Organic compounds, organic ionic compounds, polymerization initiators, photo-base generators, and photosensitive compositions

Abstract

The present application provides a novel organic compound and an organic ionic compound having excellent light absorption properties. The organic compound of an embodiment of the present application has a structure represented by the following formula (1). In formula (1), R 1 represents at least one selected from a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, and a substituted or unsubstituted phenyl group; R 2 represents at least one selected from a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkylcarbonyl group having 1 to 4 carbon atoms, a substituted or unsubstituted phenyl group, a substituted or unsubstituted benzoyl group, and a carboxymethyl group; and X represents an organic group having a heterocyclic skeleton containing at least one oxygen atom, nitrogen atom, or sulfur atom in the ring.

Description

Technical Field

[0001] This invention relates to organic compounds, organic ionic compounds, polymerization initiators, photoalkali generators, and photosensitive compositions. Background Technology

[0002] Organic compounds that are active to active energy rays such as ultraviolet light are widely used as active ingredients in photosensitive compositions. For example, organic compounds that act as photopolymerization initiators, photoacid generators, or photoalkali generators are added to photosensitive compositions to promote or assist reactions such as polymerization and crosslinking of reactive compounds and / or resins.

[0003] For example, Patent Document 1 discloses a compound with a ketoprofen skeleton, proposing to generate a base by utilizing the decarboxylation of ketoprofen, thereby causing the reactive compound to react (curing, etc.). Additionally, Patent Document 2, for example, proposes using a compound with a ketoprofen skeleton as a base generating agent, utilizing decarboxylation to cure a photosensitive composition.

[0004] Existing technical documents Patent documents Patent Document 1: Japanese Patent Application Publication No. 2007-101685 Patent Document 2: Japanese Patent Application Publication No. 2010-84144 Summary of the Invention

[0005] The technical problem that the invention aims to solve To enhance the activity of reactive compounds in photosensitive compositions, the organic compounds incorporated in the composition need to possess high light absorption properties. However, as mentioned above, compounds with a ketoprofen skeleton are difficult to obtain high absorbance and absorption coefficient. Furthermore, for use as photoalkali generators, it is also necessary to improve the curability and contrast of the composition during curing.

[0006] One object of the present invention is to provide novel organic compounds with excellent light absorption properties, and organic ionic compounds that can be used as photoalkali generators. Another object of the present invention is to provide polymerization initiators and photoalkali generators that achieve excellent curability and contrast when applied to photosensitive compositions, and photosensitive compositions with excellent curability and contrast.

[0007] Technical means for solving technical problems [1] The organic compounds of the embodiments of the present invention have the structure shown in the following formula (1). In equation (1), R 1R represents at least one group selected from hydrogen atoms, alkyl groups having 1 to 8 carbon atoms, and substituted or unsubstituted phenyl groups; 2 The group is selected from at least one group selected from hydrogen atom, alkyl group having 1 to 8 carbon atoms, alkyl carbonyl group having 1 to 4 carbon atoms, substituted or unsubstituted phenyl group, substituted or unsubstituted benzoyl group, and carboxymethyl group; X represents an organic group having a heterocyclic skeleton containing at least one oxygen atom, nitrogen atom, or sulfur atom within the ring.

[0008] [2] In the above [1], the heterocyclic skeleton comprises at least one heterocycle selected from substituted or unsubstituted furan ring, substituted or unsubstituted pyrrole ring, substituted or unsubstituted N-substituted pyrrole ring, substituted or unsubstituted benzofuran ring, substituted or unsubstituted indole ring, substituted or unsubstituted N-substituted indole ring, and substituted or unsubstituted benzothiophene ring.

[0009] [3] In [1] or [2] above, X is an organic group having at least one structure selected from the following structural formulas. [4] In any of [1] to [3] above, X is an organic group having at least one structure selected from the following structural formulas. [5] The organic ionic compounds of the embodiments of the present invention have the structure shown in the following formula (1-A). In equation (1-A), R 1 R represents at least one group selected from hydrogen atoms, alkyl groups having 1 to 8 carbon atoms, and substituted or unsubstituted phenyl groups; 2 The symbol represents at least one group selected from hydrogen atom, alkyl group having 1 to 8 carbon atoms, alkyl carbonyl group having 1 to 4 carbon atoms, substituted or unsubstituted phenyl group, substituted or unsubstituted benzoyl group, and carboxymethyl group; X represents an organic group having a heterocyclic skeleton containing at least one oxygen atom, nitrogen atom, or sulfur atom within the ring. In formula (1-A), A + The term refers to a cation of an organic base. The aforementioned organic base is at least one compound selected from primary amines, secondary amines, tertiary amines, compounds having an amidine skeleton, and compounds having a guanidine skeleton.

[0010] [6] In the above [5], the organic base is either a compound having an amidine skeleton or a compound having a guanidine skeleton.

[0011] [7] In [5] or [6] above, the above A + It is at least one cation selected from the following structural formulas. [8] In any of [5] to [7] above, X is an organic group having at least one structure selected from the following structural formulas. [9] According to another aspect of the invention, a polymerization initiator is provided. The polymerization initiator contains at least one of the organic compounds described in any one of [1] to [4].

[0012]

[10] According to another aspect of the present invention, a photoalkali generating agent is provided. The photoalkali generating agent contains at least one of the organic ionic compounds described in any one of [5] to [8].

[0013]

[11] According to another aspect of the invention, a photosensitive composition is provided. The photosensitive composition comprises: a reactive compound containing a vinyl compound, and the polymerization initiator described above [9].

[0014]

[12] According to another aspect of the present invention, a photosensitizing composition is provided. The photosensitizing composition comprises: at least one reactive compound selected from isocyanate compounds, epoxy compounds, silane compounds and polyamic acids; and the photoalkali generating agent of

[10] above.

[0015] Invention Effects According to embodiments of the present invention, novel organic compounds with excellent light absorption properties and novel organic ionic compounds that can be used as photoalkali generators are provided. According to another embodiment of the present invention, polymerization initiators and photoalkali generators that achieve excellent curability and contrast when applied to photosensitive compositions are provided, as well as photosensitive compositions with excellent curability and contrast. Attached Figure Description

[0016] Figure 1 This is the ultraviolet absorption spectrum of compound 1-1A obtained by synthesis example 1-1 of the embodiments of the present invention.

[0017] Figure 2 This is the ultraviolet absorption spectrum of compound 1-2A obtained from synthesis examples 1-2 of the embodiments of the present invention.

[0018] Figure 3 These are the ultraviolet absorption spectra of compounds 1-3A obtained from synthesis examples 1-3 of the embodiments of the present invention.

[0019] Figure 4 These are the ultraviolet absorption spectra of compounds 1-4A obtained from synthesis examples 1-4 of the embodiments of the present invention.

[0020] Figure 5These are the ultraviolet absorption spectra of compounds 1-5A obtained from synthesis examples 1-5 of the embodiments of the present invention.

[0021] Figure 6 These are the ultraviolet absorption spectra of compounds 1-6A obtained from synthesis examples 1-6 of the embodiments of the present invention.

[0022] Figure 7 These are the ultraviolet absorption spectra of compounds 1-7A obtained from synthesis examples 1-7 of the embodiments of the present invention.

[0023] Figure 8 These are the ultraviolet absorption spectra of compounds 1-8A obtained from synthesis examples 1-8 of the embodiments of the present invention.

[0024] Figure 9 These are the ultraviolet absorption spectra of compounds 1-9A obtained from synthesis examples 1-9 of the embodiments of the present invention.

[0025] Figure 10 This is the ultraviolet absorption spectrum of compound 1-10A obtained from synthesis examples 1-10 of the embodiments of the present invention.

[0026] Figure 11 This is the ultraviolet absorption spectrum of compound 1-11A obtained from synthesis examples 1-11 of the embodiments of the present invention.

[0027] Figure 12 This is the ultraviolet absorption spectrum of compound 1-12A obtained from synthesis examples 1-12 of the embodiments of the present invention.

[0028] Figure 13 This is the ultraviolet absorption spectrum of compound 1-13A obtained from synthesis examples 1-13 of the embodiments of the present invention.

[0029] Figure 14 This is the ultraviolet absorption spectrum of compound 1-1B obtained from synthesis examples 1-14 of the embodiments of the present invention.

[0030] Figure 15 This is the ultraviolet absorption spectrum of compound 1-1C obtained from synthesis examples 1-15 of the embodiments of the present invention.

[0031] Figure 16 This is the ultraviolet absorption spectrum of compound C-1A obtained from synthesis example C-1 of the embodiments of the present invention.

[0032] Figure 17 This is the ultraviolet absorption spectrum of compound C-2A obtained from synthesis example C-2 of the embodiments of the present invention.

[0033] Figure 18This is the ultraviolet absorption spectrum of compound C-3A obtained from synthesis example C-3 of the embodiments of the present invention.

[0034] Figure 19 This is the ultraviolet absorption spectrum of compound C-4A obtained from synthesis example C-4 of the embodiments of the present invention.

[0035] Figure 20 This is the ultraviolet absorption spectrum of compound 1-14A obtained from synthesis examples 1-16 of the embodiments of the present invention.

[0036] Figure 21 This is the ultraviolet absorption spectrum of compound 1-15A obtained from synthesis examples 1-17 of the embodiments of the present invention.

[0037] Figure 22 This is the ultraviolet absorption spectrum of compound 1-16A obtained from synthesis examples 1-18 of the embodiments of the present invention.

[0038] Figure 23 This is the ultraviolet absorption spectrum of compound C-5A obtained from synthesis example C-5 of the embodiments of the present invention.

[0039] Figure 24 This is the ultraviolet absorption spectrum of compound R-1, a reference example of an embodiment of the present invention. Detailed Implementation

[0040] The following describes representative embodiments of the present invention. However, the present invention is not limited to these embodiments. In this specification, "A and / or B" means any one of "A", "B", or "A and B".

[0041] In this specification, the term "organic" refers to compounds having covalent bonds formed between carbon and hydrogen atoms. In this specification, "organic ionic compound" means a compound containing an organic cation and an anion as a balancing ion. Sometimes the organic cation in an organic ionic compound is referred to as the "cation portion," and the portion constituting its balancing ion (anion) is referred to as the "anion portion." An asterisk (*) may appear in the chemical formula to indicate a valence bond.

[0042] A. The overall composition of organic compounds and organic ionic compounds The organic compounds of the embodiments of the present invention have the structure shown in the following formula (1). In equation (1), R 1 R represents at least one group selected from hydrogen atoms, alkyl groups having 1 to 8 carbon atoms, and substituted or unsubstituted phenyl groups. 2X represents at least one group selected from hydrogen atom, alkyl group having 1 to 8 carbon atoms, alkyl carbonyl group having 1 to 4 carbon atoms, substituted or unsubstituted phenyl group, substituted or unsubstituted benzoyl group, and carboxymethyl group. X is an organic group having a heterocyclic skeleton containing at least one oxygen atom, nitrogen atom, or sulfur atom within the ring.

[0043] The organic compounds of the embodiments of the present invention are novel organic compounds. The organic compounds of the embodiments of the present invention possess excellent light absorption properties by having the structure shown in formula (1) above. Furthermore, the above-described organic compounds can form organic ionic compounds as salts of any suitable base. As a result, the organic ionic compounds are also novel organic ionic compounds. Therefore, the embodiments of the present invention also include organic ionic compounds.

[0044] As described above, the organic compounds of the embodiments of the present invention possess excellent light absorption properties. Therefore, by irradiating the organic compounds with active energy rays, they can be decarboxylated, generating highly reactive free radicals. As a result, the free radicals generated by the organic compounds of the embodiments of the present invention react with reactive compounds, generating growth free radicals in the reactive compounds, thereby enabling continuous addition (polymerization) of the reactive compounds. Thus, the organic compounds of the embodiments of the present invention can achieve efficient free radical polymerization of any suitable reactive compound and can effectively solidify the reactive compounds. That is, the organic compounds of the present invention can be suitably used as polymerization initiators. Therefore, the embodiments of the present invention also include polymerization initiators. The organic compounds of the present invention are more preferably used as free radical polymerization initiators.

[0045] The polymerization initiator of the embodiments of the present invention contains at least one of the above-mentioned organic compounds, and therefore, when the polymerization initiator is applied to the photosensitive composition, the curability and contrast of the photosensitive composition can be improved.

[0046] The organic ionic compounds of the embodiments of the present invention have the structure shown in the following formula (1-A). In equation (1-A), R 1 R 2 X can have the same meaning as shown in equation (1). In equation (1-A), A + This indicates a cation of an organic base. The organic base is at least one compound selected from primary amines, secondary amines, tertiary amines, compounds with an amidine skeleton, and compounds with a guanidine skeleton.

[0047] As can be seen from the above formula (1-A), an organic ionic compound is a compound that has formed a salt with any suitable base A from at least one of the specific groups of organic compounds having the structure shown in formula (1). Therefore, the organic ionic compound of the embodiments of the present invention also has the same structure as that shown in formula (1), and thus can have excellent light absorption properties. More specifically, by irradiating the organic ionic compound with active energy rays, the organic ionic compound decarboxylates and releases base A. Alternatively, in an aqueous solution, hydroxide ions are generated in the system due to the (released) base A. As a result, the base and / or hydroxide ions generated by the organic ionic compound of the embodiments of the present invention add to the reactive compound, which is anionized, thereby enabling the reactive compound to continuously add (polymerize). Thus, the organic ionic compound of the embodiments of the present invention can achieve efficient anionic polymerization of any suitable reactive compound and can well solidify the reactive compound. That is, the organic ionic compound of the present invention is suitable for use as a photoalkali generator. Therefore, the embodiments of the present invention also include photoalkali generators.

[0048] The photoalkali generator of the embodiments of the present invention contains at least one of the above-mentioned organic ionic compounds, and therefore, when the photoalkali generator is applied to the photosensitive composition, the curability and contrast of the photosensitive composition can be improved.

[0049] In this specification, light absorption characteristics refer to the property of absorbing light in the ultraviolet wavelength range. Light absorption characteristics can be confirmed, for example, by measuring the absorption spectrum in the wavelength range of 200 nm to 500 nm and calculating the maximum absorption wavelength and absorption coefficient based on the absorption spectrum. Specific methods and conditions for measuring the absorption spectra of organic compounds and organic ionic compounds are described in the examples below.

[0050] In this specification, cureability is an indicator of the ease with which a photosensitive composition can be cured. Curability is expressed as the ratio of the degree of curing of the photosensitive composition containing the aforementioned organic compound to the degree of curing of the photosensitive composition without the organic compound. Curability is also expressed as the ratio of the degree of curing of the photosensitive composition containing the aforementioned organic ionic compound to the degree of curing of the photosensitive composition containing only the alkali corresponding to the cationic portion of the organic ionic compound.

[0051] In this specification, contrast ratio is an indicator of the developability of the photosensitive composition. Therefore, contrast ratio is also referred to as developability. Specifically, contrast ratio can be determined as follows.

[0052] First, a coating of the photosensitive composition is prepared. This coating is cured by exposure to form a cured film, and the weight of the cured film (m1) is measured. Then, the cured film is further treated with a developing solution, and the weight of the remaining film (residual film) (m2) is measured. The value obtained by dividing m2 by m1 is taken as a1. On the other hand, a coating is prepared from the photosensitive composition under the same conditions as above, and the weight of the unexposed coating (unexposed coating) (m3) is measured. The unexposed coating is not exposed, and after treatment with the same developing solution as above, the weight of the remaining film (unexposed residual film) (m4) is measured. The value obtained by dividing m4 by m3 is taken as a2. Based on the obtained a1 and a2, the contrast ratio is calculated using the following formula (M1).

[0053] Contrast ratio (%) = (a1 - a2) / a1 × 100 ・・・ (M1) The specific composition preparation methods, exposure methods, and measurement methods for calculating curability and contrast are described in detail in the examples described later.

[0054] As described above, the organic compounds and / or polymerization initiators of the embodiments of the present invention can be used in photosensitive compositions. Similarly, the organic ionic compounds and / or photoalkali generators of the present invention can be used in photosensitive compositions. Therefore, embodiments of the present invention include photosensitive compositions. The photosensitive compositions can be used for any suitable application. For example, the photosensitive compositions of the embodiments of the present invention can be used in various applications such as photocurable coatings, photocurable adhesives, printed wiring boards, plating masks, solder resists, various photoresist materials, etc.

[0055] A-1. Organic compounds The organic compounds used in embodiments of the present invention will be described in detail.

[0056] As described above, the organic compounds of the embodiments of the present invention have the structure shown in the following structural formula (1). In equation (1), R 1 R 2 X and X can be independently constructed as follows.

[0057] R 1The substituent is at least one group selected from hydrogen atoms, alkyl groups having 1 to 8 carbon atoms, and substituted or unsubstituted phenyl groups. Specifically, the alkyl groups having 1 to 8 carbon atoms are methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, or octyl. The alkyl group is preferably methyl, ethyl, propyl, or butyl. The substituted phenyl group can be a phenyl group in which at least one hydrogen atom is substituted by any suitable substituent. The number of substituents in the substituted phenyl group is not particularly limited, and can be, for example, 1 to 5. Examples of substituents include halogen atoms such as fluorine, chlorine, bromine, and iodine; and at least one group selected from alkyl groups having 1 to 4 carbon atoms, alkoxy groups having 1 to 4 carbon atoms, hydroxyl groups, nitro groups, and cyano groups. The alkyl groups having 1 to 4 carbon atoms can be, for example, methyl, ethyl, propyl, or butyl. The alkoxy groups having 1 to 4 carbon atoms can be, for example, methoxy, ethoxy, propoxy, or butoxy.

[0058] R 1 Preferably, it is selected from at least one group chosen from hydrogen atom, methyl, ethyl, propyl, butyl, and substituted or unsubstituted phenyl groups. 1 More preferably, it is a hydrogen atom, methyl, ethyl or phenyl, even more preferably a hydrogen atom, methyl or ethyl, and especially preferably a hydrogen atom or methyl.

[0059] R 2 It is at least one group selected from hydrogen atom, alkyl group having 1 to 8 carbon atoms, alkyl carbonyl group having 1 to 4 carbon atoms, substituted or unsubstituted phenyl group, substituted or unsubstituted benzoyl group, and carboxymethyl group. Regarding the alkyl group having 1 to 8 carbon atoms and the substituted or unsubstituted phenyl group, it can be respectively combined with the above-mentioned group targeting R. 1 The meanings of the descriptions are the same. The alkyl carbonyl group having 1 to 4 carbon atoms can specifically be acetyl, ethyl carbonyl, propyl carbonyl, or butyl carbonyl. The substituted or unsubstituted benzoyl group can be an unsubstituted benzoyl group in which at least one hydrogen atom is substituted by any suitable substituent. There is no particular limitation on the number of substituents in the substituted benzoyl group, for example, it can be 1 to 5. Examples of substituents include: halogen atoms such as fluorine, chlorine, bromine, and iodine; and at least one organic group selected from alkyl, alkoxy, hydroxyl, nitro, and cyano groups having 1 to 4 carbon atoms. The alkyl group having 1 to 4 carbon atoms can be methyl, ethyl, propyl, or butyl. The alkoxy group having 1 to 4 carbon atoms can be methoxy, ethoxy, propoxy, or butoxy.

[0060] R 2 Preferably, it is selected from at least one group selected from hydrogen atom, methyl, ethyl, propyl, butyl, acetyl, ethyl carbonyl, propyl carbonyl, butyl carbonyl, substituted or unsubstituted phenyl, substituted or unsubstituted benzoyl and carboxymethyl. 2More preferably, it is hydrogen atom, methyl, ethyl, acetyl, phenyl, benzoyl or carboxymethyl, even more preferably hydrogen atom, methyl, ethyl or carboxymethyl, and especially preferably hydrogen atom, methyl or carboxymethyl.

[0061] X is an organic group (hereinafter also referred to as organic group X) having a heterocyclic skeleton containing at least one oxygen, nitrogen, or sulfur atom within its ring. Organic group X may contain any suitable heterocycle, provided it has a heterocyclic skeleton containing at least one of the following atoms: oxygen, nitrogen, or sulfur. The heterocyclic skeleton in organic group X may representatively contain at least one heterocycle selected from the following: furan skeleton, benzofuran skeleton, pyrrole skeleton, N-substituted pyrrole skeleton, indole skeleton, N-substituted indole skeleton, and benzothiophene skeleton. At least one hydrogen atom in the heterocyclic skeleton of each of these heterocycles may be substituted. That is, in one embodiment, the heterocyclic skeleton in organic group X preferably contains at least one heterocycle selected from the following: a substituted or unsubstituted furan ring, a substituted or unsubstituted pyrrole ring, a substituted or unsubstituted N-substituted pyrrole ring, a substituted or unsubstituted benzofuran ring, a substituted or unsubstituted indole ring, a substituted or unsubstituted N-substituted indole ring, and a substituted or unsubstituted benzothiophene ring.

[0062] As the substituents described above, any suitable group can be used. Examples of substituents that substituted hydrogen atoms in the heterocycle (excluding hydrogen atoms on the N-side of substituted or unsubstituted N-substituted pyrrole rings and hydrogen atoms on the N-side of substituted or unsubstituted N-substituted indole rings) include: aliphatic hydrocarbon groups having 1 to 4 carbon atoms; aromatic hydrocarbon groups having 6 to 12 carbon atoms having substituted or unsubstituted carbon atoms; alkoxy groups having 1 to 8 carbon atoms; hydroxyalkyl groups having 1 to 8 carbon atoms; halogen atoms such as fluorine, chlorine, bromine, and iodine; and at least one group selected from hydroxyl, nitro, and cyano. The aliphatic hydrocarbon groups having 1 to 4 carbon atoms can be, for example, any suitable alkyl, alkenyl, alkynyl, alkylidene, or alkylideyne. Specifically, aliphatic hydrocarbon groups having 1 to 4 carbon atoms can be, for example, methyl, ethyl, propyl, butyl, methylene, ethylene, propylene, butylene, methine, propenyl, ethynyl, propynyl, butynyl, vinyl, ethyleneyl, vinylidene, or propargyl. Aromatic hydrocarbon groups having 6 to 12 carbon atoms, whether substituted or unsubstituted, can be, for example, substituted or unsubstituted phenyl, substituted or unsubstituted benzoyl, or substituted or unsubstituted benzyl. Alkoxy groups having 1 to 8 carbon atoms can be, for example, methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy, heptoxy, or octoxy. Hydroxyalkyl groups having 1 to 8 carbon atoms can be, for example, hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, hydroxypentyl, hydroxyhexyl, hydroxyheptyl, or hydroxyoctyl.

[0063] Examples of substituents that replace the hydrogen atom on the N-side of a substituted or unsubstituted N-substituted pyrrole ring, and the hydrogen atom on the N-side of a substituted or unsubstituted N-substituted indole ring, include aliphatic hydrocarbon groups having 1 to 8 carbon atoms, aromatic hydrocarbon groups having 6 to 12 carbon atoms, alkoxy groups having 1 to 8 carbon atoms, hydroxyalkyl groups having 1 to 8 carbon atoms, alkyl carbonyl groups having 1 to 4 carbon atoms, and substituted or unsubstituted benzoyl groups. The substituents that replace the hydrogen atom on the N-side of a substituted or unsubstituted N-substituted pyrrole ring, and the hydrogen atom on the N-side of a substituted or unsubstituted N-substituted indole ring, are preferably methyl, ethyl, propyl, butyl, hexyl, octyl, methoxy, ethoxy, propoxy, butoxy, hexoxy, octyloxy, hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, hydroxyhexyl, hydroxyoctyl, acetyl, or benzoyl.

[0064] The organic group X is preferably an organic group having at least one structure selected from the following structural formulas. When the organic group X is at least one of the above structural formulas, the organic compound of the embodiments of the present invention has particularly excellent light absorption properties.

[0065] Formula (X2) is a furanyl group with a 2- or 3-position bond. In formula (X2), at least one of the three hydrogen atoms on the ring can be substituted.

[0066] Formula (X3) is a pyrrole group bonded at the 2 or 3 position. In formula (X3), at least one of the three hydrogen atoms in the ring can be substituted. The three hydrogen atoms in the ring do not include the hydrogen atom on the nitrogen atom.

[0067] Formula (X4) is an N-methylpyrrole group bonded at the 2 or 3 position. In formula (X4), at least one of the three hydrogen atoms in the ring can be substituted.

[0068] Formula (X5) is a benzofuran group bonded at the 2 or 3 position. In formula (X5), at least one of the five hydrogen atoms in the ring can be substituted.

[0069] Formula (X6) is a 3-methylindolyl group bonded at the 2-position. In Formula (X6), at least one of the four hydrogen atoms in the ring can be substituted. The four hydrogen atoms in the ring do not include the hydrogen atom at the nitrogen atom.

[0070] Formula (X7) is a 2-methylindolyl group bonded at the 3-position. In Formula (X7), at least one of the four hydrogen atoms in the ring can be substituted. The four hydrogen atoms in the ring do not include the hydrogen atom at the nitrogen atom.

[0071] Formula (X8) is an indole group bonded at the 2 or 3 position. In formula (X8), at least one of the five hydrogen atoms in the ring can be substituted. The five hydrogen atoms in the ring do not include the hydrogen atom at the nitrogen atom.

[0072] Formula (X9) is an N-methyl-indolyl group bonded at the 2 or 3 position. In formula (X9), at least one of the five hydrogen atoms in the ring can be substituted.

[0073] Formula (X10) is an N-methyl-3-methylindolyl group bonded at the 2-position. In formula (X10), at least one of the four hydrogen atoms in the ring can be substituted.

[0074] Formula (X11) is an N-methyl-2-methylindolyl group bonded at the 3-position. In formula (X11), at least one of the four hydrogen atoms in the ring can be substituted.

[0075] Formula (X12) is a benzothiophene group bonded at the 2 or 3 position. In formula (X12), at least one of the five hydrogen atoms in the ring can be substituted.

[0076] Formula (X13) is an organic group having a methoxy group (-OMe) at the 5-position of the organic group in Formula (X5). Specifically, it is a 5-methoxybenzofuran group bonded at the 2- or 3-position. In Formula (X13), at least one of the four hydrogen atoms in the ring can be substituted.

[0077] In the organic groups shown in the above structural formulas, the substituents when substituted are preferably methyl, ethyl, propyl, butyl, methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy, heptoxy, octoxy, hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, hydroxypentyl, hydroxyhexyl, hydroxyheptyl, hydroxyoctyl, substituted or unsubstituted phenyl, or substituted or unsubstituted benzoyl. The substituted phenyl group can be any of the R groups described above. 1 The substituted phenyl group described herein has the same structure. The substituted benzoyl group is also the same.

[0078] The organic group X is more preferably at least one group selected from the following structural formulas. Formula (X2a) is a furanyl group bonded at the 2-position. Formula (X3a) is a pyrroleyl group bonded at the 2-position. Formula (X4a) is an N-methylpyrroleyl group bonded at the 2-position. Formula (X5a) is a benzofuranyl group bonded at the 2-position. As mentioned above, Formula (X6) is a 3-methylindoleyl group bonded at the 2-position. Formula (X12a) is a benzothiophene group bonded at the 2-position. Formula (X13a) is an organic group with a methoxy (-OMe) group at the 5-position of Formula (X5a), which is a 5-methoxybenzofuranyl group bonded at the 2-position. When the organic group X is at least one of the above, the organic compound has particularly excellent light absorption properties. In this context, any organic group having the structure shown in the above formulas (X2a), (X3a), (X4a), (X5a), (X6), (X12a) and (X13a) may have substituents, just as those described in formulas (X2) to (X13).

[0079] In one embodiment, the organic group X may be an organic group having at least one structure selected from the following structural formulas. In organic compounds, when the organic group X has at least one of the structures described above, the organic compound, when used as a polymerization initiator and applied to a photosensitive composition, exhibits particularly excellent curing and developing properties. That is, organic compounds with the organic group X having at least one of the structures described above can function as particularly excellent polymerization initiators. Furthermore, organic compounds with the organic group X having at least one of the structures described above are particularly suitable as free radical polymerization initiators.

[0080] The organic compound shown in formula (1) has a carboxyl group at its end. As a result, the organic compound shown in formula (1) can be anionized by the carboxyl group to form a salt with any suitable base, thereby forming an organic ionic compound. Organic ionic compounds will be described in the next section.

[0081] A-2. Organic ionic compounds The organic ionic compound of the present invention may be composed of a cationic portion and an anionic portion, wherein the cationic portion is derived from any suitable base; and the anionic portion is an anion that serves as a counterion and is derived from an organic compound represented by formula (1). Specifically, the organic ionic compound has the structure shown in formula (1-A). Normally, organic ionic compounds, when combined with any suitable component (e.g., a reactive compound), dissociate into ions upon dissolution. Here, the dissociation of the organic ionic compound can generate an organic cation and an anion as a counterion. The organic ionic compound of the embodiments of the present invention generates a cation of organic base A (A...). +), and anions of organic compounds having the structure shown in formula (1) above (essentially carboxylate anions of carboxylic acids).

[0082] R in equation (1-A) 1 R 2 And X as in equation (1) R 1 R 2 Explanation of X.

[0083] In equation (1-A), A + It is a cation of an organic base. Hereinafter, "A" will sometimes be referred to as organic base A.

[0084] The following is a detailed description of the unique structure of the organic ionic compounds according to embodiments of the present invention.

[0085] In one embodiment, the molar absorptivity ε of the organic ionic compound at the wavelength of maximum absorption is preferably 1.8 × 10⁻⁶. 4 The above is preferred, and more preferably is 1.9 × 10. 4 The above is further preferred to be 2.0×10 4 The above is particularly preferred, with 2.2 × 10⁻⁶ being the optimal value. 4 The above applies. There is no particular upper limit to the molar absorptivity ε at the wavelength of maximum absorption. The preferred molar absorptivity ε for organic ionic compounds at 365 nm is 1.8 × 10⁻⁶. 4 The above is preferred, and more preferably is 1.9 × 10. 4 The above is further preferred to be 2.0×10 4 The above is particularly preferred, with 2.2 × 10⁻⁶ being the optimal value. 4 The above describes the gamma-absorption coefficient E of the organic ionic compound at the wavelength of maximum absorption. This coefficient is preferably 40 or higher, more preferably 50 or higher, and even more preferably 55 or higher. There is no particular upper limit to the gamma-absorption coefficient E at the wavelength of maximum absorption. The gamma-absorption coefficient E of the organic ionic compound at a wavelength of 365 nm is preferably 25 or higher, more preferably 30 or higher, even more preferably 40 or higher, and particularly preferably 50 or higher. The molar absorptivity ε and gamma-absorption coefficient E are calculated using the absorbance measured by a spectrophotometer and the concentration of the solution prepared in the measurement. The unit of molar absorptivity is L / (mol·cm), and the unit of gamma-absorption coefficient is L / (g·cm). Specific measurement methods are described in the examples below.

[0086] As described above, organic ionic compounds having the structure shown in formula (1-A) have a common skeleton with organic compounds having the structure shown in formula (1), and therefore exhibit excellent absorption properties. Specifically, for example, such as Figures 1 to 15 and Figures 20-22As shown, these organic ionic compounds exhibit a high absorption wavelength in the vicinity of 345 nm to 380 nm. Therefore, these organic ionic compounds are particularly effective when irradiated with light of the commonly used wavelength of 365 nm. However, this does not mean that the wavelengths of light to which the organic ionic compounds of the embodiments of the present invention can be applied are limited to the aforementioned wavelengths.

[0087] Organic ionic compounds with the above absorption properties are not limited to the compounds corresponding to the illustrated figures. Any organic compound having the structure shown in formula (1) or an organic ionic compound having the structure shown in formula (1-A) can have excellent absorption properties.

[0088] When using existing compounds with a ketoprofen backbone as photoalkali generators, although anionic polymerization of reactive compounds can occur, good light absorption properties are sometimes not obtained. Therefore, alkali generation is sometimes inefficient. Furthermore, even with a ketoprofen backbone, it is difficult to achieve excellent curability in the photosensitive composition, and it is difficult to improve the contrast (developability) between the exposed and unexposed areas of the photosensitive composition.

[0089] In contrast, the organic ionic compound of the embodiments of the present invention has the structure shown in formula (1-A), and as described above, exhibits excellent light absorption properties. Furthermore, the organic ionic compound can readily release alkali upon light irradiation; therefore, a photoalkali generator containing at least one of the above-mentioned organic ionic compounds can enhance the curability and developability of the photosensitive composition.

[0090] (Organic group X) In one embodiment, the organic group X may be an organic group having at least one structure selected from the following structural formulas. When the organic group X in the organic ionic compound has at least one of the structures described above, the curing and developing properties of the organic ionic compound are particularly excellent when used as a photoalkali generator and when applied to a photosensitive composition. That is, organic ionic compounds in which the organic group X has at least one of the structures described above can function as particularly excellent photoalkali generators.

[0091] For a description of the specific composition of the organic group X having the structures shown in the above structural formulas, please refer to the description of the above formulas (X2a), (X3a), (X4a), (X5a), (X6), (X12a) and (X13a) in section A-1 above.

[0092] (Organic base) In equation (1-A), as described above, A +It is a cation of organic base A. Organic base A is at least one compound selected from primary amines, secondary amines, tertiary amines, compounds with an amidine skeleton, and compounds with a guanidine skeleton.

[0093] The acid dissociation constant (pK) of the conjugate acid of the organic base A used in the embodiments of the present invention at 25°C. a Preferably, the pK value is 6 or more, more preferably 8 or more, and even more preferably 10 or more. a There is no specific limit to the upper limit. pK a Within the aforementioned scope, when the organic ionic compounds of the embodiments of the present invention are used as photoacid generators and applied to photosensitive compositions, alkali can be generated particularly well. As a result, anionic polymerization of the photosensitive composition can be achieved more efficiently.

[0094] As primary, secondary, and tertiary amines, any suitable compound can be used. A primary amine is a compound having an -NH₂ group. A secondary amine is a compound having an organic group in which one hydrogen atom of the -NH₂ group in a primary amine is replaced by a hydrocarbon group. A tertiary amine is a compound having an organic group in which two hydrogen atom of the -NH₂ group in a primary amine is replaced by a hydrocarbon group. As a hydrocarbon group, any suitable hydrocarbon group can be used. Examples of hydrocarbon groups include aliphatic hydrocarbon groups and aromatic hydrocarbon groups. Specifically, examples of aliphatic hydrocarbon groups include alkyl, alkenyl, and ynyl groups having 1 to 10 carbon atoms, either substituted or unsubstituted. As aromatic hydrocarbon groups, an organic group having any suitable aromatic ring can be used. Specifically, examples of organic groups having an aromatic ring include aryl groups having 6 to 20 carbon atoms, either substituted or unsubstituted.

[0095] The primary amine is preferably methylamine, ethylamine, isopropylamine, n-butylamine, tert-butylamine, pentylamine, isopentylamine, hexylamine, cyclohexylamine, heptylamine, octylamine, nonylamine, decylamine, aniline, 2,6-diisopropylaniline, propanolamine, or 1,6-diaminohexane.

[0096] The secondary amine is preferably dimethylamine, diethylamine, diisopropylamine, di-n-butylamine, di-tert-butylamine, N-ethylmethylamine, dipentylamine, diisopentylamine, dihexylamine, diheptylamine, dioctylamine, bis(2-ethylhexyl)amine, dicyclohexylamine, pyrrolidine, piperidine, 2,6-dimethylpiperidine, piperazine, pyrrole, indole, N-(4-pyridylmethyl)ethylamine, diphenylamine, diethanolamine, N-methyldiethanolamine, 2-(ethylamino)ethanol, dioctylamine, morpholine, 3-(diethylamino)propylamine, 2-[2-(dimethylamino)ethoxy]ethanol, bis(2-dimethylaminoethyl) ether, 2-(dimethylamino)ethyl methacrylate, or N-[3-(dimethylamino)propyl]methacrylamide.

[0097] The preferred tertiary amines are trimethylamine, triethylamine, diisopropylethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, trinonylamine, tridecylamine, dimethyldodecylamine, tri(dodecyl)amine, hexamethylenetetramine, triethylenediamine (DABCO: 1,4-diazabicyclo[2.2.0]octane), pyridine, 4-aminopyridine, 4-dimethylaminopyridine (DMAP), N,N-dimethylbenzylamine, triphenylamine, tribenzylamine, N-tert-butoxycarbonylpyrrolidine, pyrazole, triethanolamine, 2-(dimethylamino)ethanol, 2-(diethylamino)ethanol, 2-(diisopropylamino)ethanol, and 2-(dibutylamino)ethanol. 1-Dimethylamino-2-propanol, diisopropanolamine, 2-(dimethylamino)propanol, 2-(diethylamino)propanol, 1-dimethylamino-2-propanol, triisopropanolamine, dimethylaminoisopropanol, 6-dimethylamino-1-hexanol, trioctanolamine, tri(2-methoxymethoxyethyl)amine, tri[2-(2-methoxyethoxy)ethyl]amine, tri{2-(2-methoxyethoxymethoxy)ethyl}amine, tri[2-(1-methoxyethoxy)ethyl]amine, tri[2-(1-ethoxyethoxy)ethyl]amine, tri[2-(1-ethoxypropoxy)ethyl]amine, tri[2-{2-(2-hydroxyethoxy)ethoxy}ethyl]amine or triethanolamine triacetate.

[0098] The organic base is preferably either a compound with an amidine skeleton or a compound with a guanidine skeleton. These bases can have superior basicity and therefore can play a particularly advantageous role as photobase generators in photosensitive compositions.

[0099] Compounds with an amidine skeleton are compounds that have a partial structure represented by the following general formula (Ia) within one molecule.

[0100] General formula: *-C(=NR) x )-NR y R z ・・・(Ia) In equation (Ia), R x R y and R z It can be independently composed of hydrogen atoms or hydrocarbon groups with 1 to 4 carbon atoms. In R x R y and R z When the groups are hydrocarbons, they can be linked together by carbon-carbon bonds to form a cyclic structure. For example, compounds with an amidine skeleton can include compounds with substituted or unsubstituted heterocyclic skeletons, compounds with substituted or unsubstituted fused rings, and compounds with substituted or unsubstituted fused heterocyclic skeletons. As a specific example of a fused heterocyclic skeleton, an imidazole ring can be cited.

[0101] Specific examples of compounds with an amidine skeleton include imidazoles such as imidazole, 1-methylimidazolium, 2-methylimidazolium, 2-ethyl-4-methylimidazolium, 2-phenylimidazolium, 2-benzylimidazolium, and benzimidazole; and diazabicycloundecene (DBU: 1,8-diazabicyclo[5.4.0]undec-7-ene) and diazabicyclononene (DBN: 1,5-diazabicyclo[4.3.0]non-5-ene). Compounds with an amidine skeleton are preferably diazabicycloundecene or diazabicyclononene.

[0102] Compounds with a guanidine skeleton are compounds that have a partial structure shown in the following general formula (IIa) within one molecule.

[0103] General formula: *-NR x -C(=NR y )-NR z -*・・・(IIa) In equation (IIa), R x R y and R z It can be independently composed of hydrogen atoms or hydrocarbon groups having 1 to 4 carbon atoms. In the above R... x R y and R z When the groups are hydrocarbons, they can form a cyclic structure by being linked together by carbon-carbon bonds. For example, compounds with a guanidine skeleton can include compounds with substituted or unsubstituted heterocyclic skeletons, compounds with substituted or unsubstituted fused rings, and compounds with substituted or unsubstituted fused heterocyclic skeletons. Furthermore, for example, the terminal nitrogen atoms of compounds with a guanidine skeleton can be directly linked to each other or linked via at least one carbon atom to form a cyclic structure.

[0104] Specific examples of compounds having a guanidine skeleton include guanidine, biguanide, 1,1,3,3-tetramethylguanidine, TBD (1,5,7-triazabicyclo[4.4.0]dec-5-ene), or MTBD (methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene). Compounds having a guanidine skeleton are preferably TBD or MTBD.

[0105] A + It can be any suitable cation of the above-mentioned organic base A. + Preferably, it is a cation selected from the following structural formulas. In A + When the cation is selected from at least one of the cations having the structural formula shown above, it can exhibit strong basicity. As a result, since the organic ionic compound contains at least one of the above-described cations as A... +Therefore, strong bases can be generated very efficiently when organic ionic compounds are irradiated with light. Thus, when using such cations, organic ionic compounds can be used particularly appropriately as photo-base generators. Specifically, the cation having the structure shown in formula (A-1) is a DBU cation, the cation having the structure shown in formula (A-2) is a DBN cation, and the cation having the structure shown in formula (A-3) is a TBD cation.

[0106] A-3. Synthesis of organic compounds and organic ionic compounds The organic compounds and organic ionic compounds of embodiments of the present invention can be synthesized, for example, according to the following reaction procedures. However, the following reaction procedures do not imply that the methods for producing the organic compounds and organic ionic compounds of embodiments of the present invention are limited to these procedures. Any suitable reaction procedure can be used as long as the final product (i.e., organic compound and / or organic ionic compound) can be obtained.

[0107] In one embodiment, firstly, a compound represented by formula (10) is synthesized. The compound represented by formula (10) can be obtained, for example, by reacting an acyl halide having a heterocyclic skeleton that can form an organic group X, and a substituted or unsubstituted benzene ring as starting materials (starting material) in the presence of any suitable catalyst (reaction Ia).

[0108] [Reaction Ia] In reaction Ia, X can be the organic group X described in section A-1. Therefore, the description of X (organic group) can be found in section A-1.

[0109] Y 1 Y is a halogen (atom) that constitutes an acyl halide having an organic group X. 2 Substituents in the substituted or unsubstituted benzene rings mentioned above. 2 For example, halogens. As Y... 1 and Y 2 The halogens can be fluorine, chlorine, bromine, and iodine, respectively. 1 Chlorine or bromine is preferred. 2 Fluorine is preferred.

[0110] The catalyst used in reaction Ia can be, for example, a metal halide. As a metal halide compound, aluminum chloride can be used, for example.

[0111] The amounts of raw materials, catalysts, and additives added as needed can be adjusted appropriately according to the purpose. Furthermore, the reaction conditions (heating, cooling, reaction time, etc.) can also be adjusted to any suitable condition depending on the type of raw materials, etc.

[0112] The compound shown in formula (10) can be obtained, for example, by reacting any suitable heterocyclic compound (X') that can form an organic group X and any suitable substituted or unsubstituted benzoyl halide compound as starting materials (raw materials) in the presence of any suitable catalyst (reaction Ib).

[0113] [Reaction Ib] In reaction Ib, X' has a heterocyclic skeleton that can form the organic group X. Specifically, X' can be, for example, a compound having a pyrrole skeleton, a compound having an N-methylpyrrole skeleton, a compound having an indole skeleton, or a compound having an N-methylindole skeleton.

[0114] Y 3 and Y 4 Each can be a halogen atom independently. As a halogen, it can be the same as the aforementioned Y... 1 and Y 2 The same halogens are described. Y 3 Chlorine or bromine is preferred. 4 Fluorine is preferred.

[0115] The catalyst used in reaction Ib can be the same as that used in reaction Ia above.

[0116] The amounts of raw materials, catalysts, and additives added as needed can be adjusted appropriately according to the purpose. Furthermore, the reaction conditions (heating, cooling, reaction time, etc.) can also be adjusted to any suitable condition depending on the type of raw materials, etc.

[0117] In one embodiment, for example as shown below, an indole synthesis is carried out in the presence of any suitable solvent, using any suitable substituted or unsubstituted aminoacetophenone and any suitable substituted or unsubstituted halogenated acetophenone (haloacetophenone) as starting materials (raw materials) to obtain the compound shown in formula (11) (reaction Ic). The compound shown in formula (11) may be included in the compound shown in formula (10) above.

[0118] [Reaction Ic] Y in reaction Ic 5 and Y 6 Each can be a halogen atom independently. As a halogen, it can be the same as the aforementioned Y... 1 and Y 2 The same halogens are described. Y 5 Chlorine or bromine is preferred. 6 Fluorine is preferred.

[0119] The indole ring N-alkylation can be achieved by further reacting the compound of formula (11) with an alkylating agent (e.g., iodomethane) in the presence of any suitable base.

[0120] The amounts of raw materials, catalysts, and additives added as needed can be adjusted appropriately according to the purpose. Furthermore, the reaction conditions (heating, cooling, reaction time, etc.) can also be adjusted to any suitable condition depending on the type of raw materials, etc.

[0121] Then, the compound shown in formula (10) or formula (11) is reacted with any suitable compound having amino and carboxyl groups (referred to as amino acids) in the presence of any suitable base and in any suitable solvent (reaction II). Thus, a compound having the structure shown in formula (1) can be obtained.

[0122] [Reaction II] In reaction II, Y can be the Y of reaction Ia. 2 Y of the reaction Ib 4 Or the reaction of Y with Ic 6 Any one of them. That is, Y can be any suitable halogen atom.

[0123] R in reaction II 1 and R 2 R is the organic compound with the structure shown in formula (1) that has already been described in item A-1. 1 and R 2 In other words, R of an organic compound having the structure shown in formula (1) 1 and R 2 The substituents in the amino acids used in reaction II can be used as a guideline.

[0124] Examples of amino acids include glycine, N-methylglycine (sarcosine), alanine, phenylalanine, and N-phenylglycine.

[0125] Examples of inorganic metal salts used as the base in reaction II include alkali metal carbonates, alkali metal hydroxides, alkaline earth metal carbonates, and alkaline earth metal hydroxides. Potassium carbonate is a representative example of such a base.

[0126] The amounts of the compounds, amino acids, and bases shown in formula (10) or formula (11), and any additives added as needed, can be adjusted appropriately according to the purpose. In addition, the reaction conditions (heating, cooling, reaction time, etc.) can also be adjusted to any appropriate conditions depending on the type of raw materials, etc.

[0127] The above-described operation yields an organic compound having the structure shown in formula (1). For example, an organic ionic compound can be obtained from the obtained organic compound by the following operation.

[0128] An organic compound having the structure shown in formula (1) is mixed with any suitable organic base A in any suitable solvent and reacted under any suitable temperature conditions.

[0129] Organic base A is as described in item A-2 above.

[0130] The amounts of organic compound, organic base A, and solvent, as well as the reaction conditions (heating, cooling, reaction time, etc.), can be adjusted appropriately according to the purpose. Regarding reaction conditions, for example, the temperature is room temperature (approximately 25°C), and the reaction time is, for example, in the range of 5 minutes to 5 hours.

[0131] The above-described operation yields an organic ionic compound having the structure shown in formula (1-A).

[0132] B. Photoalkali-generating agent The photoalkali generators of the embodiments of the present invention contain at least one of the above-mentioned organic ionic compounds. As described above, the organic ionic compounds of the embodiments of the present invention have excellent light absorption characteristics and can efficiently generate alkali through light irradiation, thus being particularly suitable for use as photoalkali generators.

[0133] Specifically, the photoalkali generator, by containing an organic ionic compound having the structure shown in formula (1-A), exhibits superior light absorption properties for ultraviolet light and other light compared to existing photoalkali generators (e.g., alkali generators with a ketoprofen skeleton). Furthermore, the photoalkali generator of the embodiments of the present invention, by selecting an appropriate organic group X as the organic group X in the aforementioned organic compound or the aforementioned organic ionic compound, and / or selecting an appropriate organic base as organic base A, can perform better as a photoalkali generator compared to existing photoalkali generators. As a result, when the photoalkali generator of the embodiments of the present invention is formulated together with a reactive compound into a photosensitive composition, it can react under milder conditions compared to photopolymerization initiators or photoacid generators, and thus can be used as a component to improve the curability of the composition. Therefore, the photoalkali generator of the embodiments of the present invention can significantly improve curability and contrast when applied to a photosensitive composition.

[0134] In one embodiment, the photoalkali generator contains at least one organic ionic compound having an organic group X, wherein the organic group X is selected from organic groups having the structures shown in the above structural formulas (X2a), (X3a), (X4a), (X5a), (X6), (X12a), and (X13a). With such a configuration, superior curability and contrast of the photosensitive composition can be achieved.

[0135] In one embodiment, the photoalkali generator comprises at least one organic ionic compound having an organic base A, which has the structures shown in formulas (A1), (A2), and (A3) above. With this configuration, superior curability and contrast of the photosensitive composition can be achieved.

[0136] When the photoalkali generating agent of the embodiments of the present invention is used in conjunction with a photosensitive composition, it may contain two or more of the above-described organic ionic compounds. Alternatively, the photoalkali generating agent may also be used in combination with any suitable material other than the above-described organic ionic compounds that has photoalkali generating ability. When used in conjunction with a photosensitive composition, the photoalkali generating agent preferably contains only one organic compound having the structure shown in formula (1-A) above.

[0137] C. Photosensitive composition One embodiment of the photosensitive composition of the present invention contains a reactive compound and the above-described polymerization initiator. The photosensitive composition of this embodiment contains the polymerization initiator described in section A above (essentially an organic compound having the structure shown in formula (1) above), thus enabling efficient generation of free radicals within the reaction system by light irradiation, and appropriate polymerization and / or crosslinking of the reactive compound through free radical polymerization. As a result, the photosensitive composition of this embodiment exhibits excellent curability under irradiation with ultraviolet light and excellent contrast during development after light irradiation.

[0138] Another embodiment of the photosensitive composition of the present invention contains a reactive compound and the aforementioned photoalkali generating agent. The photosensitive composition of this embodiment contains the photoalkali generating agent described in section B above (essentially an organic ionic compound having the structure shown in formula (1-A) above), thus enabling efficient generation of alkali within the reaction system by light irradiation, and appropriate polymerization and / or crosslinking of the reactive compound through anionic polymerization. As a result, the photosensitive composition of this embodiment exhibits excellent curability under irradiation with ultraviolet light and excellent contrast during development after light irradiation.

[0139] As the reactive compound used in the photosensitive composition, any suitable compound applicable to the photosensitive composition can be used. In the photosensitive composition of one embodiment of the present invention, the reactive compound may contain a vinyl compound. In the photosensitive composition of another embodiment of the present invention, the reactive compound may be at least one compound selected from isocyanate compounds, epoxy compounds, silane compounds, and polyamic acids.

[0140] As vinyl compounds, any suitable compound having one or more carbon-carbon double bonds within its molecule can be cited as examples. The vinyl compound preferably contains a (meth)acrylic acid compound. In this specification, "(meth)acrylic acid" means at least one of "acrylic acid" and "methacrylic acid," that is, a superordinate concept of "acrylic acid" and "methacrylic acid." A (meth)acrylic acid compound is a compound having one or more (meth)acryloyl groups within its molecule. Examples of (meth)acrylic acid compounds include, for example, monofunctional (meth)acrylic acid compounds and polyfunctional (meth)acrylic acid compounds. A polyfunctional (meth)acrylic acid ester is preferred. Furthermore, the (meth)acrylic acid compound can be a monomer, an oligomer, or a prepolymer.

[0141] Examples of monofunctional (meth)acrylic acid compounds include, for example, acrylic acid, methacrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, 1,1-dimethylethyl (meth)acrylate, amyl (meth)acrylate, isoamyl (meth)acrylate, 1,1-dimethylpropyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, and so on. 2-Hydroxypropyl acrylate, 4-Hydroxybutyl acrylate, ethoxyethyl acrylate, isobornyl acrylate, ethyl diethylene glycol (meth)acrylate, benzyl acrylate, cresol (meth)acrylate, dicyclopentenyl acrylate, dicyclopentenyl ethyl acrylate, phenyl acrylate, phenoxyethyl acrylate, 7-amino-3,7-dimethyloctyl acrylate, dimethylaminoethyl acrylate, diethylaminoethyl acrylate, glycidyl acrylate, polyester mono(meth)acrylate.

[0142] Examples of polyfunctional (meth)acrylate compounds include difunctional (meth)acrylates, trifunctional (meth)acrylates, and (meth)acrylates with four or more functionalities. In one embodiment, the (meth)acrylate compound is preferably a hexafunctional methacrylate compound.

[0143] Examples of difunctional (meth)acrylates include, for example, di(meth)acrylates of alkyl diols. Specifically, examples of difunctional (meth)acrylates include 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, and 1,12-dodecanediol di(meth)acrylate.

[0144] Examples of trifunctional (meth)acrylates include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, and polyester tri(meth)acrylate.

[0145] Examples of tetrafunctional (meth)acrylates include di(trimethylolpropane)tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, and polyester tetra(meth)acrylate.

[0146] Examples of 5-functional (meth)acrylates include pentaerythritol penta(meth)acrylate and tripentaerythritol penta(meth)acrylate.

[0147] Examples of hexafunctional (meth)acrylates include dipentaerythritol hexa(meth)acrylate and tripentaerythritol hexa(meth)acrylate.

[0148] Examples of 7-functional or higher (meth)acrylates include octa(meth)acrylates such as tripentaerythritol hepta(meth)acrylate and tripentaerythritol octa(meth)acrylate, as well as polyester poly(meth)acrylates with 4 or higher functionality.

[0149] Isocyanate compounds are compounds having at least one isocyanate group (*-N=C=O) within one molecule. By using isocyanate compounds as reactive compounds, polymeric compounds can be obtained when a photosensitive composition is irradiated with light. Polyurethane can be cited as an example of a polymeric compound.

[0150] As isocyanate compounds, examples include: linear aliphatic diisocyanates such as hexamethylene diisocyanate; branched aliphatic diisocyanates such as 2-methylpentane-1,5-dimethyldiisocyanate and trimethylhexamethylene diisocyanate; cyclic aliphatic isocyanates such as isoflurone diisocyanate, 1,4-diisocyanate cyclohexane, 1,3-bis(isocyanate methyl)cyclohexane, and dicyclohexyl-4,4'-methane diisocyanate; cross-linked cyclic aliphatic diisocyanates such as norbornane-2,6-dimethylbis(methylene)diisocyanate and norbornane-2,5-dimethylbis(methylene)diisocyanate; and 4,4'-diisocyanate- Aromatic isocyanate compounds such as 3,3'-dimethylbiphenyl, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, bibenzyl-4,4'-diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, toluene-2,4-diisocyanate, toluene-2,6-diisocyanate, toluene diisocyanate, isophthalimide diisocyanate, 1,3-bis(2-isocyanate-2-propyl)benzene, 3,3'-dichloro-4,4'-diisocyanate biphenyl, and 2,2-bis(4-isocyanate-phenyl)hexafluoropropane; and isocyanates with fused-ring aromatic compounds such as 1,5-naphthalene diisocyanate. The above-mentioned isocyanate compounds can be used alone or in combination of two or more.

[0151] In order to synthesize polyurethane, in addition to using the above-mentioned isocyanate compounds, any suitable compound having at least two or more hydroxyl groups, i.e., a polyol, can be used to prepare the photosensitive composition. As polyols, examples include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, 2-methyl-1,2-propanediol, 1,4-butanediol, 1,5-pentanediol, 2-methyl-2,3-butanediol, 1,6-hexanediol, 1,2-hexanediol, 2,5-hexanediol, 2-methyl-2,4-pentanediol, 2,3-dimethyl-2,3-butanediol, 2-ethyl-hexanediol, 1,2-octanediol, 1,8-octanediol, 1,2-decanediol, 2,2,4- Trimethylpentanediol, 2-butyl-2-ethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, glycerol, trimethylolpropane, 1,2,4-butanetriol, 2-methyl-1,2,4-butanetriol, 1,2,5-pentanetriol, 1,2,3,6-hexanetetrol, 1,4-sorbitol, pentaerythritol, diglycerol, di(trimethylol)propane, dipentaerythritol, D-threitol, tripentaerythritol, L-arabinitol, ribitol, xylitol, L-rhamnitol, D-glucitol, D-mannitol, galactitol, sorbitol, trehalose, sucrose, maltose, gentiobiose, lactose, melibiose, etc., can be used alone or in combination of two or more.

[0152] An epoxy compound is a compound having at least one epoxy group per molecule. However, epoxy resins are also included in the category of epoxy compounds as long as they have at least one epoxy group per molecule.

[0153] As epoxy compounds, examples include, for instance, diglycidyl ether, spiroglycol diglycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, butanediol diglycidyl ether, glycerol diglycidyl ether, glycidyl propoxytrimethoxysilane, allyl glycidyl ether, butyl glycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, phenyl glycidyl ether, tolyl glycidyl ether, alkylphenol glycidyl ether, 3',4'-epoxycyclohexanecarboxylic acid-3,4-epoxycyclohexylmethyl ester, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, polyglycidyl methacrylate, glycerol polyglycidyl ether, diglycerol polyglycidyl ether, and trimethylolpropane polyglycidyl ether. Glyceryl ether, sorbitol polyglycidyl ether, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, bixylenol type epoxy resin, phenolic varnish type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, anthracene type epoxy resin, naphthol type epoxy resin, dicyclopentadiene type epoxy resin, triphenol type epoxy resin, naphtholic varnish type epoxy resin, glycidylamine type epoxy resin, glycidyl ester type epoxy resin, glycidyl ether type epoxy resin, cresolic varnish type epoxy resin, biphenyl type epoxy resin, alicyclic epoxy resin, heterocyclic epoxy resin, spirocyclic epoxy resin, cyclohexane type epoxy resin, cyclohexanediol type epoxy resin, naphthyl ether type epoxy resin, tris(hydroxymethyl) type epoxy resin, tetraphenylethane type epoxy resin, etc. Among the above. Epoxy compounds can be used alone or in combination of two or more. Preferably, the epoxy compound comprises at least one compound selected from diglycidyl ether, spiroglycol diglycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, phenyl glycidyl ether, tolyl glycidyl ether, 3',4'-epoxycyclohexanecarboxylic acid-3,4-epoxycyclohexylmethyl ester, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, polyglycidyl methacrylate, glycerol polyglycidyl ether, diglycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether, sorbitol polyglycidyl ether, bisphenol A type epoxy resin, bisphenol F type epoxy resin, cresol phenolic varnish type epoxy resin, and biphenyl type epoxy resin.

[0154] In the presence of a photoalkali generator, silane compounds undergo a sol-gel reaction to form polysiloxanes upon light irradiation in a photosensitive composition. Polysiloxanes are polymeric compounds with siloxane bonds (*-O-Si-*) in their main chain and organic groups in their side chains. Specifically, the silane compound can be an organosilane compound having the aforementioned siloxane bonds and any suitable organic group at its terminal.

[0155] Silane compounds can be any suitable compound as long as they contain a siloxane bond. Examples of silane compounds include monoalkylsilanes, monoalkoxysilanes, dialkylsilanes, dialkoxysilanes, trialkylsilanes, trialkoxysilanes, tetraalkylsilanes, tetraalkoxysilanes, and their related compounds. Silane compounds can be, for example, dimers, oligomers, or prepolymers of the above. As silane compounds, examples include, for instance, trimethylmethoxysilane, dimethyldimethoxysilane, methyltrimethoxysilane, tetramethoxysilane, trimethylethoxysilane, dimethyldiethoxysilane, methyltriethoxysilane, tetraethoxysilane, diphenyldimethoxysilane, phenyltrimethoxysilane, diphenyldiethoxysilane, phenyltriethoxysilane, hexyltrimethoxysilane, tetrapropoxysilane, tetrabutoxysilane, poly(methyldimethoxysilyl)propyl methacrylate, poly(methyldiethoxysilyl)propyl methacrylate, poly(trimethoxysilyl)propyl methacrylate, poly(trimethoxysilyl)propyl methacrylate, vinyltrichlorosilane, vinyltrimethoxysilane, etc. Methoxysilanes, vinyltriethoxysilanes, vinyltri(β-methoxyethoxy)silanes, γ-methacryloyloxypropyltrimethoxysilanes, γ-methacryloyloxypropylmethyldimethoxysilanes, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilanes, γ-epoxypropoxypropyltrimethoxysilanes, γ-epoxypropoxypropylmethyldiethoxysilanes, γ-aminopropyltrimethoxysilanes, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilanes, N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilanes, N-phenyl-γ-aminopropyltrimethoxysilanes, γ-mercaptopropyltrimethoxysilanes, γ-chloropropylmethyldimethoxysilanes, γ-chloropropylmethyldiethoxysilanes, etc. Among the above, silane compounds can be used alone or in combination of two or more.

[0156] Polyamic acid (also known as polyamic acid) is a compound that serves as a precursor to polyimide. Polyamic acid is, for example, composed of a condensation product of an acid dianhydride and a diamine compound. Polyimide can be synthesized when a photosensitive composition contains polyamic acid and a photoalkali-generating agent.

[0157] The dianhydride and diamine compounds used in the synthesis of polyamic acid can each be any suitable compound. Examples of dianhydrides include, for instance, 3,3',4,4'-biphenyltetracarboxylic acid dianhydride, 2,3',3,4'-biphenyltetracarboxylic acid dianhydride, pyromellitic acid dianhydride, 3,3',4,4'-benzophenone tetracarboxylic acid dianhydride, 3,3',4,4'-diphenylsulfone tetracarboxylic acid dianhydride, 1,4,5,8-naphthalene tetracarboxylic acid dianhydride, 2,3,6,7-naphthalene tetracarboxylic acid dianhydride, 1,2,5,6-naphthalene tetracarboxylic acid dianhydride, 4,4'-oxophthalic acid dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride (BPAF), 3,4,9,10-dinaphthalene-2,3,5,6-tetracarboxylic acid dianhydride, and bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic acid dianhydride. Tetracarboxylic dianhydrides, including anhydrides such as 5-(dioxotetrahydrofuran-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride), 4-(2,5-dioxotetrahydrofuran-3-yl)-tetrahydronaphthalene-1,2-dicarboxylic anhydride, tetrahydrofuran-2,3,4,5-tetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,4-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, and their related compounds. Among the above, two or more anhydrides may be used alone or in combination.

[0158] Examples of diamine compounds include hexamethylenediamine, octamethylenediamine, 1,9-nonanediamine, 2-methyl-1,8-octanediamine, 1,10-decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine, 1,2-diaminocyclohexane, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, 1,2-bis(2-aminoethyl)cyclohexane, 1,3-bis(2-aminoethyl)cyclohexane, 1,4-bis(2-aminoethyl)cyclohexane, and bis(4- (aminocyclohexyl)methane, 2,6-bis(aminomethyl)bicyclo[2.2.1]heptane, 2,5-bis(aminomethyl)bicyclo[2.2.1]heptane, p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,3'-diaminodibenzophenone, 4,4'-diaminodibenzophenone, 3,4'-diaminodibenzophenone, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane 2,2-Di(3-aminophenyl)propane, 2,2-Di(4-aminophenyl)propane, 2-(3-aminophenyl)-2-(4-aminophenyl)propane, 2,2-Di(3-aminophenyl)-1,1,1,3,3,3-hexafluoropropane, 2,2-Di(4-aminophenyl)-1,1,1,3,3,3-hexafluoropropane, 2-(3-aminophenyl)-2-(4-aminophenyl)-1,1,1,3,3,3-hexafluoropropane, 2-(3-aminophenyl)-2-(4-aminophenyl)-1,1,1,3,3, 3-Hexafluoropropane, 1,1-bis(3-aminophenyl)-1-phenylethane, 1,1-bis(4-aminophenyl)-1-phenylethane, 3,3'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 1,4-diaminonaphthalene, 1,5-diaminonaphthalene, 2,6-diaminonaphthalene, 2,7-diaminonaphthalene, 1,4-diaminoanthracene. Among the above, two or more diamine compounds may be used alone or in combination.

[0159] In addition to the aforementioned reactive compounds, polymerization initiators, and / or photoalkali generators, the photosensitive compositions of embodiments of the present invention may also contain any other suitable additives. Examples of such additives include surfactants, plasticizers, fillers, leveling agents, antioxidants, ultraviolet absorbers, catalysts, dispersants, sensitizers, crosslinking agents, pigments, dyes, inorganic compounds, colorants, solvents, and polymerization inhibitors.

[0160] There are no particular limitations on the use of this photosensitive composition; it can be used for any suitable application. For example, it can be used in photocurable coatings, photocurable inks, photocurable adhesives, printing plates, printing inks, dental compositions, holographic recording materials, image recording materials and other recording materials, printed wiring boards, color filters in display components of televisions, monitors, portable information terminals, digital cameras, etc., plating masks, solder resists, magnetic recording materials, optical switches, electronic circuits, various photoresists, insulating films, protective films or sealants for various electronic materials, and various other applications.

[0161] In one embodiment, the ratio of the reactive compound to the polymerization initiator in the photosensitive composition can be any suitable ratio. The ratio of the polymerization initiator to the total 100 parts by weight of the reactive compound is preferably 0.05 parts by weight or more, more preferably 0.10 parts by weight or more, and even more preferably 0.15 parts by weight or more. On the other hand, the ratio of the polymerization initiator to the total 100 parts by weight of the reactive compound is preferably 20 parts by weight or less, more preferably 10 parts by weight or less, and even more preferably 5 parts by weight or less. Within such ranges, the effect of the photosensitive composition according to the embodiments of the present invention becomes significant.

[0162] In another embodiment, the amount of reactive compound and photoalkali generating agent in the photosensitizing composition can be any suitable ratio. The ratio of photoalkali generating agent to the total 100 parts by weight of the reactive compound is preferably 1 part by weight or more, more preferably 3 parts by weight or more, and even more preferably 5 parts by weight or more. On the other hand, the ratio of photoalkali generating agent to the total 100 parts by weight of the reactive compound is preferably 50 parts by weight or less, more preferably 40 parts by weight or less, and even more preferably 30 parts by weight or less. Within such ranges, the effect of the photosensitizing composition according to the embodiments of the present invention becomes significant.

[0163] [Example] The present invention will now be specifically described using examples, but the present invention is not limited to these examples. The measurement and evaluation methods in the examples are as follows. Unless otherwise specified, "parts" and "%" in the examples are based on weight.

[0164] [Ultraviolet absorption spectrum and absorption coefficient] Methanol solutions (0.02 g / L) of the organic ionic compounds obtained in each synthesis example were prepared, and the absorption spectra and absorbance were measured using a spectrophotometer (Hitachi High Technology Co., Ltd., trade name "U-3900H"). The absorption maximum wavelength (λmax) from 200 nm to 500 nm was read from the obtained absorption spectra, and the results are shown in Table 1. Furthermore, the molar absorptivity ε (L·mol⁻¹) at the maximum absorption wavelength and at 365 nm was calculated based on the solution concentration and absorbance, respectively. -1 ·cm -1 ) and g absorptivity E (L·g) -1 ·cm -1 The results are also shown in Table 1. In addition, the ultraviolet absorption spectra of the organic ionic compounds of each synthetic example are shown in Table 1. Figures 1 to 24 .in, Figures 1 to 24 In the spectra shown in the figures, the horizontal axis represents wavelength (nm) and the vertical axis represents absorbance.

[0165] The following illustrates the synthesis of the compounds used in the Examples, Comparative Examples, and Reference Examples.

[0166] [Synthetic Example 1-1] Synthesis of Compound 1-1 and Compound 1-1A Organic compounds and organic ionic compounds were synthesized according to the following synthetic methods. (First reaction) 3.0 parts by weight of 2-furanoyl chloride and 20.5 parts by weight of fluorobenzene were added to a four-necked flask, followed by 3.1 parts by weight of aluminum chloride at room temperature. The mixture was stirred overnight at 40°C. The liquid was then cooled to room temperature and added to 100 parts by weight of ice water. The mixture was separated into organic and aqueous layers. The organic layer was then washed with water and concentrated under reduced pressure. This yielded 4.0 parts by weight of a compound (hereinafter referred to as compound 1-1a) as a brown oil (yield 91.5%).

[0167] (Second reaction) In a four-necked flask, 4.0 parts by weight of compound 1-1a obtained in the first reaction, 3.2 parts by weight of glycine, 5.8 parts by weight of potassium carbonate, 30.0 parts by weight of dimethyl sulfoxide (DMSO), and 5.0 parts by weight of water were added, and the mixture was stirred at 120°C for 3 hours. The liquid was then cooled to room temperature, and 50.0 parts by weight of water and 30 parts by weight of ethyl acetate were added. After filtration to remove insoluble matter, the organic layer was separated from the aqueous layer. 10.1 parts by weight of concentrated hydrochloric acid was added to the aqueous layer to prepare an acidic solution with pH = 1–2, which was then extracted with ethyl acetate. 0.1 parts by weight of activated carbon was added to the extracted organic layer, and the mixture was stirred at room temperature for 5 minutes. The activated carbon was then removed by filtration from the organic layer, and the mixture was concentrated under reduced pressure. 5.0 parts by weight of methanol was added to the residue after reduced pressure concentration, and crystallization was performed. The precipitated crystals were filtered and dried to obtain 0.9 parts by weight (yield 17.1%) of a yellow solid having the structure shown in formula (1-1).

[0168] (Third reaction) 0.3 parts by weight (1.22 mmol) of the obtained compound 1-1, 0.186 parts by weight (1.22 mmol) of 1,8-diazabicyclo[5.4.0]-7-undecene (DBU), and 5.0 parts by weight of tetrahydrofuran (THF) were added to a sample vial and stirred at room temperature for 0.5 hours. Then, the mixture was concentrated under reduced pressure to obtain a yellowish-brown solid containing a compound with the structure shown in formula (1-1A) below (hereinafter referred to as compound 1-1A). Using 1 The structures of the obtained compounds 1-1 and 1-1A were confirmed by 1H-NMR (DMSO-d6) spectra. 1 The results of the H-NMR spectrum are shown below. • Compound 1-1 (400MHz, DMSO-d6)δ[ppm]: 12.74(br: 1H), 8.02(d: 1H), 7.82(d: 2H),7.27(d: 1H), 6.94(br: 1H), 6.73(dd: 1H), 6.66(d: 2H), 3.93(s: 2H) • Compound 1-1A (400MHz, DMSO-d6)δ[ppm]: 8.00(d: 1H), 7.81(d: 2H), 7.24(d: 1H), 6.72(dd: 1H), 6.62(dd: 2H), 6.30(t: 1H), 3.52-3.50(m: 2H), 3.44(t: 2H), 3.37(d:2H), 3.24(t: 2H), 2.73-2.71(m: 2H), 1.88(quin: 2H), 1.65-1.58(m: 6H) [Synthetic Examples 1-2] Synthesis of Compounds 1-2 and 1-2A Except for replacing glycine with DL-alanine, compounds 1-2 having the structure shown in formula (1-2) and 1-2A having the structure shown in formula (1-2A) were synthesized in the same manner as in Synthesis Example 1-1. The yield of compound 1-2 was 38.1%. Using... 1 H-NMR spectroscopy (DMSO-d6) confirmed the structures of compounds 1-2 and 1-2A. 1 The results of the H-NMR spectrum are shown below. • Compounds 1-2 (400MHz, DMSO-d6)δ[ppm]: 12.73(br: 1H), 8.01(d: 1H), 7.82(d: 2H),7.27(d: 1H), 6.93(d: 1H), 6.73(dd: 1H), 6.65(d: 2H), 4.14-4.07(m: 1H), 1.42(d: 3H) • Compound 1-2A (400MHz, DMSO-d6)δ[ppm]: 11.23(br: 1H), 8.00(d: 1H), 7.79(d: 2H),7.23(d: 1H), 6.72(dd: 1H), 6.61(d: 2H), 6.54(d: 1H), 3.52-3.51(m: 2H), 3.44(t: 2H), 3.24(t: 2H), 2.73-2.70(m: 2H), 1.88(quin: 2H), 1.65-1.58(m: 6H),1.27(d: 3H) [Synthetic Examples 1-3] Synthesis of Compounds 1-3 and 1-3A Except for replacing glycine with sarcosine (N-methylglycine), the same procedure as in Synthesis Example 1-1 was followed to synthesize compounds 1-3 having the structure shown in formula (1-3) and compound 1-3A having the structure shown in formula (1-3A). The yield of compound 1-3 obtained was 71.8%. Using... 1 H-NMR spectroscopy (DMSO-d6) confirmed the structures of compounds 1-3 and 1-3A. 1 The results of the H-NMR spectrum are shown below. • Compounds 1-3 (400MHz, DMSO-d6)δ[ppm]: 12.77(br: 1H), 8.03(d: 1H), 7.88(d: 2H),7.29(d: 1H), 6.77(d: 2H), 6.74(dd: 1H), 4.24(s: 2H), 3.08(s: 3H) • Compound 1-3A (400MHz, DMSO-d6)δ[ppm]: 11.27(br: 1H), 8.00(d: 1H), 7.83(d: 2H),7.23(d: 1H), 6.72(dd: 1H), 6.63(d: 2H), 3.67(s: 2H), 3.51-3.49(m: 2H), 3.43(t: 2H), 3.20(t: 2H), 3.02(s: 3H), 2.69-2.67(m: 2H), 1.86(quin: 2H), 1.64-1.57(m: 6H) [Synthetic Examples 1-4] Synthesis of Compounds 1-4 and 1-4A Except for replacing 2-furanoyl chloride with 2-benzofuranoyl chloride, the same procedure as in Synthesis Example 1-1 was followed to synthesize compound 1-4 having the structure shown in formula (1-4) and compound 1-4A having the structure shown in formula (1-4A). The yield of compound 1-4 obtained was 29.5%. Using 1 H-NMR spectroscopy (DMSO-d6) confirmed the structures of compounds 1-4 and 1-4A. 1 The results of the H-NMR spectrum are shown below. • Compounds 1-4 (400MHz, DMSO-d6)δ[ppm]: 12.78(br: 1H), 7.92(d: 2H), 7.83(d: 1H),7.75(d: 1H), 7.68(s: 1H), 7.53(t: 1H), 7.37(t: 1H), 7.07(t: 1H), 6.70(d: 2H),3.97(d: 2H) • Compound 1-4A (400MHz, DMSO-d6)δ[ppm]: 11.17(br: 1H), 7.91(d: 2H), 7.83(d: 1H),7.75(d: 1H), 7.65(s: 1H), 7.52(t: 1H), 7.37(t: 1H), 6.68(d: 2H), 6.46(t: 1H),3.53-3.51(m: 2H), 3.45(t: 2H), 3.40(d: 2H), 3.25(t: 2H), 2.74-2.72(m: 2H),1.89(quin: 2H), 1.66-1.61(m: 6H) [Synthetic Examples 1-5] Synthesis of Compounds 1-5 and 1-5A Organic compounds and organic ionic compounds were synthesized according to the following synthetic methods. (First reaction) Add 1.8 parts by weight of pyrrole and 50.0 parts by weight of dichloromethane to a four-necked flask, and cool the mixture to below 5°C. Maintain the temperature below 5°C and add 3.7 parts by weight of anhydrous aluminum chloride to the liquid. Then, at a temperature below 5°C, add dropwise a solution of 5.0 parts by weight of 4-bromobenzoyl chloride dissolved in 10.0 parts by weight of dichloromethane. Stir for 1 hour at below 5°C, then stir for 3 hours at room temperature. Then, add the liquid to 100.0 parts by weight of ice water at room temperature. Separately, dissolve the adhering material on the inner wall of the flask with methanol and add it to the ice water. Separate the liquid to separate the organic layer from the aqueous layer. After concentrating the obtained organic layer under reduced pressure, add 10.0 parts by weight of water, 3.0 parts by weight of 30% sodium hydroxide aqueous solution, and 20.0 parts by weight of methanol to the concentrated residue. Stir the liquid overnight at room temperature to decompose the unreacted acyl chloride (4-bromobenzoyl chloride) and to allow the reaction product to crystallize out. The precipitated crystals were then filtered, washed with water, and dried to obtain the compound (hereinafter referred to as compound 1-5a) (yield 50.8%).

[0169] (Second reaction) In a four-necked flask, 2.8 parts by weight of the obtained compound 1-5a, 1.7 parts by weight of glycine, 3.1 parts by weight of potassium carbonate, 0.2 parts by weight of copper iodide (I), 20.0 parts by weight of DMSO, and 2.0 parts by weight of water were added, and the mixture was stirred at 110°C for 2 hours. The liquid was then cooled to room temperature, and 50.0 parts by weight of water and 5.5 parts by weight of concentrated hydrochloric acid were added to prepare an acidic solution with a pH of 1–2. The precipitated solid was removed by filtration, and the filtrate was extracted with ethyl acetate. The extracted organic layer was concentrated under reduced pressure, and 30.0 parts by weight of water were added to induce crystallization. The precipitated crystals were then filtered, washed with water, and dried to obtain compound 1-5 (yield 30.3%) having the structure shown in formula (1-5). 1 The structures of compounds 1-5 were confirmed by H-NMR spectroscopy (DMSO-d6). 1 The results of the H-NMR spectrum are shown below.

[0170] (Third reaction) Except for replacing compound 1-1 with compound 1-5, the third reaction of synthetic example 1-1 was performed in the same manner to obtain a compound having the structure shown in formula (1-5A) (hereinafter referred to as compound 1-5A). 1 H-NMR spectroscopy (DMSO-d6) confirmed the structure of the obtained compounds 1-5A. 1 The results of the H-NMR spectrum are shown below. • Compounds 1-5 (400MHz, DMSO-d6)δ[ppm]: 12.73(br: 1H), 11.80(s: 1H), 7.71(d: 2H),7.10(dd: 1H), 6.77-6.72(m: 2H), 6.64(d: 2H), 6.22(dd: 1H), 3.91(s: 2H) • Compound 1-5A (400MHz, DMSO-d6)δ[ppm]: 11.78(br: 1H), 7.68(d: 2H), 7.07(s: 1H),6.75(d: 1H), 6.59(d: 2H), 6.21(t: 1H), 6.04(br: 1H), 3.52-3.50(m: 2H), 3.44(t: 2H), 3.34(d: 2H), 3.25(t: 2H), 2.73-2.71(m: 2H), 1.88(quin: 2H), 1.66-1.58(m: 6H) [Synthetic Examples 1-6] Synthesis of Compounds 1-6 and 1-6A Organic compounds and organic ionic compounds were synthesized according to the following synthetic methods. (First reaction) 5.0 parts by weight of 4-fluorobenzoyl chloride, 5.1 parts by weight of 1-methylpyrrole, and 50.0 parts by weight of dichloromethane were added to a four-necked flask. Then, while stirring the liquid, 4.6 parts by weight of anhydrous aluminum chloride were added in batches at room temperature, followed by further stirring for 1 hour at room temperature. The liquid was then added to 100.0 parts by weight of ice water at room temperature for separation. The organic layer was concentrated under reduced pressure, and 15.0 parts by weight of methanol, 4.0 parts by weight of 30% sodium hydroxide aqueous solution, and 10.0 parts by weight of water were added to the concentrated residue. The mixture was stirred at room temperature to decompose unreacted 4-fluorobenzoyl chloride. Then, 100.0 parts by weight of water was added, followed by extraction with ethyl acetate. The organic layer was washed with water and then concentrated under reduced pressure to obtain a brown oily compound (hereinafter referred to as compound 1-6a) (yield 49.5%).

[0171] (Second and third reactions) Except that compound 1-6a was used instead of compound 1-1a, the same procedure as in Synthesis Example 1-1 was followed to synthesize compounds 1-6 having the structure shown in formula (1-6) and compounds 1-6A having the structure shown in formula (1-6A). The yield of compound 1-6 obtained was 61.9%. 1 H-NMR spectroscopy (DMSO-d6) confirmed the structures of compounds 1-6 and 1-6A. 1 The results of the H-NMR spectrum are shown below. • Compounds 1-6 (400MHz, DMSO-d6)δ[ppm]: 12.69(br: 1H), 7.62(d: 2H), 7.13(s: 1H),6.71(br: 1H), 6.60(t: 3H), 6.12(dd: 1H), 3.90(s: 2H), 3.86(s: 3H) • Compound 1-6A (400MHz, DMSO-d6)δ[ppm]: 10.51(br: 1H), 7.59(d: 2H), 7.11(t: 1H),6.58-6.54(m: 3H), 6.11(dd: 1H), 6.00(t: 1H), 3.85(s: 3H), 3.54-3.52(m: 2H),3.46(t: 2H), 3.28-3.23(m: 4H), 2.70-2.67(m: 2H), 1.90(quin: 2H), 1.67-1.59(m:6H) [Synthetic Examples 1-7] Synthesis of Compounds 1-7 and 1-7A Organic compounds and organic ionic compounds were synthesized according to the following synthetic methods. (First reaction) 2.9 parts by weight of 2-aminoacetophenone, 4.7 parts by weight of 2-bromo-4'-fluoroacetophenone, and 29.0 parts by weight of N,N-dimethylformamide (DMF) were added to a four-necked flask and stirred at 100°C for 3 hours. The liquid was then cooled to room temperature and added to 200.0 parts by weight of water. The mixture was extracted with ethyl acetate to separate the organic layer from the aqueous layer. The organic layer was then washed with water and concentrated under reduced pressure. 10.0 parts by weight of acetonitrile was added to the concentrated residue to induce crystallization. The precipitated crystals were then filtered, washed with water, and dried to obtain a light brown solid compound (hereinafter referred to as compounds 1-7a) (yield 44.0%).

[0172] (Second and third reactions) Except that compound 1-7a was used instead of compound 1-1a, the same procedure as in Synthesis Example 1-1 was followed to synthesize compound 1-7 having the structure shown in formula (1-7) and compound 1-7A having the structure shown in formula (1-7A). The yield of compound 1-7 obtained was 40.3%. 1 H-NMR spectroscopy (DMSO-d6) confirmed the structures of compounds 1-7 and 1-7A. 1 The results of the H-NMR spectrum are shown below. Compounds 1-7 (400MHz, DMSO-d6)δ[ppm]: 12.72(br: 1H), 11.34(s: 1H), 7.63(d: 3H),7.40(d: 1H), 7.24(t: 1H), 7.07(t: 1H), 6.91(br: 1H), 6.67(d: 2H), 3.94(s:2H), 2.31(s: 3H) • Compound 1-7A (400MHz, DMSO-d6)δ[ppm]: 11.34(br: 1H), 7.61(dd: 3H), 7.40(d: 1H),7.23(t: 1H), 7.06(t: 1H), 6.62(d: 2H), 6.23(t: 1H), 3.52-3.50(m: 2H), 3.44(t:2H), 3.34(d: 2H), 3.24(t: 2H), 2.71-2.69(m: 2H), 2.31(s: 3H), 1.88(quin: 2H),1.66-1.58(m: 6H) [Synthetic Examples 1-8] Synthesis of Compounds 1-8 and 1-8A Organic compounds and organic ionic compounds were synthesized according to the following synthetic methods. (First reaction) In a four-necked flask, 6.5 parts by weight of compound 1-7a obtained in Synthetic Examples 1-7 and 32.5 parts by weight of THF were added. 1.2 parts by weight of 60% sodium hydride were added in portions at room temperature, and the mixture was stirred for 5 minutes at room temperature. Then, 4.7 parts by weight of iodomethane were added dropwise at room temperature, and the mixture was stirred for 3 hours at room temperature. The liquid was then added to 200.0 parts by weight of water at room temperature, and the mixture was extracted with ethyl acetate to separate the organic layer from the aqueous layer. The organic layer was then washed with water, and the washed organic layer was concentrated under reduced pressure. This yielded a brown, oily compound (hereinafter referred to as compound 1-8a).

[0173] (Second and third reactions) Except that compound 1-8a was used instead of compound 1-1a, compounds 1-8 having the structure shown in formula (1-8) and compound 1-8A having the structure shown in formula (1-8A) were synthesized in the same manner as in Synthesis Example 1-1. The yield of compound 1-8 obtained was 65.2%. 1 H-NMR spectroscopy (DMSO-d6) confirmed the structures of compounds 1-8 and 1-8A. 1The results of the H-NMR spectrum are shown below. • Compounds 1-8 (400MHz, DMSO-d6)δ[ppm]: 12.75(br: 1H), 7.62(d: 3H), 7.49(d: 1H),7.31(t: 1H), 7.12(t: 1H), 7.03(t: 1H), 6.66(d: 2H), 3.95(d: 2H), 3.68(s: 3H),2.12(s: 3H) • Compound 1-8A (400MHz, DMSO-d6)δ[ppm]: 10.95(br: 1H), 7.61(d: 1H), 7.57(d: 2H),7.48(d: 1H), 7.29(t: 1H), 7.11(t: 1H), 6.61(d: 2H), 6.39(t: 1H), 3.67(s: 3H),3.52-3.50(m: 2H), 3.44(t: 2H), 3.34(d: 2H), 3.24(t: 2H), 2.71-2.68(m: 2H),2.13(s: 3H), 1.88(quin: 2H), 1.66-1.59(m: 6H) [Synthetic Examples 1-9] Synthesis of Compounds 1-9 and 1-9A Except for replacing pyrrole with 1-(p-toluenesulfonyl)-1H-indole, compounds 1-9 having the structures shown in formulas (1-9) and 1-9A having the structures shown in formula (1-9A) were synthesized in the same manner as in Synthetic Examples 1-5. The yield of compounds 1-9 obtained was 23.0%. Using... 1 H-NMR spectroscopy (DMSO-d6) confirmed the structures of compounds 1-9 and 1-9A. 1 The results of the H-NMR spectrum are shown below. • Compounds 1-9 (400MHz, DMSO-d6)δ[ppm]: 12.69(br: 1H), 11.88(s: 1H), 8.17(d: 1H),7.92(d: 1H), 7.67(d: 2H), 7.49(d: 1H), 7.24-7.16(m: 2H), 6.65(d:3H), 3.91(s:2H) • Compound 1-9A (400MHz, DMSO-d6)δ[ppm]: 8.16(d: 1H), 7.90(s: 1H), 7.65(d: 2H), 7.50(d: 1H), 7.23-7.14(m: 2H), 6.62(d: 2H), 5.95(t: 1H), 3.49-3.46(m: 2H), 3.41(t: 2H), 3.37(d: 2H), 3.23(t: 2H), 2.67-2.64(m: 2H), 1.86(quin: 2H), 1.65-1.57(m: 6H) [Synthetic Examples 1-10] Synthesis of Compounds 1-10 and 1-10A Except for replacing 1-methylpyrrole with 1-methylindole, compounds 1-10 having the structure shown in formula (1-10) and compound 1-10A having the structure shown in formula (1-10A) were synthesized in the same manner as in Synthetic Examples 1-6. The yield of compound 1-10 was 15.2%. Using... 1 H-NMR spectroscopy (DMSO-d6) confirmed the structures of compounds 1-10 and 1-10A. 1 The results of the H-NMR spectrum are shown below. • Compounds 1-10 (400MHz, DMSO-d6)δ[ppm]: 12.70(br: 1H), 8.20(d: 1H), 7.99(s: 1H),7.68(d: 2H), 7.54(d: 1H), 7.29(t: 1H), 7.23(t: 1H), 6.66(d: 3H), 3.92(s: 2H),3.88(s: 3H) • Compound 1-10A (400MHz, DMSO-d6)δ[ppm]: 10.85(br: 1H), 8.19(d: 1H), 7.98(s: 1H),7.65(d: 2H), 7.54(d: 1H), 7.28(t: 1H), 7.22(t: 1H), 6.61(d: 2H), 5.93(t: 1H),3.88(s: 3H), 3.53-3.51(m: 2H), 3.45(t: 2H), 3.32(d : 2H), 3.25(t: 2H), 2.72-2.69(m: 2H), 1.89(quin: 2H), 1.66-1.59(m: 6H) [Synthetic Examples 1-11] Synthesis of Compounds 1-11 and 1-11A Except for replacing 2-furanoyl chloride with 2-benzo[b]thiophenecarboxyl chloride, compounds 1-11 having the structure shown in formula (1-11) and 1-11A having the structure shown in formula (1-11A) were synthesized in the same manner as in Synthesis Example 1-1. The yield of compound 1-11 was 17.0%. 1 H-NMR spectroscopy (DMSO-d6) confirmed the structures of compounds 1-11 and 1-11A. 1 The results of the H-NMR spectrum are shown below. • Compounds 1-11 (400MHz, DMSO-d6)δ[ppm]: 12.76(br: 1H), 8.06(dd: 3H), 7.81(d: 2H),7.54-7.45(m: 2H), 7.02(t: 1H), 6.71(d: 2H), 3.96(d: 2H) • Compound 1-11A (400MHz, DMSO-d6)δ[ppm]: 11.05(br: 1H), 8.05(dd: 3H), 7.79(d: 2H),7.53-7.45(m: 2H), 6.68(d: 2H), 6.40(t: 1H), 3.54-3.51(m: 2H), 3.45(t: 2H),3.39(d: 2H), 3.26(t: 2H), 2.74-2.72(m: 2H), 1.89(quin: 2H), 1.66-1.59(m: 6H) [Synthetic Examples 1-12] Synthesis of Compounds 1-12 and 1-12A Except for replacing 1-methylpyrrole with benzo[b]thiophene, compounds 1-12 having the structure shown in formula (1-12) and compound 1-12A having the structure shown in formula (1-12A) were synthesized in the same manner as in Synthetic Examples 1-6. The yield of compound 1-12 was 19.2%. 1 H-NMR spectroscopy (DMSO-d6) confirmed the structures of compounds 1-12 and 1-12A. 1 The results of the H-NMR spectrum are shown below. • Compounds 1-12 (400MHz, DMSO-d6)δ[ppm]: 12.76(br: 1H), 8.27(s: 1H), 8.18-8.09(m:2H), 7.71(d: 2H), 7.48-7.45(m: 2H), 6.97(br: 1H), 6.68(d: 2H), 3.95(d: 2H) • Compound 1-12A (400MHz, DMSO-d6)δ[ppm]: 10.86(br: 1H), 8.22(s: 1H), 8.14-8.08(m:2H), 7.67(d: 2H), 7.46-7.44(m: 2H), 6.62(d: 2H), 6.29(t: 1H), 3.54-3.51(m:2H), 3.45(t: 2H), 3.34(d: 2H), 3.25(t: 2H), 2.72-2.69(m: 2H), 1.89(quin: 2H),1.66-1.60(m: 6H) [Synthetic Examples 1-13] Synthesis of Compounds 1-13 and 1-13A Organic compounds and organic ionic compounds are synthesized according to the following synthetic methods. (Synthesis of compounds 1-13a) 25.0 parts by weight of DMF were added to a four-necked flask, and 22.0 parts by weight of phosphoric acid chloride were added dropwise at room temperature. After stirring for 10 minutes at room temperature, 5.0 parts by weight of 2-butylbenzofuran were added dropwise at room temperature, and the temperature was raised to 85°C. After stirring at 85°C for 2 hours, 13.2 parts by weight of phosphoric acid chloride were added dropwise at 85°C, and the mixture was stirred further at 85°C for 2.5 hours. Then, the liquid was added to 200.0 parts by weight of ice water at room temperature, and the mixture was extracted with ethyl acetate to separate the organic layer from the aqueous layer. The organic layer was then washed with water, and the washed organic layer was concentrated under reduced pressure. The concentrated residue was purified using a silica gel column (100% hexane) to give a pale yellow oily compound (hereinafter referred to as compound 1-13a) (yield 62.8%).

[0174] (Synthesis of compounds 1-13b) In a four-necked flask, 3.1 parts by weight of compound 1-13a, 15.7 parts by weight of acetonitrile, and 0.2 parts by weight of 85% phosphoric acid were added. 2.0 parts by weight of 35% hydrogen peroxide were added dropwise at a temperature below 10°C. Then, 6.7 parts by weight of a 25% sodium hypochlorite aqueous solution was added dropwise while maintaining the temperature below 10°C. The temperature was then raised to 35°C, and the 25% sodium hypochlorite aqueous solution and 35% hydrogen peroxide were added continuously while observing the reaction. The total amount added was 6.0 parts by weight of 25% sodium hypochlorite aqueous solution and 1.0 part by weight of 35% hydrogen peroxide. After stirring at 35°C for 1.5 hours, 80.0 parts by weight of water were added to induce crystallization. The precipitated crystals were filtered, washed with water, and dried to obtain the compound (hereinafter referred to as compound 1-13b) (yield 76.1%).

[0175] (Synthesis of compounds 1-13c) In a four-necked flask, 2.5 parts by weight of compound 1-13b, 25.0 parts by weight of toluene, and 2 drops of DMF were added, followed by the addition of 2.7 parts by weight of thionyl chloride at room temperature. The mixture was then heated to 80°C and stirred at 80°C for 1 hour. The reaction solution was then cooled to room temperature and concentrated under reduced pressure to obtain a brown oily compound (hereinafter referred to as compound 1-13c).

[0176] (First reaction, second reaction, and third reaction) Except for changing 2-furanoyl chloride to compound 1-13c, the same procedure as in Synthetic Example 1-1 was followed to synthesize compound 1-13 having the structure shown in formula (1-13) and compound 1-13A having the structure shown in formula (1-13A). The yield of compound 1-13 obtained was 20.6%. Using... 1 H-NMR spectroscopy (DMSO-d6) confirmed the structures of compounds 1-13 and 1-13A. 1 The results of the H-NMR spectrum are shown below. • Compounds 1-13 (400MHz, DMSO-d6)δ[ppm]: 12.75(br: 1H), 7.62(d: 3H), 7.37-7.29(m:2H), 7.24(t: 1H), 6.98(t: 1H), 6.65(d: 2H), 3.94(d: 2H), 2.82(t: 2H), 1.70-1.63(m: 2H), 1.30-1.21(m: 2H), 0.82(t: 3H) • Compound 1-13A (400MHz, DMSO-d6)δ[ppm]: 11.18(br: 1H), 7.61(d: 1H), 7.57(d: 2H),7.36(d: 1H), 7.31(t: 1H), 7.23(t: 1H), 6.60(d: 2H), 6.35(t: 1H), 3.53-3.51(m:2H), 3.45(t: 2H), 3.35(d: 2H), 3.25(t: 2H), 2.82(t: 2H), 2.74-2.71(m: 2H),1.89(quin: 2H), 1.70-1.59(m: 8H), 1.30-1.21(m: 2H), 0.82 (t: 3H) [Synthetic Example 1-14] Synthesis of Compound 1-1B Except for replacing 1,8-diazabicyclo[5.4.0]-7-undecene (DBU) with 1,5-diazabicyclo[4.3.0]-5-nonene (DBN), the same procedure as in Synthesis Example 1-1 was followed to synthesize compound 1-1B having the structure shown in formula (1-1B). The yield of compound 1-1B obtained was 15.6%. Using 1 The structure of the obtained compound 1-1B was confirmed by 1H-NMR spectroscopy (DMSO-d6). 1 The results of the H-NMR spectrum are shown below. • Compound 1-1B (400MHz, DMSO-d6)δ[ppm]: 8.00(d: 1H), 7.80(d: 2H), 7.23(d: 1H), 6.71(dd: 1H), 6.62(d: 2H), 6.28(t: 1H), 3.56(t: 2H), 3.36-3.33(m: 4H), 3.28(t:2H), 2.78(t: 2H), 2.00(quin: 2H), 1.88(quin: 2H) [Synthetic Examples 1-15] Synthesis of Compound 1-1C Except for replacing 1,8-diazabicyclo[5.4.0]-7-undecene (DBU) with 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD), the same procedure as in Synthesis Example 1-1 was followed to synthesize compound 1-1C having the structure shown in formula (1-1C). The yield of compound 1-1C obtained was 15.6%. Using 1 H-NMR spectroscopy (DMSO-d6) confirmed the structure of the obtained compound 1-1C. 1The results of the H-NMR spectrum are shown below. • Compound 1-1C (400MHz, DMSO-d6)δ[ppm]: 10.14(br: 1H), 8.00(d: 1H), 7.80(d: 2H),7.23(d: 1H), 6.71(dd: 1H), 6.64(d: 2H), 6.41(t: 1H), 3.47(d: 2H), 3.25(t:4H), 3.14(t: 4H), 1.86(quin: 4H) [Synthetic Examples 1-16] Synthesis of Compounds 1-14 and 1-14A Organic compounds and organic ionic compounds were synthesized according to the following synthetic methods. (First reaction) 15.0 parts by weight of 2-furanoyl chloride and 27.1 parts by weight of bromobenzene were added to a four-necked flask, followed by the addition of 16.7 parts by weight of aluminum chloride at room temperature. The mixture was heated to 80°C and stirred at 80°C for 2 hours. 15 parts by weight of ethyl acetate were added to the liquid, and the mixture was cooled to room temperature. Then, the liquid was added to 150 parts by weight of ice water, followed by the addition of 40 parts by weight of ethyl acetate. The mixture was separated into organic and aqueous layers. The organic layer was concentrated under reduced pressure, and 150 parts by weight of cyclohexane were added to the concentrated residue. The mixture was cooled with ice water to allow crystallization. The precipitated crystals were filtered and dried to obtain 21.7 parts by weight of a grayish-white solid compound (hereinafter referred to as compound 1-14a) (yield 75.4%).

[0177] (Second and third reactions) Except that compounds 1-14a were used instead of compounds 1-5a and glycine was replaced with DL-2-phenylglycine, compounds 1-14 having the structure shown in formula (1-14) and compounds 1-14A having the structure shown in formula (1-14A) were synthesized in the same manner as in Synthetic Examples 1-5. The yield of compounds 1-14 obtained was 43.4%. 1 The structures of compounds 1-14 and 1-14A were confirmed by 1H-NMR (DMSO-d6) spectra. 1 The results of the H-NMR spectrum are shown below. • Compounds 1-14 (400MHz, DMSO-d6)δ[ppm]: 13.07(br: 1H), 7.98(d: 1H), 7.78(d: 2H),7.53(d: 1H), 7.39(t: 2H), 7.32(t: 1H), 7.25(d: 1H), 7.21(d: 1H), 6.79(d: 2H),6.70(dd: 1H), 5.27(d: 1H) • Compound 1-14A (400MHz, DMSO-d6)δ[ppm]: 10.49(br: 1H), 7.94(d: 1H), 7.70(d: 2H),7.39(d: 2H), 7.23(t: 2H), 7.19(d: 1H), 7.14(t: 1H), 6.94(d: 1H), 6.67(dd:1H), 6.55(d: 2H), 4.52(d: 1H), 3.52-3.50(m: 2H), 3.43(t: 2H).3.21(t: 2H),2.66-2.64(m: 2H), 1.88(quin: 2H), 1.64-1.57(m: 6H) [Synthetic Examples 1-17] Synthesis of Compounds 1-15 and 1-15A Organic compounds and organic ionic compounds were synthesized according to the following synthetic methods. Except that compounds 1-14a were used instead of compounds 1-5a and glycine was replaced with iminodiacetic acid, compounds 1-15 having the structure shown in formula (1-15) and 1-15A having the structure shown in formula (1-15A) were synthesized in the same manner as in Synthetic Examples 1-5. The yield of compound 1-15 was 15.6%. 1 The structures of compounds 1-15 and 1-15A were confirmed by 1H-NMR (DMSO-d6) spectra. 1 The results of the H-NMR spectrum are shown below. • Compounds 1-15 (400MHz, DMSO-d6)δ[ppm]: 12.79(br: 1H), 8.02(d: 1H), 7.88(d: 2H),7.29(d: 1H), 6.73(dd: 1H), 6.67(d: 2H), 4.23(s: 4H) • Compound 1-15A (400MHz, DMSO-d6)δ[ppm]: 7.99(br: 1H), 7.82(d: 2H), 7.24(br: 1H),6.71(dd: 1H), 6.51(d: 2H), 4.00(br: 4H), 3.43-3.41(m: 4H), 3.36(t: 4H), 3.19-3.16(m: 4H), 2.59-2.57(m: 4H), 1.82(quin: 4H), 1.63-1.56(m: 12H) [Synthetic Examples 1-18] Synthesis of Compounds 1-16 and 1-16A Organic compounds and organic ionic compounds were synthesized according to the following synthetic methods. (First reaction) 2.2 parts by weight of 2-hydroxy-5-methoxybenzaldehyde, 3.0 parts by weight of 2-bromo-4'-fluoroacetophenone, 2.1 parts by weight of potassium carbonate, and 15.0 parts by weight of acetonitrile were added to a four-necked flask and mixed. The mixture was heated to 80°C and stirred at 80°C for 2 hours. The liquid was then cooled to room temperature, and 50 parts by weight of water were added to induce crystallization. The precipitated crystals were then filtered and washed with water. The crystals were added to 30 parts by weight of methanol, stirred, filtered, and dried to obtain 3.1 parts by weight of a grayish-white solid compound (hereinafter referred to as compound 1-16a) (yield 83.4%).

[0178] (Second and third reactions) Except that compound 1-16a was used instead of compound 1-1a as described above, compounds 1-16 having the structure shown in formula (1-16) and 1-16A having the structure shown in formula (1-16A) were synthesized in the same manner as in Synthesis Example 1-1. The yield of compound 1-16 obtained was 33.5%. 1 H-NMR spectroscopy (DMSO-d6) confirmed the structures of compounds 1-16 and 1-16A. 1 The results of the H-NMR spectrum are shown below. • Compounds 1-16 (400MHz, DMSO-d6)δ[ppm]: 12.74(br: 1H), 7.92(d: 2H), 7.65(d: 1H),7.59(s: 2H), 7.29(d: 1H), 7.12(dd: 1H), 7.02(br: 1H), 6.71(d: 2H), 3.98(d:2H), 3.82(s: 3H) • Compound 1-16A (400MHz, DMSO-d6)δ[ppm]: 7.88(d: 2H), 7.65(d: 1H), 7.55(d: 2H), 7.29(d: 1H), 7.10(dd: 1H), 6.65(d: 2H), 6.38(t: 1H), 3.82(s: 3H), 3.53-3.51(m:2H), 3.45(t: 2H), 3.36(d: 2H), 3.25(t: 2H), 2.72-2.70(m: 2H), 1.89(quin: 2H),1.66-1.59(m: 6H) [Synthetic Example C-1] Synthesis of Compound C-1 and Compound C-1A Except for replacing compound 1-1 with N-phenylglycine (the compound shown in formula (C-1) below), compound C-1A as shown in formula (C-1A) below was synthesized by operating in the same manner as in synthetic example 1-1. Using 1 The structure of the obtained compound C-1A was confirmed by H-NMR spectroscopy (DMSO-d6). 1 The results of the H-NMR spectrum are shown below. • Compound C-1A (400MHz, DMSO-d6)δ[ppm]: 11.58(br: 1H), 7.03(dd: 2H), 6.48(t: 3H),5.11(br: 1H), 3.53-3.50(m: 2H), 3.44(t: 2H), 3.25(t: 2H), 3.24(s: 2H), 2.76-2.73(m: 2H), 1.88(quin: 2H), 1.66-1.59(m: 6H) [Synthetic Example C-2] Synthesis of Compound C-2 and Compound C-2A Except for replacing compound 1-1 with ketoprofen (the compound shown in formula (C-2) below), the same procedure as in synthetic example 1-1 was followed to synthesize compound C-2A as shown in formula (C-2A) below. Using 1The structure of the obtained compound C-2A was confirmed by H-NMR spectroscopy (DMSO-d6). 1 The results of the H-NMR spectrum are shown below. • Compound C-2A (400MHz, DMSO-d6)δ[ppm]: 11.65(br: 1H), 7.73-7.66(m: 4H), 7.56(t:3H), 7.49(d: 1H), 7.41(t: 1H), 3.51-3.48(m: 2H), 3.44-3.36(m: 3H), 3.18(t:2H), 2.68-2.66(m: 2H), 1.85(quin: 2H), 1.63-1.52(m: 6H), 1.28(d: 3H) [Synthetic Example C-3] Synthesis of Compound C-3 and Compound C-3A Organic compounds and organic ionic compounds were synthesized according to the following synthetic methods. (First reaction and second reaction) 2.0 parts by weight of thiosalicylic acid and 40.0 parts by weight of 98% sulfuric acid were added to a four-necked flask, followed by the partial addition of 7.7 parts by weight of phenoxyacetic acid at room temperature. The liquid was maintained at room temperature and stirred for 1 hour, then stirred further at 80°C for 2 hours. The liquid was then cooled to room temperature and added to 200.0 parts by weight of ice water. The liquid was then heated to 100°C and stirred for 5 minutes, followed by cooling to room temperature. The precipitated crystals were filtered, washed with water, and dried to give yellow crystals of compound C-3 with the structure shown in formula (C-3) (yield 51.2%).

[0179] (Third reaction) Then, except that compound 1-1 was replaced with the above-mentioned compound C-3, the same procedure as in Synthesis Example 1-1 was followed to synthesize compound C-3A as shown in the following formula (C-3A). Using 1 H-NMR spectroscopy (DMSO-d6) confirmed the structures of the obtained compounds C-3 and C-3A. 1 The results of the H-NMR spectrum are shown below. • Compound C-3 (400MHz, DMSO-d6)δ[ppm]: 13.19(br: 1H), 8.47(d: 1H), 7.87-7.82(m:3H), 7.78(t: 1H), 7.59(t: 1H), 7.48(dd: 1H), 4.87(s: 2H) • Compound C-3A (400MHz, DMSO-d6)δ[ppm]: 11.12(br: 1H), 8.46(d: 1H), 7.83(d: 1H),7.79-7.73(m: 3H), 7.57(t: 1H), 7.35(dd: 1H), 4.30(s: 2H), 3.52-3.49(m: 2H),3.44(t: 2H), 3.22(t: 2H), 2.70-2.68(m: 2H), 1.87(quin: 2H), 1.63-1.56(m: 6H) [Synthetic Example C-4] Synthesis of Compound C-4 and Compound C-4A Except for replacing glycine with β-alanine, the same procedure as in Synthesis Example 1-1 was followed to synthesize compound C-4 (C-4) and compound C-4A (C-4A). The yield of compound C-4 was 28.0%. 1 H-NMR spectroscopy (DMSO-d6) confirmed the structures of the obtained compounds C-4 and C-4A. 1 The results of the H-NMR spectrum are shown below. • Compound C-4 (400MHz, DMSO-d6)δ[ppm]: 12.32(br: 1H), 8.01(d: 1H), 7.83(d: 2H),7.27(d: 1H), 6.77(t: 1H), 6.73(dd: 1H), 6.67(d: 2H), 3.37(t: 2H), 2.54(t: 2H) • Compound C-4A (400MHz, DMSO-d6)δ[ppm]: 8.00(s: 1H), 7.81(d: 2H), 7.25(d: 1H), 6.8(br: 1H), 6.72(dd: 1H), 6.62(d: 2H), 3.51-3.49(m: 2H), 3.43(t: 2H), 3.24(t:4H), 2.74-2.72(m: 2H), 2.20(t: 2H), 1.87(quin: 2H), 1.65-1.58(m: 6H) [Synthetic Example C-5] Synthesis of Compound C-5 and Compound C-5A Organic ionic compounds were synthesized according to the following synthetic method. 1.0 part by weight of 2-bromoacetylnaphthalene, 0.86 parts by weight of dimethyldodecylamine, and 5.0 parts by weight of acetonitrile were added to a four-necked flask. After stirring at room temperature for 6 hours, the mixture was concentrated under reduced pressure. Then, 10 parts by weight of methanol, 0.61 parts by weight of N-phenylglycine, and 0.8 parts by weight of sodium methoxide were added to the residue after reduced pressure concentration, and the mixture was stirred at room temperature for 1 hour. Then, 10.0 parts by weight of ethyl acetate and 10 parts by weight of water were added to the liquid, and the mixture was separated into organic and aqueous layers. The organic layer was washed with water, and the washed organic layer was concentrated under reduced pressure to obtain 2.0 parts by weight (93.5%) of a brown solid compound having the structure shown in formula (C-5) (hereinafter referred to as compound C-5). The structure of the obtained compound C-5 was confirmed by 1H-NMR spectroscopy (DMSO-d6). 1 The results of the H-NMR spectrum are shown below. • Compound C-5 (400MHz, DMSO-d6)δ[ppm]: 8.76(s: 1H), 8.16(d: 1H), 8.12(d: 1H), 8.06(d: 1H), 8.01(d: 1H), 7.75(t: 1H), 7.69(t: 1H), 7.02(t: 2H), 6.47-6.44(m:3H), 5.42(s: 2H), 5.06(br: 1H), 3.63-3.59(m: 2H), 3.32(s: 6H), 1.75(br: 2H),1.29-1.22(m: 20H), 0.85(t: 3H) [Reference example compound R-1] As a reference example, a compound R-1 having the structure shown in the following formula (R-1) is prepared. Specifically, as compound R-1, 1-[({1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]ethylene}amino)oxy]ethane-1-one manufactured by Tokyo Chemical Industry Co., Ltd. is used. The following illustrates the preparation and evaluation of the photosensitive composition.

[0180] [Example 1] Aurethane-based photosensitive composition (1) Preparation of urethane-based photosensitive compositions As a reactive compound, 1.0 parts by weight of hexamethylene diisocyanate (manufactured by Tokyo Chemical Industry Co., Ltd., referred to as "HDI" in the table), 1.5 parts by weight of polyethylene glycol 600 (manufactured by Tokyo Chemical Industry Co., Ltd., referred to as "PEG" in the table), and 5.0 parts by weight of tetrahydrofuran were added to a container and mixed at room temperature to prepare a resin solution. Then, 0.02 parts by weight of the organic ionic compound (compound 1-1A) of Synthesis Example 1-1, which serves as a photoalkali generator, was added to 1.0 parts by weight of the resin solution at room temperature and mixed to prepare a photosensitive composition.

[0181] (2) Exposure and development of urethane-based photosensitive compositions The obtained photosensitive composition was coated onto a pre-weighed glass plate (manufactured by Matsunami Glass Industry Co., Ltd.) using a spin coater (manufactured by I-DEN VIETNAM CO.,LTD., trade name "SC2005"). The coated glass plate was dried at 60°C for 5 minutes using a hot plate to form a coating (photosensitive layer). Two such samples with the coating formed on the glass plate were prepared and their weights were measured.

[0182] For a sample with a coating, a high-pressure mercury lamp (manufactured by USHIO LIGHTING, INC., trade name "ML-251A / B") was used with a 365nm light source after passing through a bandpass filter (manufactured by USHIO LIGHTING, INC.) at 735mJ / cm². 2 (illuminance 21mW / cm) 2 The exposure was performed under the condition of 35 seconds (referred to as "Condition 1" below, except for Example 11). Thus, a sample with an exposed coating was obtained.

[0183] Then, samples with exposed coatings (exposed samples) and samples with unexposed coatings (unexposed samples) were placed on a hot plate and heated at 120°C for 1 hour. The weight of the exposed sample and the unexposed sample after heating were measured, and the weight of the glass plate before coating was subtracted. The calculated weight was taken as the "cured film weight (film weight)". The exposed sample is the "exposed cured film weight", and the unexposed sample is the "unexposed film weight".

[0184] Then, the heated sample was cooled to room temperature, immersed in tetrahydrofuran at 26–28°C for 90 seconds, and dried at 80°C. The weight of the immersed sample was measured, and then the weight of the glass plate before coating was subtracted. The weight calculated was taken as the "residual film weight". The exposed sample was called the "exposed residual film weight", and the unexposed sample was called the "unexposed residual film weight".

[0185] Next, instead of the photoalkali generator (organic ionic compound), the "theoretical production amount" of the base corresponding to the evaluated photoalkali generator was calculated, and the composition was prepared using this corresponding base in the same manner as described above. Here, the corresponding base is the base constituting the anti-cation (cationic portion) of the organic ionic compound in each synthetic example. The theoretical production amount is the theoretical amount of base that may be produced when the reactive compound in the composition is used with the photoalkali generator; it is a theoretical amount estimated as the base produced by light irradiation, calculated by plotting a calibration curve of the corresponding base.

[0186] Then, 1.0 part by weight of the corresponding alkali, which is estimated as the theoretical amount of alkali produced by light irradiation, is mixed with the above-mentioned resin solution to prepare a composition containing the corresponding alkali. A coating film of the composition is formed on a glass plate in the same manner as above to prepare a sample. After heating the sample, its weight is measured, and then the weight of the glass plate before coating is subtracted. The resulting weight is taken as the "theoretical cured film weight". The weight of the sample after further impregnation is subtracted from the weight of the glass plate before coating, and the resulting weight is taken as the "theoretical residual film weight".

[0187] (3) Evaluation Using the measured values ​​obtained above, the curing properties and contrast are calculated using the following formula.

[0188] Exposure curing property a1 (%) = Weight of residual film after exposure ÷ Weight of cured film after exposure × 100 Unexposed curing property a2 (%) = Unexposed residual film weight ÷ Unexposed film weight × 100 Theoretical alkali curing property a3 (%) = Theoretical residual film weight ÷ Theoretical cured film weight × 100 Curing property (%) = a1 ÷ a3 × 100 Contrast ratio (%) = (a1 - a2) ÷ a1 × 100 Based on the calculated curing properties and contrast, the results were evaluated according to the following criteria. The results are shown in Tables 2 and 3.

[0189] A: (Good): Value is above 70%.

[0190] B: (Acceptable): Values ​​above 40% and below 70%.

[0191] C: (Defective): Value less than 40%.

[0192] [Examples 2-10, 12 and Comparative Examples 1-4] Except for changing the organic ionic compound in the photosensitive composition to the photoalkali generating agent (organic ionic compound) listed in Tables 2-3, the photosensitive composition was prepared in the same manner as in Example 1. Then, the photosensitive composition was evaluated in the same manner as in Example 1, as described in (2) and (3). The results are shown in Tables 2-3.

[0193] [Example 11] Except for the change of exposure conditions (referred to as Condition 2) as described below, the evaluation is performed in the same manner as in Example 1.

[0194] Condition 2: Prevent light from the high-pressure mercury lamp (manufactured by USHIO LIGHTING, INC., trade name "ML-251A / B") from passing through the bandpass filter to achieve a cumulative light intensity of 750 mJ / cm². 2 (illuminance 25mW / cm) 2 Exposure for 30 seconds (×30 seconds).

[0195] [Table 1] [Table 2] [Table 3] [Example 13] Epoxy-based photosensitive composition (1) Preparation of epoxy-based photosensitive compositions As reactive compounds, 6.0 parts by weight of epoxy resin (manufactured by Mitsubishi Chemical Corporation, designated "jER828" in the table), 2.0 parts by weight of PMA-PMMA copolymer (manufactured by Sigma-Aldrich, designated "PMA-PMMA" in the table), and 36.0 parts by weight of tetrahydrofuran were added to a container, mixed at 40°C, and cooled to room temperature to prepare a resin solution. Then, at room temperature, 0.01 parts by weight of the organic ionic compound (compound 1-1A) of Synthesis Example 1-1, which serves as a photoalkali generator, and 0.08 parts by weight of pentaerythritol tetra(3-mercaptopropionate) (manufactured by Tokyo Chemical Industry Co., Ltd., designated "PEMP" in the table) were added to 1.0 parts by weight of the resin solution and mixed to prepare an epoxy-based photosensitive composition.

[0196] (2) Exposure and development of epoxy-based photosensitive compositions Similar to (2) of [Example 1] above, the obtained epoxy-based photosensitive composition was coated onto a pre-weighed glass plate (manufactured by I-DEN VIETNAM CO.,LTD., trade name "SC2005") using a spin coater and dried to form a coating film (photosensitive layer). Two such samples with coatings formed on the glass plates were prepared and their weights were measured.

[0197] Then, similarly to (2) of [Example 1] above, a sample with a coating was exposed using a high-pressure mercury lamp (manufactured by USHIO LIGHTING, INC., trade name "ML-251A / B") under the conditions described above. Thus, a sample with an exposed coating was obtained.

[0198] Then, samples with the exposed coating (exposed sample) and samples with the unexposed coating (unexposed sample) were placed on a hot plate and heated at 40°C for 1 hour. The weight of the exposed sample and the unexposed sample after heating were measured, and the weight of the glass plate before coating was subtracted. The calculated weight was taken as the "cured film weight (film weight)". The exposed sample is the "exposed cured film weight", and the unexposed sample is the "unexposed film weight".

[0199] Then, the heated sample was cooled to room temperature, immersed in tetrahydrofuran at 26–28°C for 30 seconds, and dried at 80°C. The weight of the immersed sample was measured, and then the weight of the glass plate before coating was subtracted. The weight calculated was taken as the "residual film weight". The exposed sample was called the "exposed residual film weight", and the unexposed sample was called the "unexposed residual film weight".

[0200] (3) Evaluation Using the measured values ​​obtained above, the curing properties and contrast are calculated using the following formula.

[0201] Exposure curing property a1 (%) = Weight of residual film after exposure ÷ Weight of cured film after exposure × 100 Unexposed curing property a2 (%) = Unexposed residual film weight ÷ Unexposed film weight × 100 Curing property (%) = a1 Contrast ratio (%) = (a1 - a2) ÷ a1 × 100 Based on the calculated curing properties and contrast ratios, the results were evaluated according to the following criteria. The results are shown in Tables 4 and 5.

[0202] A: (Good): Value is above 70%.

[0203] B: (Acceptable): Values ​​above 40% and below 70%.

[0204] C: (Defective): Value less than 40%.

[0205] [Examples 14-23 and Comparative Example 5] Except for changing the organic ionic compound in the epoxy-based photosensitive composition to the photoalkali generating agent (organic ionic compound) listed in Tables 4-5, the photosensitive composition was prepared in the same manner as in Example 13. Then, the epoxy-based photosensitive composition was evaluated in the same manner as in Example 13, as described in (2) and (3) above. The results are shown in Tables 4-5.

[0206] [Table 4] [Table 5] [Example 24] Free radical polymeric photosensitive composition (1) Preparation of free radical polymeric photosensitive compositions 3.0 parts by weight of dipentaerythritol hexaacrylate (manufactured by Tokyo Chemical Industry Co., Ltd., referred to as "DPHA" in the table), 0.38 parts by weight of PMA-PMMA copolymer (manufactured by Sigma-Aldrich, referred to as "PMA-PMMA" in the table), and 18.0 parts by weight of tetrahydrofuran were mixed at 40°C and then cooled to room temperature to prepare a resin solution. Then, 0.01 parts by weight of the organic compound (compound 1-1) of Synthesis Example 1-1, which serves as a free radical polymerization initiator, was added to 1.0 parts by weight of the resin solution at room temperature and mixed to prepare a free radical polymerizable photosensitive composition.

[0207] (2) Exposure and development of free radical polymeric photosensitive compositions Similar to (2) of [Example 1] above, the obtained free radical polymeric photosensitive composition was coated onto a pre-weighed glass plate (manufactured by I-DEN VIETNAM CO.,LTD., trade name "SC2005") using a spin coater and dried to form a coating film (photosensitive layer). Two such samples with coatings formed on the glass plates were prepared and their weights were measured.

[0208] Then, similarly to (2) of [Example 1] above, a sample with a coating was exposed using a high-pressure mercury lamp (manufactured by USHIO LIGHTING, INC., trade name "ML-251A / B") under the conditions described above. Thus, a sample with an exposed coating was obtained.

[0209] Then, the weights of the sample with the exposed coating (exposed sample) and the sample with the unexposed coating (unexposed sample) are measured, and the weight of the glass plate before coating is subtracted. The weight calculated in this way is the "cured film weight (film weight)". The exposed sample is the "exposed cured film weight", and the unexposed sample is the "unexposed film weight".

[0210] Then, samples with exposed coatings (exposed samples) and samples with unexposed coatings (unexposed samples) were immersed in tetrahydrofuran at 26–28°C for 30 seconds, and then dried at 80°C. The weight of the immersed samples was measured, and the weight of the glass plate before coating was subtracted. The calculated weight was taken as the "residual film weight". The weight of the exposed samples was the "exposed residual film weight", and the weight of the unexposed samples was the "unexposed residual film weight".

[0211] (3) Evaluation The curing properties and contrast were calculated using the measured values ​​obtained in (2) of Example 13, in the same manner as in (3) of Example 13. The results are shown in Tables 6 and 7.

[0212] [Examples 25-33, Comparative Examples 6-9, and Reference Example 1] Except for changing the organic compound in the free radical polymeric photosensitive composition to the free radical polymerization initiator (organic compound) listed in Tables 6-7, the free radical polymeric photosensitive composition was prepared in the same manner as in Example 24. Then, the free radical polymeric photosensitive composition was evaluated in (2) and (3) above in the same manner as in Example 24. The results are shown in Tables 6-7.

[0213] [Table 6] [Table 7] As shown in Examples 1-12, organic ionic compounds 1-1A to 1-7A, 1-11A, 1-1B, 1-1C, and 1-14A achieved particularly good results in terms of curability and contrast of the photosensitive compositions. These results indicate that organic ionic compounds 1-1A to 1-7A, 1-11A, 1-1B, 1-1C, and 1-14A are particularly suitable as photoalkali generators.

[0214] On the other hand, as shown in Tables 1 and 2-3, the photoalkali generating agents (organic ionic compounds) of these Comparative Examples 1-4 are substances that do not have the structure shown in Formula (1-A), do not have a maximum absorption wavelength near 365 nm, and have poor light absorption properties. Furthermore, these photosensitive compositions also have low curability and contrast.

[0215] It can also be seen that the organic ionic compounds of Examples 1 to 12 are significantly superior as photoalkali generating agents compared to the compounds C-1A to C-4A used in Comparative Examples 1 to 4, which do not have the structure shown in formula (1-A) and contain existing organic compounds.

[0216] Furthermore, as shown in Examples 13-23, even when an epoxy compound was used instead of a urethane compound as the reactive compound in the photosensitive composition, the curability and contrast of the photosensitive composition containing the organic ionic compound were obtained in particularly good results.

[0217] As shown in Examples 24-33, when the above-described organic compounds are used relative to vinyl compounds ((meth)acrylic acid compounds) used as reactive compounds, particularly the organic compounds used in Examples 24-26 and 32-33, they exhibit the same or better curability and contrast as Reference Example 1 (compound R-1), which is typically used as a free radical polymerization initiator with good curability. It is evident that the organic compounds used in Examples 27-31 (compounds 1-4, 1-7, 1-8, 1-11, 1-12) exhibit excellent curability and contrast compared to the compounds (C-1, C-2, C-4, C-5) shown in Comparative Examples 6-9 that do not have the structure shown in formula (1), and exhibit acceptable curability and contrast. This demonstrates that the organic compounds of the embodiments of the present invention are suitable for use as free radical polymerization initiators.

[0218] Industrial availability The organic compound of one embodiment of the present invention is capable of forming organic ionic compounds well. The organic compound of another embodiment of the present invention is suitable for use as a polymerization initiator. The organic ionic compound of yet another embodiment of the present invention is suitable for use as a photoalkali generator. The polymerization initiator of another embodiment of the present invention is suitable for use in the preparation of photosensitive compositions and cured products using the photosensitive compositions. The photoalkali generator of yet another embodiment of the present invention is suitable for use in the preparation of photosensitive compositions and cured products using the photosensitive compositions.

Claims

1. An organic compound, characterized in that, It has the structure shown in the following formula (1), In equation (1), R 1 It represents at least one group selected from hydrogen atoms, alkyl groups having 1 to 8 carbon atoms, and substituted or unsubstituted phenyl groups; R 2 It represents at least one group selected from hydrogen atom, alkyl with 1 to 8 carbon atoms, alkyl carbonyl with 1 to 4 carbon atoms, substituted or unsubstituted phenyl, substituted or unsubstituted benzoyl, and carboxymethyl; X represents an organic group having a heterocyclic skeleton containing at least one oxygen, nitrogen, or sulfur atom within the ring.

2. The organic compound according to claim 1, characterized in that, The heterocyclic skeleton comprises at least one heterocycle selected from substituted or unsubstituted furan rings, substituted or unsubstituted pyrrole rings, substituted or unsubstituted N-substituted pyrrole rings, substituted or unsubstituted benzofuran rings, substituted or unsubstituted indole rings, substituted or unsubstituted N-substituted indole rings, and substituted or unsubstituted benzothiophene rings.

3. The organic compound according to claim 1, characterized in that, X is an organic group having at least one structure selected from the following structural formulas. 。 4. The organic compound according to claim 1, characterized in that, X is an organic group having at least one structure selected from the following structural formulas. 。 5. An organic ionic compound, characterized in that, It has the structure shown in the following formula (1-A), In equation (1-A), R 1 It represents at least one group selected from hydrogen atoms, alkyl groups having 1 to 8 carbon atoms, and substituted or unsubstituted phenyl groups; R 2 It represents at least one group selected from hydrogen atom, alkyl with 1 to 8 carbon atoms, alkyl carbonyl with 1 to 4 carbon atoms, substituted or unsubstituted phenyl, substituted or unsubstituted benzoyl, and carboxymethyl; X represents an organic group having a heterocyclic skeleton containing at least one oxygen, nitrogen, or sulfur atom within the ring; A + The cation representing an organic base, The organic base is at least one compound selected from primary amines, secondary amines, tertiary amines, compounds with an amidine skeleton, and compounds with a guanidine skeleton.

6. The organic ionic compound as described in claim 5, characterized in that, The organic base is either a compound having an amidine skeleton or a compound having a guanidine skeleton.

7. The organic ionic compound according to claim 5, characterized in that, The A + It is at least one cation selected from the following structural formulas. 。 8. The organic ionic compound according to claim 5, characterized in that, X is an organic group having at least one structure selected from the following structural formulas. 。 9. A polymerization initiator, characterized in that, It contains at least one of the organic compounds according to any one of claims 1 to 4.

10. A photoalkali generating agent, characterized in that, It contains at least one of the organic ionic compounds according to any one of claims 5 to 8.

11. A photosensitizing composition, characterized in that, Contains a vinyl compound and the polymerization initiator as described in claim 9.

12. A photosensitizing composition, characterized in that, contain: A reactive compound selected from at least one of isocyanate compounds, epoxy compounds, silane compounds, and polyamic acids; and The photoalkali generator according to claim 10.

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