Benzophenone derivatives, methods of preparation, and uses thereof

Abstract

The present application relates to a benzophenone derivative, a preparation method thereof, and its use. The benzophenone derivative has a structure represented by formula (1), formula (2), or formula (3). The bis(dialkylamino)benzophenone compound having an acrylate group side chain according to the present application has a significantly increased molecular weight compared to EMK, contains a polymerizable double bond, and has a significantly low mobility in the cured film, and can be used in fields such as food packaging and printing formulations.

Description

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims priority to a Chinese patent application bearing application number 202210217084.9 and entitled "Benzophenone derivatives, preparation methods, and uses thereof," filed with the China Patent Office on March 7, 2022, the entire contents of which are incorporated herein by reference. [Technical Field]

[0002] The present application relates to the technical field of photocuring and relates to benzophenone derivatives, methods of preparation and uses thereof. [Background technology]

[0003] N,N,N,N-tetraethyl-4,4'-diaminobenzophenone, abbreviated as EMK, is a commonly used, high-performance auxiliary photoinitiator that is highly useful in inks, especially UV-LED-cured inks. Synthetic methods for these compounds have been reported in patent documents such as CN107686450A, CN112707830A, DE2226039A1, and DE44077C. Patents such as EP1078598A1, US2010081071A1, CN105974736A, CN104749882A, and CN104710843A use EMK in combination with a hydrogen abstraction photoinitiator as an auxiliary photoinitiator in various compositions to achieve photopolymerization. However, EMK has drawbacks, including its low molecular weight, some toxicity, and tendency to migrate from cured materials, which can affect the stability and safety of product properties.

[0004] Patent CN101796015A reports that aniline-based compounds derivatized with acrylate groups are used as polymerizable ammonia coagents in radiation-curable liquid compositions for inkjet printing. Their drawbacks include low molecular weight, complex manufacturing processes, and high manufacturing costs. Patent CN102212151A reports that 4-acrylamido-4'-dialkylaminobenzophenone-based compounds can be used alone as photoinitiators, but their drawbacks include low photoinitiation efficiency and complex manufacturing processes.

[0005] Since the contamination issue of low-molecular-weight photoinitiators came to the fore in the use of photocurable inks, the demand for low-volatility, low-migration photoinitiators has continued to grow as the use of coatings has increased. For example, inks requiring low odor and low migration are widely used in the civilian sector, such as paper and flooring. In particular, stricter detection standards are in place to limit the amount of substance migration in food and pharmaceutical packaging. Therefore, because it is difficult to meet the strict migration standards and they are not included in the list of permitted uses, many users are left without an effective formulation combination and have difficulty finding alternative technologies that meet the standards, which presents a challenge for engineers in this industry. Summary of the Invention [Problem to be solved by the invention]

[0006] The technical problem to be solved by the present application is to provide a benzophenone derivative, a preparation method and its use, in order to overcome the drawback of high migration of photoinitiators or auxiliary photoinitiators in the prior art. [Means for solving the problem]

[0007] In order to solve the above technical problems, the present application adopts the following technical solutions:

[0008] A benzophenone derivative having a structure represented by formula (1): JPEG0007822582000001.jpg51140 (where n1 is an integer from 1 to 10, R1 is an optionally substituted C1 to C8 alkyl, and R2 is H or -CH3 and R3 is H or JPEG0007822582000002.jpg1974, G1 is an optionally substituted C1-C12 alkylene; JPEG0007822582000003.jpg2063 or JPEG0007822582000004.jpg2357, where m1 is an integer from 1 to 11, and m2 is an integer from 1 to 12.

[0009] The term "substituted" means that any one or more hydrogen atoms on a particular atom may be replaced by a substituent, as long as the substituted compound is stable. The term "optionally substituted" means that the atom may or may not be substituted. Unless otherwise specified, the type and number of substituents may be any, as long as they are achievable.

[0010] In the present application, the alkyl may be a straight chain alkyl or a branched alkyl.

[0011] In the present application, n1 is an integer from 1 to 10, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, and in any embodiment of the present application, n1 is an integer from 1 to 4.

[0012] For R1, examples of C1-C8 alkyl include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, 2-methyl-1-propyl, 2-methyl-2-propyl, 2-methyl-1-butyl, 3-methyl-1-butyl, 2-methyl-3-butyl, 2,2-dimethyl-1-propyl, 2,2-dimethyl-1-butyl, 3,3-dimethyl-1-butyl, 2-ethyl-1-butyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, isopentyl, neopentyl, etc. In some embodiments, alkyl is C1-C8 alkyl, C1-C7 alkyl, C1-C6 alkyl, C1-C5 alkyl, C1-C4 alkyl, C1-C3 alkyl, C1-C2 alkyl, or C1 alkyl. R1 is preferably C1-C4 alkyl, more preferably —CH2CH3.

[0013] In any embodiment of the present application, R2 is H.

[0014] In any embodiment of the present application, R3 is JPEG0007822582000005.jpg1970, and the definitions of R2 and G1 are the same as those in formula (1) above. In G1, examples of C1-C12 alkylene include, but are not limited to, methylene, ethylene, propylene, butylene, pentylene, and 3-methylpentylene. In any embodiment of the present application, G1 is JPEG0007822582000006.jpg1393, JPEG0007822582000007.jpg1393 or JPEG0007822582000008.jpg954.

[0015] The present application also provides a benzophenone derivative having a structure represented by formula (2). JPEG0007822582000009.jpg42137 (wherein n2 is an integer from 1 to 10, R1 is an optionally substituted C1 to C8 alkyl, R2 is H or -CH3, and R4 is H or JPEG0007822582000010.jpg20104, G2 is an optionally substituted C1-C12 alkylene or JPEG0007822582000011.jpg1866, where m3 is an integer between 1 and 11.

[0016] In the present application, n2 is an integer from 1 to 10, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10; in any embodiment of the present application, n2 is an integer from 1 to 6.

[0017] For R1, examples of C1-C8 alkyl include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, 2-methyl-1-propyl, 2-methyl-2-propyl, 2-methyl-1-butyl, 3-methyl-1-butyl, 2-methyl-3-butyl, 2,2-dimethyl-1-propyl, 2,2-dimethyl-1-butyl, 3,3-dimethyl-1-butyl, 2-ethyl-1-butyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, isopentyl, neopentyl, etc. In some embodiments, alkyl is C1-C8 alkyl, C1-C7 alkyl, C1-C6 alkyl, C1-C5 alkyl, C1-C4 alkyl, C1-C3 alkyl, C1-C2 alkyl, or C1 alkyl. R1 is preferably C1-C4 alkyl, more preferably —CH2CH3.

[0018] In any embodiment of the present application, R2 is H.

[0019] In any embodiment of the present application, R4 is JPEG0007822582000012.jpg23105, and the definitions of R2 and G2 are the same as those in formula (2) above. In G2, examples of C1-C12 alkylene include, but are not limited to, methylene, ethylene, propylene, butylene, pentylene, and 3-methylpentylene.

[0020] The present application also provides a benzophenone derivative having a structure represented by formula (3). JPEG0007822582000013.jpg39137 (wherein n3 is an integer from 1 to 10, R1 is an optionally substituted C1 to C8 alkyl, R2 is H or -CH3, and R5 is H or JPEG0007822582000014.jpg21121, G2 is an optionally substituted C1-C12 alkylene or JPEG0007822582000015.jpg1764, and m3 is an integer from 1 to 11, G3 is an optionally substituted C1-C12 alkylene; JPEG0007822582000016.jpg1768, JPEG0007822582000017.jpg2463 or JPEG0007822582000018.jpg2281, and m4 is an integer between 1 and 11.

[0021] In the present application, n3 is an integer from 1 to 10, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, and in any embodiment of the present application, n3 is an integer from 1 to 6.

[0022] For R1, examples of C1-C8 alkyl include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, 2-methyl-1-propyl, 2-methyl-2-propyl, 2-methyl-1-butyl, 3-methyl-1-butyl, 2-methyl-3-butyl, 2,2-dimethyl-1-propyl, 2,2-dimethyl-1-butyl, 3,3-dimethyl-1-butyl, 2-ethyl-1-butyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, isopentyl, neopentyl, etc. In some embodiments, alkyl is C1-C8 alkyl, C1-C7 alkyl, C1-C6 alkyl, C1-C5 alkyl, C1-C4 alkyl, C1-C3 alkyl, C1-C2 alkyl, or C1 alkyl. R1 is preferably C1-C4 alkyl, more preferably —CH2CH3.

[0023] In any embodiment of the present application, R2 is H.

[0024] In any embodiment of the present application, R5 is JPEG0007822582000019.jpg20112, where R2, G2, and G3 are defined as in formula (3) above. For G3, examples of C1-C12 alkylene include, but are not limited to, methylene, ethylene, propylene, butylene, pentylene, and 3-methylpentylene.

[0025] In any embodiment of the present application, G2 and G3 are each independently JPEG0007822582000020.jpg933, JPEG0007822582000021.jpg11101 or JPEG0007822582000022.jpg1070.

[0026] This application also The method comprises the steps of reacting a compound represented by formula (4) with a compound represented by formula (5), adding at least one of the hydroxy groups at both ends of the compound represented by formula (4), and then terminating the reaction to obtain a benzophenone derivative having the structure of formula (1), The molar ratio of the compound represented by formula (4) to the compound represented by formula (5) is 1:1 to 2, and R1, R2, and G1 have the same definitions as in formula (1), thereby providing a method for producing the above-mentioned benzophenone derivative having the structure of formula (1). JPEG0007822582000023.jpg42133

[0027] In any embodiment of the present application, the reaction temperature is 40 to 120° C., and the reaction time is 10 to 100 hours.

[0028] In the above reaction, the reaction is completed when at least one of the hydroxy groups at both ends of the compound represented by formula (4) is completely added. The reaction may be carried out with stirring.

[0029] In any embodiment of the present application, after the reaction is completed, the resulting reaction solution is washed to recover the solvent, thereby obtaining a benzophenone derivative having a structure represented by formula (1).

[0030] An exemplary washing method is to first wash with a 1 to 5% diluted weak alkaline aqueous solution, and then wash with water, where the weak alkaline aqueous solution may be an aqueous solution of sodium bicarbonate, sodium carbonate, or ammonium carbonate.

[0031] An exemplary solvent recovery method is to recover the solvent by distillation.

[0032] Optionally, the method for preparing a benzophenone derivative having the structure of formula (1) above includes: The method comprises the steps of mixing a compound represented by formula (4), a compound represented by formula (5), a polymerization inhibitor, a catalyst, and a solvent, heating the mixture in a nitrogen or inert atmosphere to cause a reaction, and after the reaction is completed, cooling the mixture, washing the mixture with an alkaline solution, washing the mixture with water until the mixture is neutral, and removing the solvent to obtain a benzophenone derivative having the structure of formula (1), The molar ratio of the compound represented by formula (4) to the compound represented by formula (5) is 1:1-2, and R1, R2, and G1 have the same definitions as in formula (1). JPEG0007822582000024.jpg36133

[0033] Optionally, the reaction temperature is 40 to 120°C, and the reaction time is 10 to 100 hours. Optionally, the reaction of the compound of formula (4) and the reaction of the monoaddition product can be detected by HPLC until completion.

[0034] Optionally, the polymerization inhibitor is at least one selected from polyphenols, substituted phenol-based polymerization inhibitors, quinone-based polymerization inhibitors, or diarylamine-based polymerization inhibitors, preferably at least one of hydroquinone, p-methoxyphenol, 2,6-di-tert-butylphenol, p-benzoquinone, phenothiazine, or hindered amine oxide, more preferably hydroquinone and / or phenothiazine.

[0035] Optionally, the amount of the polymerization inhibitor used is 0.001% to 10%, for example 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, or 10%, of the mass of the compound represented by formula (5).

[0036] Optionally, the catalyst is one or more of organic sulfonic acid, strong acid cation exchange resin, or organic sulfonate, preferably para-aminobenzenesulfonic acid or poly(4-vinylpyridinium-p-toluenesulfonate), and the amount of catalyst used is 0.1% to 20% of the mass of the compound represented by (4).

[0037] Optionally, the solvent is a water-immiscible organic solvent, preferably toluene. The amount of solvent used can be adjusted according to actual needs, preferably to ensure that the raw materials are dissolved. Optionally, the amount of solvent used is 0.5 to 100 times the mass of the compound represented by (4).

[0038] Optionally, the amount of alkaline solution added may be 1 to 100 times the amount of catalyst used. The alkaline solution may be a sodium carbonate solution, and the mass concentration of the sodium carbonate solution is 1 to 10%.

[0039] Optionally, after the reaction is completed, the temperature is lowered to 20 to 40°C.

[0040] Optionally, the content of effective groups in the benzophenone derivative having the structure of formula (1) is 30 to 60%, and the effective groups are molecular groups Points to JPEG0007822582000025.jpg47113.

[0041] This application also The method comprises the steps of reacting a compound represented by formula (6) with a compound represented by formula (7), adding at least one of the hydroxy groups at both ends of the compound represented by formula (6), and then adding a compound represented by formula (8) to react the compound, and stopping the reaction until the content of the compound represented by formula (8) no longer decreases; The molar ratio of the compound represented by formula (6) to the compound represented by formula (7) is 1:(1-2), the molar ratio of the compound represented by formula (6) to the compound represented by formula (8) is 1:(0.5-3), and R1, R2, and G2 have the same meanings as in formula (2), thereby providing a method for producing the above-mentioned benzophenone derivative having a structure of formula (2). JPEG0007822582000026.jpg35134

[0042] In any embodiment of the present application, the reaction temperature is 40 to 120° C., and the reaction time is 10 to 100 hours.

[0043] The reaction may be carried out with stirring.

[0044] In any embodiment of the present application, after all double bonds in the vinyl in the compound represented by formula (8) have been added, the reaction is terminated, and the resulting reaction solution is washed to recover the solvent, thereby obtaining a benzophenone derivative having a structure represented by formula (2).

[0045] An exemplary washing method is to first wash with a dilute weak alkaline aqueous solution, and then wash with water.

[0046] An exemplary solvent recovery method is to recover the solvent by distillation.

[0047] Optionally, the method for producing the benzophenone derivative having the structure of the above formula (2) includes the steps of mixing a compound represented by formula (6), a compound represented by formula (7), a polymerization inhibitor, a catalyst, and a solvent, and heating them in a nitrogen or inert atmosphere to cause a reaction; after the reaction is completed, adding a compound represented by formula (8), and continuing to keep the temperature to cause a reaction; stopping the reaction until the content of the compound represented by formula (8) no longer decreases; lowering the temperature, adding an alkaline solution to wash, then washing with water until neutral, and removing the solvent to obtain the benzophenone derivative having the structure of formula (2); The molar ratio of the compound represented by formula (6) to the compound represented by formula (7) is 1:(1-2), the molar ratio of the compound represented by formula (6) to the compound represented by formula (8) is 1:(0.5-3), and R1, R2, and G2 have the same meaning as in formula (2). JPEG0007822582000027.jpg32130

[0048] Optionally, the heating reaction temperature is 40 to 120°C, and the heating reaction time is 10 to 100 hours. Optionally, the reaction of the compound of formula (6) and the reaction of the monoaddition product can be detected by HPLC until completion.

[0049] Optionally, the polymerization inhibitor is at least one selected from polyphenols, substituted phenol-based polymerization inhibitors, quinone-based polymerization inhibitors, or diarylamine-based polymerization inhibitors, preferably at least one of hydroquinone, p-methoxyphenol, 2,6-di-tert-butylphenol, p-benzoquinone, phenothiazine, or hindered amine oxide, more preferably hydroquinone and / or phenothiazine.

[0050] Optionally, the amount of the polymerization inhibitor used is 0.001% to 10%, for example 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, or 10%, of the mass of the compound represented by formula (7).

[0051] Optionally, the catalyst is one or more of organic sulfonic acid, strong acid cation exchange resin, or organic sulfonate, preferably para-aminobenzenesulfonic acid or poly(4-vinylpyridinium-p-toluenesulfonate). The amount of catalyst used is 0.1% to 20% of the mass of the compound represented by (6).

[0052] Optionally, the solvent is a water-immiscible organic solvent, preferably toluene. The amount of solvent used can be adjusted according to actual needs, preferably to ensure that the raw materials are dissolved. Optionally, the amount of solvent used is 0.5 to 100 times the mass of the compound represented by (6).

[0053] Optionally, the amount of alkaline solution added is 1 to 100 times the amount of catalyst used. The alkaline solution may be a sodium carbonate solution, and the mass concentration of the sodium carbonate solution is 1 to 10%.

[0054] Optionally, after the reaction is completed, the temperature is lowered to 20 to 40°C.

[0055] Optionally, the content of effective groups in the benzophenone derivative having the structure of formula (2) is 30 to 60%, and the effective groups are molecular groups Points to JPEG0007822582000028.jpg3484.

[0056] This application also The method comprises the steps of reacting a compound represented by formula (9) with a compound represented by formula (10), adding at least one of the hydroxy groups at both ends of the compound represented by formula (9), and then adding the compound represented by formula (11) until all of the double bonds in the vinyl groups in the compound represented by formula (11) are added; The molar ratio of the compound represented by formula (9) to the compound represented by formula (10) is 1:(1-2), the molar ratio of the compound represented by formula (9) to the compound represented by formula (11) is 1:(1-3), and R1, R2, G2, and G3 have the same meanings as in formula (3), thereby providing a method for producing the above-mentioned benzophenone derivative having a structure represented by formula (3). JPEG0007822582000029.jpg34132

[0057] The reaction may be carried out with stirring.

[0058] In any embodiment of the present application, the reaction temperature is 40 to 120° C., and the reaction time is 10 to 100 hours.

[0059] In any embodiment of the present application, after all double bonds in the vinyl in the compound represented by formula (11) have been added, the reaction is terminated, and the resulting reaction solution is washed to recover the solvent, thereby obtaining a benzophenone derivative having a structure represented by formula (3).

[0060] An exemplary washing method is to first wash with a dilute weak alkaline aqueous solution, and then wash with water.

[0061] An exemplary solvent recovery method is to recover the solvent by distillation.

[0062] Optionally, the method for producing the benzophenone derivative having the structure of the above formula (3) includes the steps of mixing a compound represented by formula (9), a compound represented by formula (10), a polymerization inhibitor, a catalyst, and a solvent, and heating them in a nitrogen or inert atmosphere to cause a reaction; after the reaction is completed, adding a compound represented by formula (11), and continuing to keep the temperature to cause a reaction; stopping the reaction until the content of the compound represented by formula (11) no longer decreases; lowering the temperature, adding an alkaline solution to wash, then washing with water until neutral, and removing the solvent to obtain a benzophenone derivative having the structure of formula (2); The molar ratio of the compound represented by formula (9) to the compound represented by formula (10) is 1:(1-2), the molar ratio of the compound represented by formula (9) to the compound represented by formula (11) is 1:(1-3), and R1, R2, G2, and G3 have the same meaning as in formula (3). JPEG0007822582000030.jpg31127

[0063] Optionally, the reaction temperature is 40 to 120°C, and the reaction time is 10 to 100 hours. Optionally, the reaction of the compound of formula (9) and the reaction of the monoaddition product can be detected by HPLC until completion.

[0064] Optionally, the polymerization inhibitor is at least one selected from polyphenols, substituted phenol-based polymerization inhibitors, quinone-based polymerization inhibitors, and diarylamine-based polymerization inhibitors, preferably at least one of hydroquinone, p-methoxyphenol, 2,6-di-tert-butylphenol, p-benzoquinone, phenothiazine, and hindered amine oxide, more preferably hydroquinone and / or phenothiazine. Optionally, the amount of the polymerization inhibitor used is 0.001% to 10%, for example, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, or 10%, of the mass of the compound represented by formula (10).

[0065] Optionally, the catalyst is one or more of organic sulfonic acid, strong acid cation exchange resin, or organic sulfonate, preferably para-aminobenzenesulfonic acid or poly(4-vinylpyridinium-p-toluenesulfonate). The amount of catalyst used is 0.1% to 20% of the mass of the compound represented by (9).

[0066] Optionally, the solvent is a water-immiscible organic solvent, preferably toluene. The amount of solvent used can be adjusted according to actual needs, preferably to ensure that the raw materials are dissolved. Optionally, the amount of solvent used is 0.5 to 100 times the mass of the compound represented by (9).

[0067] Optionally, the amount of alkaline solution added may be 1 to 100 times the amount of catalyst used. The alkaline solution may be a sodium carbonate solution, and the mass concentration of the sodium carbonate solution is 1 to 10%. Optionally, after completion of the reaction, the temperature is lowered to 20 to 40°C.

[0068] Optionally, the content of effective groups in the benzophenone derivative having the structure of formula (3) is 30 to 60%, and the effective groups are molecular groups Points to JPEG0007822582000031.jpg43104.

[0069] The production of the compound of formula (1), formula (2) or formula (3) of the present invention is preferably carried out in the presence of a polymerization inhibitor, a catalyst and a solvent.

[0070] Optionally, the polymerization inhibitor is at least one selected from polyphenols, substituted phenol-based polymerization inhibitors, quinone-based polymerization inhibitors, and diarylamine-based polymerization inhibitors, preferably at least one of hydroquinone, p-methoxyphenol, 2,6-di-tert-butylphenol, p-benzoquinone, phenothiazine, and hindered amine oxide, more preferably hydroquinone and / or phenothiazine. Optionally, the amount of the polymerization inhibitor used is 0.001% to 10%, for example, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, or 10%, of the mass of the compound represented by formula (5), (8), or (11).

[0071] Optionally, the catalyst is one or more of an organic sulfonic acid, a strong acid cation exchange resin, or an organic sulfonate, preferably para-aminobenzenesulfonic acid or poly(4-vinylpyridinium-p-toluenesulfonate). The amount of catalyst used is 0.1% to 20% of the mass of the compound represented by (4), (6), or (9).

[0072] Optionally, the solvent is a water-immiscible organic solvent, preferably toluene.

[0073] According to another aspect of the present application, there is provided a photohardener composition comprising a photoinitiator usable for radical polymerization and the above-described benzophenone derivative.

[0074] According to another aspect of the present application, there is provided a photocurable composition comprising a photocurable component and a radically polymerizable ethylenically unsaturated compound, wherein the photocurable component comprises the photocurable composition described above.

[0075] In any embodiment of the present application, the photocurable composition includes (a) the benzophenone derivative described above, (b) a photoinitiator usable for radical polymerization, and (c) a radically polymerizable ethylenically unsaturated compound.

[0076] Photocurable compositions containing the above photoinitiator compositions have low mobility.

[0077] In any embodiment of the present application, the amount of component (a) added is 0.1 to 20%, for example 1%, 5%, 10%, 15%, or 20%, of the total weight of the photocurable composition.

[0078] In any embodiment of the present application, component (b) is a commercially available or laboratory-available compound commonly used in the industry, and is one or more compounds selected from benzophenones (benzophenones other than those of the present application and derivatives thereof), thioxanthone compounds, α-hydroxyketone compounds, α-aminoketone compounds, acylphosphine oxide compounds, or oxime ester compounds, preferably at least one compound selected from benzophenone, 2-isopropylthioxanthone, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholinylphenyl)-1-butanone, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, photoinitiator Omnipol TX, photoinitiator Omnipol 910, or photoinitiator Omnipol TP. Optionally, the photoinitiator Omnipol TX, photoinitiator Omnipol 910, or photoinitiator Omnipol TP is selected from Omnipol TX, Omnipol 910, or Omnipol TP, which are large molecule photoinitiator series products manufactured by IGM Resins.

[0079] In any embodiment of the present application, the amount of component (b) added is 0.1 to 10%, for example, 0.1%, 2%, 4%, 6%, 8%, or 10%, of the total weight of the photocurable composition.

[0080] The ethylenically unsaturated compound refers to a radically polymerizable ethylenically unsaturated monomer, oligomer, prepolymer, and a mixture thereof.

[0081] In any embodiment of the present application, the component (c) is at least one selected from epoxy acrylate resins, polyurethane acrylate resins, polyester acrylate resins, polyether acrylate resins, acrylated polyacrylates, epoxy methacrylate resins, polyurethane methacrylate resins, polyester methacrylate resins, polyether methacrylate resins, acrylated polymethacrylates, allyl ether compounds, acrylate monomers, or methacrylate monomers. The acrylate monomers or methacrylate monomers are independently monofunctional, difunctional, or polyfunctional. These radically polymerizable ethylenically unsaturated compounds are readily available commercially or in laboratories to those skilled in the art.

[0082] The photocurable composition may contain other additives such as pigments, fillers, leveling aids, polymerization inhibitors, solvents, etc. to meet performance requirements.

[0083] According to a further aspect of the present application, there is provided the use of the photocurable composition described above in food packaging printing, pharmaceutical packaging printing, furniture painting, book printing or advertisement printing.

[0084] According to a further aspect of the present application, there is provided a photocured product formed by photocuring a photocurable composition, wherein the photocurable composition is the photocurable composition described above, and preferably the photocured product is selected from the group consisting of paints, adhesives, and printing inks.

[0085] According to a further aspect of the present application, there is provided a method for curing a photocurable composition, the method comprising the steps of applying the above-described photocurable composition onto a substrate and curing the photocurable composition with a light source having an emission band in the UV-visible region.

[0086] Substrates include, but are not limited to, wood, paper, plastic, coatings, or metal, etc. Application methods include, but are not limited to, offset printing, gravure printing, flexography, inkjet printing, or 3D printing, etc.

[0087] Optionally, after application to a substrate, the photocurable composition is cured by irradiation with UV-visible light having a wavelength of 200 to 425 nm, preferably by irradiation with UV-visible light having a wavelength of 365 to 405 nm. [Effects of the Invention]

[0088] The beneficial effects are as follows:

[0089] The bis(dialkylamino)benzophenone compound having an acrylate group side chain according to the present invention has a significantly increased molecular weight compared to EMK and contains a polymerizable double bond, resulting in significantly lower mobility in the cured film.

[0090] The benzophenone derivatives are important co-initiators in UV light curing formulations, and can initiate photopolymerization of unsaturated carbon-carbon double bond compounds together with other photoinitiators. Because of their large molecular weight, the compounds have very low migration properties and can be used in fields such as food packaging and printing formulations, replacing N,N,N,N-tetraethyl-4,4'-diaminobenzophenone. DETAILED DESCRIPTION OF THE INVENTION

[0091] JPEG0007822582000032.jpg139137

[0092] * The structure of HEMK is as follows: JPEG0007822582000033.jpg66137

[0093] Omnipol TX is a polybutylene glycol bis(9-oxo-9H-thioxanthenyloxy) acetate photoinitiator manufactured by IGM RESINS. Omnirad EMK is 4,4'-bis(diethylamino)benzophenone and is manufactured by IGM Resins. Photomer 4072 is trimethylolpropane propoxy (3) triacrylate manufactured by IGM Resins. Photomer 3316 is a low viscosity modified epoxy acrylate manufactured by IGM Resins.

[0094] Example 1 A 100 mL three-neck flask equipped with a mechanical stirrer was charged sequentially with 1.78 g (5 mmol) of HEMK, 1.86 g (10 mmol) of 2-[2-(vinyloxy)ethoxy]ethyl acrylate (VEEA), 0.022 g (0.2 mmol) of hydroquinone, 0.086 g (0.5 mmol) of para-aminobenzenesulfonic acid, and 12.0 g of toluene. After thorough nitrogen purge at room temperature with stirring, the nitrogen quantitation tube was sealed and the reaction was heated and stirred at 55°C for 48 hours. Samples were taken and analyzed by HPLC. The reaction was stopped until the reaction of HEMK and the monoaddition product was complete. The temperature was lowered to 30°C, and 3.0 g of a 5% aqueous sodium carbonate solution (1.4 mmol) was added. The mixture was then washed with water until neutral. The solvent was removed by vacuum distillation to yield 3.44 g of product Formula IX with an active group content of 55%. The effective group refers to the residue remaining after removing the hydrogens on the two hydroxyls from the HEMK structure. JPEG0007822582000034.jpg43138

[0095] [Table 1]

[0096] Example 2 A 100 mL three-neck flask equipped with mechanical stirring was sequentially charged with 1.78 g (5 mmol) of HEMK, 1.86 g (10 mmol) of 2-[2-(vinyloxy)ethoxy]ethyl acrylate (VEEA), 0.022 g (0.2 mmol) of hydroquinone, 0.086 g (0.11 mmol) of poly(4-vinylpyridinium-p-toluenesulfonate), and 12.0 g of toluene. After thorough nitrogen purge at room temperature with stirring, the nitrogen quantitation tube was sealed and the reaction was continued at 55 °C for 48 hours with heating and stirring. Samples were taken and analyzed by HPLC. The reaction was stopped until the reaction of HEMK and the monoaddition product was complete. The temperature was lowered to 30 °C, and 3.0 g of a 5% aqueous sodium carbonate solution (1.4 mmol) was added. The mixture was then washed with water until neutral. The solvent was removed by vacuum distillation to yield 3.40 g of the product represented by Formula IX. JPEG0007822582000036.jpg42138

[0097] [Table 2]

[0098] Example 3 A 100 mL three-neck flask equipped with mechanical stirring was sequentially charged with 1.78 g (5 mmol) of HEMK, 2.00 g (10 mmol) of 2-(vinyloxyethoxy)ethyl methacrylate (VEEM), 0.022 g (0.2 mmol) of hydroquinone, 0.086 g (0.5 mmol) of para-aminobenzenesulfonic acid, and 12.0 g of toluene. After thorough nitrogen purge at room temperature with stirring, the nitrogen quantitation tube was sealed and the reaction was heated and stirred at 55 °C for 48 hours. Samples were taken and analyzed by HPLC. The reaction was stopped until the reaction of HEMK and the monoaddition product was complete. The temperature was lowered to 30 °C, and 3.0 g of a 5% aqueous sodium carbonate solution (1.4 mmol) was added. The mixture was then washed with water until neutral. The solvent was removed by vacuum distillation, yielding 3.51 g of a product of formula X. JPEG0007822582000038.jpg45139

[0099] [Table 3]

[0100] Example 4 A 100 mL three-neck flask equipped with mechanical stirring was sequentially charged with 1.78 g (5 mmol) of HEMK, 1.42 g (10 mmol) of 2-(vinyloxy)ethyl acrylate (VEA), 0.022 g (0.2 mmol) of hydroquinone, 0.086 g (0.5 mmol) of para-aminobenzenesulfonic acid, and 12.0 g of toluene. After thorough nitrogen purge at room temperature with stirring, the nitrogen quantitation tube was sealed and the reaction was heated and stirred at 55°C for 48 hours. Samples were taken and analyzed by HPLC. The reaction was stopped until the reaction of HEMK and the monoaddition product was complete. The temperature was lowered to 30°C, and 3.0 g of a 5% aqueous sodium carbonate solution (1.4 mmol) was added. The mixture was then washed with water until neutral. The solvent was removed by distillation under reduced pressure, yielding 2.91 g of product (formula XI) with an available group content of 55%. JPEG0007822582000040.jpg55156

[0101] [Table 4]

[0102] Example 5 A 100 mL three-neck flask equipped with mechanical stirring was sequentially charged with 1.78 g (5 mmol) of HEMK, 1.42 g (10 mmol) of 2-(vinyloxy)ethyl acrylate (VEA), 0.022 g (0.2 mmol) of hydroquinone, 0.086 g (0.5 mmol) of p-toluenesulfonic acid, and 12.0 g of dichloroethane. After thorough nitrogen purge at room temperature with stirring, the nitrogen quantitation tube was sealed and the reaction was heated and stirred at 55 °C for 48 hours. Samples were taken and analyzed by HPLC. The reaction was stopped until the reaction of HEMK and the monoaddition product was complete. The temperature was lowered to 30 °C, and 3.0 g of a 5% aqueous sodium carbonate solution (1.4 mmol) was added. The mixture was then washed with water until neutral. The solvent was removed by vacuum distillation to yield 2.88 g of product (Formula XI). JPEG0007822582000042.jpg58156

[0103] [Table 5]

[0104] Example 6 A 100 mL three-neck flask equipped with mechanical stirring was sequentially charged with 1.78 g (5 mmol) of HEMK, 1.56 g (12 mmol) of 2-(vinyloxy)ethyl methacrylate (VEM), 0.022 g (0.2 mmol) of hydroquinone, 0.086 g (0.5 mmol) of para-aminobenzenesulfonic acid, and 12.0 g of toluene. After thorough nitrogen purge at room temperature with stirring, the nitrogen quantitation tube was sealed and the reaction was continued at 55 °C for 48 hours with heating and stirring. Samples were taken and analyzed by HPLC. The reaction was stopped until the reaction of HEMK and the monoaddition product was complete. The temperature was lowered to 30 °C, and 3.0 g of a 5% aqueous sodium carbonate solution (1.4 mmol) was added. The mixture was then washed with water until neutral. The solvent was removed by vacuum distillation to yield 3.07 g of the product, Formula XII. JPEG0007822582000044.jpg59158

[0105] [Table 6]

[0106] Example 7 A 100 mL three-neck flask equipped with a mechanical stirrer was charged sequentially with 1.78 g (5 mmol) of HEMK, 1.58 g (10 mmol) of diethylene glycol divinyl ether, 0.022 g (0.2 mmol) of hydroquinone, 0.086 g (0.5 mmol) of para-aminobenzenesulfonic acid, and 12.0 g of toluene. After thorough nitrogen purge with stirring at room temperature, the nitrogen quantitation tube was sealed and the reaction was carried out at 55°C for 48 hours with heating and stirring. Samples were taken and analyzed by HPLC until the reaction of HEMK and the monoaddition product was complete. Next, 0.86 g (12 mmol) of acrylic acid was added, and the reaction was continued with stirring while maintaining the temperature. Samples were taken and analyzed every 4 hours of reaction, and the reaction was stopped until the acrylic acid content no longer decreased. The temperature was lowered to 30°C, and 6.4 g of a 5% aqueous sodium carbonate solution (3.0 mmol) was added, followed by washing with water until neutral. The solvent was removed by distillation under reduced pressure to give 3.91 g of the product as shown in formula XIII with an available group content of 40%. JPEG0007822582000046.jpg32150

[0107] [Table 7]

[0108] Example 8 A 100 mL three-neck flask equipped with a mechanical stirrer was charged sequentially with 1.78 g (5 mmol) of HEMK, 0.99 g (6.25 mmol) of diethylene glycol divinyl ether, 0.022 g (0.2 mmol) of hydroquinone, 0.086 g (0.5 mmol) of para-aminobenzenesulfonic acid, and 12.0 g of toluene. After thorough nitrogen purge with stirring at room temperature, the nitrogen quantitation tube was sealed and the reaction was carried out at 55°C for 72 hours with heating and stirring. Samples were taken and analyzed by HPLC until the reaction of HEMK and the monoaddition product was complete. Next, 0.22 g (3 mmol) of acrylic acid was added, and the reaction was continued while maintaining the temperature and stirring. Samples were taken and analyzed every 4 hours, and the reaction was stopped until the acrylic acid content no longer decreased. The temperature was lowered to 30°C, and 6.4 g of a 5% aqueous sodium carbonate solution (3.0 mmol) was added, followed by washing with water until neutral. The solvent was removed by vacuum distillation to give 2.58 g of the product as formula XIII. JPEG0007822582000048.jpg32150

[0109] [Table 8]

[0110] Example 9 A 100 mL three-neck flask equipped with a mechanical stirrer was charged sequentially with 1.78 g (5 mmol) of HEMK, 1.58 g (10 mmol) of diethylene glycol divinyl ether, 0.022 g (0.2 mmol) of hydroquinone, 0.086 g (0.5 mmol) of para-aminobenzenesulfonic acid, and 12.0 g of toluene. After sufficient nitrogen replacement with stirring at room temperature, the nitrogen quantitation tube was sealed and the reaction was continued for 48 hours at 55°C with heating and stirring. Samples were taken and analyzed by HPLC until the reaction of HEMK and the monoaddition product was complete. Next, 1.39 g (12 mmol) of hydroxyethyl acrylate was added, and the reaction was continued with stirring while maintaining the temperature. Samples were taken and analyzed every 4 hours. The reaction was stopped until the hydroxyethyl acrylate content no longer decreased. The temperature was lowered to 30°C, and 6.4 g of a 5% by mass aqueous solution of sodium carbonate (3.0 mmol of sodium carbonate) was added, followed by washing with water until neutral. The solvent was removed by distillation under reduced pressure to obtain 4.15 g of a product of formula XIV with an available group content of 40%. JPEG0007822582000050.jpg35148

[0111] [Table 9] Example

[0112] Example 10 A 100 mL three-neck flask was equipped with a mechanical stirrer and sequentially charged with 1.78 g (5 mmol) of HEMK, 0.99 g (6.25 mmol) of diethylene glycol divinyl ether, 0.022 g (0.2 mmol) of hydroquinone, 0.086 g (0.5 mmol) of para-aminobenzenesulfonic acid, and 12.0 g of toluene. After thorough nitrogen purge with stirring at room temperature, the nitrogen quantitation tube was sealed and the reaction was continued for 72 hours at 55°C with heating and stirring. Samples were taken and analyzed by HPLC until the reaction of HEMK and the monoaddition product was complete. Next, 0.35 g (3 mmol) of hydroxyethyl acrylate was added and the reaction was continued with stirring while maintaining the temperature. Samples were taken and analyzed every 4 hours. The reaction was stopped until the hydroxyethyl acrylate content no longer decreased. The temperature was lowered to 30°C, and 6.4 g of a 5% by mass aqueous solution of sodium carbonate (3.0 mmol of sodium carbonate) was added, followed by washing with water until neutral. The solvent was removed by distillation under reduced pressure to obtain 2.74 g of a product of formula XIV. JPEG0007822582000052.jpg33153

[0113] [Table 10]

[0114] Example 11 A 100 mL three-neck flask equipped with a mechanical stirrer was charged sequentially with 1.78 g (5 mmol) of HEMK, 2.02 g (10 mmol) of triethylene glycol divinyl ether, 0.022 g (0.2 mmol) of hydroquinone, 0.086 g (0.5 mmol) of para-aminobenzenesulfonic acid, and 12.0 g of toluene. After sufficient nitrogen replacement with stirring at room temperature, the nitrogen quantitation tube was sealed and the reaction was continued for 48 hours at 55°C with heating and stirring. Samples were taken and analyzed by HPLC until the reaction of HEMK and the monoaddition product was complete. Next, 1.39 g (12 mmol) of hydroxyethyl acrylate was added, and the reaction was continued with stirring while maintaining the temperature. Samples were taken and analyzed every 4 hours. The reaction was stopped until the hydroxyethyl acrylate content no longer decreased. The temperature was lowered to 30°C, and 6.4 g of a 5% by mass aqueous solution of sodium carbonate (3.0 mmol of sodium carbonate) was added, followed by washing with water until neutral. The solvent was removed by distillation under reduced pressure to obtain 4.66 g of a product of formula XV with an available group content of 40%. JPEG0007822582000054.jpg28149

[0115] [Table 11]

[0116] Example 12 A 100 mL three-neck flask was equipped with a mechanical stirrer and sequentially charged with 1.78 g (5 mmol) of HEMK, 1.26 g (6.25 mmol) of triethylene glycol divinyl ether, 0.022 g (0.2 mmol) of hydroquinone, 0.086 g (0.5 mmol) of para-aminobenzenesulfonic acid, and 12.0 g of toluene. After thorough nitrogen purge with stirring at room temperature, the nitrogen quantitation tube was sealed and the reaction was continued at 55°C for 96 hours with heating and stirring. Samples were taken and analyzed by HPLC until the reaction of HEMK and the monoaddition product was complete. Next, 0.35 g (3 mmol) of hydroxyethyl acrylate was added and the reaction was continued with stirring while maintaining the temperature. Samples were taken and analyzed every 4 hours. The reaction was stopped until the hydroxyethyl acrylate content no longer decreased. The temperature was lowered to 30°C, and 6.4 g of a 5% by mass aqueous solution of sodium carbonate (3.0 mmol of sodium carbonate) was added, followed by washing with water until neutral. The solvent was removed by distillation under reduced pressure to obtain 3.06 g of a product of formula XV. JPEG0007822582000056.jpg34155

[0117] [Table 12]

[0118] Example 13 A 100 mL three-neck flask equipped with a mechanical stirrer was charged sequentially with 1.78 g (5 mmol) of HEMK, 1.42 g (10 mmol) of 1,4-butanediol divinyl ether, 0.022 g (0.2 mmol) of hydroquinone, 0.086 g (0.5 mmol) of para-aminobenzenesulfonic acid, and 12.0 g of toluene. After sufficient nitrogen replacement with stirring at room temperature, the nitrogen quantitation tube was sealed and the reaction was continued for 48 hours at 55°C with heating and stirring. Samples were taken and analyzed by HPLC until the reaction of HEMK and the monoaddition product was complete. Next, 1.39 g (12 mmol) of hydroxyethyl acrylate was added, and the reaction was continued with stirring while maintaining the temperature. Samples were taken and analyzed every 4 hours. The reaction was stopped until the hydroxyethyl acrylate content no longer decreased. The temperature was lowered to 30°C, and 6.4 g of a 5% by mass aqueous solution of sodium carbonate (3.0 mmol of sodium carbonate) was added, followed by washing with water until neutral. The solvent was removed by distillation under reduced pressure to obtain 4.09 g of a product of formula XVI. JPEG0007822582000058.jpg33146

[0119] [Table 13]

[0120] Example 14 This example provides a photocurable composition containing as ingredients 4.57g Photomer 4072, 4.57g Photomer 3316, 0.36g of the Formula IX product of Example 1, and 0.5g Omnipol TX.

[0121] The method for producing the photocurable composition includes the steps of stirring the above components at 60° C. to dissolve them uniformly, then cooling them to room temperature, and compounding them into the photocurable composition.

[0122] Example 15 This example provides a photocurable composition containing as ingredients 4.57 g of Photomer 4072, 4.57 g of Photomer 3316, 0.36 g of the Formula XI product of Example 4, and 0.5 g of Omnipol TX.

[0123] The method for producing the photocurable composition includes the steps of stirring the above components at 60° C. to dissolve them uniformly, then cooling them to room temperature, and compounding them into the photocurable composition.

[0124] Example 16 This example provides a photocurable composition containing as ingredients 4.5 g of Photomer 4072, 4.5 g of Photomer 3316, 0.5 g of the Formula XIII product of Example 7, and 0.5 g of Omnipol TX.

[0125] The method for producing the photocurable composition includes the steps of stirring the above components at 60° C. to dissolve them uniformly, then cooling them to room temperature, and compounding them into the photocurable composition.

[0126] Example 17 This example provides a photocurable composition containing as ingredients 4.5 g of Photomer 4072, 4.5 g of Photomer 3316, 0.5 g of the Formula XIV product of Example 9, and 0.5 g of Omnipol TX.

[0127] The method for producing the photocurable composition includes the steps of stirring the above components at 60° C. to dissolve them uniformly, then cooling them to room temperature, and compounding them into the photocurable composition.

[0128] Example 18 This example provides a photocurable composition containing as ingredients 4.5 g of Photomer 4072, 4.5 g of Photomer 3316, 0.5 g of the Formula XV product of Example 11, and 0.5 g of Omnipol TX.

[0129] The method for producing the photocurable composition includes the steps of stirring the above components at 60° C. to dissolve them uniformly, then cooling them to room temperature, and compounding them into the photocurable composition.

[0130] Comparative Example 1 This comparative example provides a photocurable composition containing the following ingredients: 4.65g Photomer 4072, 4.65g Photomer 3316, 0.2g Omnirad EMK, and 0.5g Omnipol TX.

[0131] The method for producing the photocurable composition includes the steps of stirring the above components at 60° C. to dissolve them uniformly, then cooling them to room temperature, and compounding them into the photocurable composition.

[0132] Test Example The hardness and cure transition characteristics of the photocurable compositions prepared in Examples 14 to 18 and Comparative Example 1 were tested.

[0133] Pendulum hardness test: Using a 25 μm wire, the above photocurable composition was cured once on a coated glass plate (under a 395 nm LED light) at a tape speed of 10 m / min, and the pendulum hardness after curing was tested.

[0134] Mobility test: Using a 25 μm wire, the above photocurable composition was cured once on a coated paper measuring 5 × 20 cm under a 395 nm LED light at a tape speed of 10 m / min, and 100 cm of the cured paper was immersed in 100 g of an aqueous solution of 3% acetic acid. 2 The mixture was placed in a container and left at 40°C for 10 days, and then HPLC was used to quantitatively analyze the photoinitiator components (photoinitiator components refer to the product components of formula IX in Example 1, the product components of formula XI in Example 4, the product components of formula XIII in Example 7, the product components of formula XIV in Example 9, the product components of formula XV in Example 11, or the Omnirad EMK components) that had migrated into the aqueous acetic acid solution. The EU model was used to calculate the results, and 1 kg of food was converted to 600 cm 2The results can be converted to μg / kg, or μg of analyte per kg of food, assuming the product is packaged with a printed area of ​​100 μg (analyte refers to the Formula IX product of Example 1, the Formula XI product of Example 4, the Formula XIII product of Example 7, the Formula XIV product of Example 9, the Formula XV product of Example 11, or Omnirad EMK). The results of the hardness and mobility analysis experiments are shown in Table 14.

[0135] [Table 14]

[0136] The test data show that when the present bis(dialkylamino)benzophenone compounds with acrylate alkoxy side chains are used as coinitiators in photocurable compositions, compared to the commonly used commercially available EMK, the present compounds have similar hardness and cure rates after curing. However, due to their higher molecular weight and polymerizable double bonds, the mobility of the present compounds is significantly reduced. Therefore, the present compounds are more suitable for use in food and pharmaceutical packaging, children's toys, and other applications with strict requirements for material mobility.

[0137] Obviously, the above examples are merely examples for clear explanation and are not intended to limit the embodiments. Those skilled in the art can make other different modifications or modifications based on the above description. It is not necessary and cannot be possible to list all the embodiments here. Any obvious modifications or modifications derived therefrom still fall within the protection scope of the present invention.

Claims

1. A benzophenone derivative having a structure represented by formula (1): (where, n １ is an integer from 1 to 10, and R １ is an optionally substituted C1-C8 alkyl, and R ２ is H or -CH ３ and R ３ is H or and G １ is an optionally substituted C1-C12 alkylene, , or and m １ is an integer from 1 to 11, and m ２ is an integer from 1 to 12.

2. n １ The benzophenone derivative according to claim 1, wherein is an integer of 1 to 4.

3. The benzophenone derivative according to claim 1, wherein R 1 is C1 to C4 alkyl.

4. The benzophenone derivative according to claim 1, wherein R 1 is —CH 2 CH 3 .

5. The benzophenone derivative according to claim 1, wherein R 2 is H.

6. R 3 is The benzophenone derivative according to claim 1, wherein R 2 and G 1 are defined as in formula (1) of claim 1.

7. G 1 is 、 or The benzophenone derivative according to claim 1, wherein

8. A benzophenone derivative having a structure represented by formula (2): (where, n ２ is an integer from 1 to 10, and R １ is an optionally substituted C1-C8 alkyl, and R ２ is H or —CH ３ and R ４ is H or and G ２は、 optionally substituted C1-C12 alkylene or and m ３ is an integer from 1 to 11.

9. The benzophenone derivative according to claim 8, wherein n 2 is an integer of 1 to 6.

10. The benzophenone derivative according to claim 8, wherein R 1 is C1 to C4 alkyl.

11. The benzophenone derivative according to claim 8, wherein R 1 is —CH 2 CH 3 .

12. The benzophenone derivative according to claim 8, wherein R 2 is H.

13. R 4 is The benzophenone derivative according to claim 8, wherein R 2 and G 2 are defined as in formula (2) of claim 8.

14. A benzophenone derivative having a structure represented by formula (3): (where, n ３ is an integer from 1 to 10, and R １ is an optionally substituted C1-C8 alkyl, and R ２ is H or —CH ３ and R ５ is H or and G ２ is an optionally substituted C1-C12 alkylene or and m ３ is an integer from 1 to 11, and G ３ is an optionally substituted C1-C12 alkylene, , or and m ４ is an integer from 1 to 11.

15. The benzophenone derivative according to claim 14, wherein n 3 is an integer of 1 to 6.

16. The benzophenone derivative according to claim 14, wherein R 1 is C1 to C4 alkyl.

17. The benzophenone derivative according to claim 14, wherein R 1 is —CH 2 CH 3 .

18. The benzophenone derivative according to claim 14, wherein R 2 is H.

19. R 5 is The benzophenone derivative according to claim 14, wherein R 2 , G 2 and G 3 are defined as in formula (3) of claim 14.

20. G 2 and G 3 each independently represent: 、 , or The benzophenone derivative according to claim 14, wherein

21. The method includes a step of reacting a compound represented by formula (4) with a compound represented by formula (5), adding at least one of the hydroxy groups at both ends of the compound represented by formula (4), and then terminating the reaction to obtain a benzophenone derivative having a structure represented by formula (1), The molar ratio of the compound represented by formula (4) to the compound represented by formula (5) is 1:1 to 2, and R １ , R ２ , and G １ The method for producing a benzophenone derivative according to any one of claims 1 to 7, wherein has the same definition as in formula (1).

22. The method for producing a benzophenone derivative according to claim 21, wherein the reaction temperature is 40 to 120°C and the reaction time is 10 to 100 hours.

23. A method for producing the benzophenone derivative according to any one of claims 8 to 13, comprising the steps of reacting a compound represented by formula (6) with a compound represented by formula (7), adding at least one of the hydroxyl groups at both ends of the compound represented by formula (6), and then adding a compound represented by formula (8) to react the compound, and terminating the reaction until the content of the compound represented by formula (8) no longer decreases. (wherein the molar ratio of the compound represented by formula (6) to the compound represented by formula (7) is 1:(1-2), the molar ratio of the compound represented by formula (6) to the compound represented by formula (8) is 1:(0.5-3), and R １ , R ２ , and G ２ has the same meaning as in formula (2).

24. The method for producing a benzophenone derivative according to claim 23, wherein the reaction temperature is 40 to 120°C and the reaction time is 10 to 100 hours.

25. A method for producing the benzophenone derivative according to any one of claims 14 to 20, comprising the steps of reacting a compound represented by formula (9) with a compound represented by formula (10), adding at least one of the hydroxy groups at both ends of the compound represented by formula (9), and then adding the compound represented by formula (11) until all of the double bonds in the vinyl groups in the compound represented by formula (11) are added. (wherein the molar ratio of the compound represented by formula (9) to the compound represented by formula (10) is 1:(1-2), the molar ratio of the compound represented by formula (9) to the compound represented by formula (11) is 1:(1-3), and R １ , R ２ , G ２ , and G ３ has the same meaning as in formula (3).

26. The method for producing a benzophenone derivative according to claim 25, wherein the reaction temperature is 40 to 120°C and the reaction time is 10 to 100 hours.

27. A photoinitiator composition comprising a photoinitiator usable for radical polymerization and the benzophenone derivative according to any one of claims 1 to 20.

28. A photocurable composition comprising a photoinitiator component and a radically polymerizable ethylenically unsaturated compound, wherein the photocurative component (a) the benzophenone derivative according to any one of claims 1 to 20; (b) a photoinitiator usable for radical polymerization; and (c) a radically polymerizable ethylenically unsaturated compound, component (b) is one or more compounds selected from the group consisting of benzophenones, thioxanthone compounds, α-hydroxyketone compounds, α-aminoketone compounds, acylphosphine oxide compounds, and oxime ester compounds; The photocurable composition, wherein component (c) is at least one selected from an epoxy acrylate resin, a polyurethane acrylate resin, a polyester acrylate resin, a polyether acrylate resin, an acrylated polyacrylate, an epoxy methacrylate resin, a polyurethane methacrylate resin, a polyester methacrylate resin, a polyether methacrylate resin, an acrylated polymethacrylate, an allyl ether compound, an acrylate monomer, or a methacrylate monomer.

29. The photocurable composition of claim 28, wherein component (b) is at least one selected from benzophenone, 2-isopropylthioxanthone, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholinylphenyl)-1-butanone, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, photoinitiator Omnipol TX, photoinitiator Omnipol 910, and photoinitiator Omnipol TP.

30. The photocurable composition of claim 28, wherein the amount of component (a) added is 0.1 to 20% of the total weight of the photocurable composition.

31. The photocurable composition described in Claim 28, wherein the amount of component (b) added is 0.1 to 10% of the total weight of the photocurable composition.

32. Use of the photocurable composition according to any one of claims 28 to 31 in food packaging printing, pharmaceutical packaging printing, furniture painting, book printing, or advertisement printing.

33. A photocured product obtained by photocuring a photocurable composition, wherein the photocurable composition is the photocurable composition according to any one of claims 28 to 31.

34. A method for curing a photocurable composition, comprising: applying the photocurable composition according to any one of claims 28 to 31 onto a substrate; and curing the photocurable composition with a light source having an emission band in the UV-visible region.

35. The method for curing a photocurable composition according to claim 34, wherein the substrate is selected from the group consisting of wood, paper, plastic, coating, and metal.

36. A method for curing the photocurable composition described in claim 34, wherein the application method is selected from the group consisting of offset printing, gravure printing, flexographic printing, inkjet printing, and 3D printing.

37. A method for curing a photocurable composition according to claim 34, wherein after application to a substrate, the photocurable composition is cured by irradiating it with UV-visible light having a wavelength of 200 to 425 nm.

38. A method for curing a photocurable composition according to claim 34, wherein the photocurable composition is cured by irradiating it with UV-visible light having a wavelength of 365 to 405 nm.

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