A photocurable composition, its preparation and use

Abstract

The present application relates to a kind of photocuring composition and its preparation method and application, the photocuring composition includes the following components: resin, active monomer and photoinitiator.The photocuring composition described in the present application has low photoinitiator mobility, good solubility of photoinitiator in monomer, low energy required when the photocuring composition is cured, high adhesion on the surface of various substrates such as plastic, metal and other difficult to adhere substrates, and the photocuring composition has low odor during curing process, low yellowing degree after curing, high stability and repeatability of the system, and excellent comprehensive performance.

Description

A photocurable composition, its preparation method and application Technical Field

[0001] This invention relates to the field of coating technology, and in particular to a photocurable composition, its preparation method, and its application. Background Technology

[0002] Photocurable systems are playing an increasingly important role in various industries, but their applications place high demands on the corresponding photocurable compositions. For example, the migration of photoinitiators, their solubility in monomers, the odor during the curing process of the photocurable composition, curing energy, adhesion to the substrate, the repeatability and stability of the system, all affect their practical application.

[0003] For example, regarding adhesion to substrates, plastics differ from wood and paper in that they are non-absorbent substrates. They cannot achieve adhesion through mechanical bonding caused by the penetration of coatings into the substrate. Compared to metals, which are also non-absorbent substrates, plastics are "inert" materials with almost no active sites on their surface that can react with the components in the coating. Therefore, they cannot form the chemical bonds required for effective adhesion, making it quite difficult to achieve high adhesion between plastics and UV-cured compositions.

[0004] In conclusion, it is crucial to develop a photocurable composition that can overcome the aforementioned defects. Summary of the Invention

[0005] To address the shortcomings of existing technologies, the present invention aims to provide a photocurable composition, its preparation method, and its application. The photocurable composition of the present invention features a low photoinitiator migration rate, good solubility of the photoinitiator in the monomer, low energy required for curing, high adhesion to various substrates such as plastics and metals, low odor during curing, low yellowing after curing, high system stability and repeatability, and excellent overall performance.

[0006] To achieve this objective, the present invention adopts the following technical solution:

[0007] In a first aspect, the present invention provides a photocurable composition comprising the following components: a resin, an active monomer, and a photoinitiator;

[0008] The photoinitiator includes at least the structural formula shown in Formula I:

[0009]

[0010] Z1 and Z2 are each independently selected from any one of hydrogen, deuterium, halogen, substituted or unsubstituted C1-C10 (e.g., C2, C4, C6, C8, etc.) straight-chain or branched alkylene groups, and substituted or unsubstituted C3-C20 (e.g., C4, C6, C8, C10, C12, C14, C16, C18, etc.) cycloalkylene groups;

[0011] Z3 is selected from C1-C20 (e.g., C2, C4, C6, C8, C10, C12, C14, C16, C18, etc.) straight-chain or branched alkylene groups containing carbonyl groups, C1-C20 (e.g., C2, C4, C6, C8, C10, C12, C14, C16, C18, etc.) straight-chain or branched alkylene groups containing ester groups, and C1-C10 (e.g., C2, C4, C6, C8, etc.) straight-chain or branched heteroalkylene groups.

[0012] M1, M2, M3 and M4 are each independently selected from any one of O, S or NR, and R is selected from H or C1-C5 (e.g. C1, C2, C3, C4, etc.) alkyl groups;

[0013] The substituents are each independently selected from at least one of hydrogen, deuterium, C1-C10 (e.g., C2, C4, C6, C8, etc.) straight-chain or branched alkyl groups, C3-C20 (e.g., C4, C6, C8, C10, C12, C14, C16, C18, etc.) cycloalkyl groups, or halogens.

[0014] Traditional high-performance photoinitiators such as photoinitiator 907, photoinitiator 369, and photoinitiator 379, when used to form photocurable compositions, often fail to achieve high adhesion on plastic substrates due to the poor solubility of the photoinitiators themselves, high system shrinkage, and the inability to achieve adhesion through mechanical bonding caused by the penetration of the coating into the plastic substrate. Furthermore, plastic is an "inert" material with almost no active sites on its surface capable of reacting with the components in the coating. Additionally, without the addition of adhesion-promoting additives, the photocurable composition also struggles to achieve ideal adhesion to metals. One reason for this is the dense surface of metal substrates, which makes them difficult to cure with photocuring. The composition has several limitations. First, it is difficult for the material to penetrate and absorb, resulting in a small effective contact interface. Second, the rapid curing of the photocurable composition on the metal substrate surface prevents the release of internal stress caused by volume shrinkage, which in turn affects the adhesion of the film layer to the metal substrate, thus reducing adhesion. Third, many metals are easily oxidized in air, forming an oxide film on the surface, which relatively reduces the surface free energy and further affects the adhesion of the photocurable composition to that surface. In summary, photocurable compositions are unlikely to have excellent adhesion to a variety of substrates, such as plastics and metals. In addition, the odor of the photocurable composition during the curing process, the degree of yellowing after curing, the stability and repeatability of the system also limit its widespread application.

[0015] The photoinitiator in the photocurable composition of the present invention has low migration rate and good solubility in monomers. The photocurable composition requires low energy during curing, has high adhesion to various substrates such as plastics and metals, and exhibits low odor during curing, low yellowing after curing, high stability and repeatability, and excellent overall performance.

[0016] In this invention, "C1~C10" refers to the number of carbon atoms in the main chain being 1 to 10, such as C2, C4, C6, C8, etc., and other similar expressions are expressed in the same way.

[0017] In this invention, the term "heteroalkyl" refers to a structure containing heteroatoms, including but not limited to O, S, N, Si, etc.

[0018] Preferably, the photocurable composition comprises the following components in parts by weight:

[0019] 5-70 parts of resin

[0020] 10-50 parts of active monomer

[0021] Photoinitiator 1-18 parts.

[0022] In this invention, the photocurable composition formed by using the components in a specific weight range has the advantages of high adhesion to the surface of various plastic substrates and low energy required for curing, resulting in excellent overall performance.

[0023] In this invention, the resin is in the form of 5-70 parts by weight, for example, 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, 45 parts, 50 parts, 55 parts, 60 parts, 65 parts, etc.

[0024] The active monomer is present in parts by weight of 10-50, such as 15, 20, 25, 30, 35, 40, 45, etc.

[0025] The photoinitiator is present in parts by weight of 1-18, such as 2, 4, 6, 8, 10, 12, 14, 16, 18, etc.

[0026] Preferably, the resin comprises any one or a combination of at least two of polyurethane acrylate, epoxy acrylate resin, or polyester acrylate resin, wherein typical but non-limiting combinations include: a combination of polyurethane acrylate and epoxy acrylate resin, a combination of epoxy acrylate resin and polyester acrylate resin, a combination of polyurethane acrylate, epoxy acrylate resin, and polyester acrylate resin, etc.

[0027] Preferably, the polyester acrylate resin includes a halogenated polyester acrylate resin, and more preferably a chlorinated polyester acrylate resin.

[0028] Preferably, the resin comprises polyurethane acrylate and / or chlorinated polyester resin.

[0029] In this invention, the resin is further preferably polyurethane acrylate and / or chlorinated polyester resin. Polyurethane acrylate can provide a faster curing rate, sufficient flexibility, comprehensive mechanical strength and certain adhesion, while chlorinated polyester acrylate resin can provide a strong adhesion promoting effect. The two work synergistically with the photoinitiator described in this invention to form a photocurable composition with excellent comprehensive performance.

[0030] Preferably, the polyurethane acrylate comprises a polyurethane acrylate with a functionality of 2-6 (e.g., 3, 4, 5, etc.).

[0031] Preferably, when the resin is selected from a combination of polyurethane acrylate and chlorinated polyester resin, the polyurethane acrylate is in the amount of 30-50 parts by weight (e.g., 32 parts, 34 parts, 36 parts, 38 parts, 40 parts, 42 parts, 44 parts, 46 parts, 48 ​​parts, etc.), and the chlorinated polyester resin is in the amount of 5-20 parts by weight (e.g., 6 parts, 8 parts, 10 parts, 12 parts, 14 parts, 16 parts, 18 parts, etc.).

[0032] In this invention, the photocurable composition formed by using polyurethane acrylate and chlorinated polyester resin in specific weight parts exhibits better overall performance. Specifically, a higher weight part of polyurethane acrylate results in poorer overall hardness of the coating formed by the photocurable composition; a lower weight part of polyurethane acrylate leads to a decrease in the curing rate of the photocurable composition and a decrease in the adhesion of the formed coating; a higher weight part of chlorinated polyester resin leads to poorer compatibility among the components of the photocurable composition; and a lower weight part of chlorinated polyester resin results in insignificant improvement in adhesion.

[0033] Preferably, the functionality of the active monomer is ≥2, for example, 3, 4, 5, 6, etc.

[0034] Preferably, the active monomer includes a first active monomer and / or a second active monomer.

[0035] Preferably, the first active monomer comprises a difunctional active monomer.

[0036] Preferably, the first active monomer comprises any one or a combination of at least two of 1,6-hexanediol diacrylate, tripropylene glycol diacrylate, diethylene glycol diacrylate, or diethylene glycol diacrylate, wherein typical but non-limiting combinations include: a combination of 1,6-hexanediol diacrylate and tripropylene glycol diacrylate, a combination of diethylene glycol diacrylate and diethylene glycol diacrylate, a combination of 1,6-hexanediol diacrylate, tripropylene glycol diacrylate, diethylene glycol diacrylate, and diethylene glycol diacrylate, etc.

[0037] Preferably, the second active monomer comprises a trifunctional active monomer.

[0038] Preferably, the second active monomer comprises any one or a combination of at least two of trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, or pentaerythritol triacrylate, wherein typical but non-limiting combinations include: a combination of trimethylolpropane triacrylate and ethoxylated trimethylolpropane triacrylate, a combination of ethoxylated trimethylolpropane triacrylate and pentaerythritol triacrylate, a combination of trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, and pentaerythritol triacrylate, etc.

[0039] In this invention, the first and second active monomers work synergistically to form a photocurable composition with better overall performance.

[0040] Preferably, the first active monomer is 20-30 parts by weight, such as 22 parts, 24 parts, 26 parts, 28 parts, etc.

[0041] Preferably, the second active monomer is 10-20 parts by weight, such as 12 parts, 14 parts, 16 parts, 18 parts, etc.

[0042] Preferably, Z3 is selected from... Any one of them;

[0043] Where m, n and l are each independent positive integers from 1 to 10, such as 2, 4, 6, 8, etc.

[0044] k is a positive integer between 8 and 12, such as 9, 10, 11, etc.

[0045] z is a positive integer from 1 to 10 (e.g., 2, 4, 6, 8, etc.), and R1, R2, R3 and R4 are each independently selected from any one of hydrogen, deuterium, halogen, substituted or unsubstituted C1 to C10 (e.g., 2, 4, 6, 8, etc.) straight-chain or branched alkyl groups, and substituted or unsubstituted C3 to C20 (e.g., C4, C6, C8, C10, C12, C14, C16, C18, etc.) cycloalkyl groups;

[0046] The substituents are each independently selected from at least one of hydrogen, deuterium, C1-C10 (e.g., 2, 4, 6, 8, etc.) straight-chain or branched alkyl groups, C3-C20 (e.g., C4, C6, C8, C10, C12, C14, C16, C18, etc.) cycloalkyl groups, or halogens.

[0047] Preferably, the photoinitiator comprises a compound of formula II, formula III or formula IV;

[0048]

[0049]

[0050] Wherein, m, n and l are each independent positive integers from 1 to 10, such as 2, 4, 6, 8, etc.;

[0051] k is a positive integer between 8 and 12, such as 9, 10, 11, etc.

[0052] The z is a positive integer from 1 to 10 (e.g., 2, 4, 6, 8, etc.), and R1, R2, R3 and R4 are each independently selected from hydrogen, deuterium, and any one of unsubstituted C1 to C10 (e.g., C2, C4, C6, C8, etc.) straight-chain or branched alkyl groups.

[0053] M1, M2, M3 and M4 are each independently selected from any one of O, S or NR, and R is selected from H or C1-C5 (e.g. C1, C2, C3, C4, etc.) alkyl groups;

[0054] Z1 and Z2 are each independently selected from any one of hydrogen, deuterium, unsubstituted C1-C10 (e.g., C2, C4, C6, C8, etc.) straight-chain or branched alkylene groups, and unsubstituted C3-C20 (e.g., C4, C6, C8, C10, C12, C14, C16, C18, etc.) cycloalkylene groups, with hydrogen, deuterium, or unsubstituted C2-C6 straight-chain alkylene groups being more preferred.

[0055] Preferably, the photoinitiator comprises any one or a combination of at least two of the following compounds:

[0056]

[0057]

[0058]

[0059]

[0060]

[0061]

[0062] Preferably, the photocurable composition further includes additives.

[0063] Preferably, the additive includes any one or a combination of at least two of leveling agents, wetting agents, or adhesion promoters, wherein typical but non-limiting combinations include: a combination of leveling agents and wetting agents, a combination of wetting agents and adhesion promoters, a combination of leveling agents, wetting agents, and adhesion promoters, etc.

[0064] Preferably, the amount of the additive is 0-3.5 parts by weight, such as 0.5 parts, 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, etc.

[0065] Preferably, the leveling agent comprises an organosilicon leveling agent.

[0066] Preferably, the silicone leveling agent comprises polyether-modified silicone oil and / or polyester-modified silicone oil.

[0067] Preferably, the leveling agent is present in a weight ratio of 0.5-1.5 parts, such as 0.5 parts, 1 part, 1.5 parts, etc.

[0068] Preferably, the wetting aid comprises polyether-modified silicone oil.

[0069] Preferably, the wetting agent is present in 0-1 parts by weight, such as 0.2 parts, 0.4 parts, 0.6 parts, 0.8 parts, etc.

[0070] Preferably, the adhesion promoter comprises an organosilicon compound or an organophosphate compound.

[0071] Preferably, the adhesion promoter is present in 0-1 parts by weight, such as 0.2 parts, 0.4 parts, 0.6 parts, 0.8 parts, etc.

[0072] In a second aspect, the present invention provides a method for preparing the photocurable composition described in the first aspect, the method comprising the following steps:

[0073] The resin, active monomer, and photoinitiator are mixed to obtain the photocurable composition.

[0074] Preferably, the mixed raw materials also include additives.

[0075] Preferably, the mixing method includes stirring.

[0076] Preferably, the stirring rate is 800-1000 r / min, such as 820 r / min, 840 r / min, 860 r / min, 880 r / min, 900 r / min, 920 r / min, 940 r / min, 960 r / min, 980 r / min, etc.

[0077] Preferably, the mixing time is 20-30 minutes, such as 22 minutes, 24 minutes, 26 minutes, 28 minutes, etc.

[0078] For example, the method for preparing the photoinitiator includes the following steps:

[0079] Will The compound is obtained by reacting with a carbonyl-containing C1-C20 (e.g., C2, C4, C6, C8, C10, C12, C14, C16, C18, etc.) straight-chain or branched alkylene compounds, a C1-C20 (e.g., C2, C4, C6, C8, C10, C12, C14, C16, C18, etc.) straight-chain or branched heteroalkylene compounds, or a C1-C10 (e.g., C2, C4, C6, C8, etc.) straight-chain or branched heteroalkylene compounds.

[0080] Among them, M1, M2, M3 and M4, as well as Z1 and Z2, are the same as the aforementioned range.

[0081] Preferably, the preparation method includes the following steps:

[0082] The reactants were reacted in the presence of an alkali and an inert gas, followed by post-treatment and recrystallization to obtain the compound.

[0083] Preferably, the reaction is carried out under stirring conditions.

[0084] Preferably, the reaction process includes: under inert gas protection and stirring conditions, first dissolving the first reactant in a solvent, then adding an alkali, controlling the temperature, adding the second reactant to the system, and reacting.

[0085] in, The first reactant is a C1-C20 (e.g., C2, C4, C6, C8, C10, C12, C14, C16, C18, etc.) straight-chain or branched alkylene reactants containing carbonyl groups, C1-C20 (e.g., C2, C4, C6, C8, C10, C12, C14, C16, C18, etc.) straight-chain or branched heteroalkylene reactants containing ester groups, or C1-C10 (e.g., C2, C4, C6, C8, etc.) straight-chain or branched heteroalkylene reactants.

[0086] Preferably, the dissolving solvent includes any one or a combination of at least two of N,N-dimethylformamide, N,N-dimethylacetamide, acetonitrile, dimethyl sulfoxide (DMSO), dichloromethane, 1,2-dichloroethane, benzene, or toluene. Typical but non-limiting combinations include: a combination of N,N-dimethylformamide and dichloromethane; a combination of dichloromethane and toluene; a combination of N,N-dimethylacetamide, acetonitrile, and dimethyl sulfoxide; a combination of N,N-dimethylformamide, dichloromethane, and toluene; a combination of dimethyl sulfoxide, dichloromethane, 1,2-dichloroethane, benzene, and toluene, etc.

[0087] Preferably, the base includes any one or a combination of at least two of sodium hydride, amine base, carbonate, or tert-butoxide, wherein typical but non-limiting combinations include: a combination of sodium hydride and amine base, a combination of amine base, carbonate, and tert-butoxide, a combination of sodium hydride, amine base, carbonate, and tert-butoxide, etc.

[0088] Preferably, the amine base includes any one or a combination of at least two of triethylamine, N,N-dimethylaniline, or diazabicyclo(DBU), wherein typical but non-limiting combinations include: a combination of triethylamine and N,N-dimethylaniline, a combination of N,N-dimethylaniline and diazabicyclo, a combination of triethylamine, N,N-dimethylaniline, and diazabicyclo, etc.

[0089] Preferably, the carbonate includes any one or a combination of at least two of cesium carbonate, sodium carbonate, or potassium carbonate, wherein typical but non-limiting combinations include: a combination of cesium carbonate and sodium carbonate, a combination of sodium carbonate and potassium carbonate, a combination of cesium carbonate, sodium carbonate, and potassium carbonate, etc.

[0090] Preferably, the tert-butoxide comprises sodium tert-butoxide and / or potassium tert-butoxide.

[0091] Preferably, the volume ratio of the first reactant to the dissolving solvent is 1:(3-8), wherein 3-8 can be 3.2, 3.4, 3.6, 3.8, 4, 4.2, 4.4, 4.6, 4.8, 5, 5.5, 6, 6.5, 7, 7.5, etc., and more preferably 3-5.

[0092] Preferably, the molar ratio of the first reactant to the base is 1:(1–1.1), wherein 1–1.1 can be 1.02, 1.04, 1.06, 1.07, 1.08, 1.09, etc., and more preferably 1:(1.05–1.1).

[0093] Preferably, the molar ratio of the second reactant to the first reactant is 1:(2.0–2.1), wherein 2.0–2.1 can be 2.02, 2.04, 2.06, 2.08, etc.

[0094] Preferably, the temperature for temperature control is 0-100℃, such as 2℃, 4℃, 6℃, 8℃, 10℃, 20℃, 40℃, 60℃, 80℃, etc.

[0095] Preferably, the reaction temperature is 15-100℃, such as 16℃, 18℃, 20℃, 22℃, 24℃, 26℃, 28℃, 30℃, 32℃, 34℃, 40℃, 60℃, 80℃, etc., and more preferably 15-30℃.

[0096] Preferably, the reaction time is 2–20 h, for example 2.2 h, 2.4 h, 2.6 h, 2.8 h, 3 h, 3.2 h, 3.4 h, 3.6 h, 3.8 h, 4 h, 6 h, 8 h, 10 h, 12 h, 14 h, 16 h, 18 h, etc.

[0097] Preferably, the post-processing includes: pouring the reaction solution into ice water, adjusting the pH, extracting, washing, and desolvating under reduced pressure to obtain the crude product.

[0098] Preferably, the pH is adjusted to 1-4, such as 1.5, 2, 2.5, 3, 3.5, etc.

[0099] Preferably, the solvent for extraction includes any one or a combination of at least two of dichloromethane, dichloroethane, ethyl acetate, isopropyl acetate, benzene, or toluene, wherein typical but non-limiting combinations include: a combination of dichloromethane, dichloroethane, and ethyl acetate; a combination of isopropyl acetate, benzene, and toluene; a combination of dichloroethane, ethyl acetate, isopropyl acetate, and benzene, etc.

[0100] Preferably, the object of the washing is the extracted organic phase.

[0101] Preferably, the washing is performed at least once, such as twice, three times, four times, etc.

[0102] Preferably, the solvent for recrystallization includes any one or a combination of at least two of methanol, ethanol, isopropanol, ethyl acetate, isopropyl acetate, n-hexane, cyclohexane, or petroleum ether. Typical but non-limiting combinations include: a combination of isopropanol and isopropyl acetate; a combination of n-hexane, cyclohexane, and petroleum ether; a combination of isopropyl acetate and n-hexane; a combination of isopropanol, isopropyl acetate, and n-hexane; a combination of methanol, ethanol, isopropanol, ethyl acetate, and isopropyl acetate, etc.

[0103] Preferably, the recrystallization process further includes drying.

[0104] As a preferred technical solution, the preparation method includes the following steps:

[0105] (1) Under the protection of an inert gas and under stirring conditions, the first reactant is dissolved in a solvent at 15-100℃, wherein the volume ratio of the first reactant to the solvent is 1:(3-8).

[0106] (2) Add alkali to the system, control the temperature to 0-100℃, add the second reactant to the system, wherein the molar ratio of the first reactant, alkali and the second reactant is 1:(1.0–1.1):(0.500–0.476), and react for 2-10 h;

[0107] (3) The product obtained in step (2) is subjected to post-treatment, recrystallization and drying to obtain the compound.

[0108] Thirdly, the present invention provides an application of the photocurable composition described in the first aspect in a plastic substrate.

[0109] Compared with the prior art, the present invention has the following beneficial effects:

[0110] (1) The photoinitiator in the photocurable composition of the present invention has low migration rate and good solubility in monomers. The photocurable composition requires low energy during curing and has high adhesion to various substrates such as plastics and metals. Furthermore, the photocurable composition has low odor during curing, low yellowing after curing, high stability and repeatability of the system, and excellent overall performance.

[0111] (2) The photoinitiator migration rate in the photocurable composition of the present invention is between 26.4% and 46.2%, the solubility of the photoinitiator in the monomer is between 20% and 39%, and the adhesion to various plastic substrates such as polyethylene, polycarbonate, polyvinyl chloride, polyethylene terephthalate, polystyrene, acrylonitrile-butadiene-styrene copolymer, and metal surfaces is high. Furthermore, the odor of the photocurable composition during the curing process is between A and B, the yellowing value after curing is between 1.6 and 2.9, the stability of the system is between A and B, and the repeatability is high between A and B. Attached Figure Description

[0112] Figure 1 is the standard judgment chart for adhesion testing. Detailed Implementation

[0113] To facilitate understanding of the present invention, the following embodiments are provided. Those skilled in the art should understand that these embodiments are merely illustrative and should not be construed as limiting the scope of the invention.

[0114] In this invention, some of the raw materials are sourced as follows:

[0115] Polyurethane acrylate resin: purchased from Zhanxin Resin, brand name: 270;

[0116] Chlorinated polyester resin: purchased from Zhanxin Resin, brand name is 436;

[0117] Epoxy acrylate resin: purchased from Zhanxin Resin, brand name is 605

[0118] The active monomers, such as 1,6-hexanediol diacrylate and ethoxylated trimethylolpropane triacrylate, and the photoinitiators are sourced from Tianjin Jiuri New Materials Co., Ltd.; the additives, such as leveling agent (brand name Tech-229N), wetting agent (brand name Tech-240) and adhesion promoter (brand name Tech-7145), are sourced from Shanghai Tiger Polymer Technology Co., Ltd.

[0119] Example 1

[0120] This embodiment provides a photocurable composition, which is composed of the following components in parts by weight:

[0121]

[0122] The structural formula of the photoinitiator is as follows:

[0123]

[0124] The photoinitiator is obtained by the following preparation method:

[0125] (1) Under inert gas protection and stirring conditions, 1 mol Dissolves in 1200 mL of solvent (dichloromethane) at 15°C;

[0126] (2) Add 1.05 mol of alkali (triethylamine) to the system, control the temperature to 5℃, and then add 0.49 mol of alkali (triethylamine) to the system. The reaction lasted for 2 hours.

[0127] (3) The product obtained in step (2) is subjected to post-treatment, recrystallization and drying to obtain the compound.

[0128] The structure of the aminoketone photoinitiator obtained in this embodiment was analyzed, and the test methods and results are shown below:

[0129] Mass spectrometry analysis results: MS: m / z = [M+1] + =813.41 (MW=812.41).

[0130] 1 The H-NMR test results are shown below:

[0131] 1 H-NMR (400MHz, CDCl3): δ8.51~8.49(m,4H),7.34~7.26(m,4H),4.31~4.27(t,4H),3.70~3.68(m,8H),3.25~3 .21(m,2H),2.58~2.54(m,8H),2.30~2.28(m,4H),1.62~1.56(m,6H),1.32(s,12H),1.30(s,6H)1.28(m,6H).

[0132] Example 2

[0133] This embodiment provides a photocurable composition, which is composed of the following components in parts by weight:

[0134]

[0135] The structural formula of the photoinitiator is as follows:

[0136]

[0137] The photoinitiator is obtained by the following preparation method:

[0138] (1) Under inert gas protection and stirring conditions, 1 mol It dissolves in 1200 mL of solvent (N,N-dimethylformamide) at 18°C.

[0139] (2) Add 1.05 mol of alkali (sodium hydride) to the system, control the temperature to 5℃, and then add 0.49 mol of alkali to the system. The reaction lasted 4 hours.

[0140] (3) The product obtained in step (2) is subjected to post-treatment, recrystallization and drying to obtain the compound.

[0141] The photoinitiator obtained in this embodiment was subjected to structural analysis. The test methods and results are shown below:

[0142] The mass spectrometry analysis results are: MS: m / z = [M+1] + =873.43 (MW=872.43).

[0143] 1 The H-NMR testing methods and results are shown below:

[0144] 1 H-NMR (400MHz, CDCl3): δ7.52~7.48(m,4H),7.37~7.34(m,4H),4.17~4.14(m,4H),3.79~3.75(t,4H),3.66~3.64(t,8H),3.50~ 3.48(t,4H),2.98~2.94(t,4H),2.51~2.48(m,8H),2.37~2.33(t,H),1.78~1.75(m,4H),1.74~1.63(m,8H),1.52~1.50(m,12H).

[0145] The photocurable composition is obtained by the following preparation method, which includes the following steps:

[0146] The components were stirred and mixed at 800 r / min for 30 min according to the formula to obtain the photocurable composition.

[0147] Example 3

[0148] This embodiment provides a photocurable composition, which is composed of the following components in parts by weight:

[0149]

[0150] The photoinitiator is obtained by the following preparation method:

[0151] The structural formula of the photoinitiator is as follows:

[0152]

[0153] (1) Under inert gas protection and stirring conditions, 1 mol Dissolves in 1200 mL of solvent (toluene) at 15°C;

[0154] (2) Add 1.05 mol of alkali (triethylamine) to the system, control the temperature to 4℃, and then add 0.49 mol of alkali to the system. The reaction lasted for 3 hours.

[0155] (3) The product obtained in step (2) is subjected to post-treatment, recrystallization and drying to obtain the compound.

[0156] The photoinitiator obtained in this embodiment was subjected to structural analysis. The test methods and results are shown below:

[0157] The mass spectrometry analysis results are shown below: MS: m / z = [M+1] + =761.34 (MW=760.34).

[0158] 1 The H-NMR results are shown below:

[0159] 1 H-NMR (400MHz, CDCl3): δ7.80~7.79(m,2H),7.50~7.48(m,2H),7.41~7.40(m,2H),7.36~7.34(m,2H),4.21~4.17( m,4H),3.66~3.64(m,8H),3.08~3.01(m,4H),2.50~2.48(t,8H),1.57~1.52(dd,12H),0.58(s,4H),0.08(s,12H).

[0160] The photocurable composition is obtained by the following preparation method, which includes the following steps:

[0161] The components were stirred and mixed at 1000 r / min for 20 min according to the formula to obtain the photocurable composition.

[0162] Example 4

[0163] This embodiment provides a photocurable composition, which is composed of the following components in parts by weight:

[0164]

[0165]

[0166] The first photoinitiator is the photoinitiator described in Example 1, and the second photoinitiator is the photoinitiator described in Example 2.

[0167] The photocurable composition is obtained by the following preparation method, which includes the following steps:

[0168] The components were stirred and mixed at 850 r / min for 24 min according to the formula to obtain the photocurable composition.

[0169] Example 5

[0170] This embodiment provides a photocurable composition, which is composed of the following components in parts by weight:

[0171]

[0172] The third photoinitiator is the photoinitiator described in Example 3, and the second photoinitiator is the photoinitiator described in Example 2.

[0173] The photocurable composition is obtained by the following preparation method, which includes the following steps:

[0174] The components were stirred and mixed at 850 r / min for 22 min according to the formula to obtain the photocurable composition.

[0175] Example 6

[0176] This embodiment provides a photocurable composition, which is composed of the following components in parts by weight:

[0177]

[0178] The third photoinitiator is the photoinitiator described in Example 3, and the first photoinitiator is the photoinitiator described in Example 1.

[0179] The photocurable composition is obtained by the following preparation method, which includes the following steps:

[0180] The components were stirred and mixed at 850 r / min for 22 min according to the formula to obtain the photocurable composition.

[0181] Example 7

[0182] This embodiment provides a photocurable composition, which is composed of the following components in parts by weight:

[0183]

[0184] The first photoinitiator is the photoinitiator described in Example 1, the second photoinitiator is the photoinitiator described in Example 2, and the third photoinitiator is the photoinitiator described in Example 3.

[0185] The photocurable composition is obtained by the following preparation method, which includes the following steps:

[0186] The components were stirred and mixed at 900 r / min for 25 min according to the formula to obtain the photocurable composition.

[0187] Example 8

[0188] The difference between this embodiment and Example 1 is that the 1,6-hexanediol diacrylate is replaced with an equal mass of ethoxylated trimethylolpropane triacrylate; all other aspects are the same as in Example 1.

[0189] Example 9

[0190] The difference between this embodiment and Example 1 is that the ethoxylated trimethylolpropane triacrylate is replaced with an equal mass of 1,6-hexanediol diacrylate; all other aspects are the same as in Example 1.

[0191] Example 10

[0192] The difference between this embodiment and Embodiment 1 is that the polyurethane acrylate resin is replaced with an equal mass of epoxy acrylate resin; all other aspects are the same as in Embodiment 1.

[0193] Example 11

[0194] The difference between this embodiment and Embodiment 1 is that the chlorinated polyester resin is replaced with an equal mass of polyurethane acrylate resin; all other aspects are the same as in Embodiment 1.

[0195] Example 12

[0196] The difference between this embodiment and Embodiment 1 is that the photoinitiator is replaced with a photoinitiator with the following structure; all other aspects are the same as in Embodiment 1:

[0197]

[0198] The photoinitiator is obtained by the following preparation method:

[0199] (1) Under inert gas protection and stirring conditions, 1 mol Dissolves in 1200 mL of solvent (dichloromethane) at 15°C;

[0200] (2) Add 1.05 mol of alkali (triethylamine) to the system, control the temperature to 5℃, and then add 0.49 mol of alkali (triethylamine) to the system. The reaction lasted for 2 hours.

[0201] (3) The product obtained in step (2) is subjected to post-treatment, recrystallization and drying to obtain the compound.

[0202] The structure of the aminoketone photoinitiator obtained in this embodiment was analyzed, and the test methods and results are shown below:

[0203] Mass spectrometry analysis results: MS: m / z = [M+1]+ = 799.39 (MW = 798.39).

[0204] 1 The H-NMR test results are shown below: 1 H-NMR (400MHz, CDCl3): δ7.85~7.83(d,2H), 7.75~7.43(d,2H), 7.38~7.35(m,2H), 7.35~7.33(m,2H), 4.50~4.47(t,4H) ), 3.66~3.64(m,8H), 3.09~3.05(t,4H), 2.50~2.48(t,8H), 2.37~2.33(m,4H), 1.55~1.50(m,12H), 1.30~1.25(m,10H).

[0205] Example 13

[0206] The difference between this embodiment and Embodiment 1 is that the photoinitiator is replaced with a photoinitiator with the following structure; all other aspects are the same as in Embodiment 1:

[0207]

[0208] The compound was obtained by the following preparation method, which includes the following steps:

[0209] (1) Under inert gas protection and stirring conditions, 1 mol Dissolves in 1200 mL of solvent (dichloromethane) at 15°C;

[0210] (2) Add 1.05 mol of alkali (triethylamine) to the system, control the temperature to 5℃, and then add 0.49 mol of alkali (triethylamine) to the system. The reaction lasted for 2 hours.

[0211] (3) The product obtained in step (2) is subjected to post-treatment, recrystallization and drying to obtain the compound.

[0212] The structure of the aminoketone photoinitiator obtained in this embodiment was analyzed, and the test methods and results are shown below:

[0213] Mass spectrometry analysis results: MS: m / z = [M+1] + =813.41 (MW=812.41).

[0214] 1 The H-NMR test results are shown below:

[0215] 1 H-NMR (400MHz, CDCl3): δ8.51~8.49(m,4H),7.34~7.26(m,4H),4.31~4.27(t,4H),3.70~3.68(m,8H),3.25 ~3.21(t,4H),2.58~2.54(m,8H),2.30~2.28(m,4H),1.62~1.56(m,6H),1.30(s,12H),1.29~1.28(m,10H).

[0216] Example 14

[0217] The difference between this embodiment and Embodiment 1 is that the photoinitiator is replaced with a photoinitiator with the following structure; all other aspects are the same as in Embodiment 1:

[0218]

[0219] The photoinitiator is obtained by the following preparation method:

[0220] (1) Under inert gas protection and stirring conditions, 1 mol Dissolves in 1200 mL of solvent (dichloromethane) at 15°C;

[0221] (2) Add 1.05 mol of alkali (triethylamine) to the system, control the temperature to 5℃, and then add 0.49 mol of alkali (triethylamine) to the system. The reaction lasted for 2 hours.

[0222] (3) The product obtained in step (2) is subjected to post-treatment, recrystallization and drying to obtain the compound.

[0223] The structure of the aminoketone photoinitiator obtained in this embodiment was analyzed, and the test methods and results are shown below:

[0224] Mass spectrometry analysis results: MS: m / z = [M+1]+ = 841.44 (MW = 840.44).

[0225] 1 The H-NMR test results are shown below: 1H-NMR (400MHz, CDCl3): δ7.84~7.79(m,4H), 7.41~7.37(m,4H), 4.82~4.78(m,1H), 4.58~4.54(m,1H), 4.44~4.37(m,2H),4.17~4.15(m,4H),4.10~4.04(m,2H),3.78~3.71(m,1H),3.55~3.50(m,1H),3.24~3 .19(m,2H),2.70~2.64(m,2H),2.61~2.48(m,3H),2.47~2.45(m,1H),2.37~2.25(m,3H),2.22~2.21(m ,3H),1.92~1.85(m,1H),1.60~1.57(m,7H),1.55~1.44(m,7H),1.37~1.27(m,10H),1.25~1.10(m,6H).

[0226] Example 15

[0227] The difference between this embodiment and Embodiment 1 is that the photoinitiator is replaced with a photoinitiator with the following structure; all other aspects are the same as in Embodiment 1:

[0228]

[0229] The photoinitiator is obtained by the following preparation method:

[0230] (1) Under inert gas protection and stirring conditions, 1 mol Dissolves in 1200 mL of dissolving solvent (DMF) at 25°C;

[0231] (2) Add 1.05 mol of alkali (potassium carbonate) and 0.1 mol of catalyst (sodium iodide) to the system, control the temperature to 75°C, and slowly add 0.49 mol of alkali (potassium carbonate) to the system. The reaction lasted 8 hours.

[0232] (3) The product obtained in step (2) is subjected to post-treatment, recrystallization and drying to obtain the compound.

[0233] The structure of the aminoketone photoinitiator obtained in this embodiment was analyzed, and the test methods and results are shown below:

[0234] Mass spectrometry analysis results: MS: m / z = [M+1] + =899.49 (MW=898.49).

[0235] 1 The H-NMR test results are shown below: 1H-NMR (400MHz, CDCl3): δ7.81~7.79(m,4H),7.39~7.37(m,4H),4.17~4.14(t,4H),3.66~3.64(t,8H),3.10~3.08(t,4H),2.91~2.88(t,4H),2.7 1~2.74(t,4H),2.50~2.48(t,8H),3.37~3.33(t,4H),2.27(s,6H),1.77 ~1.71(m,4H),1.57~1.55(d,12H),1.50~1.44(m,4H),1.31~1.29(m,4H).

[0236] Example 16

[0237] The difference between this embodiment and Example 1 is that the photoinitiator is replaced with a compound with the following structure; all other aspects are the same as in Example 1:

[0238]

[0239] The compound was obtained by the following preparation method, which includes the following steps:

[0240] (1) Under inert gas protection and stirring conditions, 1 mol Dissolves in 1200 mL of solvent (dichloromethane) at 25°C;

[0241] (2) Add 1.05 mol of alkali (triethylamine) to the system, control the temperature to 10℃, and then add 0.49 mol of alkali (triethylamine) to the system. The reaction lasted for 2 hours.

[0242] (3) The product obtained in step (2) is subjected to post-treatment, recrystallization and drying to obtain the compound.

[0243] The photoinitiator described in this embodiment was subjected to structural analysis, and the test methods and results are shown below:

[0244] Mass spectrometry analysis test: MS: m / z = [M+1] + =757.35 (MW=756.35).

[0245] 1 The H-NMR test results are shown below:

[0246] 1H-NMR (400MHz, CDCl3): δ8.50~8.48(m,4H),7.32~7.24(m,4H),4.50~4.46(t,4H),3.68~3.66(m,8H) ), 3.09~3.05(t,4H), 2.52~2.50(m,8H), 1.66~1.60(m,4H), 1.55~1.54(m,12H), 1.29~1.25(m,4H).

[0247] Example 17

[0248] The difference between this embodiment and Example 1 is that the photoinitiator is replaced with a compound with the following structure; all other aspects are the same as in Example 1:

[0249]

[0250] The compound was obtained by the following preparation method, which includes the following steps:

[0251] (1) Under inert gas protection and stirring conditions, 1 mol Dissolves in 1200 mL of solvent (dichloromethane) at 16°C;

[0252] (2) Add 1.05 mol of alkali (triethylamine) to the system, control the temperature to 4℃, and then add 0.49 mol of alkali to the system. The reaction lasted for 2 hours.

[0253] (3) The product obtained in step (2) is subjected to post-treatment, recrystallization and drying to obtain the compound.

[0254] The photoinitiator described in this embodiment was subjected to structural analysis, and the test methods and results are shown below:

[0255] The mass spectrometry analysis results are shown below: MS: m / z = [M+1] + =869.47 (MW=868.47).

[0256] 1 The H-NMR testing methods and results are shown below:

[0257] 1H-NMR (400MHz, CDCl3): δ8.52~8.49(m,4H),7.34~7.26(m,4H),4.50~4.46(t,4H),3.66~3.64(t,8H),3.09~3 .05(t,4H),2.50~2.48(t,8H),2.36~2.33(m,4H),1.66~1.54(m,4H),1.55~1.53(m,12H),1.32~1.24(m,21H).

[0258] Comparative Example 1

[0259] The difference between this comparative example and Example 1 is that the photoinitiator is replaced with an equal weight of photoinitiator 907, while the rest are the same as in Example 1.

[0260] Comparative Example 2

[0261] The difference between this comparative example and Example 1 is that the photoinitiator is replaced with an equal weight of photoinitiator 369, while the rest is the same as Example 1.

[0262] Comparative Example 3

[0263] The difference between this comparative example and Example 1 is that the photoinitiator is replaced with an equal weight of photoinitiator 379, and all other aspects are the same as in Example 1.

[0264] Performance testing

[0265] The photocurable compositions described in Examples 1-17 and Comparative Examples 1-3 were tested as follows:

[0266] (1) Photocuring energy test method: The photocuring composition is coated on white cardstock using a wire bar coater, and then irradiated once under a mercury lamp light source to cure into a film. The standard for complete curing is that no scratches are produced when pressing A4 paper with a 1kg weight and pulling it repeatedly three times. The energy required for curing is recorded using a UV energy meter.

[0267] (2) Adhesion test method:

[0268] 1) Apply the photocurable composition to a substrate (aluminum sheet, polyethylene PE, polycarbonate PC, polyvinyl chloride PVC, polyethylene terephthalate PET, polystyrene PS, acrylonitrile-butadiene-styrene copolymer ABS sheet) using a wire bar coater. The plastic substrate must be wiped clean with anhydrous ethanol before use. The mixture is then cured into a film. The curing light source is a 120W / cm medium-pressure mercury lamp with a light intensity of 50mW / cm. 2 A photocurable coating material with a coating thickness of 20 μm was obtained.

[0269] 2) Use the cross-cut test to test adhesion. Use a utility knife to apply even force perpendicular to the material surface and make 6 parallel cut lines with a cutting interval of 2mm. Then, make 6 more parallel lines perpendicular to the cut lines at 90° to form a grid pattern. Then, stick tape to the center of the grid and pull it off steadily at an angle of about 60° 10 times. Observe the phenomenon of paint film peeling off and judge by calculating the state of the grid in the cross-cut test and corresponding to the standard in Figure 1.

[0270] (3) Mobility

[0271] The specific testing method is as follows:

[0272] ① Apply the photocurable composition to a glass slide using a coating applicator with a thickness of 10 μm, and cure it once under a mercury lamp.

[0273] ②Immerse the film-forming glass slide in a brown sample bottle containing 10 mL of acetonitrile for 4 days, and take samples to test the ultraviolet absorption; substitute the absorbance A and molar absorptivity into the following formula to obtain the residual mass and relative mobility of the photoinitiator: C=A / (εL); R=100×C1 / C2;

[0274] In the formula: C - concentration of initiator in the extract, mol / L; A - absorbance; ε - molar extinction coefficient, L / (mol·cm⁻¹) -1 L - optical path length, taken as 1 cm here; C1 is the concentration of polyimide (PI) in the test sample extract; C2 is the concentration of photoinitiator 907 in the control sample extract; R is the relative mobility.

[0275] (4) Resistance to yellowing

[0276] Test method: The photocurable composition was coated onto white test card paper using a 20μm wire bar coater. The sample was exposed to a mercury lamp light source to cure completely. Finally, the surface yellowness value b was tested using a color density meter.

[0277] (5) Odor

[0278] Test method: 10 odor judges evaluated the odor of the samples during the curing process according to five levels: A-no odor, B-slight odor, C-odor, D-pungent odor, and E-very pungent odor; the final average value is the test result.

[0279] (6) Solubility in monomers

[0280] Test method: The photoinitiators described in Examples 1-3, 12-17 and Comparative Examples 1-3 were dissolved in trimethylolpropane triacrylate (TMPTA), tripropylene glycol diacrylate (TPGDA) or 1,6-hexanediol diacrylate (HDDA) to prepare samples with a concentration increment of 1%. After ultrasonic dissolution, the samples were allowed to stand at 40°C in the dark for 72 hours. The solubility of the photoinitiator was obtained with no obvious precipitation as the standard.

[0281] (7) Repeatability:

[0282] Test method: The viscosity, curing speed, and yellowing after curing of the photocurable composition were tested in twenty batches under the same conditions, and the test results were evaluated. If the test results of all twenty batches were consistent, the repeatability was grade A; if the test results of 18-19 batches were consistent, the repeatability was grade B; if the test results of 16-17 batches were consistent, the repeatability was grade C; and if the test results of 15 or fewer batches were consistent, the repeatability was grade D.

[0283] (8) Stability

[0284] Test method: The viscosity, curing speed, and yellowing after curing of the light-cured composition were tested. Then, after storing it at room temperature in the dark for one month, the viscosity, curing speed, and yellowing after curing were tested again. If the test results of viscosity, curing speed, and yellowing did not change, the stability was grade A; if two of the test results did not change, the stability was grade B; if only one of the test results did not change, the stability was grade C.

[0285] The test results are summarized in Tables 1 and 2.

[0286] Table 1

[0287]

[0288]

[0289] Table 2

[0290]

[0291]

[0292] Analysis of the data in Tables 1 and 2 shows that the photoinitiator migration rate in the photocurable composition of the present invention is between 26.4% and 46.2%, the solubility of the photoinitiator in the monomer is between 20% and 39%, and it exhibits high adhesion to various plastic substrates such as polyethylene, polycarbonate, polyvinyl chloride, polyethylene terephthalate, polystyrene, and acrylonitrile-butadiene-styrene copolymer, as well as metal surfaces. Furthermore, the odor during the curing process is between A and B, the yellowing value after curing is between 1.6 and 2.9, the system stability is between A and B, and the repeatability is high between A and B. Compared to traditional photocurable compositions formed with high-performance photoinitiators, the photocurable composition of the present invention has low photoinitiator migration rate, good solubility of the photoinitiator in the monomer, low energy required for curing, high adhesion to various substrates such as plastics and metals, low odor during curing, low yellowing after curing, and high system stability and repeatability, demonstrating excellent overall performance.

[0293] Analysis of Comparative Examples 1-3 and Example 1 shows that the performance of Comparative Examples 1-3 is not as good as that of Example 1, proving that the photocurable composition of the present invention has better performance.

[0294] Analysis of Examples 8-9 and Example 1 shows that the performance of Examples 8-9 is not as good as that of Example 1, proving that the photocurable composition formed by the combined use of the first active monomer and the second active monomer has better performance.

[0295] Analysis of Examples 10-11 and Example 1 shows that the performance of Examples 10-11 is not as good as that of Example 1, proving that the photocurable composition formed by the combined use of polyurethane acrylate and chlorinated polyester resin has better performance.

[0296] Analysis of Examples 16-17 and Example 1 shows that the performance of Examples 16-17 is not as good as that of Example 1, proving that the photocurable composition formed by the photoinitiator within the preferred range has better performance.

[0297] The applicant declares that the detailed method of the present invention is illustrated by the above embodiments, but the present invention is not limited to the above detailed method, that is, it does not mean that the present invention must rely on the above detailed method to be implemented. Those skilled in the art should understand that any improvements to the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Claims

1. A photocurable composition, characterized in that, The photocurable composition comprises the following components: resin, reactive monomer, and photoinitiator; the photoinitiator at least comprises the structural formula shown in Formula I: Formula I; wherein Z1 and Z2 are each independently selected from hydrogen, deuterium, halogen, substituted or unsubstituted C1-C10 straight-chain or branched alkylene, substituted or unsubstituted C3-C20 cycloalkylene; Z3 is selected from C1-C20 straight-chain or branched alkylene containing a carbonyl group, C1-C20 straight-chain or branched alkylene containing an ester group, and C1-C10 straight-chain or branched heteroalkylene; M1, M2, M3 and M4 are each independently selected from O, S or NR, and R is selected from H or C1-C5 alkyl; the substituents of the substituted C1-C10 straight-chain or branched alkylene are selected from at least one of deuterium, C1-C10 straight-chain or branched alkyl, C3-C20 cycloalkyl or halogen; the substituents of the substituted C3-C20 cycloalkylene are selected from at least one of deuterium, C1-C10 straight-chain or branched alkyl, C3-C20 cycloalkyl or halogen.

2. The photocurable composition according to claim 1, characterized in that, The photocurable composition comprises the following components in parts by weight: 5-70 parts resin, 10-50 parts active monomer, and 1-18 parts photoinitiator.

3. The photocurable composition according to claim 1, characterized in that, The resin includes any one or a combination of at least two of polyurethane acrylate, epoxy acrylate resin, or polyester acrylate resin.

4. The photocurable composition according to claim 3, characterized in that, The polyester acrylate resin includes halogenated polyester acrylate resin.

5. The photocurable composition according to claim 4, characterized in that, The polyester acrylate resin includes chlorinated polyester acrylate resin.

6. The photocurable composition according to claim 1, characterized in that, The resins include polyurethane acrylate and chlorinated polyester resin.

7. The photocurable composition according to claim 3, characterized in that, The polyurethane acrylates include polyurethane acrylates with a functionality of 2-6.

8. The photocurable composition according to claim 6, characterized in that, When the resin is selected from a combination of polyurethane acrylate and chlorinated polyester resin, the polyurethane acrylate is in the amount of 30-50 parts by weight and the chlorinated polyester resin is in the amount of 5-20 parts by weight.

9. The photocurable composition according to claim 1, characterized in that, The functionality of the active monomer is ≥2.

10. The photocurable composition according to claim 9, characterized in that, The active monomer includes a first active monomer and / or a second active monomer.

11. The photocurable composition according to claim 10, characterized in that, The first active monomer includes a difunctional active monomer.

12. The photocurable composition according to claim 11, characterized in that, The first active monomer includes any one or a combination of at least two of 1,6-hexanediol diacrylate, tripropylene glycol diacrylate, diethylene glycol diacrylate, or diethylene glycol diacrylate phthalate.

13. The photocurable composition according to claim 10, characterized in that, The second active monomer includes a trifunctional active monomer.

14. The photocurable composition according to claim 13, characterized in that, The second active monomer includes any one or a combination of at least two of trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, or pentaerythritol triacrylate.

15. The photocurable composition according to claim 10, characterized in that, The first active monomer has a weight of 20-30 parts; the second active monomer has a weight of 10-20 parts.

16. The photocurable composition according to claim 1, characterized in that, Z3 is selected from 、 or Any one of the following; wherein m, n and l are each independently a positive integer from 1 to 10; k is a positive integer from 8 to 12; z is a positive integer from 1 to 10; R1, R2, R3 and R4 are each independently selected from hydrogen, deuterium, halogen, substituted or unsubstituted C1-C10 straight-chain or branched alkyl, substituted or unsubstituted C3-C20 cycloalkyl; the substituent of the substituted C1-C10 straight-chain or branched alkyl is selected from at least one of deuterium, C1-C10 straight-chain or branched alkyl, C3-C20 cycloalkyl or halogen; the substituent of the substituted C3-C20 cycloalkyl is selected from at least one of deuterium, C1-C10 straight-chain or branched alkyl, C3-C20 cycloalkyl or halogen.

17. The photocurable composition according to claim 16, characterized in that, The photoinitiator includes compounds represented by Formula II, Formula III or Formula IV; Formula II; Formula III; Formula IV; wherein m, n, and l are each independently a positive integer from 1 to 10; k is a positive integer from 8 to 12; z is a positive integer from 1 to 10; R1, R2, R3, and R4 are each independently selected from hydrogen, deuterium, and any one of unsubstituted C1-C10 straight-chain or branched alkyl groups; M1, M2, M3, and M4 are each independently selected from any one of O, S, or NR; R is selected from H or C1-C5 alkyl groups; Z1 and Z2 are each independently selected from any one of hydrogen, deuterium, unsubstituted C1-C10 straight-chain or branched alkylene groups, and any one of unsubstituted C3-C20 cycloalkylene groups.

18. The photocurable composition according to claim 17, characterized in that, Z1 and Z2 are each independently selected from hydrogen, deuterium, or unsubstituted C2-C6 straight-chain alkylene groups.

19. The photocurable composition according to claim 1, characterized in that, The photoinitiator comprises any one or a combination of at least two of the following compounds: 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 。 20. The photocurable composition according to claim 1, characterized in that, The photocurable composition also includes additives.

21. The photocurable composition according to claim 20, characterized in that, The additives include any one or a combination of at least two of the following: leveling agents, wetting agents, or adhesion promoters.

22. The photocurable composition according to claim 20, characterized in that, The additive is present in parts by weight of 0-3.5 parts.

23. The photocurable composition according to claim 21, characterized in that, The leveling agent includes an organosilicon leveling agent.

24. The photocurable composition according to claim 23, characterized in that, The silicone leveling agent includes polyether-modified silicone oil and / or polyester-modified silicone oil.

25. The photocurable composition according to claim 21, characterized in that, The additives include the leveling agent, wherein the leveling agent is present in a weight ratio of 0.5-1.5 parts.

26. The photocurable composition according to claim 21, characterized in that, The wetting aid includes polyether-modified silicone oil.

27. The photocurable composition according to claim 21, characterized in that, The additives include the wetting agent, which is 0-1 parts by weight.

28. The photocurable composition according to claim 21, characterized in that, The adhesion promoter includes organosilicon compounds or organophosphate compounds.

29. The photocurable composition according to claim 21, characterized in that, The additives include the adhesion promoter, which is 0-1 parts by weight.

30. A method for preparing a photocurable composition according to any one of claims 1-29, characterized in that, The preparation method includes the following steps: mixing resin, active monomer and photoinitiator to obtain the photocurable composition.

31. The preparation method according to claim 30, characterized in that, The mixed raw materials also include additives.

32. The preparation method according to claim 30, characterized in that, The mixing method includes stirring.

33. The preparation method according to claim 32, characterized in that, The stirring rate is 800-1000 r / min.

34. The preparation method according to claim 33, characterized in that, The mixing time is 20-30 minutes.

35. The use of a photocurable composition as described in any one of claims 1-29 in a plastic substrate.

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