Photocatalytic composition, photocurable composition containing the same, and method for producing photocurable resin using the same

Abstract

The present invention relates to a photocatalytic composition, a photocurable composition containing the same, and a method for producing a photocurable resin using the same. The photocatalytic composition of the present invention comprises a photocatalyst having thermally activated delayed fluorescence (TADF) properties and an ionic co-initiator. By combining these and optimizing their composition, a photoinitiation system with excellent radical generation efficiency can be formed even with a small amount of photocatalyst. Therefore, when a monomer is polymerized using the photocatalytic composition of the present invention, not only can a photocurable resin with an excellent polymerization rate be produced, but deep curing is also possible because only a small amount of photocatalyst is required. Furthermore, since the polymerization reaction is initiated using visible light, curing within a matrix that cannot transmit UV light is possible, and a resin with high transparency can be produced even when absorbing visible light.

Description

[Technical Field]

[0001] [1] The present invention relates to a photocatalytic composition, a photocurable composition containing the same, and a method for producing a photocurable resin using the same. More specifically, the present invention relates to a photocatalytic composition that has excellent radical generation efficiency by combining a photocatalyst and a coinitiator, a photocurable composition containing the same, and a method for producing a photocurable resin with an excellent polymerization rate using the same. [Background technology]

[0002] [2] Photocuring resin refers to a resin formed by polymerizing a monomer under the influence of light. The photocuring method not only allows for easier control of time and space compared to existing heat curing methods, but also has the advantages of being applicable to heat-sensitive substrates, being highly energy-efficient, and being environmentally friendly. In particular, when using the heat curing method to produce acrylic resins, residual heat treatment is required in the subsequent process, so the photocuring method is attracting attention as a means to solve this process inefficiency problem. [3] A typical example of such a photocuring method is a method using irradiation with radiation such as ultraviolet light. A typical photocurable composition typically contains a polymerization initiator, a so-called photoinitiator, that absorbs light and decomposes to generate free radicals or cations. For example, Korean Patent Publication No. 10-2010-0072003 describes a photocurable resin composition that can be cured by ultraviolet light, which contains an acrylate compound and a photopolymerization initiator. [4] However, typical photoinitiators are disposable and can only be used once, so a relatively high percentage of photoinitiator must be included to achieve the desired properties and viscosity. Furthermore, when curing with UV light, there is a limitation in that curing cannot occur within a matrix of a material that UV light cannot penetrate, such as a polyimide. [5] As a technology to solve the above-mentioned problems associated with UV curing, Korean Patent Publication No. 10-2019660 and others describe a photocurable resin composition that can be cured with visible light by using an initiator with enhanced sensitivity to visible light. However, even when the photosensitivity of the initiator is improved, there is still a limitation in that it is difficult to achieve a sufficient polymerization rate with a small amount of initiator. In addition, substances that absorb visible light generally have low transparency, which limits their use in optical applications. [6] Therefore, there is a need for technological development of photocurable resins that contain very small amounts of components for photoinitiation but can be efficiently polymerized by visible light, have high resin transparency, and can be applied to optical applications without restrictions.

[0003] technical challenges

[0004] [7] An object of the present invention is to provide a photocatalytic composition capable of forming a photoinitiation system with excellent radical generation efficiency. [8] Another object of the present invention is to provide a photocurable composition containing the above photocatalyst composition and a monomer, which has an excellent polymerization rate of the monomer. [9] Another object of the present invention is to provide a method for producing a photocurable resin with an excellent polymerization rate using the above photocatalytic composition and a monomer.

[0005]

[10] To achieve the above object, the present invention provides a photocatalytic composition comprising a photocatalyst having thermally activated delayed fluorescence (TADF) properties; and an ionic co-initiator.

[11] In the present invention, the photocatalyst may absorb light in the wavelength range of 400 nm to 600 nm.

[12] In the present invention, the photocatalyst may be a cyanoarene compound.

[13] In the present invention, the photocatalyst can be represented by the following chemical formula 1:

[14] [Chemical formula 1]

[15] JPEG2026505534000002.jpg97117

[16] In the above chemical formula 1,

[17] R1 and R2 are each independently hydrogen, deuterium, a halogen atom, a nitro group (-NO2), a cyano group (-CN), or -COOR (where R is hydrogen or C1-C 24 alkyl), or substituted or unsubstituted C1-C 24 Alkyl, C2-C 24 Alkenyl, C2-C 24 Alkynyl, C1-C 24 Alkoxy or C4-C 18 aryl; or linked together to form a substituted or unsubstituted carbazole structure;

[18] X is a halogen atom selected from the group consisting of F, Cl, Br and I;

[19] n is 1 or 2, m is an integer from 3 to 5, l is 0 or 1, and n+m+l is an integer from 4 to 6.

[20] In the present invention, the photocatalyst can be represented by the following chemical formula 2 or 3:

[21] [Chemical formula 2] [twenty two] JPEG2026505534000003.jpg116150

[23] [Chemical formula 3] [twenty four] JPEG2026505534000004.jpg94143

[25] In the above chemical formula 2, X1 to X 10 are each independently hydrogen, deuterium, halogen atoms, -NO2, -CN, -COOR (where R is hydrogen or C1-C 24 alkyl), or substituted or unsubstituted C1-C 24 Alkyl, C2-C 24 Alkenyl, C2-C 24 Alkynyl, C1-C 24 Alkoxy or C4-C 18 is aryl,

[26] In the above formula 3, X1 to X8 each independently represent hydrogen, deuterium, a halogen atom, -NO2, -CN, -COOR (where R is hydrogen or C1-C 24 alkyl), or substituted or unsubstituted C1-C 24 Alkyl, C2-C 24 Alkenyl, C2-C 24 Alkynyl, C1-C 24 Alkoxy or C4-C 18 is aryl,

[27] In the above chemical formulas 2 and 3, each X is independently a halogen atom selected from the group consisting of F, Cl, Br, and I; n is 1 or 2; m is an integer from 3 to 5; l is 0 or 1; and n+m+l is an integer from 4 to 6.

[28] In the present invention, the molar ratio of the photocatalyst and the coinitiator can be 1:10 to 1:5,000.

[29] In the present invention, the ionic coinitiator can include an anionic coinitiator and a cationic coinitiator.

[30] In the present invention, the anionic coinitiator can be a borate salt compound, which can preferably be represented by the following formula 4:

[31] [Chemical formula 4]

[32] JPEG2026505534000005.jpg7896

[33] In the above chemical formula 4,

[34] R3 is C1-C 24 Alkyl or -CH2SiR'3 (R' is hydrogen or C1-C 24 alkyl),

[35] Ar1 to Ar3 each independently represent a substituted or unsubstituted C4-C 18 is aryl,

[36] Z + Li + , K. + , Na + , Rb +or a substituted or unsubstituted safranine ion, pyrylium ion, cyanine ion, iodonium ion, sulfonium ion, phosphonium ion or ammonium ion.

[37] In the present invention, the cationic coinitiator can be one or more compounds selected from the group consisting of iodonium salts, sulfonium salts, and phosphonium salts.

[38] Specifically, the cationic coinitiator can be an iodonium salt compound represented by the following formula 6:

[39] [Chemical formula 6]

[40] JPEG2026505534000006.jpg5698

[41] In the above chemical formula 6,

[42] Ar4 and Ar5 each independently represent a substituted or unsubstituted C4-C 18 is aryl,

[43] Z - PF6 - , SbF6 - , AsF6 - , BF4 - , (C6F5)4B - , Cl - , Br - , HSO4 - , CF3SO3 - , FSO3 - , CH3SO3 - , ClO4 - , PO4 - , NO3 - , SO4 - , CH3SO4 - , or substituted or unsubstituted C1-C 20 Alkyl sulfonates, C2-C 20 Haloalkylsulfonates, C4-C 10 Aryl sulfonates, camphorsulfonate, C1-C 20 Perfluoroalkylsulfonylmethides or C1-C 20It is a perfluoroalkylsulfonylimide ion.

[44] Specifically, the cationic coinitiator can be a sulfonium salt compound represented by the following formula 7:

[45] [Chemical formula 7]

[46] JPEG2026505534000007.jpg60101

[47] In the above chemical formula 7,

[48] ​​Ar6 to Ar8 are each independently a substituted or unsubstituted C4-C 18 is aryl,

[49] Z - PF6 - , SbF6 - , AsF6 - , BF4 - , (C6F5)4B - , Cl - , Br - , HSO4 - , CF3SO3 - , FSO3 - , CH3SO3 - , ClO4 - , PO4 - , NO3 - , SO4 - , CH3SO4 - , or substituted or unsubstituted C1-C 20 Alkyl sulfonates, C2-C 20 Haloalkylsulfonates, C4-C 10 Aryl sulfonates, camphorsulfonate, C1-C 20 Perfluoroalkylsulfonylmethides or C1-C 20 It is a perfluoroalkylsulfonylimide ion.

[50] Specifically, the cationic coinitiator can be a phosphonium salt compound represented by the following formula 8:

[51] [Formula 8]

[52] JPEG2026505534000008.jpg95118

[53] In the above chemical formula 8,

[54] R4 is hydrogen, deuterium, a halogen atom, -NO2, -CN, -COOR, -NRCOCH3, -SR, or -COONH X R 2-X , N.H. X R 2-X , or substituted or unsubstituted C1-C 24 Alkyl, C2-C 24 Alkenyl, C2-C 24 Alkynyl, C1-C 24 Alkoxy, or C4-C 18 aryl, where R is hydrogen or C1-C 24 alkyl, and x is an integer from 0 to 2.

[55] Ar9 to Ar 11 are each independently a substituted or unsubstituted C4-C 18 is aryl,

[56] Z - PF6 - , SbF6 - , AsF6 - , BF4 - , (C6F5)4B - , Cl - , Br - , HSO4 - , CF3SO3 - , FSO3 - , CH3SO3 - , ClO4 - , PO4 - , NO3 - , SO4 - , CH3SO4 - , or substituted or unsubstituted C1-C 20 Alkyl sulfonates, C2-C 20 Haloalkylsulfonates, C4-C 10 Aryl sulfonates, camphorsulfonate, C1-C 20 Perfluoroalkylsulfonylmethides or C1-C 20 It is a perfluoroalkylsulfonylimide ion.

[57]

[58] The present invention also provides a photocurable composition using the above photocatalyst composition.

[59] The photocurable composition of the present invention comprises a polymerizable monomer having an ethylenically unsaturated bond; a photocatalyst having thermally activated delayed fluorescence properties; and an ionic coinitiator.

[60] In the present invention, the photocatalyst can be used in an amount of 0.00001 to 0.01 moles per 100 moles of the polymerizable monomer.

[61]

[62] The present invention also provides a method for producing a photocurable resin using the photocurable composition.

[63] The method for producing a photocurable resin of the present invention includes the step of irradiating a photocurable composition containing a polymerizable monomer having an ethylenically unsaturated bond; a photocatalyst having thermally activated delayed fluorescence properties; and an ionic coinitiator with visible light to polymerize the polymerizable monomer to produce a photocurable resin.

[64] In the present invention, the visible light irradiation can be carried out for 1 to 240 seconds.

[65] In the present invention, it is preferable to perform a degassing step with nitrogen gas before irradiating the visible light.

[66] In the present invention, a step of additionally irradiating the produced resin with visible light can be further carried out.

[67] Specifically, after the prepared resin is coated on a substrate to a thickness of 1 μm to 8 mm, an additional step of irradiating the resin with visible light can be performed. Effect of the invention

[68] The photocatalytic composition of the present invention comprises a photocatalyst with thermally activated delayed fluorescence (TADF) properties and an ionic co-initiator. By combining these and optimizing their composition, a photoinitiation system with excellent radical generation efficiency can be formed even with a small amount of photocatalyst. As a result, when a monomer is polymerized using the photocatalytic composition of the present invention, not only can a photocurable resin with a high polymerization rate be produced, but deep curing is also possible with a small amount of photocatalyst. Furthermore, since the present invention uses visible light to initiate the polymerization reaction, curing within a matrix that cannot transmit UV light is possible, and highly transparent resins can be produced even when absorbing visible light. [Brief explanation of the drawings]

[0006]

[69] Figure 1 is a graph showing the measured conversion rate of resin over time and the irradiation intensity of visible light under the condition of a photocatalytic equivalent of 10 ppm according to one embodiment of the present invention.

[70] Figure 2 is a graph showing the measured conversion rate of resin over time and the irradiation intensity of visible light under the condition of a photocatalyst equivalent of 1 ppm according to one embodiment of the present invention.

[71] Figure 3 is a graph showing the measured resin conversion rate over time and the irradiation intensity of visible light when the equivalent amount of an anionic coinitiator is 200 ppm, according to one embodiment of the present invention.

[72] Figure 4 is a graph showing the measured resin conversion rate over time and the irradiation intensity of visible light when the equivalent amount of an anionic coinitiator is 300 ppm, according to one embodiment of the present invention.

[73] Figure 5 is a graph showing the conversion rate of a film resin measured according to an embodiment of the present invention as a function of the irradiation time of secondary visible light.

[0007]

[74] Specific embodiments of the present invention are described in more detail below. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one skilled in the art to which this invention belongs. Generally, the nomenclature used herein is that which is commonly known and commonly used in the art.

[75] For purposes of describing this invention, "substitution" of a functional group means that one or more hydrogen atoms of the functional group have been replaced with another functional group, for example, one or more hydrogen atoms are each independently replaced with a deuterium atom, a halogen atom, a nitro group (-NO), a cyano group (-CN), -COOR, -NRCOCH, -SR, or -COONH. X R 2-X , N.H. X R 2-X , -CONH X R 2-X , -OR, -SR, -SOR, -SOOR, -NH X R 2-X , -PH X R2-X , -P(OR)2, C1-C 24 Alkyl, C2-C 24 Alkenyl, C2-C 24 Alkynyl, C1-C 24 Alkoxy or C4-C 18 Here, the above "R" is used to describe the bonding form of the functional group, and is not particularly limited, and may be, for example, hydrogen, C1-C 24 Alkyl, C2-C 24 Alkenyl, C2-C 24 Alkynyl or C4-C 18 It may also be a hydrocarbon group such as an aryl of the formula:

[76] In the present invention, the alkyl is a hydrocarbon group consisting of a single bond (methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methylbutyl, 1-ethylbutyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylmethyl ... and aryl refers to hydrocarbon groups containing one or more aromatic rings (e.g., phenyl, biphenyl, naphthyl, anthracyl, phenanthryl, terphenyl, fluorenyl, furan, pyrrole, thiophenyl, thiazole, etc.).

[77] For purposes of describing the present invention, the terms alkyl, alkenyl, alkynyl, and aryl are understood to include not only functional groups consisting of carbon and hydrogen atoms, but also heteroalkyl, heteroalkenyl, heteroalkynyl, and heteroaryl in which one or more carbon atoms are replaced by nitrogen, oxygen, or sulfur. The terms alkyl, alkenyl, and alkynyl are intended to include linear, branched, and cyclic groups.

[78]

[0008]

[79] The present invention relates to a photocatalytic composition, a photocurable composition containing the same, and a method for producing a photocurable resin using the same.

[80] The photocatalytic composition of the present invention contains a photocatalyst and a coinitiator capable of electron transfer with a free radical generator in a resin after light absorption, forming a photoinitiating system. This allows the catalyst to be circulated by electron transfer, enabling repeated use. Unlike conventional photoinitiators, even a small amount of photocatalyst can initiate a polymerization reaction, increasing penetration depth and enabling deep curing. Furthermore, because the photoinitiating system is activated by visible light, it is possible to cure even in a matrix that does not allow UV transmission, making it possible to produce a resin with high transparency even when absorbing visible light.

[81] The photocatalyst used in the present invention absorbs light in the visible light region, particularly in the wavelength region of 400 nm to 600 nm, and has the property of thermally activated delayed fluorescence (TADF) emission.

[82] In the general fluorescent method, three of the four triplet excitons are annihilated, resulting in low light efficiency. However, in the thermally activated delayed fluorescence method, three triplet excitons are transferred to the singlet exciton level to emit light, resulting in all four excitons emitting light, resulting in very high light efficiency.

[0009]

[83] In the present invention, the photocatalyst can be a cyanoarene-based compound with thermally activated delayed fluorescence properties.

[84] Specifically, the cyanoarene-based photocatalyst may be a compound represented by the following chemical formula 1:

[85] [Chemical formula 1]

[86] JPEG2026505534000009.jpg106122

[87] In the above chemical formula 1, R1 and R2 are each independently hydrogen, deuterium, a halogen atom, a nitro group (-NO2), a cyano group (-CN), -COOR (where R is hydrogen or C1-C 24 alkyl), or substituted or unsubstituted C1-C 24 Alkyl, C2-C 24 Alkenyl, C2-C 24 Alkynyl, C1-C 24 Alkoxy or C4-C 18 or they are linked together to form a substituted or unsubstituted carbazole structure. Preferably, R1 and R2 are each independently a substituted or unsubstituted C6-C 18 They can be aryl or can be linked together to form a substituted or unsubstituted carbazole structure.

[88] In the above formula 1, X may be a halogen atom selected from the group consisting of F, Cl, Br and I, and preferably F.

[89] In the above Chemical Formula 1, n is 1 or 2, m is an integer from 3 to 5, l is 0 or 1, and n+m+l is an integer from 4 to 6. Preferably, in the above Chemical Formula 1, n is 1 or 2, m is 3 or 4, l is 0 or 1, and n+m+l can be 5 or 6.

[90] In one embodiment of the present invention, the photocatalyst of Formula 1 above can be represented by Formula 2 below:

[91] [Chemical formula 2]

[92] JPEG2026505534000010.jpg109139

[93] In the above chemical formula 2, X1 to X 10are each independently hydrogen, deuterium, halogen atoms, -NO2, -CN, -COOR (where R is hydrogen or C1-C 24 alkyl), or substituted or unsubstituted C1-C 24 Alkyl, C2-C 24 Alkenyl, C2-C 24 Alkynyl, C1-C 24 Alkoxy or C4-C 18 Preferably, X1 to X2 are aryl. 10 may each independently be hydrogen, a halogen atom, a cyano group, or a substituted or unsubstituted C1-C4 alkyl or C1-C4 alkoxy.

[94] In the above Chemical Formula 2, the definition of X and the definitions of n, m, and l are the same as those in Chemical Formula 1.

[95] In one embodiment of the present invention, the photocatalyst of Formula 1 above can be represented by Formula 3 below:

[96] [Chemical formula 3]

[97] JPEG2026505534000011.jpg103141

[98] In the above chemical formula 3, X1 to X8 each independently represent hydrogen, deuterium, a halogen atom, -NO2, -CN, -COOR (R is hydrogen or C1-C 24 alkyl), or substituted or unsubstituted C1-C 24 Alkyl, C2-C 24 Alkenyl, C2-C 24 Alkynyl, C1-C 24 Alkoxy or C4-C 18 Preferably, X1 to X8 are each independently a hydrogen atom, a halogen atom, a cyano group, or a substituted or unsubstituted C1-C4 alkyl or C1-C4 alkoxy.

[99] In the above Chemical Formula 3, the definition of X and the definitions of n, m, and l are as defined in Chemical Formula 1.

[0100] In an exemplary embodiment of the present invention, the photocatalyst may be 2,4,5,6-tetrakis(diphenylamino)isophthalonitrile (4DP-IPN), 2,4,5,6-tetrakis(carbazol-9-yl)isophthalonitrile (4Cz-IPN), One or more of 2,4,5,6-tetrakis(3,6-di-tert-butylcarbazol-9-yl)isophthalonitrile (4tCz-IPN), 2,4,6-tris(diphenylamino)-5-fluoroisophthalonitrile (3DP-F-IPN), 2,4,6-tris(carbazol-9-yl)-5-fluoroisophthalonitrile (3Cz-F-IPN), 2,4,5,6-tetrakis(bis(4-methoxyphenyl)amino)isophthalonitrile (4DMDP-IPN), 2,4,5,6-tetrakis(bis(4-cyanophenyl)amino)isophthalonitrile (4DCDP-IPN), 2,3,5,6-tetrakis(diphenylamino)benzonitrile (4DP-BN), and the like can be used. Preferably, the photocatalyst can be one or more selected from the group consisting of 4DP-IPN, 3DP-F-IPN, and 4DCDP-IPN. In this regard, in the examples of the present invention, various types of photocatalysts were used to form photoinitiation systems, and it was confirmed that the conversion rate was further improved when 4DP-IPN, 3DP-F-IPN, or 4DCDP-IPN was used.

[0101] The structures of the compounds exemplified above can be represented as follows:

[0102] [4DP-IPN]

[0103] JPEG2026505534000012.jpg130132

[0104] [4Cz-IPN]

[0105] JPEG2026505534000013.jpg123122

[0106] [4tCz-IPN]

[0107] JPEG2026505534000014.jpg147148

[0108] [3DP-F-IPN]

[0109] JPEG2026505534000015.jpg111125

[0110] [3Cz-F-IPN]

[0111] JPEG2026505534000016.jpg126148

[0112] [4DMDP-IPN]

[0113] JPEG2026505534000017.jpg97133

[0114] [4DCDP-IPN]

[0115] JPEG2026505534000018.jpg146167

[0116] [4DP-BN]

[0117] JPEG2026505534000019.jpg93129

[0010]

[0118] In the present invention, the co-initiator is an ionic substance that induces the polymerization reaction of monomers by forming radicals through a dissociation mechanism. The present invention is characterized by improving polymerization efficiency by combining a photocatalyst, particularly a cyanoarene-based photocatalyst having thermally activated delayed fluorescence properties, with a co-initiator.

[0119] In the photoinitiation system of the present invention, the photocatalyst efficiently forms an excited triplet state through intersystem crossing between the singlet and triplet states after light absorption. This excited state photocatalyst can generate a radical ion species of the co-initiator through an oxidation-reduction reaction with the co-initiator. The radical ion species of the co-initiator generated by electron transfer can undergo bond dissociation to form alkyl or aryl radicals that are highly reactive in polymerization reactions.

[0120] The coinitiators can be classified into anionic substances and cationic substances, and in the present invention, the coinitiator can include an anionic coinitiator, a cationic coinitiator, or both, and preferably includes both an anionic coinitiator and a cationic coinitiator.

[0121] In the present invention, the anionic coinitiator can include one or more borate salts.

[0122] The anionic coinitiators include boron atoms in borate salts with or without substituted C4-C 18 The anionic coinitiator can have a structure in which one or more aryls are bonded. Specifically, the anionic coinitiator can be represented by the following chemical formula 4:

[0123] [Chemical formula 4]

[0124] JPEG2026505534000020.jpg84112

[0125] In the above chemical formula '4, R3 is C1-C 24 alkyl or -CH2SiR'3 (R' is hydrogen or C1-C 24 Ar1 to Ar3 are each independently a substituted or unsubstituted C4-C6 alkyl. 18 aryl, preferably substituted or unsubstituted C-C 12 It may be aryl.

[0126] In the above chemical formula 4, Z + Li + , K. + , Na + , Rb + or a substituted or unsubstituted safranin ion, pyrylium ion, cyanine ion, iodonium ion, sulfonium ion, phosphonium ion or ammonium ion, preferably an ammonium ion.

[0127] In one embodiment of the present invention, the anionic coinitiator may be a coinitiator having a structure represented by the following formula 5:

[0128] [Chemical formula 5]

[0129] JPEG2026505534000021.jpg160135

[0130] In the above formula 5, R3 is C1-C 24 alkyl or -CH2SiR'3, where R' is hydrogen or C1-C 24 Preferably, R3 is C1-C6 alkyl.

[0131] In the above Chemical Formula 5, X'1 to X' 15 are each independently hydrogen, deuterium, a halogen atom, -NO2, -CN, -COOR, -NRCOCH3, -SR, or -COONH X R 2-X , N.H. X R 2-X , or substituted or unsubstituted C1-C 24 Alkyl, C2-C 24 Alkenyl, C2-C 24 Alkynyl, C1-C 24 Alkoxy or C4-C 18 aryl, where R is hydrogen or C1-C 24 alkyl, and x is an integer of 0 to 2. Preferably, X'1 to X' 15 may each independently be hydrogen or substituted or unsubstituted C1-C4 alkyl.

[0132] In the above chemical formula 5, Z + Li + , K. + , Na + , Rb +or a substituted or unsubstituted safranin ion, pyrylium ion, cyanine ion, iodonium ion, sulfonium ion, phosphonium ion or ammonium ion, preferably an ammonium ion.

[0133] In an exemplary embodiment of the present invention, the anionic coinitiator may be selected from the group consisting of [2-(butanoyloxy)ethyl]trimethylazanium butyltriphenylborate, tetrabutylammonium butyltriphenylborate, tetramethylammonium methyl(biphenyl)dimesitylborate, tetramethylammonium methyl(1-naphthyl)dimesitylborate, tetrabutylammonium butyltrinaphthylborate, tetramethylammonium butyl(1-naphthyl)dimesitylborate, tetradodecylammonium methyl(1-naphthyl)dimesitylborate, tetramethylammonium methyl(1-naphthyl)dimesitylborate, tetramethylammonium butyl(1-naphthyl)dichloromesitylborate, cyanine butyl(1-naphthyl)dichloromesitylborate, tetramethylammonium methyl(2-naphthyl)dimesitylborate, tetramethylammonium butyl(2-naphthyl)dimesitylborate, tetramethylammonium butyl(1-naphthyl)dimesitylborate, tetramethylammonium butyl(1-naphthyl)dichloromesitylborate, tetramethylammonium butyl(1-naphthyl)dichloromesitylborate, tetramethylammonium methyl(2-naphthyl)dimesitylborate, tetramethylammonium butyl(2-naphthyl)dimesitylborate, tetramethylammonium butyl(1-naphthyl)dichloro ...2-naphthyl)dimesitylborate, tetramethylammonium butyl(2-naphthyl)dimesitylborate, tetramethylammonium butyl(1-naphthyl)dichloromesitylborate, tetramethylammonium butyl(1-naphthyl)di One or more borate salts selected from the group consisting of ammonium methyl(9-anthracyl)bis(2-methylphenyl)borate, tetramethylammonium butyl(9-anthracyl)bis(2-methylphenyl)borate, tetramethylammonium butyl(9-phenanthryl)dimesitylborate, tetramethylammonium butyl(9-phenanthryl)dichloromesitylborate, tetramethylammonium butyl(9-phenanthryl)bis(dichloromesityl)borate, tetramethylammonium butyl(1-pyrenyl)dimesitylborate, tetramethylammonium butyl(1-pyrenyl)dichloromesitylborate, tetramethylammonium methyl(biphenyl)bis(dichloromesityl)borate, iodonium hexyltris(3-fluorophenyl)borate, pyrylium hexyltris(3-fluorophenyl)borate, and safranine hexyltris(3-fluorophenyl)borate can be used.

[0134] In the present invention, the cationic coinitiator can include one or more compounds selected from the group consisting of iodonium salts, sulfonium salts, and phosphonium salts.

[0135] Specifically, the cationic coinitiators include iodonium salts, sulfonium salts, and phosphonium salts having a structure in which one or more substituted or unsubstituted aryls are bonded to the central atom of iodine (I), sulfur (S), or phosphorus (P), respectively. The iodonium salt, sulfonium salt, and phosphonium salt coinitiators can be represented by the following chemical formulas 6 to 8, respectively:

[0136] [Chemical formula 6]

[0137] JPEG2026505534000022.jpg56114

[0138] [Chemical formula 7]

[0139] JPEG2026505534000023.jpg69119

[0140] [Chemical formula 8]

[0141] JPEG2026505534000024.jpg88115

[0142] In the above Chemical Formulas 6 to 8, Ar4 to Ar 11 are each independently a substituted or unsubstituted C4-C 18 aryl, preferably substituted or unsubstituted C6-C 12 It may be aryl.

[0143] In addition, in the above chemical formula 8, R4 is independently hydrogen, deuterium, a halogen atom, -NO2, -CN, -COOR, -NRCOCH3, -SR, or -COONH. X R 2-X , N.H. X R 2-X , or substituted or unsubstituted C1-C 24 Alkyl, C2-C 24 Alkenyl, C2-C 24Alkynyl, C1-C 24 Alkoxy or C4-C 18 aryl, where R is hydrogen or C1-C 24 alkyl, and x is an integer from 0 to 2.

[0144] In the above chemical formulas 6 to 8, Z - PF6 - , SbF6 - , AsF6 - , BF4 - , (C6F5)4B - , Cl - , Br - , HSO4 - , CF3SO3 - , FSO3 - , CH3SO3 - , ClO4 - , PO4 - , NO3 - , SO4 - , CH3SO4 - , or substituted or unsubstituted C1-C 20 Alkyl sulfonates, C2-C 20 Haloalkylsulfonates, C6-C 10 Aryl sulfonates, camphorsulfonate, C1-C 20 Perfluoroalkylsulfonylmethides or C1-C 20 It is a perfluoroalkylsulfonylimide ion.

[0145] In one embodiment of the present invention, the iodonium salt coinitiator can be a compound of formula 9:

[0146] [Chemical formula 9]

[0147] JPEG2026505534000025.jpg76163

[0148] In the above Chemical Formula 9, X"1 to X" 10 are each independently hydrogen, deuterium, a halogen atom, -NO2, -CN, -COOR, -NRCOCH3, -SR, or -COONH X R 2-X , N.H. X R2-X , or substituted or unsubstituted C1-C 24 Alkyl, C2-C 24 Alkenyl, C2-C 24 Alkynyl, C1-C 24 Alkoxy or C4-C 18 aryl, where R is hydrogen or C1-C 24 alkyl, and x is an integer from 0 to 2.

[0149] In the above chemical formula 9, Z - PF6 - , SbF6 - , AsF6 - , BF4 - , (C6F5)4B - , Cl - , Br - , HSO4 - , CF3SO3 - , FSO3 - , CH3SO3 - , ClO4 - , PO4 - , NO3 - , SO4 - , CH3SO4 - , or substituted or unsubstituted C1-C 20 Alkyl sulfonates, C2-C 20 Haloalkylsulfonates, C4-C 10 Aryl sulfonates, camphorsulfonate, C1-C 20 Perfluoroalkylsulfonylmethides or C1-C 20 It is a perfluoroalkylsulfonylimide ion.

[0150] In an exemplary embodiment of the invention, the iodonium salt coinitiator includes diphenyliodonium hexafluorophosphate, (4-methylphenyl)(4-(2-methylpropyl)phenyl)iodonium hexafluorophosphate, bis(4-methylphenyl)iodonium hexafluorophosphate, bis(dodecylphenyl)iodonium hexafluorophosphate, bis(4-hexylphenyl)iodonium hexafluoroantimonate, bis(4-hexylphenyl)iodonium hexafluorophosphate, phosphate, (4-hexylphenyl)phenyliodonium hexafluoroantimonate, (4-hexylphenyl)phenyliodonium hexafluorophosphate, [4-(octyloxy)phenyl](phenyl)iodonium hexafluoroantimonate, bis(4-octylphenyl)iodonium hexafluoroantimonate, (4-sec-butylphenyl)-(4'-methylphenyl)iodonium hexafluorophosphate, (4-isopropylphenyl)-(4'-methylphenyl)iodonium Iodonium hexafluorophosphate, bis(4-octylphenyl)iodonium hexafluorophosphate, (4-octylphenyl)phenyliodonium hexafluoroantimonate, (4-octylphenyl)phenyliodonium hexafluorophosphate, bis(4-decylphenyl)iodonium hexafluoroantimonate, bis(4-decylphenyl)iodonium hexafluorophosphate, (4-decylphenyl)phenyliodonium hexafluoroantimonate, (4-decylphenyl)phenyliodonium phenyliodonium hexafluorophosphate, bis(4-hexylphenyl)iodonium tetrafluoroborate, (4-hexylphenyl)phenyliodonium tetrafluoroborate, bis(4-octylphenyl)tetrafluoroborate, (4-octylphenyl)phenyliodonium tetrafluoroborate, bis(4-decylphenyl)iodonium tetrafluoroborate, (4-decylphenyl)phenyliodonium tetrafluoroborate, bis(4-methoxyphenyl)iodonium bromide,(4-Methoxyphenyl)phenyliodonium trifluoromethanesulfonate, Bis(4-phenoxyphenyl)iodonium tetrafluoroborate, Bis(3-methoxysulfonylphenyl)iodonium hexafluorophosphate, Bis(4-fluorophenyl)iodonium trifluoromethanesulfonate, Bis(4-bromophenyl)iodonium trifluoromethanesulfonate, Bis(4-chlorophenyl)iodonium hexafluorophosphate, Bis(2,4-dichlorophenyl)iodonium hexafluorophosphate One or more members selected from the group consisting of iodonium nitrate, bis(4-iodophenyl)iodonium tetrafluoroborate, di(3-carboxyphenyl)iodonium hexafluorophosphate, di(3-methoxycarbonylphenyl)iodonium hexafluorophosphate, di(4-acetamidophenyl)iodonium hexafluorophosphate, (4-nitrophenyl)phenyliodonium nitrate, bis(3-nitrophenyl)iodonium nitrate, and dinaphthyliodonium tetrafluoroborate can be used.

[0151] In one embodiment of the present invention, the sulfonium salt coinitiator can be a compound of formula 10:

[0152] [Chemical formula 10]

[0153] JPEG2026505534000026.jpg111170

[0154] In the above Chemical Formula 10, X"1 to X" 15 are each independently hydrogen, deuterium, a halogen atom, -NO2, -CN, -COOR, -NRCOCH3, -SR, or -COONH X R 2-X , N.H. X R 2-X , or substituted or unsubstituted C1-C 24 Alkyl, C2-C 24 Alkenyl, C2-C 24 Alkynyl, C1-C 24 Alkoxy or C4-C 18aryl, where R is hydrogen or C1-C 24 alkyl, and x is an integer from 0 to 2.

[0155] In the above chemical formula 10, Z - PF6 - , SbF6 - , AsF6 - , BF4 - , (C6F5)4B - , Cl - , Br - , HSO4 - , CF3SO3 - , FSO3 - , CH3SO3 - , ClO4 - , PO4 - , NO3 - , SO4 - , CH3SO4 - , or substituted or unsubstituted C1-C 20 Alkyl sulfonates, C2-C 20 Haloalkylsulfonates, C4-C 10 Aryl sulfonates, camphorsulfonate, C1-C 20 Perfluoroalkylsulfonylmethides or C1-C 20 It is a perfluoroalkylsulfonylimide ion.

[0156] In an exemplary embodiment of the present invention, the sulfonium salt coinitiator may be one or more of triphenylsulfonium hexafluoroantimonate, triphenylsulfonium hexafluorophosphate, diphenyl-4-methylsulfonium trifluoromethanesulfonate, and the like.

[0157] In one embodiment of the present invention, the phosphonium salt coinitiator can be a compound of formula 11:

[0158] [Chemical formula 11]

[0159] JPEG2026505534000027.jpg178161

[0160] In the above formula 11, R4 and X"1 to X" 15are each independently hydrogen, deuterium, a halogen atom, -NO2, -CN, -COOR, -NRCOCH3, -SR, or -COONH X R 2-X , N.H. X R 2-X , or substituted or unsubstituted C1-C 24 Alkyl, C2-C 24 Alkenyl, C2-C 24 Alkynyl, C1-C 24 Alkoxy or C4-C 18 aryl, where R is hydrogen or C1-C 24 alkyl, and x is an integer from 0 to 2.

[0161] In the above chemical formula 11, Z - PF6 - , SbF6 - , AsF6 - , BF4 - , (C6F5)4B - , Cl - , Br - , HSO4 - , CF3SO3 - , FSO3 - , CH3SO3 - , ClO4 - , PO4 - , NO3 - , SO4 - , CH3SO4 - , or substituted or unsubstituted C1-C 20 Alkyl sulfonates, C2-C 20 Haloalkylsulfonates, C4-C 10 Aryl sulfonates, camphorsulfonate, C1-C 20 Perfluoroalkylsulfonylmethides or C1-C 20 It is a perfluoroalkylsulfonylimide ion.

[0162] In an exemplary embodiment of the present invention, the phosphonium salt coinitiator may be one or more of ethyltriphenylphosphonium hexafluoroantimonate, tetraphenylphosphonium hexafluoroantimonate, and the like.

[0163] In the present invention, the total molar ratio of the photocatalyst and coinitiator may be 1:10 to 1:5,000, preferably 1:50 to 1:3,000, and more preferably 1:70 to 1:1,500.

[0164] In the present invention, the optimal combination of the photocatalyst having thermally activated delayed fluorescence properties and the coinitiator is preferably a cyanoarene-based photocatalyst combined with an anionic coinitiator and a cationic coinitiator. In this case, the radical generation efficiency of the photoinitiator system is much higher than that of conventional photoinitiators, and therefore, when the photoinitiator system is applied to a polymerizable monomer and irradiated with light, an excellent effect on the polymerization rate can be achieved.

[0165] When an anionic coinitiator and a cationic coinitiator are used in combination, the molar ratio of the photocatalyst to the anionic coinitiator can be 1:5 to 1:2,000, preferably 1:10 to 1:1,000, and specifically 1:50 to 1:500. The molar ratio of the photocatalyst to the cationic coinitiator can be 1:5 to 1:3,000, preferably 1:10 to 1:2,000, and more preferably 1:20 to 1:1,000.

[0166] The photoinitiating system using the photocatalyst composition of the present invention can induce an effective photopolymerization reaction and achieve deep curing even with a very small amount of photocatalyst. Furthermore, because the photoinitiating system is activated by visible light, it can be cured even in a matrix that does not allow UV transmission, and it is possible to produce a resin that has high transparency even when absorbing visible light.

[0011]

[0167] Accordingly, the present invention also provides a photocurable composition comprising the above photocatalyst composition and a polymerizable monomer.

[0168] In the present invention, the polymerizable monomer means a monomer having an ethylenically unsaturated bond, and a polymerization reaction occurs between the above-mentioned monomers due to radicals generated by a photoinitiation system formed by the photocatalytic composition of the present invention upon light irradiation, thereby forming a resin, which is a cured product.

[0169] Illustratively, the polymerizable monomer used in the present invention can be represented by the following chemical formula 12:

[0170] [Chemical formula 12]

[0171] JPEG2026505534000028.jpg5666

[0172] In the above formula 12, R5 is hydrogen, deuterium, a halogen atom, or a substituted or unsubstituted C1-C4 alkyl, and R6 is hydrogen, deuterium, a halogen atom, -CN, -COOR", -CONH X R” 2-X ,-OR”,-SR”,-SOR”,-SOOR”,-NH X R” 2-X , -PH X R” 2-X , -P(OR")2, or substituted or unsubstituted C1-C 24 Alkyl, C2-C 24 Alkenyl, C2-C 24 Alkynyl, C1-C 24 Alkoxy or C4-C 18 aryl, where R" is hydrogen or a substituted or unsubstituted C-C 24 Alkyl, C2-C 24 Alkenyl, C2-C 24 Alkynyl or C6-C 18 aryl, and x is an integer from 0 to 2.

[0173] In an exemplary embodiment of the present invention, the polymerizable monomer may be a (meth)acrylate or (meth)acrylamide compound, in which case "(meth)acryl" is used to refer to both acryl and methacryl.

[0174] Specifically, the polymerizable monomers include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, lauryl (meth)acrylate, 2-ethylhexyl (meth)acrylate, dicyclopentadiene (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, dicyclopentenyl (meth)acrylate, isobornyl (meth)acrylate, (meth)acrylamide, N,N-dimethyl (meth)acrylamide, (meth)acryloylmorpholine, isobutoxymethyl (meth)acrylamide, t-octyl (meth)acrylamide, diacetone (meth)acrylamide, ethyl diethylene glycol (meth)acrylate, and polyethylene glycol mono(meth)acrylate. , Polypropylene glycol mono(meth)acrylate, Bornyl (meth)acrylate, Methyl triethylene glycol (meth)acrylate, Ethylene glycol di(meth)acrylate, Dicyclopentenyl di(meth)acrylate, Triethylene glycol diacrylate, Tetraethylene glycol di(meth)acrylate, Tricyclodecanediyldimethylene di(meth)acrylate, Tris(2-hydroxyethyl)isocyanurate di(meth)acrylate, Tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate, Trimethylolpropane tri(meth)acrylate, Tripropylene glycol di(meth)acrylate, Neopentyl glycol di(meth)acrylate, 1,4-Butanediol di(meth)acrylate, 1,6-Hexanediol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, polyester di(meth)acrylate, polyethylene glycol di(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol tetra(meth)acrylate, trimethylolpropane tetra(meth)acrylate, tetrachlorophenyl (meth)acrylate, 2-tetrachlorophenoxyethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, tetrabromophenyl One or more compounds selected from the group consisting of phenyl (meth)acrylate, 2-tetrabromophenoxyethyl (meth)acrylate, 2-trichlorophenoxyethyl (meth)acrylate, tribromophenyl (meth)acrylate, 2-tribromophenoxyethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, phenoxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, pentachlorophenyl (meth)acrylate, and pentabromophenyl (meth)acrylate can be used.

[0175] In the photocurable composition of the present invention, the amount of photocatalyst used is 0.00001 to 0.01 mol, preferably 0.0001 to 0.005 mol, per 100 mol of polymerizable monomer. Thus, by utilizing the present invention, photopolymerization can be efficiently carried out even with a very small amount of photocatalyst relative to the monomer, and deep curing is possible.

[0176] In addition to the above components, the photocurable composition of the present invention may further contain one or more additional components such as a radical curable component, a free radical photoinitiator, a photosensitizer, etc., as needed.

[0177] When the photocurable composition of the present invention is irradiated with visible light, a photocurable resin can be obtained.

[0178] Specifically, when the photocurable composition is irradiated with visible light, the photoinitiator system formed by the photocatalytic composition of the present invention causes polymerization of the polymerizable monomer, producing a resin in the form of a cured product.

[0179] The method for producing a photocurable resin of the present invention includes the step of irradiating a photocurable composition containing a polymerizable monomer, a photocatalyst, and a coinitiator with visible light to polymerize the polymerizable monomer, thereby producing a photocurable resin.

[0180] The above-mentioned composition can be mixed and irradiated with visible light to obtain a bulk polymer resin, or the mixture can be applied to a substrate and then irradiated with visible light to produce a film of the polymer resin. In this case, the mixture can be applied to a release liner, and after producing the resin, the release liner can be removed to obtain a film, or the film can be formed by applying the mixture directly to the target object.

[0181] In the present invention, it is preferable to further include a step of degassing the mixture with nitrogen gas before irradiating the mixture with visible light. In one embodiment of the present invention, it has been confirmed that when photopolymerization is performed in a nitrogen atmosphere after removing oxygen through a degassing process, the photopolymerization efficiency is significantly higher than that in a general air atmosphere.

[0182] In the visible light irradiation step, the light irradiation can be carried out for 1 to 240 seconds, preferably 2 to 120 seconds, and more preferably 4 to 100 seconds. By using the photocatalytic composition of the present invention, a small amount of photocatalyst can be used in the photoinitiation system, and an excellent polymerization rate can be achieved even with a short irradiation time.

[0183] In the visible light irradiation step, the light irradiation intensity is 1 mW / cm 2 ~1W / cm 2 , preferably 10 mW / cm 2 ~100mW / cm 2 If the intensity of the irradiated light is too low, the polymerization reaction may not be properly initiated, and if the intensity of the light is too high, the concentration of radicals generated from the coinitiator in the early stage of the polymerization reaction may increase rapidly, causing the termination reaction between radicals to prevail over the polymerization rate, which may hinder the polymerization reaction. From these points of view, a light intensity of 40 mW / cm is used during the photocuring process according to the present invention. 2 ~80mW / cm 2 When irradiated with light of this order, the radical concentration and polymerization rate are optimized, and an excellent conversion rate can be obtained in the polymerization reaction.

[0184] In one embodiment of the present invention, a resin having a further improved polymerization rate can be produced by additionally irradiating the produced resin with visible light. Specifically, a bulk resin produced by the above light irradiation is applied to a substrate and then additionally irradiated with visible light, or a film resin produced by the above light irradiation is additionally irradiated with visible light, thereby producing a film resin having a further improved polymerization rate.

[0185] When a film resin is produced using a bulk resin, the produced bulk resin is applied to a substrate before additional irradiation with visible light. For example, after applying the bulk resin to a release paper, a uniform film can be formed by adjusting the thickness using a micro-applicator.

[0186] In this case, the thickness of the resin before the additional light irradiation may be 1 μm to 8 mm. The thickness can be adjusted as needed, but if the thickness is too thin, it is difficult to form a uniform coating, and if the thickness is too thick, the polymerization rate decreases, so the thickness is preferably 10 mm to 2 mm, and more preferably 40 μm to 80 μm from the viewpoints of ease of coating and polymerization rate.

[0187] In the additional visible light irradiation step, the light irradiation can be performed for 10 to 600 seconds, preferably 40 to 120 seconds, for example, 40 to 80 seconds. The additional light irradiation can produce a film resin with an excellent polymerization rate.

[0188] The photocurable composition of the present invention can be polymerized by visible light, so it can be cured even in materials that do not transmit UV (e.g., polyimide). It also uses a much smaller amount of photocatalyst than conventional techniques, making it possible to cure deep areas, and it is possible to produce a resin that has very high transmittance even when absorbing visible light.

[0189] As a result, the photocurable composition of the present invention can be used in various fields where photocurable resins are used, such as sealing layers, adhesive layers, protective layers, coating layers, printing layers, and solder masks, and is particularly useful in fields where transparency is required (e.g., optically transparent adhesives (OCA), transparent protective layers, etc.).

[0190]

[0191] [Example]

[0012]

[0192] The present invention will be described in more detail through the following examples, but these examples are merely illustrative of some experimental methods and configurations for the purpose of illustrating the present invention, and the scope of the present invention is not limited to these examples.

[0194]

[0195] Production Example 1: Production of photocurable composition and photocurable resin using the same

[0196]

[0197] A photocatalytic composition containing a photocatalyst and a coinitiator and a photocurable composition containing a polymerizable monomer were prepared, and then cured to prepare a resin.

[0198] First, the photocatalyst (4DP-IPN), anionic co-initiator I (Borate V), and cationic co-initiator II (HNu254) were mixed and stirred at room temperature until a homogeneous composition was obtained. The monomer (2-EHA) was used as the solvent for bulk polymerization. To improve reproducibility, stock solutions of the photocatalyst and co-initiator were prepared and diluted, then stirred to obtain a homogeneous mixture. For each composition, the molar ratio of monomer to photocatalyst, co-initiator I, and co-initiator II was 100:0.001:0.01:0.1, and the photocatalyst, co-initiator I, and co-initiator II equivalents were 10 ppm, 100 ppm, and 1,000 ppm, respectively.

[0199] The prepared photocurable composition was degassed with nitrogen gas for 30 minutes to remove oxygen, and then cured in a blue LED curing device (wavelength: 455 nm) at 100 mW / cm 2The stirred composition was cured by irradiating it with light at an intensity of 1000 kJ / min for 10 seconds to produce a photocurable resin.

[0200] In the following experimental examples, the raw materials of the compositions are shown by their common names in Table 1 below.

[0201]

[0202] [Table 1] JPEG2026505534000029.jpg245170

[0203]

[0204] Experimental method: Measurement of conversion rate of photocurable resin

[0205]

[0206] To measure the conversion rate of the photocurable composition before and after curing, the degree of curing was analyzed using Fourier Transform Infrared (FT-IR) spectroscopy. From the analysis results, the ratio of C=O bonds to C=C bonds in the composition and resin was compared, and the conversion rate was calculated according to the following formula.

[0207] JPEG2026505534000030.jpg51155

[0208] In the above formula, A 0(C=C) , A 0(C=O) , A t(C=C) and A t(C=O) At time 0 seconds, C=C(830-790cm -1 ), and at time 0 seconds, C=O (1760-1660 cm -1 ), means the average peak area of ​​C═C at time t seconds and C═O at time t seconds.

[0209]

[0210] Experimental Example 1: Comparison of conversion rates depending on the type of coinitiator

[0013]

[0211]

[0212] The method of Preparation Example 1 was used, but resins were produced by changing the type of coinitiator as shown in Table 2, and the conversion rates before and after curing were measured and the results were compared.

[0213]

[0214] [Table 2] JPEG2026505534000031.jpg45159

[0215]

[0216] As a result of the experiment, when a photoinitiation system was formulated using 10 ppm of photocatalyst and exposed to visible light for 10 seconds, the conversion rate was about 2.7% when only one type of co-initiator was used, meaning that polymerization hardly occurred. However, when both co-initiators I and II were used, the conversion rate increased significantly to 46.8%.

[0217] This confirms that when I and II are used in combination as coinitiators, the cure conversion rate is significantly improved due to their synergistic effect.

[0218]

[0219] Experimental example 2: Comparative experiment of conversion rate depending on the type of photocatalyst

[0220]

[0221] The method of Preparation Example 1 was used, but resins were produced by changing the type of photocatalyst as shown in Table 3, and the conversion rates before and after curing were measured and the results were compared.

[0222]

[0223] [Table 3] JPEG2026505534000032.jpg90167

[0224]

[0225] According to the above experimental results, when various types of photocatalysts were used, the conversion rate was 23.7% at minimum and 46.8% at maximum. Among them, when 4DP-IPN, 3DP-F-IPN and 4DCDP-IPN were used, the conversion rate was confirmed to be high at over 40%.

[0226] This confirmed that the present invention is effective for various photocatalysts, but it was found that the effect of increasing the conversion rate differs depending on the type of photocatalyst.

[0227]

[0228] Experimental Example 3: Analysis of changes in conversion rate depending on visible light irradiation time

[0229]

[0230] The method of Preparation Example 1 was used, but the light irradiation time was changed as shown in Table 4, and the conversion rate before and after curing was measured and the results were compared.

[0231]

[0232] [Table 4] JPEG2026505534000033.jpg69169

[0233]

[0234] As a result of the experiment, it was confirmed that when the photocatalytic composition of the present invention is used, a considerable amount of polymerization occurs even when the light irradiation time is as short as 2 seconds, and that when the light irradiation time is 4 seconds or more, the polymerization conversion rate becomes saturated within the experimental error (±5%).

[0235]

[0236] Experimental Example 4: Analysis of changes in conversion rate depending on visible light irradiation time (2)

[0237]

[0238] The method of Preparation Example 1 was used, but the photocatalyst equivalent was changed to 1 ppm as shown in Table 5, and the curing was carried out while changing the light irradiation time, and then the conversion rate was measured and the results were compared.

[0239]

[0240] [Table 5] JPEG2026505534000034.jpg138170

[0241]

[0242] As a result of the experiment, it was confirmed that even when 1 ppm of photocatalyst was used, a conversion rate of approximately 41% was achieved when light was irradiated for 10 seconds, and that by extending the light irradiation time, the conversion rate could be increased to a maximum of 87.7%, which is an extremely excellent result.

[0243] This confirmed that when the present invention is used, the polymerization rate can be significantly improved even with a very small amount of photocatalyst.

[0244]

[0245] Experimental Example 5: Comparative analysis of conversion rate depending on the intensity of visible light

[0246]

[0247] The method of Preparation Example 1 was used, but the irradiation intensity of visible light was reduced to 50% and 25% as shown in Table 6, and then the resin conversion rate was measured and the results were compared.

[0248]

[0249] [Table 6] JPEG2026505534000035.jpg26123

[0250]

[0251] The experimental results confirmed that even when the irradiation intensity was reduced to 1 / 4, the conversion rate remained at a relatively high level of 36.8%. Based on the above experimental results, it was found that when a photoinitiation system is formed using a combination of a photocatalyst and a coinitiator according to the present invention, polymerization can be sufficiently achieved even with a low light dose.

[0252] Furthermore, the above experimental results confirmed that when the irradiation intensity was reduced to 50%, the conversion rate actually increased from 45.7% to 53.3%. This is interpreted as being due to the fact that when the irradiation intensity is high, the concentration of radicals generated from the coinitiator in the early stage of the polymerization reaction increases rapidly, causing the termination reaction, which is a reaction between radicals, to take precedence over the rate of polymer polymerization.

[0253]

[0254] Experimental Example 6: Analysis of changes in conversion rate depending on the intensity and irradiation time of visible light

[0255]

[0256] The resin conversion rate was measured after curing by varying the irradiation intensity and irradiation time of visible light using the same method as in Preparation Example 1. The experimental results are shown in Figure 1 and Table 7 below.

[0257]

[0258] [Table 7] JPEG2026505534000036.jpg100122

[0259]

[0260] The above experimental results show that even when the light irradiation intensity is reduced to 50% or 25%, a relatively high conversion rate can be achieved within a short time, and when the irradiation time is extended to 20 seconds, the conversion rate reaches 40% or more for samples with various intensities.

[0261] Therefore, it was confirmed that when a combination of a photocatalyst and a coinitiator is used according to the present invention, effective polymerization is possible in a short time even with low-intensity light.

[0262]

[0263] Experimental Example 7: Analysis of changes in conversion rate depending on the intensity and irradiation time of visible light (2)

[0264] The same procedure as in Preparation Example 1 was used, except that the photocatalyst equivalent was changed to 1 ppm, and the curing was carried out under various irradiation intensities and times with visible light, after which the resin conversion rate was measured. The experimental results are shown in Figure 2 and Table 8 below.

[0266]

[0267] [Table 8] JPEG2026505534000037.jpg106122

[0268]

[0269] As a result of the experiment, it was confirmed that even when the amount of photocatalyst was reduced to 1 ppm, the conversion rate was at least as high as 41% if the irradiation time was adjusted to 10 seconds or more, and even when the light irradiation intensity was significantly reduced to 50% or 25%, if the irradiation time was adjusted to 20 seconds, conversion rates of approximately 40% and 30%, respectively, could be achieved. This shows that the use of the present invention can achieve an improvement in conversion rate at various light intensities even with a very small amount of photocatalyst.

[0270]

[0271] Experimental Example 8: Comparison of conversion rates depending on photocatalytic equivalent

[0272]

[0273] The method of Preparation Example 1 was used, but the photocatalyst equivalent was changed to 0.5, 1, 5, and 10 ppm as shown in Table 9, and the coating was cured by irradiating light for 5 seconds, and then the conversion rate was measured and the results were compared.

[0274]

[0275] [Table 9] JPEG2026505534000038.jpg38118

[0276]

[0277] The results of the experiment showed that when the photocatalyst was 0.5 ppm, the conversion rate was about 13.5%, but at 1 ppm, a conversion rate of 24.7% was confirmed even with a short light irradiation time of 5 seconds, and that at 5 ppm or more, an excellent conversion rate of over 40% was shown. This shows that a photocatalyst equivalent of 1 ppm or more is preferable, and that especially at 5 ppm or more, excellent effects can be obtained even with short light irradiation times.

[0278]

[0279] Experimental Example 9: Comparison of conversion rates depending on the type of coinitiator I

[0280]

[0281] Photoinitiating systems were prepared using the method of Preparation Example 1, but by changing the type of coinitiator I as shown in Table 10. The systems were cured by irradiating visible light for 30 seconds, and the conversion rates were measured and compared.

[0282]

[0283] [Table 10] JPEG2026505534000039.jpg37168

[0284]

[0285] The experimental results showed that when the type of coinitiator I was changed, a minimum conversion rate of 50% was achieved. In particular, when Borate V ([2-(butanoyloxy)ethyl]trimethylazanium·butyltriphenylborate) and P3B (tetrabutylammonium·butyltriphenylborate) were used, higher conversion rates were observed than when N3B (tetrabutylammonium·butyltrinaphthylborate) was used.

[0286] This demonstrates that the effects of the present invention are exhibited with various types of coinitiators I, and that the effects can be further improved when a phenylborate-based coinitiator is used.

[0287]

[0288] Experimental Example 10: Comparison of conversion rates depending on the equivalent amount of coinitiator I

[0289]

[0290] The method of Preparation Example 1 was used, but 1 ppm of photocatalyst was used, and the equivalent amount of coinitiator I was changed as shown in Table 11 to prepare a photoinitiating system. After curing, the conversion rate was measured and the results were compared.

[0291]

[0292] [Table 11] JPEG2026505534000040.jpg38167

[0293]

[0294] The experimental results showed that the conversion rate was excellent even when 100 ppm of co-initiator I was used, but when the amount of co-initiator I was increased from 100 ppm to 300 ppm, the conversion rate increased significantly from 41.0% to 53.2%. This confirmed that even a small amount of co-initiator can improve the conversion rate, and that this effect can be further enhanced by increasing the equivalent weight of co-initiator I.

[0295]

[0296] Experimental Example 11: Analysis of changes in conversion rate depending on the intensity and irradiation time of visible light (3)

[0297]

[0298] The same procedure as in Preparation Example 1 was used, except that the amount of coinitiator I was changed to 200 ppm, and the curing was carried out under various irradiation intensities and times with visible light, after which the resin conversion rate was measured. The experimental results are shown in Figure 3 and Table 12 below.

[0299]

[0300] [Table 12] JPEG2026505534000041.jpg82122

[0301]

[0302] As a result of the experiment, it was confirmed that even when the light irradiation intensity was significantly reduced to 50% or 25%, excellent conversion rates could be achieved by adjusting the irradiation time, and that when irradiated for 30 seconds, maximum conversion rates of 78.1% and 73.3%, respectively, could be achieved. This confirmed that the use of the present invention can achieve excellent conversion rates at various light intensities even with a very small amount of photocatalyst.

[0303]

[0304] Experimental Example 12: Analysis of changes in conversion rate depending on the intensity and irradiation time of visible light (4)

[0305]

[0306] The same procedure as in Preparation Example 1 was used, except that the amount of coinitiator I was changed to 300 ppm, and the resin was cured under different irradiation intensities and times, and the resin conversion rate was measured. The experimental results are shown in Figure 4 and Table 13 below.

[0307]

[0308] [Table 13] JPEG2026505534000042.jpg100120

[0309]

[0310] As a result of the experiment, when 300 ppm of coinitiator I was used, it was confirmed that excellent conversion rates could be achieved by adjusting the irradiation time even when the light irradiation intensity was significantly reduced to 50% or 25%, and that maximum conversion rates of 74.3% and 80.6%, respectively, could be achieved when irradiated for 30 seconds. This confirmed that when a photoinitiation system is formed using the present invention, excellent conversion rates can be achieved at various light intensities even with a very small amount of photocatalyst.

[0311]

[0312] Experimental Example 13: Comparison of conversion rates depending on the type of coinitiator II

[0313]

[0314] The method of Preparation Example 1 was used, but the type of coinitiator II was changed as shown in Table 14 to prepare a photoinitiating system, and the conversion rate was measured after curing and the results were compared.

[0315]

[0316] [Table 14] JPEG2026505534000043.jpg38169

[0317]

[0318] The experimental results showed that even when the type of coinitiator II was changed, a higher conversion rate was obtained compared to when only coinitiator I was used (see Samples 1-3). Among these, Tiod (bis(4-methylphenyl)iodonium hexafluorophosphate) and HNu254 ([4-(octyloxy)phenyl](phenyl)iodonium hexafluoroantimonate) were suitable, with HNu254 being particularly favorable in terms of improving the conversion rate.

[0319]

[0320] Experimental Example 14: Comparison of conversion rate depending on the equivalent amount of coinitiator II

[0321]

[0322] Photoinitiating systems were prepared using the method of Preparation Example 1, but the equivalent amounts of photocatalyst and coinitiator II were changed as shown in Table 15. The systems were cured by irradiating visible light for 5 seconds, and the conversion rates were measured and compared.

[0323]

[0324] [Table 15] JPEG2026505534000044.jpg117118

[0325]

[0326] The experimental results showed that when a trace amount of photocatalyst was used (0.5 ppm), the conversion rate was low at 1.3% to 5.7% when the co-initiator II was 1, 2, or 5 ppm, but significantly improved to 13.5% to 15.6% when the co-initiator II was 10 ppm to 1,000 ppm. This indicates that a high conversion rate is achieved when 20 moles or more of co-initiator II are used per mole of photocatalyst, and even better when 200 moles or more are used.

[0327]

[0328] Experimental Example 15: Comparative analysis of conversion rate with and without degassing

[0329]

[0330] The method of Preparation Example 1 was used, but the nitrogen degassing step was omitted. Curing was carried out in an ordinary air atmosphere, and the conversion rate was measured. The difference in conversion rate between the presence and absence of degassing was compared and is shown in Table 16 below.

[0331]

[0332] [Table 16] JPEG2026505534000045.jpg32123

[0333]

[0334] The experimental results confirmed that the conversion rate varies greatly depending on whether or not degassing is performed before curing. This indicates that in order to achieve a high conversion rate, it is preferable to degas the mixture before curing to remove oxygen and then cure in a nitrogen (N2) atmosphere.

[0335]

[0336] Manufacturing Example 2: Manufacturing of photocurable resin film

[0014]

[0337]

[0338] The photocurable resin produced using the photocatalytic composition of the present invention was subjected to secondary curing to produce a film resin.

[0339] First, a photocurable resin was prepared by irradiating visible light for 5 seconds using the same method as in Preparation Example 1, except that the photocatalyst equivalent was changed to 1 ppm. For secondary curing, the photocurable resin was applied between two sheets of silicone release paper, and the resin thickness was adjusted to a uniform 50 μm using a microapplicator. The resin was then cured for 100 seconds in a blue LED curing device.

[0340]

[0341] Experimental Example 16: Conversion rate analysis of post-cured resin film

[0342]

[0343] The conversion rate of the film resin of Production Example 2 was measured after 5 seconds of primary curing (bulk polymerization) and after 100 seconds of secondary curing (film curing). The results are shown in Table 17.

[0344]

[0345] [Table 17] JPEG2026505534000046.jpg42169

[0346]

[0347] As a result of the experiment, it was confirmed that when bulk resin produced by primary curing was made into a film and then secondary cured, the conversion rate in the film state was very high even when 1 ppm of photocatalyst was used. This shows that when the present invention is applied to the production of resin films, films with excellent curing polymerization rates can be produced even with a small amount of photocatalyst.

[0348]

[0349] Experimental Example 17: Analysis of film conversion rate by equivalent amount of coinitiator II

[0350]

[0351] A photocurable composition was prepared using the method of Preparation Example 1, except that the photocatalyst equivalent was 1 ppm, the coinitiator I equivalent was 300 ppm, and the coinitiator II equivalent was 1,000 ppm, 500 ppm, 200 ppm, and 100 ppm, respectively, and irradiated with light for 5 seconds to produce a photocurable resin. This was then cured for 100 seconds according to the method of Preparation Example 2 to produce a film resin, and the conversion rates after primary curing (bulk polymerization) and secondary curing (film curing) were measured, and the results are shown in Table 18.

[0352]

[0353] [Table 18] JPEG2026505534000047.jpg90168

[0354]

[0355] As a result of the experiment, when the amount of co-initiator II was reduced from 1,000 ppm to 100 ppm under the same conditions, the conversion rate during bulk polymerization decreased slightly, but after resin film production, it was confirmed that the conversion rate was excellent at 66.6%, even when co-initiator II was used at a low amount of 100 ppm.

[0356] In particular, when the concentration was 200 ppm or more, a high conversion rate of approximately 80% or more was obtained, indicating that a conversion rate of the resin film is more preferable when the equivalent amount of coinitiator II per mole of photocatalyst is 200 moles or more.

[0357]

[0358] Experimental Example 18: Analysis of film conversion rate depending on film curing time

[0359]

[0360] A photoinitiating system was prepared using the same method as in Preparation Example 1, except that the photocatalyst equivalent was changed to 1 ppm, the coinitiator I equivalent to 300 ppm, and the coinitiator II equivalent to 500 ppm. Light was irradiated for 5 seconds to produce a photocurable resin with a conversion rate of 22.0%.

[0361] Using the photocurable resin, film resins were produced by the method of Production Example 2, except that the secondary light irradiation time was adjusted to 20, 40, 60, 80, and 100 seconds. The conversion rate after secondary curing (film curing) for each film resin was measured and the results are shown in Table 19 below, and a conversion rate graph is shown in Figure 5.

[0362]

[0363] [Table 19] JPEG2026505534000048.jpg58170

[0364]

[0365] The experimental results showed that when the secondary light irradiation time was 20 seconds, the conversion rate increased from 22.0% to 49.5%, and when the secondary light irradiation time was extended to 40 seconds or more, the conversion rate increased to over 80%, up to a maximum of 90%. This shows that the conversion rate increases with secondary curing, and is particularly significant when the irradiation time is 40 seconds or more.

[0366]

[0367] Experimental Example 19: Conversion rate analysis by film thickness

[0368]

[0269] Using the same method as in Preparation Example 1, a photoinitiation system was prepared by changing the photocatalyst equivalent to 1 ppm, the coinitiator I equivalent to 300 ppm, and the coinitiator II equivalent to 500 ppm, and light was irradiated for 5 seconds to produce a photocurable resin with a conversion rate of 22.0%.

[0370] The photocurable resin was irradiated with light for 100 seconds according to the method of Preparation Example 2 to produce a film resin, but the coating thickness was changed to 1.0 mm. The conversion rate after secondary curing (film curing) for the produced film resin was measured and the results are shown in Table 20 below.

[0371]

[0372] [Table 20] JPEG2026505534000049.jpg32169

[0373]

[0374] The experimental results confirmed that the conversion rate increased with secondary curing even when the thickness was 1.0 mm. However, when the thickness was increased from 50 μm to 1.0 mm under the same conditions, the conversion rate of film curing decreased slightly from 84.1% to 70.1%, confirming that a thickness of 50 μm is more preferable.

[0375]

[0376] Although some embodiments of the present invention have been described above, the present invention is not limited to the above-described embodiments, and modifications and variations are possible within the scope of the gist of the present invention. It should be understood that such modifications and variations also fall within the technical spirit of the present invention.

Claims

1. A photocatalytic composition comprising: a photocatalyst having thermally activated delayed fluorescence (TADF) properties; and an ionic co-initiator.

2. 2. The photocatalytic composition according to claim 1, wherein the photocatalyst absorbs light in the wavelength range of 400 nm to 600 nm.

3. The photocatalytic composition according to claim 1, wherein the photocatalyst is a cyanoarene-based compound.

4. The photocatalytic composition according to claim 1, wherein the photocatalyst is represented by the following chemical formula 1: [Chemical formula 1] In the above chemical formula 1, R 1 and R 2 are each independently hydrogen, deuterium, a halogen atom, or a nitro group (-NO 2 ), cyano group (-CN), -COOR (where R is hydrogen or C 1 -C 24 alkyl), or substituted or unsubstituted C 1 -C 24 Alkyl, C 2 -C 24 Alkenyl, C 2 -C 24 Alkynyl, C 1 -C 24 Alkoxy or C 4 -C 18 aryl; or linked together to form a substituted or unsubstituted carbazole structure; X is a halogen atom selected from the group consisting of F, Cl, Br and I; n is 1 or 2, m is an integer from 3 to 5, l is 0 or 1, and n+m+l is an integer from 4 to 6.

5. The photocatalytic composition according to claim 1, wherein the photocatalyst is represented by the following chemical formula 2 or 3: [Chemical formula 2] [Chemical formula 3] In the above chemical formula 2, X 1 ~X 10 are each independently hydrogen, deuterium, a halogen atom, -NO 2 , -CN, -COOR (R is hydrogen or C 1 -C 24 alkyl), or substituted or unsubstituted C 1 -C 24 Alkyl, C 2 -C 24 Alkenyl, C 2 -C 24 Alkynyl, C 1 -C 24 Alkoxy or C 4 -C 18 is aryl, In the above chemical formula 3, X 1 ~X 8 are each independently hydrogen, deuterium, a halogen atom, -NO 2 , -CN, -COOR (R is hydrogen or C 1 -C 24 alkyl), or substituted or unsubstituted C 1 -C 24 Alkyl, C 2 -C 24 Alkenyl, C 2 -C 24 Alkynyl, C 1 -C 24 Alkoxy or C 4 -C 18 is aryl, In the above chemical formulas 2 and 3, each X is independently a halogen atom selected from the group consisting of F, Cl, Br, and I; n is 1 or 2; m is an integer of 3 to 5; l is 0 or 1; and n+m+l is an integer of 4 to 6.

6. 2. The photocatalytic composition of claim 1, wherein the molar ratio of the photocatalyst to the coinitiator is 1:10 to 1:5,000.

7. The photocatalytic composition of claim 1 , wherein the ionic coinitiator comprises an anionic coinitiator and a cationic coinitiator.

8. The photocatalytic composition of claim 7, wherein the anionic coinitiator is a borate salt compound.

9. The photocatalytic composition according to claim 7, wherein the anionic coinitiator is represented by the following chemical formula 4: [Chemical formula 4] In the above chemical formula 4, R 3 is C 1 -C 24 Alkyl or -CH 2 SiR' 3 (R' is hydrogen or C 1 -C 24 alkyl), Ar 1 ~Ar 3 are each independently a substituted or unsubstituted C 4 -C 18 is aryl, Z + Li + , K. + , Na + , Rb + , or a substituted or unsubstituted safranin ion, pyrylium ion, cyanine ion, iodonium ion, sulfonium ion, phosphonium ion or ammonium ion.

10. 8. The photocatalytic composition according to claim 7, wherein the cationic coinitiator is one or more compounds selected from the group consisting of iodonium salts, sulfonium salts, and phosphonium salts.

11. The photocatalytic composition according to claim 7, wherein the cationic coinitiator is an iodonium salt compound represented by the following chemical formula 6: [Chemical formula 6] In the above chemical formula 6, Ar 4 and Ar 5 are each independently a substituted or unsubstituted C 4 -C 18 is aryl, Z - is PF 6 - , SbF 6 - , AsF 6 - , B.F. 4 - , (C 6 F 5 ) 4 B - , Cl - , Br - , HSO 4 - , C.F. 3 SO 3 - , FSO 3 - , C.H. 3 SO 3 - , ClO 4 - , P.O. 4 - , NO 3 - , SO 4 - , C.H. 3 SO 4 - , or substituted or unsubstituted C 1 -C 20 Alkyl sulfonate, C 2 -C 20 Haloalkylsulfonates, C 4 -C 10 Aryl sulfonate, camphorsulfonate, C 1 -C 20 Perfluoroalkylsulfonylmethides or C 1 -C 20 It is a perfluoroalkylsulfonylimide ion.

12. The photocatalytic composition according to claim 7, wherein the cationic coinitiator is a sulfonium salt compound represented by the following chemical formula 7: [Chemical formula 7] In the above chemical formula 7, Ar 6 ~Ar 8 are each independently a substituted or unsubstituted C 4 -C 18 is aryl, Z - is PF 6 - , SbF 6 - , AsF 6 - , B.F. 4 - , (C 6 F 5 ) 4 B - , Cl - , Br - , HSO 4 - , C.F. 3 SO 3 - , FSO 3 - , C.H. 3 SO 3 - , ClO 4 - , P.O. 4 - , NO 3 - , SO 4 - , C.H. 3 SO 4 - , or substituted or unsubstituted C 1 -C 20 Alkyl sulfonate, C 2 -C 20 Haloalkylsulfonates, C 4 -C 10 Aryl sulfonate, camphorsulfonate, C 1 -C 20 Perfluoroalkylsulfonylmethides or C 1 -C 20 It is a perfluoroalkylsulfonylimide ion.

13. The photocatalytic composition according to claim 7, wherein the cationic coinitiator is a phosphonium salt compound represented by the following chemical formula 8: [Chemical formula 8] In the above chemical formula 8, R 4 is hydrogen, deuterium, halogen atoms, -NO 2 , -CN, -COOR, -NRCOCH 3 , -SR, -COONH X R 2-X , N.H. X R 2-X , or substituted or unsubstituted C 1 -C 24 Alkyl, C 2 -C 24 Alkenyl, C 2 -C 24 Alkynyl, C 1 -C 24 Alkoxy or C 4 -C 18 aryl, where R is hydrogen or C 1 -C 24 alkyl, x is an integer from 0 to 2, 9 ~Ar 11 are each independently a substituted or unsubstituted C 4 -C 18 aryl, and Z - is PF 6 - , SbF 6 - , AsF 6 - , B.F. 4 - , (C 6 F 5 ) 4 B - , Cl - , Br - , HSO 4 - , C.F. 3 SO 3 - , FSO 3 - , C.H. 3 SO 3 - , ClO 4 - , P.O. 4 - , NO 3 - , SO 4 - , C.H. 3 SO 4 - , or substituted or unsubstituted C 1 -C 20 Alkyl sulfonate, C 2 -C 20 Haloalkylsulfonates, C 4 -C 10 Aryl sulfonate, camphorsulfonate, C 1 -C 20 Perfluoroalkylsulfonylmethides or C 1 -C 20 It is a perfluoroalkylsulfonylimide ion.

14. a polymerizable monomer having an ethylenically unsaturated bond; A photocatalyst having thermally activated delayed fluorescence properties; and A photocurable composition comprising an ionic coinitiator.

15. 15. The photocurable composition according to claim 14, wherein the photocatalyst is used in an amount of 0.00001 mol to 0.01 mol per 100 mol of the polymerizable monomer.

16. A method for producing a photocurable resin, comprising: irradiating a photocurable composition containing a polymerizable monomer having an ethylenically unsaturated bond; a photocatalyst having thermally activated delayed fluorescence properties; and an ionic coinitiator with visible light to polymerize the polymerizable monomer to produce a photocurable resin.

17. 17. The method for producing a photocurable resin according to claim 16, wherein the visible light irradiation is performed for 1 to 240 seconds.

18. 17. The method for producing a photocurable resin according to claim 16, further comprising the step of degassing with nitrogen gas before the irradiation with visible light.

19. The method for producing a photocurable resin according to claim 16, further comprising the step of additionally irradiating the produced resin with visible light.

20. 20. The method for producing a photocurable resin according to claim 19, wherein the produced resin is coated on a substrate to a thickness of 1 μm to 8 mm, and then irradiated with visible light.

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