Benzophenone derivatives, methods for producing them, and their uses

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 method, and use 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 very useful for inks, especially UV-LED cured inks. The synthesis methods of these compounds have been reported in patent documents such as CN107686450A, CN112707830A, DE2226039A1, DE44077C, etc. In patents EP1078598A1, US2010081071A1, CN105974736A, CN104749882A, CN104710843A, etc., EMK has been used in combination with hydrogen abstraction photoinitiators as auxiliary photoinitiators in various compositions to achieve photopolymerization. However, it has the disadvantages of having a small molecular weight, a certain degree of toxicity, and being easily migrated out of the cured material, which affects the stability and safety of product properties.

[0004] In patent CN101796015A, aniline-based compounds derivatized from acrylate groups are reported as polymerizable ammonia coagents for use in radiation-curable liquid compositions for inkjet printing. The disadvantages are low molecular weight, complicated manufacturing process, and high manufacturing cost. In patent CN102212151A, 4-acrylamido-4'-dialkylaminobenzophenone-based compounds are reported to be able to be used alone as photoinitiators, but the disadvantages are low photoinitiation efficiency and complicated manufacturing process.

[0005] In the actual use of photocurable inks, since the contamination problem of low molecular weight photoinitiators was brought to attention, the demand for low volatility and low migration photoinitiators continues to increase with the increase in the use of paints. For example, inks that require low odor and low migration are widely used in the civilian sector, such as paper and flooring, and especially in food and pharmaceutical packaging materials, the migration amount of substances is limited by stricter detection standards. Therefore, it is difficult to meet the strict migration standard requirements and is not included in the list of permitted uses, so many users lose an efficient formulation combination, and it is difficult to find an alternative technology that meets the standards, which is 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, so as to overcome the defect of high migration of photoinitiator or auxiliary photoinitiator 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): JPEG2025509358000002.jpg51140 (where n 1 is an integer from 1 to 10, and R 1 is an optionally substituted C1-C8 alkyl; R 2 is H or -CH 3 and R 3 H or JPEG2025509358000003.jpg1974, G 1 represents an optionally substituted C1-C12 alkylene; JPEG2025509358000004.jpg2063 or JPEG2025509358000005.jpg2357, m 1 is an integer from 1 to 11, and m 2 is an integer between 1 and 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 it may or may not be substituted. Unless otherwise specified, the type and number of substituents may be optional, 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 this application, n 1 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, n 1 is an integer from 1 to 4.

[0012] R 1In R, 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. 1 is preferably C1 to C4 alkyl, more preferably -CH 2 CH 3 It is.

[0013] In any embodiment of the present application, R 2 is H.

[0014] In any embodiment of the present application, R 3 teeth, JPEG2025509358000006.jpg1970, R 2 , and G 1 The definition of is the same as that in formula (1) above. G 1 In the present application, examples of C1-C12 alkylene include, but are not limited to, methylene, ethylene, propylene, butylene, pentylene, and 3-methylpentylene. 1 teeth, JPEG2025509358000007.jpg1393, JPEG2025509358000008.jpg1393 or The image is JPEG2025509358000009.jpg954.

[0015] The present application also provides a benzophenone derivative having a structure represented by formula (2): JPEG2025509358000010.jpg42137 (where n 2 is an integer from 1 to 10, and R 1 is an optionally substituted C1-C8 alkyl; R 2 is H or -CH 3 and R 4 H or JPEG2025509358000011.jpg20104, G 2 is an optionally substituted C1-C12 alkylene or JPEG2025509358000012.jpg1866, m 3 is an integer from 1 to 11.

[0016] In this application, n 2 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, n 2 is an integer from 1 to 6.

[0017] R 1 In R, 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. 1 is preferably C1 to C4 alkyl, more preferably -CH 2 CH 3 It is.

[0018] In any embodiment of the present application, R 2 is H.

[0019] In any embodiment of the present application, R 4 teeth, JPEG2025509358000013.jpg23105, R 2 , and G 2 The definition of is the same as that in formula (2) above. 2 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): JPEG2025509358000014.jpg39137 (where n 3 is an integer from 1 to 10, and R 1 is an optionally substituted C1-C8 alkyl; R 2 is H or -CH 3 and R 5 H or JPEG2025509358000015.jpg21121, G 2 is an optionally substituted C1-C12 alkylene or JPEG2025509358000016.jpg1764, m 3 is an integer from 1 to 11, G 3 represents an optionally substituted C1-C12 alkylene, JPEG2025509358000017.jpg1768, JPEG2025509358000018.jpg2463 or JPEG2025509358000019.jpg2281, m 4 is an integer from 1 to 11.

[0021] In this application, n 3is 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, n 3 is an integer from 1 to 6.

[0022] R 1 In R, 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. 1 is preferably C1 to C4 alkyl, more preferably -CH 2 CH 3 It is.

[0023] In any embodiment of the present application, R 2 is H.

[0024] In any embodiment of the present application, R 5 teeth, JPEG2025509358000020.jpg20112, R 2 , G 2 , and G 3 The definition of is the same as that in formula (3) above. 3 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, G 2 , and G 3 are each independently JPEG2025509358000021.jpg933, JPEG2025509358000022.jpg11101 or JPEG2025509358000023.jpg1070.

[0026] The present application also provides: 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 hydroxyl 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; R 1 , R 2 , and G 1 provides a method for producing the above-mentioned benzophenone derivative having the structure of formula (1), which has the same definition as formula (1) above. JPEG2025509358000024.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, at least one of the hydroxyl groups at both ends of the compound represented by formula (4) is added to complete the reaction. 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 1-5% dilute 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 steps of: The method includes 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, lowering the temperature after the reaction is completed, 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 to 2; R 1 , R 2 , and G 1 has the same definition as equation (1). JPEG2025509358000025.jpg36133

[0033] Optionally, the reaction temperature is 40-120° C., and the reaction time is 10-100 h. 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). The amount of catalyst used is 0.1% to 20% of the mass of the compound represented by (4).

[0037] Optionally, the solvent is an organic solvent that is not soluble in water, preferably toluene. The amount of the solvent can be added according to actual needs, preferably to ensure that the raw materials are dissolved. Optionally, the amount of the solvent is 0.5 to 100 times the mass of the compound represented by (4).

[0038] Optionally, the amount of the alkaline solution added may be 1 to 100 times the amount of the 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 JPEG2025509358000026.jpg47113.

[0041] The present application also provides: The method includes a step 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) to each other, and then adding and reacting a compound represented by formula (8), and stopping the reaction until the content of the compound represented by formula (8) is no longer reduced; 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 2provides a method for preparing the above-mentioned benzophenone derivative having the structure of formula (2), which has the same meaning as formula (2). JPEG2025509358000027.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) are 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 preparing the benzophenone derivative having the structure of the above formula (2) includes the steps of mixing the compound represented by formula (6), the compound represented by formula (7), a polymerization inhibitor, a catalyst, and a solvent, reacting them by heating in a nitrogen or inert atmosphere, adding the compound represented by formula (8) after the reaction is completed, and continuing to react while keeping the temperature, stopping the reaction until the content of the compound represented by formula (8) does not decrease, lowering the temperature, adding an alkaline solution to wash, then washing with water until neutral, removing the solvent, and obtaining the benzophenone derivative having the structure of the 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 R 1 , R 2 , and G 2 has the same meaning as in formula (2). JPEG2025509358000028.jpg32130

[0048] Optionally, the heating reaction temperature is 40-120° C., and the heating reaction time is 10-100 h. 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 an organic solvent that is not soluble in water, preferably toluene. The amount of the solvent can be added according to actual needs, preferably to ensure that the raw materials are dissolved. Optionally, the amount of the solvent is 0.5 to 100 times the mass of the compound represented by (6).

[0053] Optionally, the amount of the alkaline solution added is 1 to 100 times the amount of the 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 JPEG2025509358000029.jpg3484.

[0056] The present application also provides: The method includes 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 R 1 , R 2 , G 2 , and G 3 provides a method for preparing the above-mentioned benzophenone derivative having a structure represented by formula (3), which has the same meaning as formula (3). JPEG2025509358000030.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) are 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 the compound represented by formula (9), the compound represented by formula (10), a polymerization inhibitor, a catalyst, and a solvent, reacting them by heating in a nitrogen or inert atmosphere, adding the compound represented by formula (11) after the reaction is completed, and continuing to react while keeping the temperature, stopping the reaction until the content of the compound represented by formula (11) does not decrease, lowering the temperature, washing with an alkaline solution, then washing with water until neutral, removing the solvent, and obtaining the 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 R 1 , R 2 , G 2 , and G 3 has the same meaning as in equation (3). JPEG2025509358000031.jpg31127

[0063] Optionally, the reaction temperature is 40-120° C., and the reaction time is 10-100 h. 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, 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. 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 an organic solvent that is not soluble in water, preferably toluene. The amount of the solvent can be added according to actual needs, preferably to ensure that the raw materials are dissolved. Optionally, the amount of the solvent is 0.5 to 100 times the mass of the compound represented by (9).

[0067] Optionally, the amount of the alkaline solution added may be 1 to 100 times the amount of the 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 the reaction is completed, 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 JPEG2025509358000032.jpg43104.

[0069] The production of the compound of the formula (1), formula (2) or formula (3) of the present application 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, 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. 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 organic sulfonic acid, strong acid cation exchange resin, or organic sulfonates, 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-mentioned benzophenone derivative.

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

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

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

[0077] In any embodiment of the present application, the amount of the 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 or laboratory available compound commonly used in the industry, and is one or more selected from benzophenones (benzophenones other than those of the present application and their derivatives), thioxanthone compounds, α-hydroxyketone compounds, α-aminoketone compounds, acylphosphine oxide compounds or oxime ester compounds, preferably 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, 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 the component (b) added is 0.1 to 10%, for example 0.1%, 2%, 4%, 6%, 8%, or 10%, based on 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 resin, polyurethane acrylate resin, polyester acrylate resin, polyether acrylate resin, acrylated polyacrylate, epoxy methacrylate resin, polyurethane methacrylate resin, polyester methacrylate resin, polyether methacrylate resin, acrylated polymethacrylate, allyl ether compound, acrylate monomer, or methacrylate monomer. The acrylate monomer or methacrylate monomer is independently monofunctional, difunctional, or multifunctional. These radically polymerizable ethylenically unsaturated compounds are easily available commercially or in the laboratory 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 a use of the above-mentioned photocurable composition 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 any one of a paint, an adhesive, and a printing ink.

[0085] According to a further aspect of the present application, there is provided a method for curing a photocurable composition, 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. Effect 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, and therefore has significantly low mobility in a 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. The compounds have a large molecular weight, so they have very low migration and can be used in fields such as food packaging and printing formulations, instead of N,N,N,N-tetraethyl-4,4'-diaminobenzophenone. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0091] JPEG2025509358000033.jpg139137

[0092] * The structure of HEMK is as follows: JPEG2025509358000034.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 was equipped with a mechanical stirrer, and 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 paraaminobenzenesulfonic acid, and 12.0 g of toluene were added in sequence. After sufficient nitrogen replacement was performed while stirring at room temperature, the nitrogen quantitative tube was sealed, and the reaction was performed at a reaction temperature of 55 ° C for 48 hours while heating and stirring. A sample was taken and subjected to HPLC detection, and the reaction was stopped until the reaction of HEMK and the reaction of the monoaddition product were completed. The temperature was lowered to 30 ° C, and 3.0 g of a 5% mass concentration aqueous sodium carbonate solution (sodium carbonate 1.4 mmol) was added, and the mixture was washed with water until neutral. The solvent was removed by distillation under reduced pressure, and 3.44 g of formula IX product with an effective group content of 55% was obtained. The available group refers to the residue remaining after removing the hydrogens on the two hydroxyls from the HEMK structure. JPEG2025509358000035.jpg43138

[0095] [Table 1]

[0096] Example 2 A 100 mL three-neck flask was equipped with a mechanical stirrer, and 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 were added in sequence. After sufficient nitrogen replacement with stirring at room temperature, the nitrogen quantitative tube was sealed, and the reaction was carried out at a reaction temperature of 55 ° C for 48 hours while heating and stirring. A sample was taken and subjected to HPLC detection, and the reaction was stopped until the reaction of HEMK and the reaction of the monoaddition product were completed. The temperature was lowered to 30 ° C, and 3.0 g of a 5% aqueous sodium carbonate solution (1.4 mmol of sodium carbonate) was added, and the mixture was washed with water until neutral. The solvent was removed by distillation under reduced pressure, and 3.40 g of a product such as formula IX was obtained. JPEG2025509358000037.jpg42138

[0097] [Table 2]

[0098] Example 3 A 100 mL three-neck flask was equipped with a mechanical stirring function, and 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 paraaminobenzenesulfonic acid, and 12.0 g of toluene were added in sequence. After sufficient nitrogen replacement was performed while stirring at room temperature, the nitrogen quantitative tube was sealed, and the reaction was performed at a reaction temperature of 55 ° C for 48 hours while heating and stirring. A sample was taken and HPLC detection was performed, and the reaction was stopped until the reaction of HEMK and the reaction of the monoaddition product were completed. The temperature was lowered to 30 ° C, and 3.0 g of a 5% mass concentration sodium carbonate aqueous solution (sodium carbonate 1.4 mmol) was added, and the mixture was washed with water until neutral. The solvent was removed by distillation under reduced pressure, and 3.51 g of a product such as formula X was obtained. JPEG2025509358000039.jpg45139

[0099] [Table 3]

[0100] Example 4 A 100 mL three-neck flask was equipped with a mechanical stirrer, and 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 paraaminobenzenesulfonic acid, and 12.0 g of toluene were added in sequence. After sufficient nitrogen replacement was performed while stirring at room temperature, the nitrogen quantitative tube was sealed, and the reaction was performed at a reaction temperature of 55 ° C for 48 hours while heating and stirring. A sample was taken and HPLC detection was performed, and the reaction was stopped until the reaction of HEMK and the reaction of the monoaddition product were completed. The temperature was lowered to 30 ° C, and 3.0 g of a 5% mass concentration aqueous sodium carbonate solution (1.4 mmol of sodium carbonate) was added, and the mixture was washed with water until it became neutral. The solvent was removed by distillation under reduced pressure, and 2.91 g of a product such as formula XI with an effective group content of 55% was obtained. JPEG2025509358000041.jpg55156

[0101] [Table 4]

[0102] Example 5 A 100 mL three-neck flask was equipped with a mechanical stirring function, and 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 were added in sequence. After sufficient nitrogen replacement was performed while stirring at room temperature, the nitrogen quantitative tube was sealed, and the reaction was performed at a reaction temperature of 55 ° C for 48 hours while heating and stirring. A sample was taken and HPLC detection was performed, and the reaction was stopped until the reaction of HEMK and the reaction of the monoaddition product were completed. The temperature was lowered to 30 ° C, and 3.0 g of a 5% mass concentration sodium carbonate aqueous solution (sodium carbonate 1.4 mmol) was added, and the mixture was washed with water until neutral. The solvent was removed by distillation under reduced pressure, and 2.88 g of a product such as formula XI was obtained. JPEG2025509358000043.jpg58156

[0103] [Table 5]

[0104] Example 6 A 100 mL three-neck flask was equipped with a mechanical stirrer, and 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 paraaminobenzenesulfonic acid, and 12.0 g of toluene were added in sequence. After sufficient nitrogen replacement was performed while stirring at room temperature, the nitrogen quantitative tube was sealed, and the reaction was performed at a reaction temperature of 55 ° C for 48 hours while heating and stirring. A sample was taken and HPLC detection was performed, and the reaction was stopped until the reaction of HEMK and the reaction of the monoaddition product were completed. The temperature was lowered to 30 ° C, and 3.0 g of a 5% mass concentration aqueous sodium carbonate solution (1.4 mmol of sodium carbonate) was added, and the mixture was washed with water until neutral. The solvent was removed by distillation under reduced pressure, and 3.07 g of a product such as formula XII was obtained. JPEG2025509358000045.jpg59158

[0105] [Table 6]

[0106] Example 7 A 100 mL three-neck flask was equipped with a mechanical stirring function, and 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 paraaminobenzenesulfonic acid, and 12.0 g of toluene were added in sequence. After sufficient nitrogen replacement was performed while stirring at room temperature, the nitrogen quantitative tube was sealed, and the reaction was performed at a reaction temperature of 55 ° C for 48 hours while heating and stirring. Samples were taken and HPLC detection was performed until the reaction of HEMK and the reaction of the monoaddition product were completed. Next, 0.86 g (12 mmol) of acrylic acid was added, and the reaction was performed while keeping the temperature and stirring. Every 4 hours of reaction, samples were taken and detected, and the reaction was stopped until the content of acrylic acid did not decrease. The temperature was lowered to 30 ° C, 6.4 g of a 5% mass concentration sodium carbonate aqueous solution (sodium carbonate 3.0 mmol) was added, and the mixture was washed with water until it became neutral. The solvent was removed by vacuum distillation to give 3.91 g of the product as formula XIII with an available group content of 40%. JPEG2025509358000047.jpg32150

[0107] [Table 7]

[0108] Example 8 A 100 mL three-neck flask was equipped with a mechanical stirring function, and 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 paraaminobenzenesulfonic acid, and 12.0 g of toluene were added in sequence. After sufficient nitrogen replacement was performed while stirring at room temperature, the nitrogen quantitative tube was sealed, and the reaction was performed at a reaction temperature of 55 ° C for 72 hours while heating and stirring. Samples were taken and HPLC detection was performed until the reaction of HEMK and the reaction of the monoaddition product were completed. Next, 0.22 g (3 mmol) of acrylic acid was added, and the reaction was continued while keeping the temperature and stirring, and samples were taken and detected every 4 hours of reaction, and the reaction was stopped until the content of acrylic acid did not decrease. The temperature was lowered to 30 ° C, and 6.4 g of a 5% mass concentration sodium carbonate aqueous solution (sodium carbonate 3.0 mmol) was added, and the mixture was washed with water until it became neutral. The solvent was removed by vacuum distillation to give 2.58 g of the product as formula XIII. JPEG2025509358000049.jpg32150

[0109] [Table 8]

[0110] Example 9 A 100 mL three-neck flask was equipped with a mechanical stirring function, and 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 paraaminobenzenesulfonic acid, and 12.0 g of toluene were added in sequence. After sufficient nitrogen replacement was performed while stirring at room temperature, the nitrogen quantitative tube was sealed, and the reaction was performed at a reaction temperature of 55 ° C for 48 hours while heating and stirring. Until the reaction of HEMK and the reaction of the monoaddition product were completed, samples were taken and HPLC detection was performed. Next, 1.39 g (12 mmol) of hydroxyethyl acrylate was added, and the reaction was continued while keeping warm and stirring. After 4 hours of reaction, samples were taken and detected, and the reaction was stopped until the content of hydroxyethyl acrylate did not decrease. The temperature was lowered to 30°C, 6.4 g of a 5% aqueous sodium carbonate solution (sodium carbonate 3.0 mmol) was added, and the mixture was washed with water until neutral. The solvent was removed by distillation under reduced pressure to obtain 4.15 g of a product such as formula XIV having an effective group content of 40%. JPEG2025509358000051.jpg35148

[0111] [Table 9] Working Example

[0112] Example 10 A 100 mL three-neck flask was equipped with a mechanical stirring function, and 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 paraaminobenzenesulfonic acid, and 12.0 g of toluene were added in sequence. After sufficient nitrogen replacement was performed while stirring at room temperature, the nitrogen quantitative tube was sealed, and the reaction was performed at a reaction temperature of 55 ° C for 72 hours while heating and stirring. Samples were taken and HPLC detection was performed until the reaction of HEMK and the reaction of the monoaddition product were completed. Next, 0.35 g (3 mmol) of hydroxyethyl acrylate was added, and the reaction was continued while keeping the temperature and stirring. After 4 hours of reaction, samples were taken and detected, and the reaction was stopped until the content of hydroxyethyl acrylate did not decrease. The temperature was lowered to 30° C., 6.4 g of a 5% by mass aqueous sodium carbonate solution (sodium carbonate 3.0 mmol) was added, and the mixture was washed with water until neutral. The solvent was removed by distillation under reduced pressure to obtain 2.74 g of a product represented by formula XIV. JPEG2025509358000053.jpg33153

[0113] [Table 10]

[0114] Example 11 A 100 mL three-neck flask was equipped with a mechanical stirring function, and 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 paraaminobenzenesulfonic acid, and 12.0 g of toluene were added in sequence. After sufficient nitrogen replacement was performed while stirring at room temperature, the nitrogen quantitative tube was sealed, and the reaction was performed at a reaction temperature of 55 ° C for 48 hours while heating and stirring. Samples were taken and HPLC detection was performed until the reaction of HEMK and the reaction of the monoaddition product were completed. Next, 1.39 g (12 mmol) of hydroxyethyl acrylate was added, and the reaction was continued while keeping the temperature and stirring. After 4 hours of reaction, samples were taken and detected, and the reaction was stopped until the content of hydroxyethyl acrylate did not decrease. The temperature was lowered to 30°C, 6.4 g of a 5% aqueous sodium carbonate solution (sodium carbonate 3.0 mmol) was added, and the mixture was washed with water until neutral. The solvent was removed by distillation under reduced pressure to obtain 4.66 g of a product such as formula XV having an effective group content of 40%. JPEG2025509358000055.jpg28149

[0115] [Table 11]

[0116] Example 12 A 100 mL three-neck flask was equipped with a mechanical stirring function, and 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 paraaminobenzenesulfonic acid, and 12.0 g of toluene were added in sequence. After sufficient nitrogen replacement was performed while stirring at room temperature, the nitrogen quantitative tube was sealed, and the reaction was performed at a reaction temperature of 55 ° C for 96 hours while heating and stirring. Samples were taken and HPLC detection was performed until the reaction of HEMK and the reaction of the monoaddition product were completed. Next, 0.35 g (3 mmol) of hydroxyethyl acrylate was added, and the reaction was continued while keeping the temperature and stirring. After 4 hours of reaction, samples were taken and detected, and the reaction was stopped until the content of hydroxyethyl acrylate did not decrease. The temperature was lowered to 30° C., 6.4 g of a 5% aqueous sodium carbonate solution (sodium carbonate 3.0 mmol) was added, and the mixture was washed with water until neutral. The solvent was removed by distillation under reduced pressure to obtain 3.06 g of a product represented by formula XV. JPEG2025509358000057.jpg34155

[0117] [Table 12]

[0118] Example 13 A 100 mL three-neck flask was equipped with a mechanical stirrer, and 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 paraaminobenzenesulfonic acid, and 12.0 g of toluene were added in sequence. After sufficient nitrogen replacement was performed while stirring at room temperature, the nitrogen quantitative tube was sealed, and the reaction was performed at a reaction temperature of 55 ° C for 48 hours while heating and stirring. Samples were taken and HPLC detection was performed until the reaction of HEMK and the reaction of the monoaddition product were completed. Next, 1.39 g (12 mmol) of hydroxyethyl acrylate was added, and the reaction was continued while keeping the temperature and stirring. After 4 hours of reaction, samples were taken and detected, and the reaction was stopped until the content of hydroxyethyl acrylate did not decrease. The temperature was lowered to 30° C., 6.4 g of a 5% by mass aqueous sodium carbonate solution (sodium carbonate 3.0 mmol) was added, and the mixture was washed with water until neutral. The solvent was removed by distillation under reduced pressure to obtain 4.09 g of a product represented by formula XVI. JPEG2025509358000059.jpg33146

[0119] [Table 13]

[0120] Example 14 This example provides a photocurable composition containing as ingredients 4.57 g Photomer 4072, 4.57 g Photomer 3316, 0.36 g Formula IX product of Example 1, and 0.5 g 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 lowering the temperature 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 Photomer 4072, 4.57 g Photomer 3316, 0.36 g Formula XI product of Example 4, and 0.5 g 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 lowering the temperature 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 Photomer 4072, 4.5 g Photomer 3316, 0.5 g Formula XIII product of Example 7, and 0.5 g 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 lowering the temperature 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 Photomer 4072, 4.5 g Photomer 3316, 0.5 g Formula XIV product of Example 9, and 0.5 g 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 lowering the temperature 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 Photomer 4072, 4.5 g Photomer 3316, 0.5 g Formula XV product of Example 11, and 0.5 g 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 lowering the temperature 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: 4.65 g Photomer 4072, 4.65 g Photomer 3316, 0.2 g Omnirad EMK, and 0.5 g 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 lowering the temperature to room temperature, and compounding them into the photocurable composition.

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

[0133] Pendulum hardness test: Using a 25 μm wire, the above photocurable composition was cured once on the 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 in length and width 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 acetic acid with a mass content of 3%. 2 and left at 40°C for 10 days, and then quantitatively analyzed 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) transferred into the aqueous acetic acid solution using HPLC. The EU model was used to calculate the results, and 1 kg of food has a mass of 600 cm 2The results can be converted to μg / kg, i.e. μg of analyte per kg of food, assuming that the product is packaged with a printed area of ​​100 μg / kg (wherein 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] As can be seen from the test data, when the bis(dialkylamino)benzophenone-based compound with acrylate alkoxy side chain according to the present application is used as a coinitiator in a photocurable composition, compared with the commonly used commercial EMK, the compound according to the present application has a similar hardness and a similar cure rate as the comparative material after curing, but the mobility of the compound according to the present application is significantly reduced due to its large molecular weight and polymerizable double bond. Therefore, the compound according to the present application is more suitable for use in food and pharmaceutical packaging, children's toys, and other applications with strict requirements for the mobility of materials.

[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 forms of 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 are still within the protection scope of the present invention.

Claims

1. A benzophenone derivative having a structure represented by formula (1): (where: n1 is an integer from 1 to 10, R1 is an optionally substituted C1 to C8 alkyl, and R2 is -CH3 or 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, m ２ is an integer from 1 to 12.

2. n1 is an integer from 1 to 4, Preferably, R1 is C1-C4 alkyl, more preferably and preferably R2 is H; Preferably, R ３ teeth, and R ２ and G １ is the same as defined in formula (1) of claim 1, Preferably, G １ teeth, 、 or The benzophenone derivative according to claim 1, wherein

3. A benzophenone derivative having a structure represented by formula (2): (where: n2 is an integer from 1 to 10, R1 is an optionally substituted C1 to C8 alkyl, and R2 is H or -CH3; R ４ is H or and G ２は、 Optionally substituted C1 to C12 alkylene or and m ３ is an integer from 1 to 11.

4. n2 is an integer from 1 to 6, Preferably, R1 is alkyl, preferably C1 to C4, more preferably Preferably, R2 is H, and preferably, R4 is and R ２ and G ２ The benzophenone derivative according to claim 3, wherein the definition of is the same as that in formula (2) of claim 3.

5. A benzophenone derivative having a structure represented by formula (3): (where: 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 and G2 is an optionally substituted C1-C12 alkylene or m3 is an integer from 1 to 11; G3 is an optionally substituted C1 to C12 alkylene; or and m4 is an integer from 1 to 11.

6. n3 is an integer from 1 to 6, Preferably, R1 is C1-C4 alkyl, more preferably and preferably R2 is H; Preferably, R5 is The definitions of R2, G2, and G3 are the same as those in formula (3) of claim 5. Preferably, G2 and G3 are each independently 、 or The benzophenone derivative according to claim 5 ,

7. 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 method for producing a benzophenone derivative according to claim 1 or 2, wherein 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 those in formula (1).

8. The method according to claim 7, characterized in that the reaction temperature is 40-120°C and the reaction time is 10-100h.

9. 5. A method for producing a benzophenone derivative according to claim 3 or 4, 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 and reacting a compound represented by formula (8), 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 R1, R2, and G2 have the same meaning as in formula (2).)

10. The method according to claim 9, wherein the reaction temperature is 40-120° C. and the reaction time is 10-100 h.

11. 7. A method for producing a benzophenone derivative according to claim 5 or 6, comprising the steps of reacting a compound represented by formula (9) with a compound represented by formula (10), adding at least one of the hydroxyl groups at both ends of the compound represented by formula (9), and then adding the compound represented by formula (11) until all 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 R1, R2, G2, and G3 have the same meaning as in formula (3).)

12. The method according to claim 11, characterized in that the reaction temperature is 40-120°C and the reaction time is 10-100h.

13. A photocuring agent composition comprising a photoinitiator usable for radical polymerization and the benzophenone derivative according to any one of claims 1 to 6.

14. A photocurable composition comprising a photohardener component and a radically polymerizable ethylenically unsaturated compound, the photohardener component comprising the photohardener composition of claim 13.

15. (a) the benzophenone derivative according to any one of claims 1 to 6; (b) a photoinitiator usable for radical polymerization; and and (c) a radically polymerizable ethylenically unsaturated compound.

16. 16. The photocurable composition according to claim 15, wherein the amount of component (a) added is 0.1 to 20% of the total weight of the photocurable composition.

17. The photocurable composition according to claim 15, wherein component (b) is one or more selected from benzophenones, thioxanthone compounds, α-hydroxyketone compounds, α-aminoketone compounds, acylphosphine oxide compounds, or oxime ester compounds, and is preferably 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, or photoinitiator Omnipol TP.

18. 16. The photocurable composition according to claim 15, wherein the amount of component (b) added is 0.1 to 10% of the total weight of the photocurable composition.

19. 16. The photocurable composition according to claim 15, wherein component (c) is at least one selected from the group consisting of 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, and methacrylate monomers.

20. Use of the photocurable composition according to any one of claims 14 to 19 in food packaging printing, pharmaceutical packaging printing, furniture painting, book printing or advertisement printing.

21. A photocurable product, which is obtained by photocuring a photocurable composition, and is characterized in that the photocurable composition is the photocurable composition according to any one of claims 14 to 19.

22. 20. A method for curing a photocurable composition, comprising: applying the photocurable composition according to any one of claims 14 to 19 onto a substrate; and curing the photocurable composition with a light source having an emission band in the UV-visible region.

23. 23. The method of claim 22, wherein the substrate is selected from wood, paper, plastic, a coating, or metal.

24. 23. The method of claim 22, wherein the application method is selected from offset printing, gravure printing, flexography, inkjet printing, or 3D printing.

25. 23. The method of claim 22, characterized in that after application to a substrate, the photocurable composition is cured by irradiation with UV-visible light of wavelengths from 200 to 425 nm.

26. 26. The method of claim 25, wherein the photocurable composition is cured by irradiation with UV-visible light having a wavelength of 365 to 405 nm.

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