Episulfide cation photopolymerization monomer, photocuring composition containing episulfide cation photopolymerization monomer, and photoresist containing episulfide cation photopolymerization monomer

Abstract

The invention belongs to the field of photocuring, and particularly relates to an episulfide cation photopolymerization monomer, a photocuring composition containing the episulfide cation photopolymerization monomer, and a photoresist containing the episulfide cation photopolymerization monomer. The structural general formula of the episulfide cation photopolymerization monomer is shown as formula (I): # imgabs0 #, R is substituted or non-substituted alkyl, substituted or non-substituted naphthenic base, substituted or non-substituted aryl or any combination of the substituted or non-substituted alkyl, substituted or non-substituted naphthenic base and substituted or non-substituted aryl, and n is greater than or equal to 3. The photocuring composition comprises a photopolymerization initiator and a photopolymerizable compound, and further comprises the episulfide cation photopolymerizable monomer. When the episulfide cationic photopolymerization monomer is applied to a photocuring composition, cationic photopolymerization can be effectively initiated, the hardness and flexibility of a curing coating are improved, and the problems of shrinkage and the like of the photocuring coating are solved.

Description

Technical Field

[0001] The invention belongs to the field of photocuring, and in particular relates to a cyclic sulfide cationic photopolymerizable monomer and a photocurable composition and a photoresist containing the same. Background Art

[0002] In recent years, photocuring technology has received attention and in-depth research due to its green, environmentally friendly and safe advantages. It has been widely used in coatings, inks, electronic communications, photoresists, dental materials and 3D printing.

[0003] In the photocuring system, the photocuring monomer is one of the important components of the photocuring system, which has a vital influence on the overall performance of the photocuring material, especially the curing rate and degree of curing. The photocuring monomer is also called a reactive diluent. It helps the photocuring reaction to proceed smoothly by reducing the viscosity of the photocuring system and improving the solubility of the system. In addition, the monomer contains functional groups that participate in the cross-linking and curing process, which further affects the curing rate of the photocuring system and the performance of the cured film. According to the difference in functionality, the photocuring monomer can be subdivided into monofunctional monomers, difunctional monomers and multifunctional monomers. Among them, the monofunctional monomer has a low viscosity and strong dilutability, but it has problems such as high volatility, low photocuring rate, insufficient crosslinking degree and low volume shrinkage during the application process; in contrast, the difunctional monomer has a low viscosity, strong dilutability, and a fast photocuring speed; the multifunctional monomer has a high curing speed, a high crosslinking degree, excellent wear resistance and weather resistance, but the disadvantages of increased shrinkage and increased brittleness after curing also limit its application range.

[0004] In order to optimize the photocuring effect, researchers usually choose different photocuring monomers according to actual needs to improve the compatibility and sensitivity of different formula compositions. According to the different polymerization mechanisms, photopolymerizable monomers can be divided into two categories: free radical photopolymerizable monomers and cationic photopolymerizable monomers. Free radical photopolymerizable monomers initiate chain polymerization reactions under the action of free radical photoinitiators. Among them, (meth)acrylate monomers are widely used due to their fast photopolymerization speed, but this type of monomer is easily affected by oxygen and has large shrinkage; while cationic photopolymerizable monomers initiate ring-opening polymerization reactions under the action of cationic photoinitiators. Commonly used cationic photopolymerizable monomers include glycidyl ether epoxy monomers, alicyclic epoxy monomers, and oxetane monomers. Although the photopolymerization speed of this type of monomer is slower than that of acrylate monomers, the polymerization process is not affected by oxygen and has less shrinkage.

[0005] However, although photocurable monomers have shown excellent performance in many aspects, it is still difficult for photocurable monomers on the market to effectively balance the performance requirements of flexibility, rigidity, low shrinkage, etc. This situation not only limits the further promotion and application of photocuring technology, but also poses new challenges and topics for researchers in related fields.

[0006] Therefore, developing a new photocurable monomer that can comprehensively improve the performance of photocurable materials has become a technical problem that needs to be solved urgently.

[0007] In view of the above problems, the present invention proposes a cyclic sulfide cationic photopolymerizable monomer, which is applied to a photocurable composition to effectively initiate cationic photopolymerization, improve the hardness and flexibility of the cured coating, and reduce the shrinkage of the photocurable coating. Summary of the invention

[0008] The purpose of the present invention is to provide a cyclic sulfide cationic photopolymerizable monomer, which can be applied to a photocurable composition to effectively initiate cationic photopolymerization, improve the hardness and flexibility of the cured coating, and reduce the shrinkage of the photocurable coating.

[0009] The present invention solves the above problems through the following technical solutions:

[0010] A cyclic sulfide cationic photopolymerizable monomer, the general structural formula of which is shown in formula (I):

[0011]

[0012] In formula (I), R is a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aromatic group, or any combination of these groups, and n≥3.

[0013] The above-mentioned cyclic sulfur cationic photopolymerizable monomer contains a plurality of cyclic sulfur structures.

[0014] A photocurable composition comprises a photopolymerization initiator, a photopolymerizable compound and the above-mentioned cyclic sulfide cationic photopolymerizable monomer.

[0015] Furthermore, the photopolymerization initiator is at least one of an iodonium salt compound, a sulfonium salt compound, and a triazine compound. The photopolymerization initiator can generate active species that initiate cationic polymerization under light irradiation and initiate cationic photopolymerization.

[0016] Preferably, the photopolymerization initiator is at least one of an iodonium salt compound and a sulfonium salt compound.

[0017] Furthermore, the chemical structure of the iodonium salt compound is shown in the following formula (II):

[0018]

[0019] In formula (II), R1 and R2 are the same or different and are independently selected from H, C1-C20 branched or unbranched alkyl, C1-C20 branched or unbranched alkoxy, C1-C20 branched or unbranched alkylthio;

[0020] X - Select one of the following ions: BF4 - PF6 - 、SbF6 - 、AsF6 - 、[PF3(C2F5)3] - 、[Al(OC(CF3)3)4] - , [B(PhF5)4] - 、[B(Ph(CF3)2)4] - 、[((CF3)2SO2)2N] - 、[((CF3)2SO2)3C] - , Cl - Br - 、F - 、[Al(Ot-C4F9)4] - 、[Al(O-(i-C3F7)CH3)4] - 、[C(O-SO2CF3)3] - 、[nC 12 H 25- TsO - , [NTf2] - .

[0021] Furthermore, the photopolymerizable compound is a cationic polymerizable compound; the cationic polymerizable compound is at least one of an alkenyl ether compound, an oxirane compound, an aziridine compound, and an oxetane compound. The cationic polymerizable compound may be in the form of a monomer or a resin (such as an oligomer or a prepolymer). The cationic polymerizable compound can be polymerized under the action of a cationic photoinitiator.

[0022] Furthermore, based on 100 wt % of the total weight of the photocurable composition, the photocurable composition includes: 1 to 30 wt % of cyclic sulfide cationic photopolymerizable monomer, 0.1 to 10 wt % of photopolymerization initiator, and 5 to 90 wt % of photopolymerizable compound.

[0023] Preferably, based on 100 wt % of the total weight of the photocurable composition, the photocurable composition comprises: 5 to 15 wt % of cyclic sulfide cationic photopolymerizable monomer, 0.1 to 5 wt % of photopolymerization initiator, and 10 to 60 wt % of photopolymerizable compound.

[0024] Furthermore, the photocurable composition further comprises 0.1 to 50 wt % of additives.

[0025] Preferably, the photocurable composition further comprises 1 to 5 wt % of additives.

[0026] Furthermore, the photocurable composition further comprises 0.1 to 10 wt % of a sensitizer.

[0027] Preferably, the photocurable composition further comprises 0.5 to 5 wt % of a sensitizer.

[0028] A use of the photocurable composition as described above in ink, coating, adhesive or color photoresist.

[0029] A photoresist is prepared from the above-mentioned photocurable composition.

[0030] The present invention has the following beneficial effects:

[0031] The cyclic sulfide cationic photopolymerizable monomer of the present invention is applied to a photocurable composition, which can effectively initiate cationic photopolymerization, improve the hardness and flexibility of the cured coating, and reduce the shrinkage of the photocurable coating. DETAILED DESCRIPTION

[0032] In order to make the purpose, technical solution and advantages of the embodiments of the present invention clearer, the technical solution in the embodiments of the present invention will be clearly and completely described below.

[0033] According to one aspect of the present invention, a cyclic sulfide cationic photopolymerizable monomer is provided, the general structural formula of which is shown in formula (I):

[0034]

[0035] In formula (I), R is a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aromatic group, or any combination of these groups, and n≥3.

[0036] According to another aspect of the present application, a photocurable composition is provided, comprising a photopolymerization initiator, a photopolymerizable compound, and the above-mentioned cyclic sulfide cationic photopolymerizable monomer.

[0037] In a specific embodiment, the photopolymerization initiator is at least one of an iodonium salt compound, a sulfonium salt compound, and a triazine compound. The photopolymerization initiator can generate active species that initiate cationic polymerization under light irradiation and initiate cationic photopolymerization.

[0038] In a preferred embodiment, the photopolymerization initiator is at least one of an iodonium salt compound and a sulfonium salt compound.

[0039] In a specific embodiment, the chemical structure of the iodonium salt compound is shown in the following formula (II):

[0040]

[0041] In formula (II), R1 and R2 are the same or different and are independently selected from H, C1-C20 branched or unbranched alkyl, C1-C20 branched or unbranched alkoxy, C1-C20 branched or unbranched alkylthio;

[0042] X - Select one of the following ions: BF4 - PF6 - 、SbF6 - 、AsF6 - 、[PF3(C2F5)3] - 、[Al(OC(CF3)3)4] - , [B(PhF5)4] - 、[B(Ph(CF3)2)4] - 、[((CF3)2SO2)2N] - 、[((CF3)2SO2)3C] - , Cl - Br - 、F - 、[Al(Ot-C4F9)4] - 、[Al(O-(i-C3F7)CH3)4] - 、[C(O-SO2CF3)3] - 、[nC 12 H 25- TsO - , [NTf2] - .

[0043] In a specific embodiment, the photopolymerizable compound is a cationic polymerizable compound; the cationic polymerizable compound is at least one of an alkenyl ether compound, an oxirane compound, an aziridine compound, and an oxetane compound. The cationic polymerizable compound may be in the form of a monomer or a resin (such as an oligomer or a prepolymer). The cationic polymerizable compound can be polymerized under the action of a cationic photoinitiator.

[0044] Specifically, exemplary, the alkenyl ether compound can be a C1-C6 alkenyl ether compound, such as vinyl ether, 1-propenyl ether, 1-butenyl ether, 1-pentenyl ether compound, etc., preferably a vinyl ether compound. The alkenyl ether compound is, for example, an alkenyl ether starting from a monohydric alcohol having 1 to 12, preferably 1 to 6 carbon atoms, a dihydric alcohol having 2 to 12, preferably 2 to 8 carbon atoms, a trihydric alcohol having 3 to 12, preferably 3 to 6 carbon atoms or more, in particular a C1-C6 alkenyl ether. As the alkenyl ether compound, polymers containing alkenyl ethers, such as vinyl ether functional groups, can also be mentioned. As specific examples, one or a combination of two or more of triethylene glycol divinyl ether, isobutyl vinyl ether, methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, isopropyl vinyl ether, butyl vinyl ether (BVE), hydroxyethyl vinyl ether, diethylene glycol divinyl ether (DEGDVE), triethylene glycol divinyl ether (TEGDVE), vinyl n-octyl ether, divinyl-1,4-butanediol ether, 2-ethylhexyl vinyl ether, 1,4-cyclohexyl dimethanol divinyl ether, 4-hydroxybutyl vinyl ether (HBVE), triethylene glycol divinyl ether (DVE-3), glycerol carbonate vinyl ether, dodecyl vinyl ether, etc. can be mentioned. In addition, compounds having both vinyl ether and (meth) alkyl acrylate structures can also be mentioned, and one or more of these compounds can be used simultaneously. The alkenyl compounds also include carbamates containing one or more, such as 1-3, alkenyl ether structures. The alkenyl ether structure-containing carbamates can be obtained by reacting an alkenyl ether having a hydroxyl group with an isocyanate compound (such as a polyisocyanate compound). Examples include divinyloxyalkyl carbamate and a trifunctional vinyl ether prepared from 1,6-hexamethylene diisocyanate trimer and 4-hydroxyvinyl ether.

[0045] Specifically, exemplary, the alkenyl ether compound can be selected from glycidyl ether epoxy compounds, glycidyl ester epoxy compounds, glycidyl amine epoxy compounds, aliphatic epoxy compounds, alicyclic epoxy compounds, etc. Oxirane compounds can be in the form of monomers or resins (such as oligomers or prepolymers). It is also possible to mention compounds having both an oxirane group and a free radical polymerizable group (such as an acrylate group), such as epoxy (meth) acrylate resins. Glycidyl ether epoxy compounds (especially aliphatic glycidyl ether epoxy compounds, bisphenol A type glyceryl ether epoxy compounds) and aliphatic epoxy resins are preferred. In addition, compounds having both an oxirane group (such as an alicyclic oxirane group or a glycidyl ether group) and an alkyl (meth) acrylate structure are preferred.

[0046] As examples of these oxirane compounds, there may be mentioned 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate (ERL-4211), bis(3,4-epoxycyclohexylmethyl) adipate (UVR-6128), trimethylolpropane glycidyl ether (TPEG), 1,2-epoxy-4-vinylcyclohexane, 3,4-epoxycyclohexanecarboxylic acid methyl ester, 4,5-epoxycyclohexane-1,2-dicarboxylic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, Acid diglycidyl ester, bisphenol A diglycidyl ether (E-03 type), 3-oxiranyl 7-oxabicyclo [4,1,0] heptane, ethylene glycol diglycidyl ether, C12-C14 alkyl glycidyl ether, polypropylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polyether polyol glycidyl ether, methacrylate glycidyl ester, trimethylol triglycidyl ether, 1,4-butanediol diglycidyl ether, and their oligomers or copolymers and other multifunctional epoxy compounds, and EPIKOTE Resin 862, EPIKOTE Resin 827, EPIKOTE Resin 869, EPIKOTE Resin 320, EPIKOTE Resin 816, EPIKOTE Resin 232, EPIKOTE Resin 144, etc. These compounds can be used alone or in combination.

[0047] Specifically, optional examples of the aziridine monomer include, but are not limited to, trimethylolpropane-tris-β-aziridine propionate, tetramethylolmethane-tris-β-aziridine propionate, or N,N-hexamethylene-1,6-bis-1-aziridine carboxamide.

[0048] Specifically, the optional examples of the oxetane compounds include, but are not limited to, 3,3'-(oxybismethylene)bis(3-ethyl)oxetane (GR-OXT-03), 3-ethyl-3-oxetane methanol, bis[(3-methyl-3-oxetanylmethoxy)methyl]ether, bis[(3-ethyl-3-oxetanylmethoxy)methyl]ether, 1,4-bis[(3-methyl-3-oxetanylmethoxy)methyl]benzene, 1,4-bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene, (3-methyl-3-oxetanyl)methyl acrylate, (3-ethyl-3-oxetanyl)methyl acrylate, (3-methyl-3-oxetanyl)methyl methacrylate, and methyl acrylate. 3-Ethyl-3-oxetanyl)methyl ester, 3-Methyl-3-vinylhydroxymethyloxetane, 3-Methyl-3-vinylhydroxypolyethoxylated methyloxetane, 1,4-bis(3-ethyl-3-oxetanylmethoxy)butane, 1,6-bis(3-ethyl-3-oxetanylmethoxy)hexane, pentaerythritol tris(3-ethyl-3-oxetanylmethyl)ether, 3-methyl-3-hydroxymethyloxetane, 3-ethyl-3-hydroxymethyloxetane, 1,3-bis[(3-ethyl-3-oxetanylmethoxy)methyl]propane, polyethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, isobutyloxymethyl(3-ethyl-3-oxetanylmethyl) ) ether, ethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether, tricyclodecanediyl dimethylene(3-ethyl-3-oxetanylmethyl) ether, trimethylolpropane tris(3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetra(3-ethyl-3-oxetanylmethyl) ether, 3-oxiranyl 7-oxabicyclo[4.1.0]heptane, and 3-ethyl-3-oxetanemethanol (GR-OXT-01), 3-ethyl-3-chloromethyloxetane (GR-OXT-02), 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane (GR-OXT-04), 3,3'-((((propane-2,2-diylbis(4,1 -phenylene))bis(oxy))bis(methylene))bis(3-ethyloxetane) (GR-OXT-05), 3-ethyl-3-(benzyloxymethyl)oxetane (GR-OXT-06), methacrylate oxetane (GR-OXT-09), bis[(3-ethyloxetane-3-yl)methyl]benzene-1,4-dicarboxylate (GR-OXT-11), etc., or a combination of two or more thereof, their oligomers or copolymers, and polyfunctional oxetane compounds, and ethers of oxetane alcohol and resins having hydroxyl groups such as novolac resins, poly(p-hydroxystyrene), Cardo-type bisphenols, calixarene, resorcinol calixarene, or silsesquioxane.In addition, there are compounds having both an oxetane structure and an alkyl (meth)acrylate structure.

[0049] In a specific embodiment, based on the total weight of the photocurable composition being 100 wt %, the photocurable composition comprises: 1 to 30 wt % of cyclic sulfide cationic photopolymerizable monomer, 0.1 to 10 wt % of photopolymerization initiator, and 5 to 90 wt % of photopolymerizable compound.

[0050] In a preferred embodiment, based on the total weight of the photocurable composition being 100 wt %, the photocurable composition comprises: 5 to 15 wt % of cyclic sulfide cationic photopolymerizable monomer, 0.1 to 5 wt % of photopolymerization initiator, and 10 to 60 wt % of photopolymerizable compound.

[0051] In a specific embodiment, the photocurable composition further comprises 0.1 to 50 wt % of additives.

[0052] In a preferred embodiment, the photocurable composition further comprises 1 to 5 wt % of additives.

[0053] In a specific embodiment, optional examples of the additives include, but are not limited to, any one or more of polymer resins, leveling agents, defoamers, plasticizers, light and heat stabilizers, adhesion promoters, antioxidants, colorants, pigments, inorganic fillers, and high refractive index materials in any proportion.

[0054] In a specific embodiment, the photocurable composition further comprises 0.1-10 wt % of a sensitizer. The sensitizer is added to improve the compatibility between the cationic photoinitiator and the light source.

[0055] In a preferred embodiment, the photocurable composition further comprises 0.5 to 5 wt % of a sensitizer.

[0056] In a specific embodiment, the sensitizer can be anthracene compounds, thioxanthone compounds, coumarin compounds, coumarin keto compounds, anthraquinone compounds, etc. For example, isopropylthioxanthone (ITX), 9,10-dibutoxyanthracene (PSS303), etc. Adding a sensitizer is used to improve the compatibility of the photoinitiator and the light source, and can improve the initiation efficiency of iodonium salt compounds, sulfonium salt compounds, and triazine compounds.

[0057] Another aspect of the present application provides a use of the photocurable composition as described above in ink, coating, adhesive, or color photoresist.

[0058] Another aspect of the present application provides a photoresist prepared from the above-mentioned photocurable composition.

[0059] In a specific embodiment, the photocurable composition may further include a solvent. Any solvent that can dissolve or disperse the above-mentioned components may be used, and the present invention is not limited thereto. Examples include alkylene glycol monoalkyl ethers, alkylene glycol alkyl ether acetates, aromatic hydrocarbons, ketones, lower and higher alcohols, cyclic esters, and the like. More specifically, as the solvent, there may be listed alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether; diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether; methoxyethyl acetate, ethoxyethyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate Alkylene glycol alkyl ether acetates such as ester, methoxybutyl acetate and methoxypentyl acetate; aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene, etc.; ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, cyclohexanone, etc.; alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerol, etc.; esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate; cyclic esters such as γ-butyrolactone, etc.

[0060] The present invention is further described below in conjunction with the embodiments. Obviously, the described embodiments are only a part of the embodiments of the present invention, not all of the embodiments, and are not limitations of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in the field without creative work are within the scope of protection of the present invention.

[0061] Unless otherwise specified, the test materials, reagents, methods and equipment used in the following examples are conventional test materials, reagents, methods and equipment in the technical field; unless otherwise specified, the test materials and reagents used in the following examples can be obtained from commercial sources. The quantitative tests in the following examples were all repeated three times, and the data are the average or average ± standard deviation of the three repeated experiments.

[0062] Synthesis Example 1-3, the general reaction formula is as follows:

[0063]

[0064] Synthesis Example 1:

[0065] Reaction step ①: dissolve isophorone diisocyanate IPDI (13.34 g, 0.06 mol) in 20 ml of N, N-dimethylacetamide (DMA), pour into a three-necked round-bottom flask equipped with a mechanical stirrer, a dropping funnel, a condenser and a drying tube, pass nitrogen protection and add a catalyst 0.1 wt% dibutyltin dilaurate (DBDTL), slowly drop a DMA (10 ml) solution dissolved with thiopropanol (5.50 g, 0.061 mol) into the reactor, and stir at 50° C. for 12 h to obtain a reaction product;

[0066] Reaction step ②: Slowly drop a solution of trimethylolpropane (0.28 g, 0.021 mol) in DMA (5 ml) into the product of reaction ①, add 0.1 wt% DBDTL, stir at 90°C for 24 h until the infrared spectrum -NCO group signal disappears, and after the reaction mixture is cooled, pour it into a large amount of distilled water for precipitation, remove the solvent, and dry it in a vacuum oven to obtain a trifunctional episulfide compound A-1.

[0067] Synthesis Examples 2 and 3 are similar to Synthesis Example 1, except that pentaerythritol and dipentaerythritol are used instead of trimethylolpropane to obtain tetrafunctional episulfide compound A-2 and hexafunctional episulfide compound A-3, respectively.

[0068] The raw materials used in preparing the photocurable compositions in the examples and comparative examples are as follows:

[0069] (A) cyclic sulfide cationic photopolymerizable monomer,

[0070] Episulfide compounds A-1, A-2 and A-3 conforming to the structure of formula (I).

[0071] (B) a photopolymerization initiator,

[0072] 4,4'-Dimethylphenyl iodide hexafluorophosphate (PAG-30101) was purchased from Changzhou Qiangli;

[0073] 4-(Phenylthio)phenyl diphenylsulfide hexafluorophosphate (PAG-20101) was purchased from Changzhou Qiangli;

[0074] Isopropylthioxanthone (ITX) was purchased from Tianjin Jiuri;

[0075] 9,10-Dibutoxyanthracene (PSS303) was purchased from Changzhou Qiangli.

[0076] (C) a cationically polymerizable compound,

[0077] 3,4-Epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate (UVR-6110) was purchased from Hubei Xinjing;

[0078] 3,3'-(Oxybis(methylene)bis(3-ethyl)oxetane (DOX) was purchased from Changzhou Qiangli.

[0079] Examples 1 to 7 and Comparative Examples 1 to 2 respectively provide a photocurable composition, and the specific amounts of the components are shown in Table 1 below (unit: wt %).

[0080] Table 1:

[0081]

[0082]

[0083] The preparation method of the photocurable composition of the embodiments and comparative examples can be conventional mechanical blending, but is not limited thereto.

[0084] The photocurable compositions prepared in the examples and comparative examples were coated on aluminum foil by blade coating, with a coating thickness of about 20.0 μm. Then, a 365 nm LED light was irradiated onto the coating with a light intensity of 100 mJ / cm 2 , light irradiation time 30 seconds. After the light-cured coating is prepared by the above method, the performance of the light-cured coating is evaluated, and the performance evaluation method is as follows:

[0085] (1) Dryness to touch test

[0086] Test method: Touch the light-cured coating with your finger, and then observe its dryness and surface condition with your naked eye;

[0087] Test evaluation criteria:

[0088] ●: The coating has no indentation at all, and the film is smooth without fingerprint marks;

[0089] ▲: The coating has slight indentations and fingerprint marks, but they are not obvious;

[0090] ╳: There are obvious indentations on the coating and obvious fingerprint marks.

[0091] (2) Adhesion test

[0092] Test method: The adhesion of the sample is tested by the 100-grid method. A cutting tool is used to cut the inkjet ink coating to the surface of the substrate to form a grid-shaped scratch. Then, 3M tape is used to stick and tear off the surface, and the coating shedding is observed. Then, the adhesion of the coating is evaluated.

[0093] Test evaluation criteria:

[0094] ●: High adhesion, no coating peeling;

[0095] ▲: Average adhesion, with slight corner loss but no flakes falling off;

[0096] ╳: Poor adhesion and obvious coating peeling.

[0097] (3) Pencil hardness test

[0098] Test method: Place the pencil hardness tester ACE-B3084 on the board to be tested, and push it forward at a speed of about 1 cm per second with force (the force may break the edge of the lead or scratch the coating). Starting from the hardest pencil, make five 5 cm long marks with each level of pencil until a pencil that does not scratch the coating is found. The hardness of this pencil represents the pencil hardness of the coating being tested.

[0099] Test evaluation criteria:

[0100] ●: Pencil hardness test reaches or exceeds 3H standard;

[0101] ▲: Pencil hardness test reaches or exceeds 1H standard, less than 3H;

[0102] ╳: Pencil hardness test is less than 1H standard.

[0103] (4) Flexibility evaluation

[0104] Test method: Test according to GB / T 1731 standard. Wrap the cured coating around a shaft with a curvature radius of 5 mm. Visually observe whether the coating has reticulation, cracks, peeling, etc.

[0105] Test evaluation criteria:

[0106] ●: No reticulation, cracks, peeling, etc.;

[0107] ▲: There are a few reticulations, cracks, peeling and other phenomena;

[0108] ╳: There are a lot of reticulation, cracks, peeling and other phenomena.

[0109] The performance test results of the photocurable compositions of the examples and comparative examples are shown in Table 2 below.

[0110] Table 2:

[0111]

[0112]

[0113] It can be seen from Table 2 above that when the cyclic sulfide cationic photopolymerizable monomer of the present invention is applied to the photocurable composition, the photocurable composition has a fast curing speed and high curing efficiency, and the obtained cured coating has excellent hardness and flexibility and good adhesion.

[0114] The preferred embodiments of the present invention are described in detail above. However, the present invention is not limited to the specific details in the above embodiments. Within the technical concept of the present invention, a variety of simple modifications can be made to the technical solution of the present invention, and these simple modifications all belong to the protection scope of the present invention.

[0115] It should also be noted that the various specific technical features described in the above specific embodiments can be combined in any suitable manner without contradiction. In order to avoid unnecessary repetition, the present invention will not further describe various possible combinations.

[0116] In addition, various embodiments of the present invention may be arbitrarily combined, and as long as they do not violate the concept of the present invention, they should also be regarded as the contents disclosed by the present invention.

Claims

1. A cyclic sulfide cationic photopolymerizable monomer, characterized in that: The general structural formula of the cyclic sulfide cationic photopolymerizable monomer is shown in formula (I): In formula (I), R is a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aromatic group, or any combination of these groups, and n≥3.

2. A photocurable composition comprising a photopolymerization initiator and a photopolymerizable compound, characterized in that: It also includes the cyclic sulfide cationic photopolymerizable monomer described in claim 1.

3. The photocurable composition according to claim 2, characterized in that: The photopolymerization initiator is at least one of an iodonium salt compound, a sulfonium salt compound, and a triazine compound.

4. The photocurable composition according to claim 3, characterized in that The chemical structure of the iodonium salt compound is shown in the following formula (II): In formula (II), R1 and R2 are the same or different and are independently selected from H, C1-C20 branched or unbranched alkyl, C1-C20 branched or unbranched alkoxy, C1-C20 branched or unbranched alkylthio; X - Select one of the following ions: BF4 - PF6 - 、SbF6 - 、AsF6 - 、[PF3(C2F5)3] - 、[Al(OC(CF3)3)4] - , [B(PhF5)4] - 、[B(Ph(CF3)2)4] - 、[((CF3)2SO2)2N] - 、[((CF3)2SO2)3C] - , Cl - Br - 、F - 、[Al(Ot-C4F9)4] - 、[Al(O-(i-C3F7)CH3)4] - 、[C(O-SO2CF3)3] - 、[nC 12 H 25- TsO - , [NTf2] - .

5. The photocurable composition according to claim 2, characterized in that: The photopolymerizable compound is a cationic polymerizable compound; the cationic polymerizable compound is at least one of an alkenyl ether compound, an oxirane compound, an aziridine compound, and an oxetane compound.

6. The photocurable composition according to claim 2, characterized in that: Based on the total weight of the photocurable composition being 100 wt %, the photocurable composition comprises: 1 to 30 wt % of cyclic sulfide cationic photopolymerizable monomer, 0.1 to 10 wt % of photopolymerization initiator, and 5 to 90 wt % of photopolymerizable compound.

7. The photocurable composition according to claim 6, characterized in that: The photocurable composition further comprises 0.1 to 50 wt % of additives.

8. The photocurable composition according to claim 6, characterized in that: The photocurable composition further comprises 0.1 to 10 wt % of a sensitizer.

9. Use of the photocurable composition according to any one of claims 2 to 8 in ink, coating, adhesive or color photoresist.

10. A photoresist prepared from the photocurable composition according to any one of claims 2 to 8.

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