Siloxane-containing (meth)acrylate compounds and methods for their preparation, photocurable compositions, and photocurable products

Abstract

The present invention provides a siloxane-containing (meth)acrylate compound, a method for preparing the same, a photocurable composition, and a photocurable product. The (meth)acrylate compound has a structure selected from any one of Formula I, Formula II, and Formula III: wherein Ra is selected from any one of a C1-C6 alkyl group, a C6-C10 substituted or unsubstituted aryl group, Rb1 is a methyl group, Rc1 is H, any one of Rb2 and Rc2 is a methyl group, the other is H, any one of Rb3 and Rc3 is a methyl group, the other is H, and Rd is H or a methyl group. The (meth)acrylate functional group in the (meth)acrylate compound improves the surface peelability of the photocurable composition from a substrate, and the siloxane group improves the compatibility of the photocurable composition with a photocurable silicone resin, thereby improving the formulation stability of the photocurable composition and effectively improving the adhesion and surface peelability of the photocurable composition from a substrate. 10 20 The present invention provides a siloxane-containing (meth)acrylate compound, a method for preparing thesame, a photocurable composition, and a photocurable product. The (meth)acrylatecompound has a structure selected from any one of Formula I, Formula II, and Formula III: wherein Rais selected from any one of a C1-C6 alkyl group, a C6-C10substituted or unsubstituted aryl group, Rb1is a methyl group, Rcis H, any one of Rb2and Rcis a methyl group, the other is H, any one of Rb3and Rcis a methyl group, the other is H, and Rdis H or a methyl group. The (meth)acrylate functional group in the (meth)aery late compound improves the surface peelability of the photocurable composition from a substrate, and the siloxanegroup improves the compatibility of the photocurable composition with a photocurable silicone resin, thereby improving the formulationstability of the photocurable composition and effectively improving the adhesion and surface peelability of the photocurablecomposition from a substrate.​

Description

Technical Field

[0001] This invention relates to the field of photocurable products, and more specifically, to a siloxane-containing (meth)acrylate compound, its preparation method, a photocurable composition, and a photocurable product. Background Technology

[0002] Acrylate-modified organosiloxanes have been widely used as the main resins in release film coating compositions, such as the combination of side-chain and terminal (meth)acrylate-modified organopolysiloxanes disclosed in U.S. Patent Application Publication No. US 6268404. However, particularly on smooth film substrates, the compositions therein are insufficient in terms of adhesion and have poor release properties.

[0003] The literature "Synthesis and Photocurability Study of (Meth)acrylic Monomers Containing Organosilicon" by Wang Siyuan and Zou Yingquan, Proceedings of the 13th China Radiation Curing Conference, 2012, pp. 211-218, reports the preparation of several silicone-containing acrylates. Dichlorodimethylsilane, dichlorodimethylsiloxane, or dichlorotetramethylbisilane are used as substrates with hydroxyethyl acrylate or hydroxyethyl methacrylate, and triethylamine is used as an acid-binding agent. However, experimental studies have found that these organosiloxanes modified with ethoxy-containing acrylates are very unstable and are prone to ethoxy hydrolysis during manufacturing, purification, or packaging and storage, i.e., the methylsilyl group is removed, causing them to deteriorate.

[0004] Similarly, Chinese patent application CN108299493 discloses the reaction of methyltrichlorosilane or silicon tetrachloride with hydroxyethyl acrylate. The resulting triethoxymethylsilane or tetraethoxysilane is also not resistant to hydrolysis. The product will hydrolyze during the purification process, thus limiting the development and application of photocurable silicone resin compositions. Summary of the Invention

[0005] The main objective of this invention is to provide a siloxane-containing (meth)acrylate compound and its preparation method, a photocurable composition, and a photocurable product, in order to solve the problems of poor water resistance of siloxane-containing (meth)acrylate compounds and poor balance between the adhesion of photocurable compositions to substrates and surface peelability in the prior art.

[0006] To achieve the above objectives, according to one aspect of the present invention, a siloxane-containing (meth)acrylate compound is provided, the structure of which is selected from any one of the following formulas I, II, and III:

[0007]

[0008]

[0009] Ra is selected from C1 to C1. 10 Alkyl groups, C6-C 20 It is any one of the substituted or unsubstituted aryl groups, where Rb1 is methyl, Rc1 is H, either Rb2 or Rc2 is methyl and the other is H, either Rb3 or Rc3 is methyl and the other is H, and Rd is H or methyl.

[0010] Furthermore, the Ra mentioned above is selected from C1-C4 alkyl groups, C6-C4 alkyl groups, and C6-C4 alkyl groups. 10 Ra is selected from any one of the substituted or unsubstituted aryl groups, preferably Ra is selected from any one of methyl, ethyl, n-propyl, isopropyl, and phenyl.

[0011] Furthermore, the above-mentioned (meth)acrylate compound is selected from one or more of the following compounds:

[0012]

[0013]

[0014]

[0015]

[0016] According to one aspect of the present invention, a method for preparing the above-mentioned siloxane-containing (meth)acrylate compound is provided, the method comprising: taking (Ra) n SiCl 4-n The reaction of (meth)acrylate with an organic amine acid-binding agent yields a product system containing (meth)acrylate compounds, wherein the (meth)acrylate is hydroxypropyl acrylate and / or hydroxypropyl methacrylate, and the structural formula of the hydroxypropyl acrylate is [insert structural formula here]. and / or The structural formula of hydroxypropyl methacrylate is: and / or Where n is an integer from 1 to 3, and Ra is selected from C1 to C2. 10 Alkyl groups, C6-C 20 Any one of the substituted or unsubstituted aryl groups.

[0017] Furthermore, the above (Ra) n SiCl 4-n The molar ratio of (meth)acrylate to organic amine acid binder is 1:(4-n)~(4-n)×1.1:(4-n)~(4-n)×1.1.

[0018] Furthermore, the temperature of the above reaction is 20–45°C.

[0019] Furthermore, the aforementioned organic amine acid-binding agent is selected from any one or more of trimethylamine, triethylamine, tripropylamine, tributylamine, pyridine, 3-methylpyridine, 4-methylpyridine, 4-dimethylaminopyridine, imidazole, 1-methylimidazolium, and 1-butylimidazolium.

[0020] According to another aspect of the present invention, a photocurable composition is provided, comprising: a siloxane-containing (meth)acrylate compound, a free radical curable resin, and a photoinitiator; wherein the siloxane-containing (meth)acrylate compound is the aforementioned siloxane-containing (meth)acrylate compound; the sum of the weights of the siloxane-containing (meth)acrylate compound and the free radical curable resin accounts for 90-99.9% of the total weight of the photocurable composition, and at least one of the photoinitiators is a silicon-containing photoinitiator, the weight of which accounts for 0.1-10% of the total weight of the photocurable composition.

[0021] Furthermore, the weight ratio of the above-mentioned siloxane-containing (meth)acrylate compound to the free radical curable resin is 1 to 9:1.

[0022] Furthermore, the aforementioned free radical curable resin is an organosilicon resin containing (meth)acrylate groups.

[0023] Furthermore, the aforementioned silicon-containing photoinitiator is an α-siloxyketone photoinitiator, and preferably, the silicon-containing photoinitiator has the structures shown in Formulas IV and V:

[0024]

[0025] Wherein, R1 and R2 are each independently selected from any one of C1-C4 alkyl groups, or CR1R2 is a cyclohexanediol or a cyclopentanediol; R3 and R5 are each independently selected from any one of C1-C4 alkyl groups or phenyl groups; R4 is selected from any one of C1-C4 alkyl groups or -SiR3R5R6, and R6 is selected from H or any one of C1-C4 alkyl groups; Ar1 ​​is selected from... Any one of them, wherein R7, R8, and R9 are each independently selected from H, halogen atoms, C1 to C2 atoms. 18 Alkyl groups, C1-C 18 alkoxy, allyloxy, C1-C 12 alkyl acyloxy-substituted C1-C 14 Alkyl, -OSiR3R4R5, -OSi(OR4)R3R5 substituted C1-C 14 Alkyl groups, C3-C9 alkyl groups with one or more oxygen atoms inserted, C1-C 18 Any one of the alkyl thio groups; R 10The alkyl group is selected from any one of C1 to C8; Y1 is selected from any one of straight bond, -CH2, -CHCH3, -C(CH3)2, -O-, -S-; R7', R8', and R9' are each independently selected from H, C1 to C4 alkyl group, F atom, C1 to C 18 Any one of the alkoxy groups, Ar2 is selected from Any one of them: where R 11 R 12 Each is independently selected from H, C1-C4 alkyl, C1-C4 allyl, and Y2 is selected from -CH2, -CHCH3, -C(CH3)2, -O-, -S-.

[0026] Furthermore, R1, R2, R3, R5, and R6 are each independently methyl, or CR1R2 is a cyclohexane subunit, R4 is methyl or -Si(CH3)3, R7 and R9 in Ar1 are each independently H, and R8 is selected from H, F atoms, C1 to C 14 Alkyl, C1-C8 alkoxy, allyloxy, C1-C 12 The following are all of the following: alkyl acyloxy-substituted C1-C3 alkoxy groups, -OSi(CH3)3, -OSi(CH3)3-substituted C1-C3 alkoxy groups, C3-C9 alkoxy groups with one or two oxygen atoms inserted, and C1-C4 alkyl thio groups; R 10 The R atoms are selected from any C1-C4 alkyl group, Y1 is selected from any one of -CH2, -O-, -S-, R7', R8', and R9' are each independently selected from any one of H, C1-C4 alkyl group, and F atom, and the R atoms in Ar2 are selected from any one of H, C1-C4 alkyl group, and F atom. 11 R 12 Each is independently selected from H, C1 to C4 alkyl groups, and Y2 is selected from -CH2, -O-, -S-.

[0027] Furthermore, the above-mentioned α-siloxyketone photoinitiator is selected from any one or more of the following compounds:

[0028]

[0029]

[0030]

[0031]

[0032] According to another aspect of the present invention, a photocurable product is provided, which comprises the above-described photocurable composition or is cured by the above-described photocurable composition, and the photocurable product includes any one of release film coating, substrate protective coating, 3D printing material, and silicone adhesive.

[0033] Applying the technical solution of this invention, the siloxane-containing (meth)acrylate compound provided in this application contains one or more (meth)acrylate functional groups in its structure. Since the (meth)acrylate functional groups are free radical polymers, the reaction rate is fast, resulting in better separation ability between the photocurable composition containing them and the substrate surface, thereby improving the surface peelability of the photocurable composition to the substrate. Simultaneously, the siloxane group effectively improves the compatibility between the siloxane-containing (meth)acrylate compound and the photocurable silicone resin in the molecular structure, thereby improving the formulation stability of the photocurable composition and effectively improving its adhesion to the substrate and surface peelability. Furthermore, the presence of at least one methyl substituent on the methylene group directly linked to the Si-O bond in the siloxane-containing (meth)acrylate compound, due to its steric hindrance effect, helps improve the water resistance of the siloxane-containing (meth)acrylate compound, thus aiding in its preparation and storage. Siloxane-containing (meth)acrylate compounds containing only a single silicon atom are more conducive to balancing substrate adhesion and surface peelability. Detailed Implementation

[0034] It should be noted that, unless otherwise specified, the embodiments and features described in this application can be combined with each other. The present invention will now be described in detail with reference to the embodiments.

[0035] As analyzed in the background art, existing siloxane-containing (meth)acrylate compounds have problems such as poor water resistance and a poor balance between the adhesion of the photocurable composition to the substrate and the surface peelability. In order to solve this problem, the present invention provides a siloxane-containing (meth)acrylate compound, its preparation method, a photocurable composition, and a photocurable product.

[0036] In a typical embodiment of this application, a siloxane-containing (meth)acrylate compound is provided, the structure of which is selected from any one of the following formulas I, II, and III:

[0037]

[0038] Ra is selected from C1 to C1. 10 Alkyl groups, C6-C 20It is any one of the substituted or unsubstituted aryl groups, where Rb1 is methyl, Rc1 is H, either Rb2 or Rc2 is methyl and the other is H, either Rb3 or Rc3 is methyl and the other is H, and Rd is H or methyl.

[0039] The siloxane-containing (meth)acrylate compound provided in this application contains one or more (meth)acrylate functional groups in its structure. Since (meth)acrylate functional groups are free radical polymers, the reaction rate is fast, resulting in better separation ability between the photocurable composition containing it and the substrate surface, thus improving the surface peelability of the photocurable composition. Simultaneously, the siloxane group effectively improves the compatibility of the siloxane-containing (meth)acrylate compound with the photocurable silicone resin in the molecular structure, thereby improving the formulation stability of the photocurable composition and effectively improving its adhesion and surface peelability to the substrate. Furthermore, the presence of at least one methyl substituent on the methylene group directly linked to the Si-O bond in the siloxane-containing (meth)acrylate compound, due to its steric hindrance effect, helps improve the water resistance of the siloxane-containing (meth)acrylate compound, thus aiding in its preparation and storage. Siloxane-containing (meth)acrylate compounds containing only a single silicon atom are more conducive to balancing substrate adhesion and surface peelability.

[0040] Preferably, Ra is selected from C1-C4 alkyl groups, C6-C4 alkyl groups, and C6-C4 alkyl groups. 10 The substituted or unsubstituted aryl group is selected from any one of methyl, ethyl, n-propyl, isopropyl, and phenyl groups, preferably Ra is selected from any one of methyl, ethyl, n-propyl, isopropyl, and phenyl groups. Thus, it is possible to achieve the desired effect through R. a The group stabilizes the silicon-oxygen bond without making the molecular structure of the siloxane-containing (meth)acrylate compound too large, thus affecting its compatibility and compatibility with other components in the photocurable composition.

[0041] Structure determines performance. In particular, the substituents on the silicon atoms of siloxane-containing (meth)acrylate compounds affect their polarity and solubility. To further improve the compatibility of siloxane-containing (meth)acrylate compounds with curing resins, the aforementioned (meth)acrylate compounds are preferably selected from one or more of the following compounds:

[0042]

[0043]

[0044]

[0045]

[0046] In another typical embodiment of this application, a method for preparing the aforementioned siloxane-containing (meth)acrylate compound is provided, the method comprising: (Ra) n SiCl 4-n The reaction of (meth)acrylate with an organic amine acid-binding agent yields a product system containing (meth)acrylate compounds, wherein the (meth)acrylate is hydroxypropyl acrylate and / or hydroxypropyl methacrylate, and the structural formula of the hydroxypropyl acrylate is [insert structural formula here]. and / or The structural formula of hydroxypropyl methacrylate is: and / or Where n is an integer from 1 to 3, and Ra is selected from C1 to C2. 10 Alkyl groups, C6-C 20 Any one of the substituted or unsubstituted aryl groups.

[0047] The above reaction generates an organosilicon compound that simultaneously possesses silicon-oxygen bonds and (meth)acrylate bonds, thus obtaining an organosilicon compound modified with (meth)acrylate bonds. Moreover, the above preparation method is simple, the reaction raw materials are widely available, and the cost is low.

[0048] In one embodiment of this application, the above (Ra) n SiCl 4-n The molar ratio of (meth)acrylate to organic amine acid binder is 1:(4-n)~(4-n)×1.1:(4-n)~(4-n)×1.1.

[0049] The above molar ratio is conducive to maximizing (Ra). n SiCl 4-n The protection reaction of the hydroxyl groups in (meth)acrylates is carried out to improve the yield of the target product.

[0050] A preferred reaction temperature of 20–45°C is beneficial for promoting (Ra). n SiCl 4-n The breaking of the Si-Cl bond in the middle makes (Ra) possible. n SiCl 4-n Protect the hydroxyl groups of (meth)acrylates.

[0051] Preferably, the organic amine acid-binding agent is selected from any one or more of trimethylamine, triethylamine, tripropylamine, tributylamine, pyridine, 3-methylpyridine, 4-methylpyridine, 4-dimethylaminopyridine, imidazole, 1-methylimidazolium, and 1-butylimidazolium. The above-mentioned organic amine acid-binding agent has a certain degree of alkalinity, which is beneficial for neutralization (Ra). n SiCl 4-n The acidic hydrogen chloride generated from (meth)acrylate further promotes the above reaction.

[0052] In another typical embodiment of this application, a photocurable composition is provided, comprising: a siloxane-containing (meth)acrylate compound, a free radical curable resin, and a photoinitiator; wherein the siloxane-containing (meth)acrylate compound is the aforementioned siloxane-containing (meth)acrylate compound; the sum of the weights of the siloxane-containing (meth)acrylate compound and the free radical curable resin accounts for 90-99.9% of the total weight of the photocurable composition, and at least one of the photoinitiators is a silicon-containing photoinitiator, the weight of which accounts for 0.1-10% of the total weight of the photocurable composition.

[0053] The siloxane-containing (meth)acrylate compound provided in this application contains one or more (meth)acrylate functional groups in its structure. Since the (meth)acrylate functional groups are free radical polymers, the reaction rate is fast, resulting in good separation ability between the photocurable composition containing it and the substrate surface, thus improving the surface peelability of the photocurable composition. Simultaneously, the siloxane group effectively improves the compatibility between the siloxane-containing (meth)acrylate compound and the photocurable silicone resin in the molecular structure, thereby improving the formulation stability of the photocurable composition and effectively improving the balance between its adhesion to the substrate and surface peelability. Furthermore, the at least one methyl substituent on the methylene group directly linked to the Si-O bond in the siloxane-containing (meth)acrylate compound, due to its steric hindrance effect, helps improve the water resistance of the siloxane-containing (meth)acrylate compound, thus aiding in its preparation and storage. Therefore, the photocurable composition containing this siloxane-containing (meth)acrylate compound also possesses the excellent properties of the aforementioned siloxane-containing (meth)acrylate compound.

[0054] In one embodiment of this application, the weight ratio of the siloxane-containing (meth)acrylate compound to the free radical curable resin is 1 to 9:1.

[0055] The siloxane-containing (meth)acrylate compound in the above proportion is the silicone main resin of the photocurable composition, which is more conducive to exerting its performance, thereby enabling the corresponding photocurable product to have excellent adhesion to the substrate and surface peelability.

[0056] Preferably, the free radical curable resin is an organosilicon resin with (meth)acrylate groups, so that the free radical curable resin has a more similar structure and polarity to the siloxane-containing (meth)acrylate compound, and according to the principle of similar compatibility, it can be better compatible with the siloxane-containing (meth)acrylate compound.

[0057] In one embodiment of this application, the silicon-containing photoinitiator is an α-siloxane photoinitiator, preferably having the structures shown in Formulas IV and V:

[0058]

[0059] Wherein, R1 and R2 are each independently selected from any one of C1-C4 alkyl groups, or CR1R2 is a cyclohexanediol or a cyclopentanediol; R3 and R5 are each independently selected from any one of C1-C4 alkyl groups or phenyl groups; R4 is selected from any one of C1-C4 alkyl groups or -SiR3R5R6, and R6 is selected from H or any one of C1-C4 alkyl groups; Ar1 ​​is selected from... Any one of them, wherein R7, R8, and R9 are each independently selected from H, halogen atoms, C1 to C2 atoms. 18 Alkyl groups, C1-C 18 alkoxy, allyloxy, C1-C 12 alkyl acyloxy-substituted C1-C 14 Alkyl, -OSiR3R4R5, -OSi(OR4)R3R5 substituted C1-C 14 Alkyl groups, C3-C9 alkyl groups with one or more oxygen atoms inserted, C1-C 18 Any one of the alkyl thio groups; R 10 The alkyl group is selected from any one of C1 to C8; Y1 is selected from any one of straight bond, -CH2, -CHCH3, -C(CH3)2, -O-, -S-; R7', R8', and R9' are each independently selected from H, C1 to C4 alkyl group, F atom, C1 to C 18 Any one of the alkoxy groups, Ar2 is selected from Any one of them: where R 11 R 12 Each is independently selected from H, C1-C4 alkyl, C1-C4 allyl, and Y2 is selected from -CH2, -CHCH3, -C(CH3)2, -O-, -S-.

[0060] At least one of the photoinitiators is preferably a silicon-containing photoinitiator, which can increase its compatibility with siloxane-containing (meth)acrylate compounds. Preferably, the silicon-containing photoinitiator is an α-siloxane photoinitiator, which can further promote the solubility of the photoinitiator in the whole photocurable composition so that the initiator can obtain sufficient activity in UV curing, thereby further increasing the curing rate.

[0061] In addition to silicon atoms, the substituents in α-siloxyketone photoinitiators also affect their polarity and molecular size. Preferably, R1, R2, R3, R5, and R6 are each independently methyl, or CR1R2 is a cyclohexane subunit, R4 is methyl or -Si(CH3)3, R7 and R9 in Ar1 are each independently H, and R8 is selected from H, F atoms, C1 to C1 atoms. 14 Alkyl, C1-C8 alkoxy, allyloxy, C1-C 12 The following are all of the following: alkyl acyloxy-substituted C1-C3 alkoxy groups, -OSi(CH3)3, -OSi(CH3)3-substituted C1-C3 alkoxy groups, C3-C9 alkoxy groups with one or two oxygen atoms inserted, and C1-C4 alkyl thio groups; R 10 The R atoms are selected from any C1-C4 alkyl group, Y1 is selected from any one of -CH2, -O-, -S-, R7', R8', and R9' are each independently selected from any one of H, C1-C4 alkyl group, and F atom, and the R atoms in Ar2 are selected from any one of H, C1-C4 alkyl group, and F atom. 11 R 12 Each is independently selected from H, C1 to C4 alkyl groups, and Y2 is selected from -CH2, -O-, -S-.

[0062] In some embodiments of this application, the preferred α-siloxyketone photoinitiator is selected from any one or more of the following compounds:

[0063]

[0064]

[0065]

[0066]

[0067] This maximizes the solubility of the photoinitiator in the photocurable composition, thereby enabling each component in the photocurable composition to quickly generate sufficient free radicals, further accelerating the curing reaction.

[0068] The above-mentioned photocurable composition may also include additives, such as fillers, pigments, surfactants, stabilizers, amine sensitizers, sensitizers, ultraviolet absorbers, antioxidants, antifogging agents, and solvents, to further improve the overall performance of the photocurable product.

[0069] The curing method of the above-mentioned photocurable composition can refer to the following curing method: The photocurable composition is coated onto a substrate, and the coated area is irradiated with a light source containing 200-450 nm light in air or under inert gas protection to complete the curing. This rapidly yields the corresponding photocurable product. The above curing method is not only highly efficient but also simple, fast, and low-cost.

[0070] In another typical embodiment of this application, a photocurable product is provided, which includes the above-mentioned photocurable composition or is cured by the above-mentioned photocurable composition. The photocurable product includes any one of release film coating, substrate protective coating, 3D printing material, and silicone adhesive.

[0071] The photocurable products prepared from the above photocurable compositions have excellent adhesion to substrates and surface peelability, thus offering high economic benefits and enabling wider promotion and application.

[0072] The beneficial effects of this application will be explained below with reference to specific embodiments and comparative examples.

[0073] Examples of preparation of siloxane-containing (meth)acrylate compounds:

[0074] The hydroxypropyl acrylate raw materials used in the following examples of the preparation of (meth)acrylate compounds are a mixture of (2-methyl-2-hydroxyethyl) acrylate and (1-methyl-2-hydroxyethyl) acrylate.

[0075] Preparation Example 1

[0076] 11.6 g (0.1 mol) of hydroxypropyl acrylate, 30 mL of toluene, and 13.4 g of p-dimethylaminopyridine (DMAP) were added to a 100 mL three-necked flask. The mixture was stirred and kept at 40 °C. 15 g (0.1 mol) of triethylchlorosilane was added dropwise. After 4 hours, a sample was taken for analysis; the hydroxypropyl acrylate content was less than 0.5%. The mixture was cooled to room temperature (approximately 20 °C), and 30 mL of water was added to dissolve the DMAP hydrochloride. The brine was separated, and 20 mL of water was added for washing with stirring for 10 minutes. This washing process was repeated once, and the pH of the aqueous phase was measured to be 7. Toluene was distilled off from the organic phase under reduced pressure. The residue was a colorless, transparent liquid, denoted as A-1, with a mass of 18.5 g and a yield of 80.4%. The content of A-1... 1¹H NMR data (CDCl₃, ppm) δ 0.581–0.640 (quartet, 6H), 0.943–0.983 (triplet, 9H), 1.204–1.267 (quartet, 3H), 3.696–3.747 (multiplet, 0.6H), 4.047–4.066 (doublet, 1.4H), 4.158–4.228 (multiplet, 0.7H), 5.020–5.077 (multiplet, 0.3H), 5.796–5.861 (multiplet, 1H), 6.070–6.182 (multiplet, 1H), 6.381–6.459 (multiplet, 1H).

[0077] Preparation Example 2

[0078] In a 250 mL three-necked flask, 30.0 g (0.23 mol) of hydroxypropyl acrylate, 29.63 g (0.242 mol) of DMAP, and 100 mL of toluene were added. The flask was kept at 40 °C, and 14.4 g (0.115 mol) of dimethyldichlorosilane was added dropwise. After 12 hours, a sample was taken for analysis; the hydroxypropyl acrylate content was less than 0.5%. The flask was cooled to room temperature (approximately 20 °C), and 60 mL of water was added to dissolve the DMAP hydrochloride. The brine was separated, and 30 mL of water was added for washing with stirring for 10 minutes. This washing process was repeated once, and the pH of the aqueous phase was measured to be 7. Toluene was distilled off from the organic phase under reduced pressure. The residue was a colorless, transparent liquid, denoted as A-2, with a mass of 29.8 g and a yield of 81.5%. 1 ¹H NMR data (CDCl₃, ppm) δ 0.114–0.149 (quartet, 6H), 1.204–1.267 (quartet, 6H), 3.696–3.747 (multiplet, 1.2H), 4.047–4.066 (doublet, 2.8H), 4.158–4.228 (multiplet, 1.4H), 5.020–5.077 (multiplet, 0.6H), 5.796–5.861 (multiplet, 2H), 6.070–6.182 (multiplet, 2H), 6.381–6.459 (multiplet, 2H).

[0079] Preparation Example 3

[0080] In a 100 mL three-necked flask, 13.01 g (0.1 mol) of hydroxypropyl acrylate, 10.45 g (0.103 mol) of triethylamine, 0.65 g of DMAP, and 30 mL of toluene were added. The flask was kept at 40 °C, and 4.98 g (0.033 mol) of methyltrichlorosilane was added dropwise. After 5 hours, a sample was taken for analysis; the hydroxypropyl acrylate content was less than 0.5%. The flask was cooled to room temperature (approximately 20 °C), and 20 mL of water was added to dissolve the triethylamine hydrochloride. The brine was separated, and another 20 mL of water was added for washing with stirring for 10 minutes. This washing process was repeated once, and the pH of the aqueous phase was measured to be 7. Toluene was distilled off from the organic phase under reduced pressure. The residue was a colorless, transparent, viscous liquid, denoted as A-3, with a mass of 14.2 g and a yield of 100%. 1 ¹H NMR data (CDCl₃, ppm) δ 0.141–0.161 (triplet, 3H), 1.207–1.262 (quartet, 9H), 3.770–3.787 (doublet, 1.8H), 4.053–4.074 (doublet, 4.2H), 4.250–4.296 (multiplet, 2.1H), 5.027–5.085 (multiplet, 0.9H), 5.794–5.857 (multiplet, 3H), 6.060–6.175 (multiplet, 3H), 6.374–6.456 (multiplet, 3H).

[0081] Preparation Example 4

[0082] In a 100 mL three-necked flask, 13.01 g (0.1 mol) of hydroxypropyl acrylate, 10.45 g (0.103 mol) of triethylamine, 0.65 g of DMAP, and 30 mL of toluene were added. The flask was kept at 40 °C, and 5.86 g (0.033 mol) of propyltrichlorosilane was added dropwise. After 5 hours, a sample was taken for analysis; the hydroxypropyl acrylate content was less than 0.5%. The flask was cooled to room temperature (approximately 20 °C), and 20 mL of water was added to dissolve the triethylamine hydrochloride. The brine was separated, and another 20 mL of water was added for washing with stirring for 10 minutes. This washing process was repeated once, and the pH of the aqueous phase was measured to be 7. Toluene was distilled off from the organic phase under reduced pressure. The residue was a colorless, transparent, viscous liquid, designated A-4, with a mass of 12.6 g and a yield of 83.2%. 1¹H NMR data (CDCl₃, ppm) δ 0.597–0.651 (quartet, 2H), 0.915–0.964 (triplet, 3H), 1.203–1.262 (quartet, 9H), 1.409–1.436 (multiplet, 2H), 3.771–3.791 (multiplet, 1.8H), 4.094–4.069 (multiplet, 4.2H), 4.278–4.306 (multiplet, 2.1H), 5.021–5.078 (multiplet, 0.9H), 5.790–5.854 (multiplet, 3H), 6.057–6.171 (multiplet, 3H), 6.373–6.456 (multiplet, 3H).

[0083] Preparation Example 5

[0084] In a 100 mL three-necked flask, 13.01 g (0.1 mol) of hydroxypropyl acrylate and 12.58 g (0.103 mol) of DMAP and 30 mL of toluene were added. The mixture was stirred and kept at 40 °C. 7.05 g (0.033 mol) of phenyltrichlorosilane was added dropwise. After 15 hours, a sample was taken for analysis; the hydroxypropyl acrylate content was less than 0.5%. The mixture was cooled to room temperature (approximately 20 °C), and 20 mL of water was added to dissolve the DMAP hydrochloride. The brine was separated, and another 20 mL of water was added for washing with stirring for 10 minutes. This washing process was repeated once, and the pH of the aqueous phase was measured to be 7. Toluene was distilled off from the organic phase under reduced pressure. The residue was a colorless, transparent, viscous liquid, designated A-5, with a mass of 15.95 g and a yield of 87.16%. 1 ¹H NMR data (CDCl₃, ppm) δ 1.203–1.262 (quartet, 9H), 3.771–3.791 (multiplet, 1.8H), 4.094–4.069 (multiplet, 4.2H), 4.278–4.306 (multiplet, 2.1H), 5.021–5.078 (multiplet, 0.9H), 5.790–5.854 (multiplet, 3H), 6.057–6.171 (multiplet, 3H), 6.373–6.456 (multiplet, 3H), 7.340–7.471 (multiplet, 3H), 7.671–7.690 (doublet, 2H).

[0085] Preparation of Comparative Example 1

[0086] Hydroxyethyl acrylate (0.23 mol), DMAP 29.63 g (0.242 mol), and 100 mL of toluene were added to a 250 mL three-necked flask. The flask was kept at 40 °C, and 14.4 g (0.115 mol) of dimethyldichlorosilane was added dropwise. After 12 h, a sample was taken for analysis, and the hydroxypropyl acrylate content was less than 0.5%. The flask was cooled to room temperature (about 20 °C), and 60 mL of water was added to dissolve the DMAP hydrochloride. The brine was separated, and 30 mL of water was added to wash the flask. The washing was repeated once, and the pH of the aqueous phase was measured to be 7. Toluene was distilled off from the organic phase under reduced pressure. The residue was a colorless and transparent liquid, denoted as A'-1, with a mass of 8.1 g of transparent liquid. The yield was 56.2%.

[0087] Examples of photoinitiator preparation:

[0088] Example 1 of photoinitiator preparation

[0089] Step 1: Dodecylbenzene (actually C) 10 ~C 13 24.6 g of an alkylbenzene mixture was dissolved in 100 mL of dichloromethane, cooled to -5 °C, and 14 g of anhydrous aluminum trichloride was added. The temperature was kept below 0 °C, and 24 g of 2-bromoisobutyryl bromide was added dropwise over 30 min. The mixture was then stirred for 2 h, followed by acid hydrolysis and water washing. Dichloromethane was removed by distillation, and the residue was 39.4 g of a light yellow 2-methyl-2-hydroxy-1-(4-dodecylphenyl)-1-propanone oil.

[0090] Step 2: The product from the previous step was dissolved in 100 mL of isopropanol, and the mixture was kept in a water bath at no more than 30°C. 20 g of 30% NaOH solution was added dropwise, and the mixture was stirred for 5 h. The sample analysis showed that the content of the raw material 2-methyl-2-bromo-1-(4-dodecylphenyl)-1-propanone was less than 0.1%. Isopropanol was removed by vacuum distillation. 50 mL of toluene was added, and the mixture was washed with water several times. The pH of the aqueous phase was measured to be 7. Toluene was removed by vacuum distillation, and a light yellow 2-methyl-2-hydroxy-1-(4-dodecylphenyl)-1-propanone was obtained, denoted as C-0. The total yield of the steps was 96.7%.

[0091] Example 2 of photoinitiator preparation

[0092] In a 50 mL single-necked flask, 6.6 g (0.02 mol) of 2-methyl-2-hydroxy-1-(4-dodecylphenyl)-1-propanone, the product of the second step, 2.7 g (0.022 mol) of DMAP, and 20 mL of toluene were added. The mixture was stirred magnetically and kept at 25 °C. 2.35 g (0.216 mol) of trimethylchlorosilane was added dropwise and stirred for 12 h. The sample was analyzed and found to contain less than 0.5% 2-methyl-2-hydroxy-1-(4-dodecylphenyl)-1-propanone. 20 mL of water was added, the brine was separated, and the mixture was washed twice with water until the pH of the aqueous phase was neutral. Toluene was removed by vacuum distillation. The residue was a light yellow oily liquid of 2-methyl-2-trimethylsiloxy-1-(4-dodecylphenyl)-1-propanone, denoted as C-1, weighing 8 g. The yield was 98.84%. 1 H-NMR data (CDCl3, ppm): 0.020 (s, 9H, 3CH3), 0.834-0.888 (multiplet, 6.2H, 2CH3), 1.218-1.277 (multiplet, 1 5.1H, CH2), 1.592 (s, 6H, 2CH3), 1.490-1.608 (multiplet, 4.2H, CH2), 2.550-2.778 (multiplet, 1H, CHC6H4).

[0093] Example 3 of photoinitiator preparation

[0094] In a 250 mL four-necked flask, 33 g (0.2 mol) of 2-methyl-2-hydroxy-1-phenyl-1-propanone was added. Toluene and DMAP were added in the same proportions as in Example 2 for the preparation of the photoinitiator, and trimethylsilyl chloride was added dropwise. The mixture was stirred and reacted for 12 h. After washing with water and removing toluene, the residue was a light yellow oily liquid. This residue was then subjected to vacuum distillation to obtain 37.8 g of a nearly colorless liquid, 2-methyl-2-trimethylsiloxy-1-phenyl-1-propanone, denoted as C-2, with a yield of 80%. The sample was frozen in a refrigerator to crystallize, with a melting range of 28-30 °C.

[0095] Example 4 of photoinitiator preparation

[0096] In a 50 mL three-necked flask, 4.1 g (0.02 mol) of 1-hydroxycyclohexylbenzophenone was added. Toluene and DMAP were added in the same proportions as in Example 2 of photoinitiator preparation, and trimethylsilylchlorosilane was added dropwise. The mixture was stirred and reacted for 12 h. After washing with water and removing toluene, the residue was a light yellow oily liquid of 1-trimethylsiloxycyclohexylphenyl ketone, designated C-3, weighing 5.42 g, with a yield of 98%. The sample crystallized after cooling to room temperature, with a melting range of 48–52 °C.

[0097] Example 5 of photoinitiator preparation

[0098] In a 50 mL three-necked flask, 4.5 g (0.02 mol) of 2-methyl-2-hydroxy-1-[4-(2-hydroxyethoxy)phenyl]-1-propanone (Omnirad 2959, IGM Resin Company) was added, along with 5.4 g (0.044 mol) of DMAP and 20 mL of toluene. The mixture was stirred magnetically and kept at 25 °C. 4.7 g (0.432 mol) of trimethylchlorosilane was added dropwise, and the reaction was stirred for 12 h. After washing with water and removing toluene, the residue was a light yellow oily liquid of 2-methyl-2-trimethylsiloxy-1-[4-(2-trimethylsiloxyethoxy)phenyl]-1-propanone, designated as C-4, weighing 7.2 g, with a yield of 98.2%.

[0099] The cured resin is as follows:

[0100] B-1, Guangzhou Lingying Ink Co., Ltd. silicone resin YP 3157; B-2, Guangzhou Boxin New Material Technology Co., Ltd. silicone resin T-2706; B-3, IGM Resin Company Photomer 3316; polydimethylsiloxane (trimethylsiloxane-terminated, MW2000, Alfa Easar product).

[0101] The following are siloxane-containing monomers:

[0102] HDDA, Photomer 4017 from IGM Resins; EO3TMPTA, Photomer 4149 from IGM Resins.

[0103] A-1:

[0104] A-2:

[0105] A-3:

[0106] A-4:

[0107] A-5:

[0108] A'-1:

[0109] A'-2:

[0110] The initiators are as follows:

[0111] C-0, 2-methyl-2-hydroxy-1-(4-dodecylphenyl)-1-propanone; C-1, 2-methyl-2-trimethylsiloxy-1-(4-dodecylphenyl)-1-propanone; C-2, 2-methyl-2-trimethylsiloxy-1-phenyl-1-propanone; C-3, 1-trimethylsiloxycyclohexylphenyl ketone; C-4, 2-methyl-2-trimethylsiloxy-1-[4-(2-trimethylsiloxyethoxy)phenyl]-1-propanone; Omnirad 1173, IGM Resins; Omnirad 184, IGM Resins; Omnirad 2959, IGM Resins.

[0112] The hydrolysis resistance of the above-mentioned siloxane monomers was tested as follows: 2g of monomer samples A-2, A-5, and A'-1 were added to 8g of acetone containing 5wt% water, and stirred at 40℃ for 1h, 5h, 9h, and 24h, respectively. The hydrolysis rate (i.e., the proportion of hydroxypropyl acrylate or hydroxyethyl acrylate produced) was analyzed, and the test results are listed in Table 1.

[0113] Table 1

[0114] time A-1 A-2 A-3 A-4 A-5 A’-1 1h 0.9％ 0.8％ 0.7％ 0.8％ 1％ 10％ 5h 1.6％ 1.5％ 1.2％ 1.3％ 2％ 20％ 9h 1.9％ 1.8％ 1.4％ 1.5％ 2.5％ 30％ 24h 2.0％ 1.9％ 1.7％ 1.8％ 2.6％ 60％

[0115] As can be seen from the data in Table 1, the siloxane-containing (meth)acrylate compounds of this application have good hydrolysis resistance.

[0116] The compatibility test of the above-mentioned siloxane monomers with the cured resin was conducted at 25°C. 5-50% was considered partial solvent, less than 5% was considered insoluble, and more than 50% was considered miscible. The test results are shown in Table 2.

[0117] Table 2

[0118] polydimethylsiloxane B-1 B-2 B-3 HDDA <5％ <5％ <5％ ＞50％ EO3TMPTA <5％ <5％ <5％ ＞50％ A-1 18％ ＞50％ 10％ ＞50％ A-2 15％ 45％ 6％ ＞50％ A-3 <5％ 15％ <5％ ＞50％ A-4 5％ 20％ <5％ ＞50％ A-5 <5％ 6％ <5％ ＞50％

[0119] This indicates that general monomers without silicon have too low solubility in silicone resins to be compatible with other materials, while the siloxane-containing (meth)acrylate compounds of this application have good solubility in silicone resins, thus allowing for better compatibility with other initiators, curing resins, and additives.

[0120] Solubility of photoinitiator in dimethylsiloxane:

[0121] To simulate the dissolution in silicone-containing resin, Omnirad 1173, Omnirad 184, Omnirad 2959, and C-0, C-1, C-2, C-3, and C-4 were gradually added to 10g (accurate to 0.001g) of polydimethylsiloxane (trimethylsiloxane-terminated, MW2000, manufactured by ALFA) and incubated in a constant temperature water bath at 20°C until saturation. The dissolution was observed and is shown in Table 3.

[0122] Table 3

[0123]

[0124] As shown in Table 3, the solubility of photoinitiators after trimethylsilylation in silicone oil is greatly improved, and the solubility has undergone a qualitative change.

[0125] Stability test of photocurable composition:

[0126] The monomer and B-1 resin were mixed at 40℃, and then the initiator was added. The mixture was ultrasonically dissolved for 30 minutes. Except for formulation D-5, which had crystals that were not completely dissolved, the other formulations were uniform and transparent. The mixture was stored in a 5℃ refrigerator for 2 weeks in the dark to observe whether it was uniform and transparent and whether there was any layering or turbidity. The results are shown in Table 4.

[0127] Table 4

[0128]

[0129]

[0130] The formulations containing C-1, C-2, and C-3 respectively are the technical solutions provided by this invention and have good stability.

[0131] Curing experiments of the photocurable compositions of formulations D-2, D-4, and D-6:

[0132] The photocurable compositions of formulations D-2, D-4, and D-6 were coated onto clean polypropylene films at a thickness of 5 μm and 10 μm, respectively. The residual oxygen content was controlled to be less than 50 ppm by nitrogen flow, the conveyor belt speed was 200 m / min, and the films were cured by high-pressure mercury lamp with an output power of 100 W / cm. The degree of surface dryness was tested by the touch dry test, and the adhesion was tested by the cross-cut test. The test results are listed in Table 5.

[0133] Table 5

[0134]

[0135] Conclusion: The surface cured well and the substrate adhered firmly.

[0136] Table 6

[0137] raw material Formula D-7 Formula D-8 Formula D-9 Formula D-10 Formula D-11 Formula D-12 Formula D-13 A-1 30 A-2 30 A-3 30 A-4 30 A-5 30 A’-1 30 A’-2 30 B-1 70 70 70 70 70 70 70 C-1 4 4 4 4 4 4 4

[0138] Adhesion test experiments of photocurable compositions with formulations D-7 to D-13:

[0139] The photocurable compositions D-7 to D-13 from Table 6 were coated onto clean polypropylene films to a thickness of 10 μm. Residual oxygen levels were controlled to be less than 50 ppm using nitrogen flow, and the conveyor belt speed was 200 m / min. Curing was performed using a high-pressure mercury lamp with an output power of 100 W / cm. Adhesion was tested using the cross-cut adhesion test. The adhesion test results for the photocurable compositions D-7 to D-13 are listed in Table 7. Compositions with good adhesion were further tested for peelability. Composition D-13 had poor adhesion and was not further tested for peelability.

[0140] Peelability test of photocurable compositions with formulations D-7 to D-12:

[0141] Apply the photocurable compositions D-7 to D-12 from Table 6 onto a PET sheet (200mm*100mm*0.3mm) using a 25μm wire rod. Cure once under a high-pressure mercury lamp at a belt speed of 6m / min. Take 3M tape (210mm long, 60mm wide) and stick it along the longest side of the PET sheet to the side with the cured film, ensuring the tape is completely adhered to the sheet. Brush the tape repeatedly 5 times with a soft brush to ensure complete contact between the tape and the cured film. Hold one end of the tape and peel it off from the cured film at a 45-degree angle within 1 second. If the cured film on the PET sheet is intact, the peelability is good (marked as easy to peel). If the cured film on the PET sheet is damaged, the peelability is poor (marked as difficult to peel).

[0142] The adhesion and peelability test results of the photocurable compositions of formulations D-7 to D-12 are listed in Table 7.

[0143] Table 7

[0144]

[0145] Results: Compared with formulations D-12 and D-13, it can be seen that the siloxane-containing (meth)acrylate compound of this application is more conducive to the balance between substrate adhesion and surface peelability.

[0146] As can be seen from the above description, the embodiments of the present invention achieve the following technical effects:

[0147] The siloxane-containing (meth)acrylate compound provided in this application contains one or more (meth)acrylate functional groups in its structure. Since (meth)acrylate functional groups are free radical polymers, the reaction rate is fast, resulting in better separation ability between the photocurable composition containing it and the substrate surface, thus improving the surface peelability of the photocurable composition. Simultaneously, the siloxane group effectively improves the compatibility of the siloxane-containing (meth)acrylate compound with the photocurable silicone resin in the molecular structure, thereby improving the formulation stability of the photocurable composition and effectively improving its adhesion and surface peelability to the substrate. Furthermore, the presence of at least one methyl substituent on the methylene group directly linked to the Si-O bond in the siloxane-containing (meth)acrylate compound, due to its steric hindrance effect, helps improve the water resistance of the siloxane-containing (meth)acrylate compound, thus aiding in its preparation and storage. Siloxane-containing (meth)acrylate compounds containing only a single silicon atom are more conducive to balancing substrate adhesion and surface peelability.

[0148] The above description is merely a preferred embodiment of the present invention and is not intended to limit the invention. Various modifications and variations can be made to the present invention by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A photocurable composition, characterized in that, The photocurable composition includes: (Meth)acrylate compounds containing siloxanes; Free radical curable resins; and Photoinitiator; The structure of the siloxane-containing (meth)acrylate compound is selected from any one of the following formulas I, II, and III: Formula I Formula II Formula III Ra is selected from C1~C 10 Alkyl groups, C6~C 20 Any of the non-substituted aryl groups, Rb1 is a methyl group, and Rc1 is an H group. Either Rb2 or Rc2 is a methyl group, and the other is an H group. Either Rb3 or Rc3 is a methyl group, and the other is an H group. Rd is H or methyl; The sum of the weights of the siloxane-containing (meth)acrylate compound and the free-radical curable resin accounts for 90-99.9% of the total weight of the photocurable composition. At least one of the photoinitiators is a silicon-containing photoinitiator, and the silicon-containing photoinitiator is an α-siloxane photoinitiator, wherein the weight of the silicon-containing photoinitiator accounts for 0.1% to 10% of the total weight of the photocurable composition; The silicon-containing photoinitiator has the structure shown in Formula IV and / or Formula V: Formula IV Formula V R1 and R2 are each independently selected from any one of C1 to C4 alkyl groups, or CR1R2 is a cyclohexane subunit or a cyclopentane subunit; R3 and R5 are each independently selected from any one of C1 to C4 alkyl or phenyl groups; R4 is selected from any one of C1 to C4 alkyl groups, -SiR3R5R6, and R6 is selected from any one of H and C1 to C4 alkyl groups; Ar1 is selected from , , Any one of them, Among them, R7, R8, and R9 are each independently selected from H, halogen atoms, and C1~C. 18 Alkyl, C1~C 18 alkoxy, allyloxy, C1~C 12 alkyl acyloxy-substituted C1~C 14 Alkyl, -OSiR3R4R5, -OSi(OR4)R3R5 substituted C1~C 14 Alkyl groups, C3-C9 alkyl groups with one or more oxygen atoms inserted, C1-C 18 Any one of the alkyl thio groups; R 10 Selected from any one of the C1-C8 alkyl groups; Y1 is selected from any one of the following: straight bond, -CH2, -CHCH3, -C(CH3)2, -O-, -S-; R7', R8', and R9' are each independently selected from H, C1-C4 alkyl groups, F atoms, and C1-C4 atoms. 18 Any one of the alkoxy groups, Ar2 is selected from , , , , Any one of them: Among them, R 11 R 12 Each is independently selected from H, C1-C4 alkyl, and C1-C4 allyl. Y2 is selected from any one of -CH2, -CHCH3, -C(CH3)2, -O-, -S-.

2. The photocurable composition according to claim 1, characterized in that, The weight ratio of the siloxane-containing (meth)acrylate compound to the free radical curable resin is 1 to 9:

1.

3. The photocurable composition according to claim 1 or 2, characterized in that, The free radical curable resin is an organosilicon resin with (meth)acrylate groups.

4. The photocurable composition according to claim 1, characterized in that, R1, R2, R3, R5, and R6 are each independently methyl, or CR1R2 is a cyclohexane subunit. R4 is methyl or -Si(CH3)3. In Ar1, R7 and R9 are each independently H. R8 is selected from H, F atoms, and C1~C atoms. 14 Alkyl, C1-C8 alkoxy, allyloxy, C1-C 12 The alkyl acyloxy-substituted C1-C3 alkoxy group, -OSi(CH3)3, -OSi(CH3)3-substituted C1-C3 alkoxy group, C3-C9 alkoxy group with one or two oxygen atoms inserted, and any one of the C1-C4 alkyl thio groups. The R 10 Selected from any one of C1-C4 alkyl groups, The Y1 is selected from any one of -CH2, -O-, and -S-. R7', R8', and R9' are each independently selected from any one of H, C1-C4 alkyl groups, and F atoms. The R in Ar2 11 The R 12 Each is independently selected from H and any one of C1-C4 alkyl groups. Y2 is selected from any one of -CH2, -O-, and -S-.

5. The photocurable composition according to claim 4, characterized in that, The α-siloxyketone photoinitiator is selected from any one or more of the following compounds: 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 。 6. The photocurable composition according to claim 1, characterized in that, Ra is selected from C1-C4 alkyl groups, C6-C4 alkyl groups, and C6-C4 alkyl groups 10 Any of the non-substituted aryl groups.

7. The photocurable composition according to claim 6, characterized in that, Ra is selected from any one of methyl, ethyl, n-propyl, isopropyl, and phenyl.

8. The photocurable composition according to claim 1 or 2, characterized in that, The (meth)acrylate compound is selected from one or more of the following compounds: 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 。 9. A photocurable product, characterized in that, The photocurable product comprises the photocurable composition according to any one of claims 1 to 8 or is cured by the photocurable composition according to any one of claims 1 to 8, and the photocurable product comprises any one of release film coating, substrate protective coating, 3D printing material, and silicone adhesive.

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