing a compound represented by the following formula (2) and a first radically polymerizable compound with light having a wavelength in the range of 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 16 ​each 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 a 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 , 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 Examples of the substituents represented by 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 bonded to the aromatic ring of the benzoyl group. Since a phenyl group is bonded to the phosphorus atom, the polymerization reaction proceeds by irradiating light having a wavelength 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 radically polymerizable compound (hereinafter also referred to as "raw material composition") may contain components other than the compound represented by formula (2) and the first radically polymerizable compound.

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

[0082] The other component is preferably an organic solvent. When the raw material composition contains an organic solvent, the resulting compound has excellent handleability when it is a solid or a high-viscosity liquid. In the raw material composition, the content of the organic solvent is preferably 10 parts by mass to 6000 parts by weight, with the total content of the compound represented by formula (2) and the first radically polymerizable compound being 100 parts by mass. When the content of the organic solvent is within the above range, the polymerization reaction proceeds smoothly.

[0083] Examples of the organic solvent 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 the present disclosure, from the viewpoint of suppressing the generation of by-products, it is preferable to suppress the radical generated from the compound represented by the formula (2) from extracting the hydrogen atom of the organic solvent and proceeding with radical polymerization. Therefore, the organic solvent preferably has a low chain transfer constant and is preferably a ketone or an ester. When a highly hydrophilic compound is used as the first radically polymerizable compound, the organic solvent may have a relatively high chain transfer constant and may be an alcohol, an ether, an ethylene glycol alkyl ether, a diethylene glycol alkyl ether, an aliphatic hydrocarbon, an alicyclic hydrocarbon, an aromatic hydrocarbon, water, or the like.

[0085] Hereinafter, the reaction mechanism in the method for producing the compound of the present disclosure will be described.

[0086] According to the studies of the present inventors, monoacylphosphine oxide has an absorption edge around about 410 nm and cannot be photodecomposed by visible light in the long wavelength region of 420 nm or more. On the other hand, bisacylphosphine oxide can be photodecomposed in one step by irradiating visible light in the vicinity of 420 nm to 450 nm. Therefore, by irradiating the composition containing the compound represented by the formula (2) and the first radically polymerizable compound with light including a wavelength of 420 nm to 450 nm, the photodecomposition stops in one step. Thereby, a monoacylphosphine oxide having a residue of an oligomer or polymer containing a structural unit derived from the first radically polymerizable compound at one end is obtained. Further, a compound containing a benzoyl group and a residue of an oligomer or polymer containing a structural unit derived from the first radically polymerizable compound is also obtained. The former corresponds to the compound represented by the formula (1) and is useful as a polymerization initiator. Although the latter does not function as a polymerization initiator, since it contains a structure similar to that of the compound represented by the formula (1), it is useful as a filler having excellent compatibility with the compound represented by the formula (1). Therefore, after producing the compound represented by the formula (1), it is preferably used for the polymerization reaction as a polymerization initiator composition without removing the above filler. By using the polymerization initiator composition, the curing shrinkage is suppressed. The deformation of the member is suppressed, and it is effective in improving the adhesion to the base material.

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

[0088] Examples of the light source include semiconductor light sources such as light-emitting diodes (LEDs) and laser light. Considering economy and space-saving of equipment, the light source is preferably an LED with a central wavelength of 420 nm to 450 nm. When the light emission of the LED is broad with a wide half-value width and short-wavelength light is also irradiated, it is preferable to install a light absorption film or the like between the LED and the reaction vessel to serve as a band-pass filter. A blue cut film is easily available. Further, a reactive resin containing an ultraviolet / visible light absorber is coated on a film or plate made of a plastic such as polyethylene terephthalate resin (PET), polymethyl methacrylate resin (PMMA), polystyrene resin (PS), polymethyl methacrylate-styrene copolymer (MS), polycarbonate resin (PC), etc., and this is cured by heat, moisture, etc. to serve as a band-pass filter. The reactive resin may be a urethane-based resin, an epoxy-based resin, or the like. Examples of the ultraviolet / visible light absorber include Tinuvin 477 and Tinuvin 970 manufactured by BASF.

[0089] The reaction vessel is not particularly limited as long as it is a material that transmits light having a wavelength of 420 nm to 450 nm, and examples thereof include glass and plastic. When the raw material composition contains an organic solvent, the reaction vessel is preferably 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 easily passes through, so the reaction time is shortened, but the yield decreases. On the other hand, when the inner diameter increases, although the yield increases, light does not reach the places far from the light source, so it is necessary to efficiently promote decomposition by stirring or the like.

[0090] The light source may be installed in only one direction with respect to the reaction vessel or in a plurality of directions. Particularly when the inner diameter is large, it is preferable to install the light source at a plurality of positions to shorten the reaction time and improve productivity. The reaction mode may be a batch mode or a continuous flow mode. Examples of the continuous flow mode include a mode in which the light source is continuously arranged in the direction in which the liquid flows and the reaction liquid is continuously flowed into the reaction vessel. In addition, when it is difficult to remove heat during polymerization, another transparent tube may be installed outside the reaction vessel, and cooling water may be passed through it, or air cooling may be performed with a fan from the outside of the reaction vessel.

[0091] The reaction time cannot be uniquely determined because it is determined by the compound represented by formula (2), the concentrations of the first radically polymerizable compound, the intensity of the light source, and the number of light sources. However, from the viewpoints of energy conservation and low environmental impact, the time for irradiating light is preferably as short as possible, and preferably 1 millisecond to 10 minutes. When the optical path length is long and the reaction has a time, the length of the reaction vessel can be increased, a plurality of light sources can be arranged along the vessel, and light irradiation can be performed while continuously flowing the reaction solution. In this case, even if the irradiation time becomes long, a decrease in productivity can be suppressed by flowing the reaction solution at high speed. The length of the reaction vessel may be, for example, 10 cm to 2 m, and a bypass may be provided to allow the liquid to stay and circulate in the reaction vessel several times. Also, the reaction vessel may be bent so that light from the light source is efficiently irradiated.

[0092] The reaction rate varies depending on the optical path length, light intensity, light energy amount, flow rate, etc. Practically, the reaction rate of the compound represented by formula (2) is preferably 90% or more, and more preferably 95% or more. Also, the reaction rate of the first radically polymerizable compound is preferably 70% to 100%. In the method for producing the compound of the present disclosure, even if the first radically polymerizable compound remains unreacted, in the polymerization reaction using the second radically polymerizable compound described later, the unreacted first radically polymerizable compound can be regarded as a part of the second radically polymerizable compound. Therefore, if the reaction rate of the compound represented by formula (2) is high, the reaction rate of the first radically polymerizable compound may be less than 70%.

[0093] The reaction solution after completion of the reaction may or may not be purified depending on the purpose.

[0094] [Polymerizable Composition] The polymerizable composition of the present disclosure preferably contains the polymerization initiator of the present disclosure and a second radically polymerizable compound.

[0095] The second radically polymerizable compound may be the same as or different from the first radically polymerizable compound. The second radically polymerizable compound may be only one kind or two or more kinds.

[0096] By using the polymerizable composition of the present disclosure, a polymer containing a structural unit derived from the second radically polymerizable compound can be obtained.

[0097] Specifically, as the polymer containing a structural unit derived from the second radically polymerizable compound, a compound represented by the following formula (4) and a compound represented by formula (5) can be obtained.

[0098] [Chemical formula] JPEG0007683800000011.jpg3343

[0099] R in formula (4) and formula (5) 1 , R 2 , R 3 , R 4 , R 5 , and R 11 are the same as R 1 , R 2 , R 3 , R 4 , R 5 , and R 11 in formula (1). R 21 is a residue of a polymer containing a structural unit derived from the second radically polymerizable compound. The "structural unit derived from the second radically polymerizable compound" means that it is sufficient if the structure of the second radically polymerizable compound exists, and it does not matter whether it is actually derived from the compound.

[0100] Specific examples of the second radically polymerizable compound include those similar to the specific examples of the first radically polymerizable compound described above.

[0101] Among them, from the viewpoint of polymerizability, the polymerizable group in the second radically polymerizable compound is more preferably a (meth)acryloyl group. That is, the second radically 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 radically polymerizable compound is preferably a polyfunctional polymerizable compound, more preferably a polyfunctional (meth)acrylate, and even more preferably a (meth)acrylate having three or more functional groups.

[0103] Specifically, the second radically polymerizable compound includes polyglycerol poly(meth)acrylate such as glycerol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, tri- or tetra(meth)acrylate of diglycerin, tri- or tetra(meth)acrylate of pentaerythritol, tri- or tetra(meth)acrylate of ditrimethylolpropane, and tri-, tetra-, penta- or hexa(meth)acrylate of dipentaerythritol; Poly(meth)acrylate of the alkylene oxide adduct of the above polyol is preferred.

[0104] Furthermore, in terms of the excellent flexibility of the cured product, the second radically polymerizable compound is preferably tri- or tetra(meth)acrylate of the alkylene oxide adduct of diglycerin, and more preferably tetra(meth)acrylate of the alkylene oxide adduct of diglycerin. Note that the second radically polymerizable compound may contain mono-, di- and tri(meth)acrylate of the alkylene oxide adduct of diglycerin.

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

[0106] In particular, the second radically 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, more preferably 5:95 to 50:50. When the proportion of the poly(meth)acrylate of the polyol is 5% by mass or more, the cured product is excellent in scratch resistance (steel wool resistance). When the proportion of the poly(meth)acrylate of the polyol is 55% by mass or less, the cured product is excellent in flexibility and curling properties.

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

[0108] [Use] The polymerizable composition of the present disclosure is applicable to coating agents, inks, adhesives, etc. When applying the polymerizable composition to a coating agent, ink, adhesive, etc., conventionally known additives may be added to the above polymerizable composition. Examples of the additives include light stabilizers such as ultraviolet absorbers, antioxidants, and hindered amines; inorganic fillers such as polymer fillers and silica. When applying to an ink, a colorant such as a pigment may be added.

[0109] [Method for Producing Hardened Product] The method for producing a hardened product of the present disclosure includes, for example, a step of applying the polymerizable composition of the present disclosure onto a substrate, and a step of irradiating the applied polymerizable composition with active energy rays.

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

[0111] Examples of the method for applying the polymerizable composition include known methods such as a coating method, an inkjet method, and an immersion method. The coating method can be performed using a bar coater, an extrusion die coater, an air doctor coater, a blade coater, a rod coater, a knife coater, a squeeze coater, a reverse roll coater, or the like.

[0112] Examples of the active energy rays include α-rays, γ-rays, electron beams, X-rays, ultraviolet rays, visible light, infrared light, and the like. Among them, the active energy rays are preferably visible light or ultraviolet rays. Examples of the light source for irradiating the active energy rays include an ultraviolet irradiation lamp, a halogen lamp, a high-pressure mercury lamp, a laser, an LED, and an electron beam irradiation device.

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

[0114] In the method for producing a cured product of the present disclosure, after applying the above polymerizable composition onto a substrate, the applied polymerizable composition may be directly irradiated with active energy rays. Further, in the method for producing a cured product of the present disclosure, after applying the above polymerizable composition onto a substrate, an adherend that transmits light may be disposed, and the 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 produced, for example, using the above method for producing a cured product. [Examples]

[0116] Hereinafter, examples and comparative examples will be given to more specifically explain the present disclosure, but the present disclosure is not limited thereto.

[0117] [Polymerization initiator 1] In a 100 mL volumetric flask, 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, and butyl acetate (manufactured by Fujifilm Wako Pure Chemical Corporation) was used to fill up to the calibration line to prepare a reaction solution. This was charged into a Schlenk tube with a diameter of 3 cm, and freeze-degassed three times using liquid nitrogen to remove dissolved oxygen. Then, while stirring at 400 rpm with a magnetic stirrer, a 425 nm LED (model: UVA 80×50-425) manufactured by Eye Graphics was used, and the distance between the light source and the Schlenk tube was maintained at 2 cm, and light irradiation was performed at an illuminance of 270 mW / cm 2 for 60 seconds to obtain a solution containing Polymerization initiator 1. The illuminance is a value estimated by a UV illuminometer C-9536-02 / H9958-02 manufactured by Hamamatsu Photonics K.K.

[0118] Figure 1 is a diagram showing the results of quantifying the reaction rate of BAPO by 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 (length 60 m, inner diameter 0.32 mm, film thickness 3.0 μm) manufactured by Shimadzu Corporation). Figure 3 shows the change in the UV-visible spectrum of the reaction solution with the light irradiation time. Figure 3 shows the result of diluting the reaction solution 100-fold (volume ratio) with acetonitrile and measuring it at an optical path length of 1 cm using a spectrophotometer Spectrophotometer U-2910 manufactured by Hitachi High-Tech Corporation. From Figure 3, it is clear that BAPO has an atomic group that can act as a polymerization initiator because it has absorption in the visible light region even after decomposition.

[0119] 3.40 g of the solution containing polymerization initiator 1 was added to n-hexane at a volume ratio of 10 times, and unreacted components and by-products were removed, followed by vacuum drying at 80 °C for one day and night (24 hours) to obtain 0.30 g of a mixture containing polymerization initiator 1. The mixture containing polymerization initiator 1 was subjected to gel permeation chromatography (manufactured by Tosoh Corporation, high-speed GPC device HLC-8320, column: TSKgel SuperMultipore HZ-M 4.6 mm ID × 15 cm × 3 manufactured by Tosoh Corporation, base material: styrene-divinylbenzene copolymer, particle size: 4 μm, exclusion limit molecular weight: 2000000 (polystyrene conversion), theoretical plate number: 16000 or more, molecular weight fractionation range: 500 - 1000000) ) to calculate the molecular weight, and the number average molecular weight was 1480 and the weight average molecular weight was 2610. Figure 4 shows the 1 1H NMR spectrum of the mixture containing polymerization initiator 1. From Figure 4, the terminal structures of two types of compounds obtained by the first-stage decomposition of BAPO were confirmed. The first is the compound corresponding to the peak represented by b) in Figure 4. This is a residue of a homopolymer having a structural unit derived from methyl acrylate in the compound represented by formula (1A), where R 11 was a residue of a homopolymer having a structural unit derived from methyl acrylate. The second is a compound corresponding to the peak represented by a) in Fig. 4. This is a compound represented by the formula (3A), where R 11 is the residue of a homopolymer having a structural unit derived from methyl acrylate. The number of repeating units of methyl acrylate was about 10. That is, it was found that the mixture containing the polymerization initiator 1 contains the compound represented by the formula (1A) (i.e., the polymerization initiator 1) and the compound represented by the formula (3A).

[0120] <Example 1-1> Next, it was confirmed that the obtained polymerization initiator 1 is 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 hereinafter) for 30 minutes to obtain a uniform solution. This was charged into a Schlenk tube, and after performing freeze-deaeration 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 Eye Graphics was used, and the distance between the light source and the Schlenk tube was maintained at 2 cm, and light irradiation was performed at 360 mW / cm 2 This value was estimated by a UV illuminometer C-9536-02 / H9958-02 manufactured by Hamamatsu Photonics K.K. Fig. 5 is a diagram showing the relationship between the light irradiation time and the polymerization rate of n-butyl acrylate. It was found that the mixture containing the polymerization initiator 1 does not contain components that function as polymerization initiators other than the polymerization initiator 1, and that n-butyl acrylate polymerizes upon irradiation with 385 nm light. Also, the polymerization rate levels off at around 20 seconds of irradiation time, which is thought to be because almost all of the compound represented by the formula (1A) has decomposed due to light irradiation. Fig. 6 is a diagram showing the results of sampling polymerization solutions with different light irradiation times, diluting them 100-fold (volume ratio) with butyl acetate, and measuring the UV-visible spectrum. As shown in Fig. 6, it can be seen that as the light irradiation time increases, absorption near 365 nm disappears, indicating that the compound represented by formula (1A) has decomposed. Fig. 7 is a diagram showing the change in GPC before and after light irradiation in Example 1-1. After light irradiation, a peak corresponding to a high molecular weight polymer is observed, and the peak intensity of the low molecular weight decreases. From this, it is clear that polymerization initiator 1 is useful as a polymerization initiator.

[0121] <Example 1-2> Next, 1.04 g of the obtained mixture containing 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 charged into a Schlenk tube and freeze-degassed three times using liquid nitrogen to remove dissolved oxygen. Then, while stirring at 400 rpm with a magnetic stirrer, a 385 nm LED (model: UVA 80×50-385) manufactured by Aigraphics was used, and the distance between the light source and the Schlenk tube was maintained at 2 cm, and light irradiation was performed at 270 mW / cm 2 In this polymerizable composition, since the concentration of n-butyl acrylate is low, the resulting polymer has a low molecular weight.

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

[0123] [Polymerization initiator 2] In a 50 mL volumetric flask, 1.05 g of BAPO and 20.83 g of isobornyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., IBXA) were weighed, and butyl acetate (manufactured by Fujifilm Wako Pure Chemical Corporation) was used to fill up to the calibration line to prepare a reaction solution. In the same manner as for polymerization initiator 1, a solution containing polymerization initiator 2 was obtained, except for the above. When GPC measurement was performed on the obtained solution containing polymerization initiator 2, the number average molecular weight was 4,520 and the weight average molecular weight was 24,170.

[0124] Figure 10 is a diagram showing the result of quantifying the reaction rate of BAPO by liquid chromatography (HPLC system LC-20AD manufactured by Shimadzu Corporation). Figure 11 is a diagram showing the polymerization rate of isobornyl acrylate calculated using gas chromatography (GC column Zebron ZB-1 (length 60 m, inner diameter 0.32 mm, film thickness 3.0 μm) manufactured by Shimadzu Corporation). It can be seen that BAPO and isobornyl acrylate have disappeared quantitatively. Figure 12 is a diagram showing the change in the UV-visible spectrum of the reaction solution with the light irradiation time. The spectrum in Figure 12 is the result of measuring the reaction solution diluted 100-fold (volume ratio) with butyl acetate using a spectrophotometer Spectrophotometer U-2910 manufactured by Hitachi High-Tech Corporation with an optical path length of 1 cm. From Figure 12, it is clear that BAPO has absorption in the visible light region even after decomposition and has atomic groups that can act as a polymerization initiator.

[0125] <Example 2-1> Next, an adhesive was prepared without purifying the solution containing polymerization initiator 2. That is, the obtained solution containing polymerization initiator 2 and tricyclodecane dimethylol diacrylate (manufactured by Kyoeisha Chemical Co., Ltd., product name "Light Acrylate DCP-A", hereinafter also referred to as "DCPA") were mixed so as to have the contents (parts by mass) described in Table 1 to prepare an adhesive. In Table 1, the content of polymerization initiator 2 is the content as a solid content. A polypropylene film (manufactured by Santex Co., Ltd., product name "Santex-OP", film thickness 60 μm) was coated with an adhesive using a bar coater and dried in a dryer at 90°C for 3 minutes to obtain a coating film from which butyl acetate had evaporated. A polypropylene film was placed on this as a cover film and crimped with a roller to obtain a laminate with a resin layer of 30 μm. Using a 365 nm-LED irradiation device HLDL-100X50U65 manufactured by CCS, Inc., irradiation was performed at an illuminance of 500 mW / cm 2 for 30 seconds at.

[0126] <Comparative Example 2-1> 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") were mixed so as to have the contents (parts by mass) shown in Table 1 to prepare an adhesive. Using the prepared adhesive, a laminate was obtained in the same manner as in Example 2-1.

[0127] <Comparative Example 2-2> DCPA, isobornyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., IBXA), and 1-hydroxycyclohexyl-phenyl ketone (manufactured by IGM Resins, product name "OMNIRAD184") were mixed so as to have the contents (parts by mass) shown in Table 1 to prepare an adhesive. Using the prepared adhesive, a laminate was obtained in the same manner as in Example 2-1.

[0128] (Peel strength) Using the laminates obtained in Example 2-1, Comparative Example 2-1, and Comparative Example 2-2, the peel strength (test piece width 10 mm, peel rate 50 mm / min) was measured to evaluate the performance as an adhesive.

[0129]

Table 1

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

[0131] Generally, in an active energy ray-curable adhesive, when a large amount of a polyfunctional polymerizable compound is contained, the stress generated at the interface between the base material and the adhesive layer tends to increase and the adhesive strength tends to decrease. In Example 2-1, it was found that the adhesive strength was high despite the large content of the polyfunctional polymerizable compound.

[0132] [Polymerization Initiator 3] Into a 100 mL volumetric flask, 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 (registered trademark) 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 (Biscoat #150 manufactured by Osaka Organic Chemical Industry Co., Ltd.) were weighed, and (ethyl acetate (manufactured by Fujifilm Wako Pure Chemical Corporation) was used to fill up to the calibration line (52.42 g as ethyl acetate), and in the same manner as Polymerization Initiator 1 except that a reaction solution was prepared, a solution containing Polymerization Initiator 3 was obtained.

[0133] When GPC measurement was performed on the obtained solution containing Polymerization Initiator 3, the number average molecular weight was 6000 and the weight average molecular weight was 38100. The solution containing Polymerization Initiator 3 was added to 10 times the amount (volume ratio) of n-hexane, the precipitated polymer was recovered, and GPC measurement was performed. As a result, the number average molecular weight was 6300 and the weight average molecular weight was 40300.

[0134] [Polymerization Initiator 4] Into a 100 mL volumetric flask, weigh 2.09 g of BAPO, as component (B), 6.72 g of isobornyl acrylate (IBXA manufactured by Osaka Organic Chemical Industry Co., Ltd.), 3.36 g of acryloylmorpholine (ACMO (registered trademark) 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 (Biscoat #150 manufactured by Osaka Organic Chemical Industry Co., Ltd.), and 0.34 g of 4-methacryloyloxybenzophenone (MBP manufactured by Shinryo Corporation). As component (C), fill up to the calibration line with ethyl acetate (manufactured by Fujifilm Wako Pure Chemical Corporation) (90.15 g as ethyl acetate), and a solution containing polymerization initiator 4 was obtained in the same manner as polymerization initiator 1, except that a reaction solution was prepared.

[0135] When GPC measurement was performed on the obtained solution containing polymerization initiator 4, the number average molecular weight was 2,200 and the weight average molecular weight was 5,900. The solution containing polymerization initiator 4 was added to 10 times the amount (volume ratio) of n-hexane, the precipitated polymer was recovered, and GPC measurement was performed. As a result, the number average molecular weight was 2,400 and the weight average molecular weight was 5,300.

[0136] <Examples 3-1 to 3-4> Next, a coating solution was prepared without purifying the solution containing polymerization initiator 3 and the solution containing polymerization initiator 4. That is, the obtained solution containing polymerization initiator 3 or the solution containing polymerization initiator 4, a mixture of pentaacrylate and hexaacrylate of dipentaerythritol (Aronix M-402 manufactured by Toagosei Co., Ltd.), and acrylate of ethylene oxide-modified diglycerin (Toagosei Co., Ltd., Aronix M-460) were mixed so as to have the contents (parts by mass) shown in Table 2 to prepare a coating solution. In Table 2, the contents of polymerization initiator 3 and polymerization initiator 4 are the contents as solids.

[0137] <Comparative Example 3-1> A mixture of pentaacrylate and hexaacrylate of dipentaerythritol (manufactured by Toagosei Co., Ltd., trade name: Aronix M-402), acrylate of ethylene oxide-modified diglycerin (manufactured by Toagosei Co., Ltd., trade name: Aronix M-460), and 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (manufactured by IGM Resins, trade name: OMNIRAD TPO) were mixed so as to have the contents (parts by mass) shown in Table 2 to prepare a coating solution.

[0138] <Comparative Example 3-2> A mixture of pentaacrylate and hexaacrylate of dipentaerythritol (manufactured by Toagosei Co., Ltd., trade name: Aronix M-402), acrylate of ethylene oxide-modified diglycerin (manufactured by Toagosei Co., Ltd., trade name: Aronix M-460), and 1-hydroxycyclohexyl-phenyl ketone (manufactured by IGM Resins, trade name: OMNIRAD 184) were mixed so as to have the contents (parts by mass) shown in Table 2 to prepare a coating solution.

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

[0140] (Curability) The coating solution was applied to a PET film (manufactured by Toyobo Co., Ltd., trade name: Cosmo Shine (registered trademark) A4360, film thickness: 50 μm) using a bar coater so that the thickness of the cured film would be 5 μm. Curing was performed using an LED with a wavelength of 365 nm at a light intensity of 950 mW / cm 2 and an irradiation time of 5 seconds. Based on the presence or absence of tack on the surface after curing, the curability was evaluated. The evaluation criteria are as follows. A: No tack. B: Tack present.

[0141] (Curl) A PET film (manufactured by Toyobo Co., Ltd., product name "Cosmo Shine (registered trademark)" A4360, film thickness 50 μm) was coated with a coating solution using a bar coater so that the thickness of the cured film was 30 μm. Curing was carried out with an LED of 365 nm at a light intensity of 950 mW / cm 2 , irradiation time 30 seconds. The substrate on which the cured film was formed was cut into 5 cm × 5 cm, and the lifting heights at the four corners were measured. The lifting height was taken as the average value of the four corners. In Comparative Example 3-1 and Comparative Example 3-2, since the deformation was large and it curled, the lifting height could not be measured and was described as "-".

[0142] (Adhesion) A cold-rolled steel sheet (conforming to JIS G3141:2017) subjected to Bonderite treatment N144 was coated with a coating solution using a bar coater so that the thickness of the cured film was 30 μm. Curing was carried out with an LED of 365 nm at a light intensity of 950 mW / cm 2 , irradiation time 30 seconds. The adhesion of the cured film was evaluated by the cross-cut method (JIS K5600-5-6). The numerical values of the evaluation results indicate integers from 0 to 5 in six grades according to the determination method specified in the said JIS. The smaller the number, the better the adhesion.

[0143] (Pencil hardness) A cured film was formed in the same manner as the evaluation of 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 can be obtained even with a thin film by using the polymerization initiator of the present disclosure. Also, in Examples 3-1 to 3-4, it was found that curling is suppressed even when a polyfunctional polymerizable compound is cured. Furthermore, in Comparative Example 3-1 and Comparative Example 3-2, there was no adhesion to the substrate, whereas in Examples 3-1 to 3-4, good adhesion was shown. Generally, it is difficult to achieve both good adhesion and high pencil hardness. When the pencil hardness is high, the adhesion tends to be low, and in order to ensure adhesion, surface treatment such as pre-applying a primer to the substrate may be performed. In fact, in Comparative Example 3-1 and Comparative Example 3-2, although the pencil hardness was high, the adhesion was extremely low and not practical. In contrast, in Example 3-4, it was found that both adhesion and pencil hardness could be achieved.

[0146] In Example 3-4, Photoinitiator 3 contains an acylphosphine oxide structure and a benzophenone structure. The acylphosphine oxide structure functions as an α-cleavage type photoinitiator to initiate polymerization, and at the same time, the benzophenone structure functions as a hydrogen abstraction type photoinitiator, contributing to the effect of increasing the crosslinking density of the cured film. Since the residual strain during the increase in crosslinking density is small, it is considered that both adhesion and pencil hardness can be achieved. In addition, due to the inclusion of the benzophenone structure, the compound represented by formula (4) produced as a by-product can also be given the function of a photoinitiator.

[0147] <Photoinitiator 5A> Using an LED with a wavelength of 385 nm (model: UVA 80×50-385) manufactured by Eye Graphics Co., Ltd., and an illuminance of 360 mW / cm 2 A solution containing Photoinitiator 5A was obtained in the same manner as Photoinitiator 1, except that light irradiation was performed for 60 seconds. When GPC measurement was performed on the solution containing Photoinitiator 5A, the number average molecular weight was 1140 and the weight average molecular weight was 2650. 100 mL of the solution containing Photoinitiator 5A was purified in the same manner as Photoinitiator 1, and polymerization of n-butyl acrylate was attempted in the same manner as Example 1-1. Although irradiated with 385 nm LED for 60 seconds, no polymerization occurred. This is presumably because BAPO was completely decomposed by light at 385 nm when obtaining the solution containing Photoinitiator 5A.

[0148] <Photoinitiator 6A> Irradiance 270 mW / cm 2 A solution containing Photoinitiator 6A was obtained in the same manner as Photoinitiator 1, except that light irradiation was performed for 180 seconds at this irradiance. When GPC measurement was performed on the solution containing Photoinitiator 6A, the number average molecular weight was 1200 and the weight average molecular weight was 2540. 100 mL of the solution containing Photoinitiator 6A was purified in the same manner as Photoinitiator 1, and polymerization of n-butyl acrylate was attempted in the same manner as in Example 1-1. Irradiation with a 385 nm LED for 60 seconds was performed, but no polymerization occurred at all. This is presumably because the irradiation time of light was long when obtaining the solution containing Photoinitiator 6A, and BAPO was completely decomposed.

[0149] (Toxicity evaluation) Toxicity evaluation of Photoinitiator 1 and Photoinitiator 4 was performed. Toxicity evaluation was carried out by exposing samples to zebrafish embryos, observing the morphology of zebrafish thereafter, and evaluating the presence or absence of toxicity based on the number of individuals showing abnormalities.

[0150] The conditions and determination method for toxicity evaluation are as follows. (1) Test organism: Zebrafish (Danio rerio) (2) Exposure conditions Period: 5 hours to 120 hours after fertilization Method: Static water type Test concentration: Photoinitiator 1 0.005, 0.05, 0.50, 5.0 mg / L Photoinitiator 4 0.005, 0.05, 0.50, 5.0 mg / L Positive control group: 50 mg / L sodium valproate (VA) Test solution preparation method: A dimethyl sulfoxide (DMSO) solution with a concentration 200 times the concentration of each test concentration (set concentration) was diluted with test water to prepare a test solution. Note that the test substance is handled under a yellow light. The VA aqueous solution was prepared by mixing VA and test water, stirring, dissolving, and adding DMSO so that the final concentration was 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 light-shielded 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) Facial shape (abnormal eye morphology, abnormal ear morphology, abnormal jaw morphology) Body shape (abnormal notochord morphology, abnormal tail morphology) Blood circulation (facial edema, abdominal (including around the heart) edema, 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 (-)".

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

Industrial applicability

[0152] The compounds of the present disclosure are useful as polymerization initiators for active energy ray-curable compositions with low toxicity. A block polymer mixture that usually cannot be produced without using living polymerization can be easily produced using a long-wavelength light source such as an LED. Further, the compounds of the present disclosure are applicable to adhesives, coating liquids, and the like.

Claims

1. A composition comprising a compound represented by the following formula (1) and a compound represented by the following formula (3) (excluding the compound represented by formula (1)). 【Chemistry 1】 【Chemistry 2】 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 represents the residue of an oligomer or polymer having a number average molecular weight of 200 to 1,000,000. R 1 , R 2 , R 3 , R 4 , R 5 , and R 11 in the formula (3) are the same as R 1 , R 2 , R 3 , R 4 , R 5 , and R 11 in the formula (1) above.

2. R １１ The composition of claim 1 , wherein:

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

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

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

6. A method for producing a compound represented by formula (1), comprising irradiating a composition containing a compound represented by formula (2) below and a first radical polymerizable compound with light having a wavelength of 420 nm to 450 nm: 【Chemistry 2】 【change】 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 １６ each 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.

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

8. A polymerizable composition comprising the composition according to claim 7 and a second radically polymerizable compound.

9. A coating agent comprising the polymerizable composition according to claim 8.

10. An adhesive comprising the polymerizable composition of claim 8.

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

12. A step of applying the polymerizable composition according to claim 8 onto a substrate; a step of irradiating the applied polymerizable composition with active energy rays; A method for producing a cured product comprising the steps of:

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