Cationic photo-curable compositions and their use

Abstract

The application provides a cationic photocuring composition and application thereof. The cationic photocuring composition comprises component A and component B. The component A has a structure shown in a formula, and the component B is a cationic reactive compound. The cationic photocuring composition of the application has higher responsiveness in the wavelength range of 200-500 nm based on the synergistic cooperation between the specific cationic initiator and the cationic reactive compound, has better adhesion to different printing materials, and does not have initiator migration, so that the application of the cationic photocuring composition of the application is more extensive.

Description

Technical Field

[0001] This invention relates to the field of photocuring, and more specifically, to a cationic photocurable composition and its application. Background Technology

[0002] Due to environmental protection requirements, photocurable coatings and inks have become a rapidly emerging industry that has garnered significant attention in recent years. Compared to traditional solvent-based coatings and inks, photocurable systems offer advantages such as high production efficiency, environmental friendliness, energy saving, and good adaptability. Compared to photocurable free radical and hybrid systems, cationic systems offer advantages such as smaller volume, less susceptibility to oxygen inhibition, better substrate adhesion, stronger post-curing properties, and lower odor. However, most existing cationic photocurable systems suffer from the following problems:

[0003] (1) During the curing process of the existing cationic photocurable system, there is a problem of small molecule component residue, which leads to incomplete curing of the system, resulting in poor adhesion of this cationic coating / ink product on the substrate and residual odor after curing.

[0004] (2) The absorption wavelength of most existing cationic photocuring systems is between 200 and 300 nm. However, some commercially available high-wavelength light sources such as UV-LED, mercury lamp, and electrodeless lamp have wavelengths of 365 nm, 385 nm, 395 nm, and 405 nm. Therefore, most existing photocuring products have low compatibility with this type of light source, resulting in low initiation efficiency.

[0005] (3) In the existing cationic coating ink system, there is a problem of initiator fragment residue during the curing process, namely benzene residue or initiator migration, which causes contamination of the substrate and limits its application areas. For example, its application in food packaging, daily necessities packaging, and printing is limited.

[0006] In summary, existing cationic photocurable systems suffer from poor responsiveness in the 200–500 nm wavelength range, or the presence of small molecule residues, resulting in incomplete curing on production lines, odor residue, poor adhesion, poor storage stability, or initiator migration within the system. These issues limit the application and promotion of cationic photocurable products, especially in fields with high environmental requirements such as food packaging, daily necessities packaging, and printing.

[0007] Therefore, it is necessary to provide a cationic photocurable composition that exhibits excellent responsiveness in the 200–500 nm wavelength range, complete curing on the production line, and no benzene residue or initiator migration after curing, which can be applied to paints, coatings, inks, and molding materials, especially in the printing of food and daily necessities packaging. Summary of the Invention

[0008] The main objective of this invention is to provide a cationic photocurable composition and its application, in order to solve the problems of low responsiveness, poor adhesion, or initiator migration in the 200-500 nm wavelength range of existing cationic photocurable systems.

[0009] To achieve the above objectives, according to one aspect of the present invention, a cationic photocurable composition is provided, comprising the following components: component A: a cationic initiator; component B: a cationic reactive compound; the cationic initiator is a thionium salt photoinitiator, which is a compound represented by general formula I and / or a macromolecular compound with the structure represented by general formula I as a polymerization unit; the cationic reactive compound is a reactive compound containing epoxy groups and / or a reactive compound containing alkenyl ether groups, wherein general formula I is as follows:

[0010]

[0011] In general formula I, R1, R3, and R6 are electron-withdrawing groups, R2, R4, and R5 are amplifying groups, and X... - It is a non-nucleophilic anion; and when the thioonium salt photoinitiator is a macromolecular compound, the compounds of general formula I corresponding to each polymerization unit may be the same or different.

[0012] Further, in general formula I, R1, R3, and R6 are each independently selected from halogen, cyano, nitro, alkoxy, haloalkyl, acyl, acyloxy, or sulfonyl; preferably, R1, R3, and R6 are each independently selected from halogen, cyano, nitro, haloalkyl, or acyl; R2, R4, and R5 are each independently selected from hydrogen, halogen, nitro, cyano, hydroxyl, acyl, acyloxy, sulfonyl, alkyl, substituted alkyl, alkoxy, substituted alkoxy, aryl, substituted aryl, aralkyl, or substituted aralkyl; optionally, -CH2- in R2, R4, and R5 can be replaced by -O-, -S-, or -CH=CH-.

[0013] Further, in general formula I, the halogen is fluorine, chlorine, bromine, or iodine; preferably, the halogen is fluorine; the alkoxy group is a C1-C8 straight-chain or branched alkoxy group; preferably, the alkoxy group is a C1-C4 straight-chain or branched alkoxy group; more preferably, the alkoxy group is methoxy, ethoxy, or propoxy; the alkyl group is a C1-C8 straight-chain, branched, or cyclic alkyl group; preferably, the alkyl group is selected from C1-C4 straight-chain or branched alkyl groups, or C3-C6 cyclic alkyl groups; the haloalkyl group is a C1-C8 straight-chain alkyl group in which at least one hydrogen atom is substituted by a halogen, or a C3-C8 branched or cyclic alkyl group; preferably, the haloalkyl group is methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, isopropyl, isobutyl, or tert-butyl alkyl groups in which at least one hydrogen atom is substituted by a halogen. Butyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl; more preferably, the haloalkyl group is a C1-C4 perfluoroalkyl group; in the substituted alkyl group, the substituent is a halogen, amino, or hydroxyl group, and the alkyl group is a C1-C4 straight-chain or branched alkyl group, or a C3-C6 cyclic alkyl group; preferably, the alkyl group is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, tert-pentyl, neopentyl, n-hexyl, isohexyl, 3-methylpentyl, 2-methylpentyl, 1,2-dimethylbutyl, cyclopropyl, cyclopentyl, or cyclohexyl; the sulfonyl group is methanesulfonyl, difluoromethanesulfonyl, trifluoromethanesulfonyl, benzenesulfonyl, or toluenesulfonyl; the acyl group is a C2-C8 aliphatic acyl group or a C7-C6 cycloalkyl group. 12 The aromatic acyl group; preferably, the acyl group is acetyl, propionyl, butyryl, valeryl, isovaleryl, hexanoyl, octanoyl, heptayl, benzoyl, methylbenzoyl, trimethylbenzoyl, α-phenylpropionyl, or naphthyl; the aryl group is phenyl, naphthyl, anthraceneyl, or pyrene; preferably, the substituents in the substituted aryl group are C1-C4 alkyl, halogen, C1-C3 alkoxy, acyl, sulfonyl, hydroxyl, amino, nitro, or phenyl; preferably, the C1-C4 alkyl group is methyl, ethyl, propyl, or butyl; preferably, the halogen is fluorine, chlorine, bromine, or iodine; preferably, the C1-C3 alkoxy group is methoxy or ethoxy. The alkyl group is a propoxy group; the alkyl group is an alkyl group terminated with an aryl group, preferably a C1-C6 alkylene group, preferably a C1-C6 alkylene group, preferably a methylene group or an ethylene group; more preferably, the alkyl group is benzyl, phenethyl or phenylpropyl, optionally, at least one hydrogen atom on the phenyl group is substituted by a substituent, the substituent being a C1-C4 alkyl group, a halogen, a C1-C3 alkoxy group, an acyl group, a sulfonyl group, a hydroxyl group, an amino group, a nitro group, or a phenyl group; preferably the C1-C4 alkyl group is methyl, ethyl, propyl or butyl; preferably the halogen is fluorine, chlorine, bromine or iodine, preferably the C1-C3 alkoxy group is methoxy, ethoxy or propoxy.

[0014] Furthermore, in general formula I, X - For M - ClO4 - CN- HSO4 - NO3 - CF3COO - (BM4) - (SbM6) - (AsM6) - (PM6) )- Al[OC(CF3)3]4 - R6SO3 - (R6SO2)3C - (R6SO2)2N - B(C6M5)4 - Ga(C6M5)4 - Or [(Rf)bPF] 6-b ] - Wherein, M is a halogen, preferably fluorine; R6 is a C1-C halogen. 20 Alkyl, C1-C 20 Perfluoroalkyl, C6-C 20 aryl or substituted aryl;

[0015] Rf is an alkyl group in which ≥80% of the hydrogen atoms are replaced by fluorine atoms. Preferably, the alkyl group in Rf is methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, isopropyl, isobutyl, sec-butyl, tert-butyl, or cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, or cyclohexyl. Preferably, Rf is an alkyl group in which ≥90% of the hydrogen atoms are replaced by fluorine atoms, more preferably 100%. Preferably, Rf is CF3. - CF3CF2 - (CF3)2CF - CF3CF2CF2 - CF3CF2CF2CF2 - (CF3)2CFCF2 - CF3CF2(CF3)CF - and (CF3)3C - ;

[0016] b is an integer from 1 to 5, and the b Rf groups can be the same or different from each other.

[0017] Furthermore, thionium salt photoinitiators are

[0018]

[0019]

[0020] One or more of them.

[0021] Furthermore, the functionality of the cationic reactive compound is 2 to 3; preferably, the molecular weight of the cationic reactive compound is greater than 200 g / mol, more preferably greater than 350 g / mol.

[0022] Further, by weight percentage, the content of component A in the composition is 1 to 15 wt%; preferably, the content of component A is 1 to 10 wt%; more preferably, the content of component A is 2 to 7 wt%.

[0023] Furthermore, the composition further includes component C, which includes pigments and optional fillers; preferably, the amount of pigment is 0.06 to 20 times the weight of component A; more preferably, the amount of pigment is 0.2 to 15 times the weight of component A; preferably, the amount of filler is 0.001 to 30 times the weight of component A; more preferably, the amount of filler is 0.15 to 20 times the weight of component A.

[0024] Further, the pigment is an inorganic pigment or an organic pigment. The organic pigment is one or more of the following: dinaphthalene-phthalocyanine, phthalocyanine dye, cyanine pigment, naphthalene-phthalocyanine pigment, nitroso pigment, azo pigment, diazo pigment, diazo condensation pigment, basic dye pigment, basic blue pigment, indigo pigment, root bark red pigment, quinacridone pigment, isoindolinone pigment, dioxazine pigment, carbazolium dioxazine violet pigment, alizarin lake pigment, phthalamide pigment, carmine lake pigment, tetrachloroisoindolinone pigment, violet ketone pigment, anthraquinone pigment, and quinophthalone pigment. The inorganic pigment is one or more of the following: metal oxide, iron oxide, aluminum oxide, silicon oxide, carbon black pigment, metal sulfide, and metal chloride. Preferably, the filler is at least one of the following: nano-calcium carbonate, aluminum hydroxide, barium sulfate, silicon dioxide, talc, and kaolin.

[0025] Furthermore, the composition further includes an optional component D, which is an adjuvant and / or a sensitizer; preferably, the amount of the adjuvant is 0.001 to 5 times the weight of component A; more preferably, the amount of the adjuvant is 0.001 to 3 times the weight of component A; preferably, the amount of the sensitizer is 0.001 to 5 times the weight of component A; more preferably, the amount of the sensitizer is 0.001 to 2 times the weight of component A.

[0026] Further, the sensitizer is a pyrazoline compound, an acridine compound, anthracene compound, a coumarin compound, or a tertiary amine compound; preferably, the anthracene compound is of general formula II. and / or general formula III One or more combinations of the compounds shown, wherein in general formula II, R8 is C1-C 12 Alkyl, C1-C 12 aryl, C1-C8 alkoxy or aryloxy, C3-C 12cycloalkyl, C4-C 12 The alkyl, cycloalkyl, or cycloalkylalkyl groups, wherein one or more hydrogen atoms in these groups may be replaced by halogens or hydroxyl groups, and X1 and Y1 are each independently hydrogen, alkyl, alkoxy, halogen, nitro, sulfonic acid, hydroxyl, or amino groups; in general formula III, R9 is C1-C 12 Alkyl, C1-C 12 aryl, C1-C8 alkoxy or aryloxyC3-C 12 cycloalkyl, C4-C 12 The anthracene compound is an alkyl, cycloalkyl, or cycloalkylalkyl group, wherein one or more hydrogen atoms in these groups may be replaced by halogens or hydroxyl groups; n1 and n2 are each independently integers from 0 to 4; X2 and Y2 may be the same or different, and are each independently hydrogen, alkyl, alkoxy, halogen, nitro, sulfonic acid, hydroxyl, or amino group; when n1 and n2 are 2 or more, X2 and Y2 may be the same or different from each other; preferably, the anthracene compound may be one or more combinations of the following compounds:

[0027]

[0028]

[0029] To achieve the above objectives, according to one aspect of the present invention, the aforementioned cationic photocurable composition is provided as an application in paints, coatings, inks, and molding materials.

[0030] The cationic photocurable composition of the present invention is based on a specific cationic initiator and a cationic reactive compound (synergistically, it has higher responsiveness in the wavelength range of 200-500nm, better adhesion to different substrates, and no initiator migration, which makes the cationic photocurable composition of the present invention more widely applicable and can be used in paints, coatings, inks and molding materials, especially in the printing of food, daily necessities and other packaging. Detailed Implementation

[0031] 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.

[0032] The main objective of this invention is to provide a cationic photocurable composition and its application, in order to solve the problems of low responsiveness, poor adhesion, or initiator migration in the 200-500 nm wavelength range of existing cationic photocurable systems.

[0033] To achieve the above objectives, according to one aspect of the present invention, a cationic photocurable composition is provided, comprising the following components: component A: a cationic initiator; component B: a cationic reactive compound; the cationic initiator is a thiamonium salt photoinitiator, which is a compound represented by general formula I and / or a macromolecular compound with the structure represented by general formula I as a polymerization unit; the cationic reactive compound is a reactive compound containing epoxy groups and / or a reactive compound containing alkenyl ether groups, and the reactive compound is a monomer, a prepolymer, or a reactive resin; wherein, general formula I is as follows:

[0034]

[0035] In general formula I, R1, R3, and R6 are electron-withdrawing groups, R2, R4, and R5 are amplifying groups, and X... - It is a non-nucleophilic anion; and when the thioonium salt photoinitiator is a macromolecular compound, the compounds of general formula I corresponding to each polymerization unit may be the same or different.

[0036] The cationic photocurable composition provided by this invention employs a cationic initiator with a specific structure, namely a thioonium salt photoinitiator, which is a compound represented by general formula I and / or a macromolecular compound with the structure represented by general formula I as the polymerization unit. This cationic initiator is synergistically combined with a specific type of cationic reactive compound (reactive compounds containing epoxy groups and / or reactive compounds containing alkenyl ether groups). The resulting cationic photocurable composition has an absorption wavelength in the range of 200–500 nm, exhibiting higher compatibility with existing light sources on the market (UV-LED, mercury lamp, electrodeless lamp, etc.), higher initiation efficiency, and better responsiveness. Furthermore, based on the above synergistic effect, the cationic photocurable composition has no small molecule residue, resulting in more complete curing during subsequent curing processes. This leads to better adhesion of the composition when applied to different substrates, especially when used as a coating / ink product, where it exhibits better adhesion and no odor residue on the corresponding substrate. Furthermore, the present invention, based on the selection and combination of the aforementioned specially structured thiamonium salt photoinitiator and cationic reactive compound structure, avoids the problems of benzene residue or initiator migration commonly found in existing cationic photocuring systems. This makes the composition more widely applicable and has better versatility, especially in food packaging, daily necessities packaging, and printing. In addition, when electron-withdrawing groups R1, R3, and R6 are present at the meta position of the benzene ring group in the thiamonium salt photoinitiator, the introduction of amplifying groups R2, R4, and R5 at the para position can further enhance the solubility and / or photosensitivity of the compound, improving these properties without adversely affecting other properties.

[0037] In summary, the cationic photocurable composition of the present invention is based on specific cationic initiators and cationic reactive compounds (synergistically working together), exhibiting higher responsiveness in the 200-500 nm wavelength range, better adhesion to various substrates, and no initiator migration, thus making the cationic photocurable composition of the present invention more widely applicable.

[0038] It should also be noted here that "when the thioonium salt photoinitiator is a macromolecular compound, the general formula I compounds corresponding to each polymerization unit are the same or different" means that the macromolecular compound can be obtained by polymerizing at least two general formula I compounds that are the same (R1 to R6 substituent groups are the same), or it can be obtained by polymerizing at least two general formula I compounds that are different (R1 to R6 substituent groups are different at least once).

[0039] To further improve the overall performance of the above-mentioned cationic photocurable composition, preferably, in general formula I, R1, R3, and R6 are independently selected from halogen, cyano, nitro, alkoxy, haloalkyl, acyl, acyloxy, or sulfonyl groups. More preferably, R1, R3, and R6 are independently selected from halogen, cyano, nitro, haloalkyl, or acyl groups. R2, R4, and R5 are independently selected from hydrogen, halogen, nitro, cyano, hydroxyl, acyl, acyloxy, sulfonyl, alkyl, substituted alkyl, alkoxy, substituted alkoxy, aryl, substituted aryl, aralkyl, or substituted aralkyl groups. Optionally, the -CH2- group in R2, R4, and R5 can be replaced by -O-, -S-, or -CH=CH-. Using the above groups as substituents for R1 to R6 is beneficial for further improving the response of the cationic photocurable composition. At the same time, it provides better compatibility between the components and facilitates processing.

[0040] Considering factors such as photocuring performance, adhesion of the cured material, mechanical properties, and improved stability, more preferably, in general formula I, the halogen is fluorine, chlorine, bromine, or iodine; more preferably, the halogen is fluorine. The alkoxy group is a C1-C8 straight-chain or branched alkoxy group. Preferably, the alkoxy group is a C1-C4 straight-chain or branched alkoxy group; more preferably, the alkoxy group is methoxy, ethoxy, or propoxy; the alkyl group is a C1-C8 straight-chain, branched, or cyclic alkyl group. Preferably, the alkyl group is selected from C1-C4 straight-chain or branched alkyl groups, or C3-C6 cyclic alkyl groups. The haloalkyl group is a C1-C8 straight-chain alkyl group in which at least one hydrogen atom is substituted with a halogen, or a C3-C8 branched or cycloalkyl group; preferably, the haloalkyl group is methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, isopropyl, isobutyl, sec-butyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, or cyclohexyl; more preferably, the haloalkyl group is a C1-C4 perfluoroalkyl group; in the substituted alkyl group, the substituent is a halogen, amino, or hydroxyl group, and the alkyl group is a C1-C4 straight-chain alkyl group. The alkyl group is a chain or branched alkyl group, or a C3-C6 cyclic alkyl group; preferably, the alkyl group is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, tert-pentyl, neopentyl, n-hexyl, isohexyl, 3-methylpentyl, 2-methylpentyl, 1,2-dimethylbutyl, cyclopropyl, cyclopentyl, or cyclohexyl; the sulfonyl group is methanesulfonyl, difluoromethanesulfonyl, trifluoromethanesulfonyl, benzenesulfonyl, or toluenesulfonyl; the acyl group is a C2-C8 aliphatic acyl group or a C7-C6 cyclic acyl group. 12 The aromatic acyl group; preferably, the acyl group is acetyl, propionyl, butyryl, valeryl, isovaleryl, hexanoyl, octanoyl, heptayl, benzoyl, methylbenzoyl, trimethylbenzoyl, α-phenylpropionyl, or naphthyl; the aryl group is phenyl, naphthyl, anthraceneyl, or pyrene; preferably, the substituents in the substituted aryl group are C1-C4 alkyl, halogen, C1-C3 alkoxy, acyl, sulfonyl, hydroxyl, amino, nitro, or phenyl; preferably, the C1-C4 alkyl group is methyl, ethyl, propyl, or butyl; preferably, the halogen is fluorine, chlorine, bromine, or iodine; preferably, the C1-C3 alkoxy group is methoxy or ethoxy. The alkyl group is a propoxy group; the alkyl group is an alkyl group terminated with an aryl group, preferably a C1-C6 alkylene group, and more preferably a C1-C6 alkylene group is methylene or ethylene; more preferably, the alkyl group is benzyl, phenethyl, or phenylpropyl; optionally, at least one hydrogen atom on the phenyl group is substituted by a substituent, which is a C1-C4 alkyl group, a halogen, a C1-C3 alkoxy group, an acyl group, a sulfonyl group, a hydroxyl group, an amino group, a nitro group, or a phenyl group; preferably, the C1-C4 alkyl group is methyl, ethyl, propyl, or butyl; preferably, the halogen is fluorine, chlorine, bromine, or iodine, and preferably, the C1-C3 alkoxy group is methoxy, ethoxy, or propoxy. Among these, considering cost control and environmental performance, fluorine is preferred as the halogen.

[0041] Preferably, in general formula I, X - For M - ClO4 - CN - HSO4 - NO3 - CF3COO - (BM4) - (SbM6) - (AsM6) - (PM6) )- Al[OC(CF3)3]4 - R6SO3 - (R6SO2)3C - (R6SO2)2N - B(C6M5)4 - Ga(C6M5)4 - Or [(Rf)bPF] 6-b ] - Wherein, M is a halogen, preferably fluorine; R6 is a C1-C halogen. 20 Alkyl, C1-C 20 Perfluoroalkyl, C6-C 20 The alkyl group is an aryl or substituted aryl group; Rf is an alkyl group in which ≥80% of the hydrogen atoms are replaced by fluorine atoms, preferably methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, isopropyl, isobutyl, sec-butyl, tert-butyl, or cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, or cyclohexyl; preferably Rf is an alkyl group in which ≥90% of the hydrogen atoms are replaced by fluorine atoms, more preferably 100%, and the photosensitivity of the compound is better within these ranges. Preferably, Rf is CF3. - CF3 CF2 - (CF3)2CF - CF3CF2CF2 - CF3CF2CF2CF2 - (CF3)2CFCF2 - CF3CF2(CF3)CF - and (CF3)3C - b is an integer from 1 to 5, and the b Rf groups can be the same or different from each other. In this way, the synergistic effect of the above initiator and cationic reactive compound is better, and in the final application system, it can form a more stable and better-performing photocurable composition with other components.

[0042] It should be noted that the thionium salt photoinitiator described above in this invention can be obtained commercially or prepared by existing known methods. Specifically, the thionium salt photoinitiator can be prepared by referring to the methods described in CN111018764A and CN109134711A, the entire contents of which are incorporated herein by reference.

[0043] By way of example, in the novel cationic photocurable composition of the present invention, the thionium salt initiator of component A may include one or more of the compounds shown in the following structures:

[0044]

[0045]

[0046] To further improve the overall performance of the above-mentioned cationic photocurable composition, the cationic initiator is further preferred as follows: One or more of them.

[0047] From an environmental application perspective and to improve the curing effect (such as curing efficiency, adhesion, hardness, etc.) when used in combination, the cationic reactive compound is preferably 2-3 in functionality. More preferably, the cationic reactive compound has a molecular weight greater than 200 g / mol, and more preferably greater than 350 g / mol.

[0048] Based on improving the compatibility of the composition, such as curing efficiency, developability, film hardness, and substrate adhesion, the above-mentioned compounds containing epoxy groups are further preferably bisphenol A type epoxy resins, aliphatic glycidyl ether resins and other glycidyl ether epoxy resins, aliphatic epoxy resins, and oxetane compounds.

[0049] For example, the compound containing an epoxy group can be 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate, bis(3,4-epoxycyclohexylmethyl oxoacetate), trimethylolpropane glycidyl ether, 1,2-epoxy-4-vinylcyclohexane, bisphenol A type epoxy resin, 3-epoxyethylene 7-oxabicyclo[4,1,0]heptane, ethylene glycol diglycidyl ether, C 12 -C 14Alkyl glycidyl ether, 3-methyl-3-ethylene hydroxymethyloxetane, 3-methyl-3-ethylene hydroxypolyethoxylated methyloxetane, 1,4-bis(3-ethyl-3-oxetane alkyl methoxy)butane, 1,6-bis(3-ethyl-3-oxetane alkyl methoxy)hexane, pentaerythritol tris(3-ethyl-3-oxetane methyl) ether, 3-methyl-3-hydroxymethyloxetane, 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3(2-ethylhexyloxymethyl)oxetane, 1,3-bis[( The compound contains one or more of the following: 3-ethyl-3-oxetane(methoxy)methyl]propane, polyethylene glycol bis(3-ethyl-3-oxetane(methyl) ether, isobutoxymethyl(3-ethyl-3-oxetane(methyl) ether, ethylene glycol bis(3-ethyl-3-oxetane(methyl) ether, tricyclodecanediyldimethylene(3-ethyl-3-oxetane(methyl) ether), trimethylolpropane tri(3-ethyl-3-oxetane(methyl) ether, pentaerythritol tetra(3-ethyl-3-oxetane(methyl) ether, etc. In compounds containing an alkenyl ether group, the alkenyl ether can be a vinyl ether, 1-propenyl ether, 1-butenyl ether, 1-pentenyl ether, etc., preferably a vinyl ether. More preferably, the compound containing a vinyl ether group may be selected from one or more of the following: triethylene glycol divinyl ether, 1,4-cyclohexyldiethanol diethyl ether, 4-hydroxybutyl vinyl ether, glycerol carbonate vinyl ether, dodecyl vinyl ether, etc.

[0050] It should be noted that the cationic reactive compounds described above in this invention can be obtained commercially or prepared by existing known methods. Specifically, the cationic reactive compounds can be selected from at least two of the following: glycidyl ether epoxy resins, glycidyl ester epoxy resins, glycidyl amine epoxy resins, linear aliphatic epoxy resins, aliphatic epoxy resins, or oxetane compounds, as described in the specifications of patents 201610235083.1 and 201610238062.5.

[0051] To further improve the synergistic effect of the cationic initiator and the cationic reactive compound, and thus better balance the overall performance of the composition, the content of component A in the composition is 1-15 wt% by weight; preferably, the content of component A is 1-10 wt%; more preferably, the content of component A is 2-7 wt%; and the content of component B is 10-90 wt%; preferably, the content of component B is 40-90 wt%.

[0052] In a preferred embodiment, the composition further includes component C, which comprises pigments and optional fillers, depending on product requirements. Preferably, the amount of pigment is 0.06 to 20 times the weight of component A; more preferably, the amount of pigment is 0.2 to 15 times the weight of component A; preferably, the amount of filler is 0.2 to 30 times the weight of component A; even more preferably, the amount of pigment is 0.15 to 20 times the weight of component A. The pigment can be inorganic or organic and can be any color, including but not limited to black, blue, brown, cyan, green, white, purple, magenta, red, orange, and yellow, as well as spot colors of mixtures thereof. Suitable organic pigments include phthalocyanine dyes (e.g., phthalocyanine green, phthalocyanine blue), cyanine pigments (Cy3, Cy5, and Cy7), naphthalene phthalocyanine pigments, nitroso pigments, azo pigments, diazo pigments, diazo condensation pigments, basic dye pigments, basic blue pigments, indigo pigments, root bark red pigments, quinacridone pigments, isoindolinone pigments, dioxazine pigments, carbazolium dioxazine violet pigments, alizarin lake pigments, phthalamide pigments, carmine lake pigments, tetrachloroisoindolinone pigments, violet ketone pigments, anthraquinone pigments, and quinophthalone pigments, as well as mixtures of two or more of the above or their derivatives. Suitable inorganic pigments include, for example, metal oxides (e.g., titanium dioxide, conductive titanium dioxide), iron oxides (e.g., red iron oxide, yellow iron oxide, black iron oxide, and transparent iron oxide), aluminum oxides, silicon oxides, carbon black pigments, metal sulfides, metal chlorides, as well as mixtures of two or more of them.

[0053] There are no particular restrictions on the specific type of filler; conventional types from existing radiation-curing compositions can be used. Typically, fillers can be selected from one or more of nano-calcium carbonate, aluminum hydroxide, barium sulfate, silica, talc, and kaolin.

[0054] Preferably, the composition further includes an optional component D, which is an additive and / or sensitizer. Depending on the application requirements, the photocurable composition of the present invention may also selectively add commonly used organic and / or inorganic additives in the art, including but not limited to leveling agents, plasticizers, adhesion promoters, defoamers, fillers, surface conditioners, antioxidants, anti-coagulants, catalysts, dispersants, surfactants, thickeners, sensitizers, or crosslinking agents, as will be apparent to those skilled in the art. Furthermore, other sensitizers and / or photoinitiators may also be added to the composition for compound use, provided that they do not negatively impact the application effect of the composition.

[0055] Preferably, the amount of additive is 0.001 to 5 times the weight of component A; more preferably, the amount of pigment is 0.001 to 3 times the weight of component A.

[0056] Preferably, the amount of sensitizer is 0.001 to 5 times the weight of component A; more preferably, the amount of pigment is 0.001 to 2 times the weight of component A.

[0057] Preferably, a sensitizer may be added to the system to improve the photosensitivity of the photocurable composition. Especially when the radiation source is an LED, it is preferable to add a sensitizer to the photocurable composition. The sensitizer can be a pyrazoline compound, an acridine compound, anthracene compound, coumarin compound, tertiary amine compound, etc. As anthracene sensitizer compounds, compounds having the structure shown in formula (II) and / or (III) are particularly preferred: where the sensitizer is a pyrazoline compound, an acridine compound, anthracene compound, coumarin compound, or tertiary amine compound; preferably, the anthracene compound is of general formula II. and / or general formula III One or more combinations of the compounds shown,

[0058] In general formula II, R8 is C1-C 12 Alkyl, C1-C 12 aryl, C1-C8 alkoxy or aryloxy, C3-C 12 cycloalkyl, C4-C 12 The alkyl, cycloalkyl, or cycloalkylalkyl groups, wherein one or more hydrogen atoms in these groups may be replaced by halogens or hydroxyl groups, and X1 and Y1 are each independently hydrogen, alkyl, alkoxy, halogen, nitro, sulfonic acid, hydroxyl, or amino groups; in general formula III, R9 is C1-C 12 Alkyl, C1-C 12 aryl, C1-C8 alkoxy or aryloxyC3-C 12 cycloalkyl, C4-C 12 The alkyl, cycloalkyl, or cycloalkylalkyl groups, wherein one or more hydrogen atoms in these groups may be replaced by halogens or hydroxyl groups; n1 and n2 are each independently integers from 0 to 4; X2 and Y2 may be the same or different, and each may be independently hydrogen, alkyl, alkoxy, halogen, nitro, sulfonic acid, hydroxyl, or amino; when n1 and n2 are 2 or more, X2 and Y2 may be the same or different from each other.

[0059] Preferably, the anthracene compound can be one or more combinations of the following compounds:

[0060]

[0061]

[0062] To further enhance the aforementioned superior properties of the composition, in a preferred embodiment, the photocurable composition comprises, by weight, 1-10 parts of a cationic initiator, 70-90 parts of a cationic reactive compound, 0-10 parts of a pigment, 0.5-1 part of other sensitizers, and 2-5 parts of other additives. The cationic initiator is... One or more of the above three compounds are included in the cationic initiator, and when the cationic initiator contains all three compounds, the weight ratio is (1-2):(1-3):(1-3). The cationic reactive compounds include one or more of bisphenol A epoxy resin, bis((3,4-epoxycyclohexyl)methyl) adipate, triethylene glycol divinyl ether, or 1,3-di(3-ethyl-3-methoxyoxetane)-2-hydroxypropane. The weight ratio of bisphenol A epoxy resin, bis((3,4-epoxycyclohexyl)methyl)adipate, triethylene glycol divinyl ether, and 1,3-di(3-ethyl-3-methoxyoxetane)-2-hydroxypropane is (15-25):(15-30):(10-16):(12-40). Pigments may or may not be added; they can be selected from one or more of pigment red, pigment yellow, pigment blue, pigment black, or pigment white. A sensitizer may be... One or more of the following. The additives may be selected from one or more of the following: self-leveling agent (BYK307), defoamer (BYK055) or dispersant (Lubrizol 24000). When the additives include leveling agent, defoamer and dispersant at the same time, their weight ratio is (0.2~0.7):(0.2~0.7):(1~3).

[0063] According to another aspect of the present invention, the present invention also provides the application of the above-described cationic photocurable composition as paint, coating, ink and molding material. Based on the foregoing reasons, and given the excellent performance of the cationic photocurable composition of the present invention, the photocurable composition of the present invention can be applied to paints, coatings, inks, and molding materials, specifically in the manufacture of: coatings applied to substrates such as plastics, metals, glass, ceramics, wood, walls, and optical fibers; protective film materials such as hard coating agents, antifouling films, antireflective films, and impact-absorbing films; photocurable adhesives, photodegradable coatings, films, and molded products; optical recording media such as holographic imaging materials; optical molding resins, such as inks (resins) for 3D printing, photoresists for electronic circuits and semiconductor manufacturing, and photoresists for electronic materials such as color filters, black matrices, and dry films in displays; interlayer insulating films, light extraction films, brightness enhancement films, and sealing materials; printing inks for screen printing, offset printing, gravure printing, etc., and photocurable inks for inkjet printing; optical components such as lenses, lens arrays, waveguides, light guide plates, light diffusers, and diffraction elements; optical spacers, and materials for nanoimprinting.

[0064] The present application will be further described in detail below with reference to specific embodiments, which should not be construed as limiting the scope of protection claimed in the present application.

[0065] Unless otherwise specified, all parts below refer to parts by weight. The abbreviations have the following meanings:

[0066] A1:

[0067] A2:

[0068] A3:

[0069] A4: TR-PAG20001 (High-strength Product)

[0070] A5: TR-PAG20102 (High-strength Product)

[0071] B1: Bisphenol A epoxy resin

[0072] B2: Bis((3,4-epoxycyclohexyl)methyl)adipate (TTA-26)

[0073] B3: Triethylene glycol divinyl ether

[0074] B4: 1,3-Di(3-ethyl-3-methoxyoxetane)-2-hydroxypropane (TCM202)

[0075] B5: 3-Hydroxymethyl-3-ethyloxetane

[0076] B6: 3,4-Epoxycyclohexylmethyl 3,4-epoxycyclohexyl carboxylate

[0077] C1: Pigment Red

[0078] C2: Pigment Yellow

[0079] C3: Pigment Blue

[0080] C4: Pigment Black

[0081] C5: Pigment White

[0082] Other sensitizer components:

[0083] D1:

[0084] D2:

[0085] D3:

[0086] Other components:

[0087] Leveling agent: BYK307

[0088] Defoamer: BYK055

[0089] Dispersant: Lubrizol 24000

[0090] 1. Formulation of the photocurable composition

[0091] (1) Examples 1-6 and Comparative Examples 1-2

[0092] Prepare the photocurable inks of Examples 1-6 and Comparative Examples 1-2 according to the formulations shown in Table 1. Prepare the photocurable compositions according to the formulations shown in Table 1.

[0093] Table 1

[0094]

[0095] 2. Performance Testing:

[0096] (1) Curing test under UV light source

[0097] Preparation method of the compositions in Examples 1-6 above: Under yellow light, add components A and D from the table above to component B, stir evenly at room temperature until dissolved, and simultaneously add the mixture of components A, B, and D, component C, and zirconium beads with a particle size of 0.3 μm to a high-speed disperser and grind and disperse until the pigment and filler particle size is stable and uniform.

[0098] The above combination was coated onto a PET substrate in a single pass using a 10μm wire bar coater, and then each film was individually exposed to a 385nm UV LED conveyor belt light source (at a light intensity of 500mJ / cm²). 2 Exposure once) and exposure using a traditional tracked external light source with a wavelength of 200-450nm (at a light intensity of 150mJ / cm²). 2 (Exposed 1 time), rating level as follows:

[0099] ○: The paint film is fully cured

[0100] ◎: Surface adhesion after paint film curing

[0101] ×: Paint film not cured

[0102] (2) Adhesion test

[0103] Referring to "GBT9286-1998 Scratch Test for Paint and Varnish Films", the adhesion of UV-cured compositions on different substrates was tested using the cross-cut tester with a 100-cross cutter method. Grade 0 is better than Grade 1.

[0104] The specific method is as follows:

[0105] After the paint film has cured, fix it in place. Then, use a cross-cut scrubber to make one horizontal and one vertical cut to create 100 small squares. Next, brush five times diagonally with a brush. Apply 3M 600 tape to the cuts and then peel it off. Observe the grid area with a magnifying glass. The degree of coating adhesion to the substrate is assessed by evaluating the integrity of the coating within the squares. The more intact the coating within the squares, the stronger the adhesion.

[0106] (3) Odor Residue Test

[0107] Immediately after curing, place the product in a sealed bag and leave it at room temperature for 24 hours. Then, open the bag and assess the product by smell. The evaluation levels are as follows:

[0108] ○: No obvious odor;

[0109] ◎: Has a slight odor, not pungent.

[0110] ×: Irritating odor.

[0111] (4) Flexibility test

[0112] The test was conducted according to GB / T1731-1993, "Determination of Coating Film Flexibility". The test strips were wound sequentially along their length onto rods 1, 2, 3, 4, 5, 6, and 7. After bending for 2-3 seconds, the surface of the cured film was observed using a magnifying glass. The flexibility of the cured film was represented by the smallest rod before the film was damaged. The evaluation results are summarized in Table 2.

[0113] Table 2

[0114]

[0115] (5) Benzene content test

[0116] The photocurable compositions of Examples 1-6 described above, using coated paper / plastic film, were analyzed according to YC / T207-2006, "Determination of Volatile Organic Compounds in Cigarette Carton and Box Packaging Paper by Headspace Gas Chromatography," and the benzene content in the printed matter is shown in Tables 3 and 4.

[0117] Table 3

[0118]

[0119] Table 4

[0120]

[0121] As shown in Table 3, the benzene content of the photocurable composition obtained in this invention is far lower than the requirement of the "Limit Index of Volatile Organic Compounds (VOCs) in Cigarette Cartridges and Boxes" (YC / 207-2006) (0.007 mg / m³). 2 It is used in food and cigarette packaging and fully meets the requirements for benzene content limits.

[0122] The above are merely preferred embodiments of the present invention and are not intended to limit the present 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 cationic photocurable composition, characterized in that, The cationic photocurable composition comprises the following components: Component A: Cationic initiator; Component B: Cationic reactive compound; The cationic initiator is , and And the weight ratio is (1~2):(1~3):(1~3); The cationic reactive compound is bisphenol A epoxy resin, bis((3,4-epoxycyclohexyl)methyl) adipate, triethylene glycol divinyl ether and 1,3-bis(3-ethyl-3-methoxyoxetane)-2-hydroxypropane, and the weight ratio of the four is (15~25):(15~30):(10~16):(12~40).

2. The cationic photocurable composition according to claim 1, characterized in that, The cationic reactive compound has a functionality of 2 to 3.

3. The cationic photocurable composition according to claim 1, characterized in that, The molecular weight of the cationic reactive compound is greater than 200 g / mol.

4. The cationic photocurable composition according to claim 3, characterized in that, The molecular weight of the cationic reactive compound is greater than 350 g / mol.

5. The cationic photocurable composition according to claim 1, characterized in that, The composition contains 1 to 15 wt% of component A by weight.

6. The cationic photocurable composition according to claim 5, characterized in that, The composition contains 1 to 10 wt% of component A by weight.

7. The cationic photocurable composition according to claim 6, characterized in that, The composition contains 2 to 7 wt% of component A by weight.

8. The cationic photocurable composition according to any one of claims 1 to 7, characterized in that, The composition further includes component C, which comprises pigments and fillers; the amount of pigments is 0.06 to 20 times the weight of component A; the amount of fillers is 0.001 to 30 times the weight of component A.

9. The cationic photocurable composition according to claim 8, characterized in that, The amount of pigment used is 0.2 to 15 times the weight of component A.

10. The cationic photocurable composition according to claim 8, characterized in that, The amount of the filler used is 0.15 to 20 times the weight of component A.

11. The cationic photocurable composition according to claim 8, characterized in that, The pigment is an inorganic or organic pigment. The organic pigment is one or more of the following: phthalocyanine dyes, cyanine pigments, naphthalene phthalocyanine pigments, nitroso pigments, azo pigments, diazo pigments, diazo condensation pigments, basic dye pigments, basic blue pigments, indigo pigments, root bark red pigments, quinacridone pigments, isoindolinone pigments, dioxazine pigments, carbazolium dioxazine violet pigments, alizarin lake pigments, phthalamide pigments, carmine lake pigments, tetrachloroisoindolinone pigments, violet ketone pigments, anthraquinone pigments, and quinophthalone pigments. The inorganic pigment is one or more of the following: iron oxides, aluminum oxides, silicon oxides, carbon black pigments, metal sulfides, and metal chlorides. The filler is at least one of nano-calcium carbonate, aluminum hydroxide, barium sulfate, silicon dioxide, talc, and kaolin.

12. The cationic photocurable composition according to any one of claims 1 to 7, characterized in that, The composition further includes component D, which is an auxiliary agent; the amount of the auxiliary agent is 0.001 to 5 times the weight of component A.

13. The cationic photocurable composition according to claim 12, characterized in that, The amount of the auxiliary agent is 0.001 to 3 times the weight of component A.

14. The cationic photocurable composition according to any one of claims 1 to 7, characterized in that, The composition further includes component D, which is a sensitizer; the amount of the sensitizer is 0.001 to 5 times the weight of component A.

15. The cationic photocurable composition according to claim 14, characterized in that, The amount of the sensitizer is 0.001 to 2 times the weight of component A.

16. The cationic photocurable composition according to claim 14, characterized in that, The sensitizers are pyrazoline compounds, acridine compounds, anthracene compounds, coumarin compounds, and tertiary amine compounds.

17. The cationic photocurable composition according to claim 16, characterized in that, The anthracene compound is of general formula II. and / or general formula III One or more combinations of the compounds shown, In the general formula II, R8 is C1-C 12 Alkyl, C1-C 12 aryl, C1-C8 alkoxy or aryloxy, C3-C 12 cycloalkyl, C4-C 12 The alkyl, cycloalkyl, or cycloalkylalkyl groups, wherein one or more hydrogen atoms in these groups are optionally replaced by halogens or hydroxyl groups, and X1 and Y1 are each independently hydrogen, alkyl, alkoxy, halogen, nitro, sulfonic acid, hydroxyl, or amino groups; in the general formula III, R9 is C1-C 12 Alkyl, C1-C 12 aryl, C1-C8 alkoxy or aryloxyC3-C 12 cycloalkyl, C4-C 12 The alkyl, cycloalkyl, or cycloalkylalkyl groups, wherein one or more hydrogen atoms in these groups are optionally replaced by halogens or hydroxyl groups; n1 and n2 are each independently integers from 0 to 4; X2 and Y2 are the same or different, and are each independently hydrogen, alkyl, alkoxy, halogen, nitro, sulfonic acid, hydroxyl, or amino.

18. The cationic photocurable composition according to claim 17, characterized in that, The anthracene compound is one or more combinations of the following compounds: .

19. The use of a cationic photocurable composition according to any one of claims 1 to 18 as a paint, ink, and molding material.

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