Photoacid generator and photosensitive composition using the same

Abstract

Provided are: a photoacid generator that effectively generates acid even when there is a high concentration of a substance such as a colorant that attenuates or shields irradiated light, and even when the film thickness is great and a light source is visible light to infrared light, in particular, infrared light with low energy; and a highly curable photosensitive composition using the photoacid generator. The present invention is a photoacid generator that is a metal complex having, as a ligand, a ring structure formed by bonding five-membered ring aromatic heterocyclic compounds directly or by π-conjugation, wherein a central metal has one or two axial ligands, and the axial ligand has an onium salt structure.

Description

[Technical Field]

[0001] The present invention relates to a compound that is photosensitive to light in the visible to infrared region and generates an acid, and a photosensitive composition using the same. More specifically, the present invention relates to a photoacid generator that is suitable for use in producing a photosensitive composition (e.g., coating agent, paint, lithographic printing plate, etc.) that is cured using an acid generated by irradiation with light in the visible to infrared region, or a product or member (e.g., electronic component, optical product, optical component forming material, layer forming material, adhesive, etc.) that is formed through patterning utilizing the difference in solubility in a developer between an exposed portion and an unexposed portion by utilizing an acid-catalyzed reaction caused by the acid generated by irradiation with light in the visible to infrared region. [Background technology]

[0002] UV curing technology, which cures liquid substances by irradiating them with ultraviolet (UV) light, is finding a wider range of applications, including coatings, paints, and printing inks, due to its workability (fast curing) and low VOC content. Photocurable coating agents generally consist of a photopolymerization initiator, a radical (cationic) polymerizable monomer, oligomer, or polymer, and, depending on the application, a colorant and additives. Colorants, broadly classified as pigments and dyes, are added to color the coating film. However, they not only block light, but also have light absorption properties corresponding to their color, absorbing a portion of the irradiated light. Therefore, photocurable coating agents containing colorants may not allow light to penetrate deep into the applied coating film. To address this issue, the use of specific photopolymerization initiators has been proposed (see, for example, Patent Document 1).

[0003] Furthermore, in order to use a small, inexpensive semiconductor laser as a light source, which is used in recording materials, etc., sensitivity to long wavelengths, particularly the near-infrared region, is required. However, known photopolymerizable compositions either do not have sensitivity to the near-infrared region, or even if they do, the sensitivity is not sufficiently high. If they do have high sensitivity, the photopolymerizable compositions have the disadvantage of insufficient storage stability. Therefore, specific initiators have been proposed as initiators that are highly sensitive in the long wavelength region (see, for example, Patent Documents 2 and 3).

[0004] However, photosensitive compositions using specific initiators described in Patent Documents 1 to 3 also have problems such as insufficient curability when a substance such as a colorant that attenuates or blocks irradiated light is present at a high concentration, when the film is thick, or when the light source is in the long wavelength region, and the solubility of the initiator in the composition is low.

[0005] It is known to use a sensitizer to increase the efficiency of an initiator (see, for example, Patent Documents 4 and 5). Directly incorporating a complex structure into the initiator structure to match the absorption region of the initiator makes the synthesis more complicated and is cost-inefficient. Therefore, the method of using a sensitizer as a coinitiator is considered to be simpler as the wavelength region becomes longer. However, when adding the sensitizer and initiator separately, there are issues with the solubility of the two in the composition, and the sensitizing effect is not satisfactory. As a method for enhancing the sensitizing effect, compounds in which an initiator and a sensitizer are covalently linked have been reported (see Non-Patent Document 1). However, sensitizers used in the visible to near-infrared region generally have large molecules and more complex structures, and as mentioned above, changing the structure to enhance the effect of the initiator makes synthesis more difficult, which remains a problem. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Patent Application Laid-Open No. 2009-19142 [Patent Document 2] Japanese Patent Application Publication No. 2-157760 [Patent Document 3] Japanese Patent Application Publication No. 5-247110 [Patent Document 4] Japanese Patent Application Publication No. 11-279212 [Patent Document 5] Japanese Patent Application Publication No. 09-183960 [Non-patent literature]

[0007] [Non-Patent Document 1] SPPappas, J. Photopolym. Sci. Technol., 2001, 14, 703-716. Summary of the Invention [Problem to be solved by the invention]

[0008] The problem to be solved by the present invention is to provide a photoacid generator that effectively generates acid even when a substance such as a colorant that attenuates or blocks irradiated light is present at a high concentration, when the film is thick, and when the light source is visible light to infrared light, particularly infrared light with low energy, and a photosensitive composition using the same that has excellent curability. [Means for solving the problem]

[0009] As a result of extensive research conducted by the present inventors to solve the above problems, they have discovered a photoacid generator that has excellent sensitivity to visible light to infrared light. That is, the present invention provides a photoacid generator comprising a metal complex having a ring structure in which five-membered aromatic heterocyclic compounds are connected directly or through π-conjugation as a ligand, and a central metal having one or two axial ligands, the axial ligands having an onium salt structure.

[0010] The present invention further provides a photosensitive composition comprising the above-described photoacid generator and a cationically polymerizable compound.

[0011] The present invention further relates to a cured product obtained by curing the above photosensitive composition. [Effects of the Invention]

[0012] The photoacid generator of the present invention is sensitive to light in the visible to infrared wavelength range of 400 nm to 1500 nm, and efficiently generates a strong acid, which can be used in reactions utilizing the strong acid (acid-catalyzed reactions, cationic polymerization reactions, etc.). Furthermore, even in compositions containing additives or colorants that absorb light in the ultraviolet to visible range, transmission of energy rays is not hindered, allowing for efficient production of cured products. DETAILED DESCRIPTION OF THE INVENTION

[0013] Hereinafter, embodiments of the present invention will be described in detail.

[0014] The photoacid generator of the present invention is characterized in that it is a metal complex having a ring structure in which five-membered aromatic heterocyclic compounds are connected directly or through π-conjugation as a ligand, and the central metal has one or two axial ligands, and the axial ligands have an onium salt structure.

[0015] The five-membered aromatic heterocyclic compound of the present invention is a compound having a ring structure with five atoms, including carbon atoms and one or more heteroatoms (e.g., nitrogen atoms, oxygen atoms, sulfur atoms, phosphorus atoms, silicon atoms, etc.), and having aromaticity, and examples thereof include furan, thiophene, pyrrole, oxazole, thiazole, imidazole, thiadiazole, triazole, etc. From the viewpoint of easy availability of raw materials, furan, thiophene, and pyrrole are preferred, and pyrrole is more preferred.

[0016] The compound of the present invention, in which five-membered aromatic heterocyclic compounds are connected directly or via π-conjugation to form a ring structure (hereinafter referred to as "cyclic compound"), refers to a group of compounds in which the five-membered aromatic heterocyclic compounds are connected to form a ring structure by direct bonding or via one or two carbon atoms or heteroatoms (e.g., nitrogen, oxygen, sulfur, phosphorus, silicon, etc.) while maintaining a π bond. The cyclic compound serves as a light-absorbing moiety. From the viewpoints of availability of raw materials and ease of synthesis, specific examples of the cyclic compound include porphyrin, porphyrazine, corrole, phthalocyanine, subporphyrin, subphthalocyanine, chlorin, porphycene, and corrphycene. Porphyrin and phthalocyanine are preferred.

[0017] In the present invention, the cyclic compound is used as a ligand of a metal complex (hereinafter referred to as a cyclic ligand). Here, the metal complex is formed by one metal element per molecule of the cyclic compound, and the lone electron pair on the heteroatom of the cyclic ligand is coordinated to the vacant orbital of the metal element.

[0018] In the present invention, this metal complex further has an axial ligand. The axial ligand is a ligand that is coordinated perpendicular to the plane of the cyclic ligand. The axial ligand has an onium salt structure, and the cyclic ligand, which is the light-absorbing site, absorbs light, and the onium salt decomposes to generate an acid.

[0019] A preferred structure of the photoacid generator of the present invention can be represented by general formula (1) or general formula (2).

[0020] [ka]

[0021] In formula (1), R1 to R8 are substituents on an aromatic heterocycle, and R1 and R2, R3 and R4, R5 and R6, and R7 and R8 may be bonded to each other to form a condensed polycyclic aromatic structure; Y may be a nitrogen atom, a carbon atom, or a direct bond; in the case of a carbon atom, hydrogen or an aromatic hydrocarbon having 6 to 14 carbon atoms is substituted on the carbon atom; M is selected from Al, Ga, In, Si, Ge, Sn, Fe, Ti, Co, and Mn; L 1 and L 2 is an axial ligand represented by formula (3) that coordinates to a metal, and when M is Al, Ga, In, Fe, or Mn, L 1 Only has.

[0022] [ka]

[0023] Formula (2) represents the case where the central metal M is cationic, and R1 to R8, Y, L 1 and L 2 is the same as formula (1), M is selected from the group consisting of P, Sb and Bi, and X2 - represents the monovalent counter anion corresponding to the central metal cation.

[0024] [ka]

[0025] In formula (3), D represents an oxygen atom or a sulfur atom, E represents an alkylene having 1 to 8 carbon atoms, an alkenylene having 2 to 8 carbon atoms, an alkynylene having 2 to 8 carbon atoms, or an arylene having 6 to 14 carbon atoms, and the main chain may contain an ether group, a sulfide group, a ketone group, an amide group, an ester group, a thioester group, a urea group, a sulfone group, a silyl group, or a phenylene group, and A + is a monovalent onium cation, and X1 - represents the monovalent counter anion corresponding to the onium cation.

[0026] In formula (1) and formula (2), Y may be a nitrogen atom, a carbon atom, or may be directly bonded. Here, a direct bond means that five-membered aromatic heterocyclic compounds are directly bonded to each other while forming a ring structure connected by π-conjugation. In the case of a carbon atom, a hydrogen atom or an aryl group having 6 to 30 carbon atoms may be substituted on the carbon atom.

[0027] M represented by formula (1) is the central metal of a metal complex formed with the aromatic heterocycle as a cyclic ligand, and is not particularly limited as long as it is a metal having an axial ligand. However, from the viewpoints of availability of raw materials and stability as a metal complex, a metal selected from the group consisting of Al, Ga, In, Si, Ge, Sn, Fe, Ti, Co, and Mn is preferred. M in formula (2) represents a central metal that forms a cationic metal complex with the aromatic heterocycle as a cyclic ligand, and is preferably a metal selected from the group consisting of P, Sb, and Bi from the viewpoints of availability of raw materials and stability as a metal complex.

[0028] In formulas (1) and (2), R1 to R8 are substituents on the aromatic heterocycle, and each independently represents an aryl group having 6 to 30 carbon atoms, a heteroaryl group having 4 to 30 carbon atoms, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms or an alkynyl group having 2 to 30 carbon atoms, a hydroxy group, an alkoxy group having 1 to 18 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an alkylcarbonyl group having 2 to 19 carbon atoms, an arylcarbonyl group having 7 to 11 carbon atoms, an alkoxycarbonyl group having 2 to 19 carbon atoms, an aryloxycarbonyl group having 7 to 11 carbon atoms, Examples include an arylthiocarbonyl group having 7 to 11 carbon atoms, an acyloxy group having 2 to 19 carbon atoms, an arylthio group having 6 to 20 carbon atoms, an alkylthio group having 1 to 18 carbon atoms, an alkylsulfinyl group having 1 to 18 carbon atoms, an arylsulfinyl group having 6 to 10 carbon atoms, an alkylsulfonyl group having 1 to 18 carbon atoms, an arylsulfonyl group having 6 to 10 carbon atoms, an alkyleneoxy group, an amino group, a cyano group, a nitro group, and a halogen group, and R1 and R2, R3 and R4, R5 and R6, and R7 and R8 may be bonded to each other to form a condensed polycyclic aromatic structure.

[0029] Examples of the aryl group having 6 to 30 carbon atoms include monocyclic aryl groups such as a phenyl group and a biphenylyl group, and condensed polycyclic aryl groups such as naphthyl, anthracenyl, phenanthrenyl, pyrenyl, chrysenyl, naphthacenyl, benzanthracenyl, anthraquinolyl, fluorenyl, naphthoquinone, and anthraquinone.

[0030] Examples of heteroaryl groups having 4 to 30 carbon atoms include cyclic groups containing 1 to 3 heteroatoms such as oxygen, nitrogen, and sulfur, which may be the same or different. Specific examples include monocyclic heteroaryl groups such as thienyl, furanyl, pyranyl, pyrrolyl, oxazolyl, thiazolyl, pyridyl, pyrimidyl, and pyrazinyl, and fused polycyclic heteroaryl groups such as indolyl, benzofuranyl, isobenzofuranyl, benzothienyl, isobenzothienyl, quinolyl, isoquinolyl, quinoxalinyl, quinazolinyl, carbazolyl, acridinyl, phenothiazinyl, phenazinyl, xanthenyl, thianthrenyl, phenoxazinyl, phenoxathiinyl, chromanyl, isochromanyl, dibenzothienyl, xanthonyl, thioxanthonyl, and dibenzofuranyl.

[0031] Examples of the alkyl group having 1 to 30 carbon atoms include linear alkyl groups such as methyl, ethyl, propyl, butyl, hexadecyl, and octadecyl; branched alkyl groups such as isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl, and isohexyl; and cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.

[0032] Examples of the alkenyl group having 2 to 30 carbon atoms include vinyl, allyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, and 1-methyl-1-propenyl.

[0033] Examples of the alkynyl group having 2 to 30 carbon atoms include ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-1-propynyl, and 1-methyl-2-propynyl.

[0034] Examples of the alkoxy group having 1 to 18 carbon atoms include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, and dodecyloxy.

[0035] Examples of the aryloxy group having 6 to 10 carbon atoms include phenoxy and naphthyloxy.

[0036] Examples of the alkylcarbonyl group having 2 to 19 carbon atoms include acetyl, trifluoroacetyl, propionyl, butanoyl, 2-methylpropionyl, heptanoyl, 2-methylbutanoyl, 3-methylbutanoyl, and octanoyl.

[0037] Examples of the arylcarbonyl group having 7 to 11 carbon atoms include benzoyl, 4-tert-butylbenzoyl, and naphthoyl.

[0038] Examples of the alkoxycarbonyl group having 2 to 19 carbon atoms include methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl, and tert-butoxycarbonyl.

[0039] Examples of the aryloxycarbonyl group having 7 to 11 carbon atoms include phenoxycarbonyl and naphthoxycarbonyl.

[0040] Examples of the arylthiocarbonyl group having 7 to 11 carbon atoms include phenylthiocarbonyl and naphthoxythiocarbonyl.

[0041] Examples of the acyloxy group having 2 to 19 carbon atoms include acetoxy, ethylcarbonyloxy, propylcarbonyloxy, isobutylcarbonyloxy, sec-butylcarbonyloxy, tert-butylcarbonyloxy, and octadecylcarbonyloxy.

[0042] Examples of the arylthio group having 6 to 20 carbon atoms include phenylthio, biphenylylthio, methylphenylthio, chlorophenylthio, bromophenylthio, fluorophenylthio, hydroxyphenylthio, methoxyphenylthio, naphthylthio, 4-[4-(phenylthio)benzoyl]phenylthio, 4-[4-(phenylthio)phenoxy]phenylthio, 4-[4-(phenylthio)phenyl]phenylthio, 4-(phenylthio)phenylthio, 4-benzoylphenylthio, 4-benzoyl-chlorophenylthio, 4-benzoyl-methylthiophenylthio, 4-(methylthiobenzoyl)phenylthio, and 4-(p-tert-butylbenzoyl)phenylthio.

[0043] Examples of the alkylthio group having 1 to 18 carbon atoms include methylthio, ethylthio, propylthio, tert-butylthio, neopentylthio, and dodecylthio.

[0044] Examples of the alkylsulfinyl group having 1 to 18 carbon atoms include methylsulfinyl, ethylsulfinyl, propylsulfinyl, tert-pentylsulfinyl, and octylsulfinyl.

[0045] Examples of the arylsulfinyl group having 6 to 10 carbon atoms include phenylsulfinyl, tolylsulfinyl, and naphthylsulfinyl.

[0046] Examples of the alkylsulfonyl group having 1 to 18 carbon atoms include methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, butylsulfonyl, and octylsulfonyl.

[0047] Examples of the arylsulfonyl group having 6 to 10 carbon atoms include phenylsulfonyl, tolylsulfonyl, and naphthylsulfonyl.

[0048] Halogen groups include fluoro, chloro, bromo, and iodo.

[0049] Of these R1 to R8 (substituents on the aromatic heterocycle), preferred are alkyl groups having 1 to 6 carbon atoms, aryl groups having 6 to 14 carbon atoms, hydroxy groups, alkoxy groups having 1 to 6 carbon atoms, alkylcarbonyl groups having 2 to 6 carbon atoms, arylcarbonyl groups having 7 to 11 carbon atoms, alkylthio groups having 1 to 6 carbon atoms, arylthio groups having 6 to 14 carbon atoms, aryloxy groups having 6 to 10 carbon atoms, chloro groups, and fluoro groups, and more preferred are alkyl groups having 1 to 6 carbon atoms, aryl groups having 6 to 14 carbon atoms, heteroaryl groups having 4 to 14 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, alkylcarbonyl groups having 2 to 6 carbon atoms, benzoyl groups, aryloxy groups having 6 to 10 carbon atoms, and fluoro groups.

[0050] In equation (2), X2 - is a counter anion for the cationic central metal M, and in formula (3), X1 - are counter anions for the onium cation, and are atoms (groups) that can become monovalent anions, and are anions corresponding to the acid (HX) generated by irradiating the photoacid generator of the present invention with light (visible light, ultraviolet light, electron beam, X-ray, etc.). - and X2 - is not limited except that it is a halogen anion and a monovalent polyatomic anion, for example, F - , Cl - , Br - , I - , BY a - , P.Y. a - , SbY a - , (Rf) b PF 6-b - , R 9 c BY 4-c- , R 9 c Gay 4-c - , R 10 SO3 - , (R 10 SO2)3C - and (R 10 SO2)2N - Examples include anions represented by the following formula:

[0051] P represents a phosphorus atom, B represents a boron atom, Sb represents an antimony atom, F represents a fluorine atom, and Ga represents a gallium atom. Y represents a halogen atom (preferably a fluorine atom). S represents a sulfur atom, O represents an oxygen atom, C represents a carbon atom, and N represents a nitrogen atom.

[0052] Rf represents an alkyl group (preferably an alkyl group having 1 to 8 carbon atoms) in which 80 mol % or more of the hydrogen atoms have been substituted with fluorine atoms. Examples of alkyl groups that become Rf through fluorine substitution include linear alkyl groups (methyl, ethyl, propyl, butyl, pentyl, octyl, etc.), branched alkyl groups (isopropyl, isobutyl, sec-butyl, tert-butyl, etc.), and cycloalkyl groups (cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc.). The proportion of hydrogen atoms in these alkyl groups substituted with fluorine atoms in Rf is preferably 80 mol % or more, more preferably 90 mol % or more, and particularly preferably 100%, based on the number of moles of hydrogen atoms in the original alkyl group. When the substitution ratio with fluorine atoms is within these preferred ranges, the photosensitivity of the sulfonium salt is further improved. Particularly preferred Rf include CF3-, CF3CF2-, (CF3)2CF-, CF3CF2CF2-, CF3CF2CF2CF2-, (CF3)2CFCF2-, CF3CF2(CF3)CF- and (CF3)3C-. The b Rfs are independent of each other and may therefore be the same or different.

[0053] R 9represents a phenyl group in which a portion of the hydrogen atoms has been substituted with at least one element or electron-withdrawing group. Examples of such an element include a halogen atom, such as a fluorine atom, a chlorine atom, and a bromine atom. Examples of electron-withdrawing groups include a trifluoromethyl group, a nitro group, and a cyano group. Of these, a phenyl group in which one hydrogen atom has been substituted with a fluorine atom or a trifluoromethyl group is preferred. c R 9 are mutually independent and therefore may be the same or different from each other.

[0054] R 10 represents an alkyl group having 1 to 20 carbon atoms, a perfluoroalkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, and the alkyl group and perfluoroalkyl group may be linear, branched, or cyclic, and the aryl group may be unsubstituted or may have a substituent.

[0055] a represents an integer of 4 to 6. b is an integer of 1 to 5, preferably 2 to 4, and more preferably 2 or 3. c is an integer of 1 to 4, and is preferably 4.

[0056] (Rf) b PF 6-b - The anion represented by (CF3CF2)2PF4 - , (CF3CF2)3PF3 - , ((CF3)2CF)2PF4 - , ((CF3)2CF)3PF3 - , (CF3CF2CF2)2PF4 - , (CF3CF2CF2)3PF3 - , ((CF3)2CFCF2)2PF4 - , ((CF3)2CFCF2)3PF3 - , (CF3CF2CF2CF2)2PF4 - and (CF3CF2CF2CF2)3PF3 - Among these, anions represented by (CF3CF2)3PF3 - , (CF3CF2CF2)3PF3- , ((CF3)2CF)3PF3 - , ((CF3)2CF)2PF4 - , ((CF3)2CFCF2)3PF3 - and ((CF3)2CFCF2)2PF4 - Anions represented by the following formula are preferred.

[0057] R 8 c BY 4-c - As an anion represented by (C6F5)4B - , ((CF3)2C6H3)4B - , (CF3C6H4)4B - , (C6F5)2BF2 - , C6F5BF3 - and (C6H3F2)4B - Among these, anions represented by (C6F5)4B - and ((CF3)2C6H3)4B - Anions represented by the following formula are preferred.

[0058] R 9 c Gay 4-c - The anion represented by the formula is (C6F5)4Ga - , ((CF3)2C6H3)4Ga - , (CF3C6H4)4Ga - , (C6F5)2GaF2 - , C6F5GaF3 - and (C6H3F2)4Ga - Among these, (C6F5)4Ga - and ((CF3)2C6H3)4Ga - Anions represented by the following formula are preferred.

[0059] R 10 SO3 -Examples of the anion represented by the formula (I) include a trifluoromethanesulfonate anion, a pentafluoroethanesulfonate anion, a heptafluoropropanesulfonate anion, a nonafluorobutanesulfonate anion, a pentafluorophenylsulfonate anion, a p-toluenesulfonate anion, a benzenesulfonate anion, a camphorsulfonate anion, a methanesulfonate anion, an ethanesulfonate anion, a propanesulfonate anion, and a butanesulfonate anion. Among these, a trifluoromethanesulfonate anion, a nonafluorobutanesulfonate anion, a methanesulfonate anion, a butanesulfonate anion, a camphorsulfonate anion, a benzenesulfonate anion, and a p-toluenesulfonate anion are preferred.

[0060] (R 10 SO2)3C - The anion represented by (CF3SO2)3C - , (C2F5SO2)3C - , (C3F7SO2)3C - and (C4F9SO2)3C - Examples of the anion include anions represented by the following formula:

[0061] (R 10 SO2)2N - The anion represented by (CF3SO2)2N - , (C2F5SO2)2N - , (C3F7SO2)2N - and (C4F9SO2)2N - Examples of the anion include anions represented by the following formula:

[0062] As monovalent polyatomic anions, BY a - , P.Y. a - , SbY a - , (Rf) b PF 6-b - , R 9 c BY 4-c - , R9 c Gay 4-c - , R 10 SO3 - , (R 10 SO2)3C - or (R 10 SO2)2N - In addition to the anions represented by - , BrO4 - etc.), halogenated sulfonate ions (FSO3 - , ClSO3 - etc.), sulfate ions (CH3SO4 - , CF3SO4 - , HSO4 - etc.), carbonate ions (HCO3 - , CH3CO3 - etc.), aluminate ions (AlCl4 - , AlF4 - , ( t- C4F9O)4Al - etc.), hexafluorobismuthate ion (BiF6 - ), carboxylate ion (CH3COO - , CF3COO - , C6H5COO - , CH3C6H4COO - , C6F5COO - , CF3C6H4COO - etc.), aryl borate ions (B(C6H5)4 - , CH3CH2CH2CH2B(C6H5)3 - etc.), thiocyanate ion (SCN - ) and nitrate ions (NO3 - ) etc. can be used.

[0063] Among these anions, F - , Cl - , Br - , I - , BF4 - ,SbF6 - , PF6 - , (Rf) b PF 6-b - , R 9c BY 4-c - , R 9 c Gay 4-c - , R 10 SO3 - , (R 10 SO2)3C - and (R 10 SO2)2N - The anion represented by the formula: SbF6 is preferred. - , PF6 - , (CF3CF2)3PF3 - , ((CF3)2CF)3PF3 - , (CF3CF2CF2)3PF3 - , (C6F5)4B - , ((CF3)2C6H3)4B - , (C6F5)4Ga - , ((CF3)2C6H3)4Ga - , ( t- C4F9O)4Al - , trifluoromethanesulfonate anion, nonafluorobutanesulfonate anion, (CF3SO2)3C - and (CF3SO2)2N - is more preferred from the viewpoint of solubility in the photosensitive composition. When two or more anions are present in the same molecule, they may be the same or different.

[0064] L represented by formula (1) and formula (2) 1 and L 2 is an axial ligand represented by formula (3) that coordinates to the central metal M, and the number of axial ligands varies depending on the type of M. From the viewpoint of stability as a metal complex, when the preferred central metal is Al, Ga, In, Fe, Co, or Mn, it is preferable that there is one axial ligand, and when the other central metal is Al, Ga, In, Fe, Co, or Mn, it is preferable that there are two axial ligands. When there are two axial ligands, they may be the same or different.

[0065] In formula (3), D is directly bonded to the central metal M and represents an oxygen atom or a sulfur atom.

[0066] In formula (3), E is a combination of D and an onium cation A +and represents an alkylene having 1 to 8 carbon atoms, an alkenylene having 2 to 8 carbon atoms, an alkynylene having 2 to 8 carbon atoms, or an arylene having 6 to 14 carbon atoms, and may contain an ether group, a sulfide group, a ketone group, an amide group, an ester group, a thioester group, a urea group, a sulfone group, or a silyl group in the main chain. Here, the main chain is D and the onium cation A + It is the main skeleton that connects the above. Examples of alkylene having 1 to 8 carbon atoms include linear alkylene such as methylene, ethylene, trimethylene, tetramethylene, hexamethylene, and octamethylene; branched alkylene such as 1-methylethyl, 1-methylethylidene, 1,1-dimethylethylene, 1,2-dimethylethylene, and 1-methylpropylidene; and cyclic alkylene such as cyclopropylene, cyclobutylene, cyclopentylene, cyclopentylidene, cyclohexylene, and cyclohexylidene. Examples of alkenylene having 2 to 8 carbon atoms include vinylene, 1-propenylene, 2-propenylene, 1-butenylene, 2-butenylene, 3-butenylene, 1-hexenylene, cyclohexenylene, 1,3-butadienylene, 1,3-hexadienylene, and 2,4,6-octatrienylene. Examples of the alkynylene having 2 to 8 carbon atoms include ethynylene, 1-propynylene, 2-propynylene, 1-butynylene, 2-butynylene, 3-butynylene, 1,3-butadiynylene, and hexan-1-en-3-ynylene. Examples of the arylene having 6 to 14 carbon atoms include phenylene, naphthylene, anthracenylene, and biphenylene.

[0067] Specific examples of E when the main chain contains an ether group, a sulfide group, a ketone group, an amide group, an ester group, a thioester group, a urea group, a sulfone group, or a silyl group include the following. * indicates the bond position.

[0068] [ka]

[0069] In formula (3), A + is a monovalent onium cation bound to the metal via D and E as axial ligands. A monovalent onium cation is a cation formed when a proton or a cationic atomic group (such as an alkyl group) coordinates with a compound containing an element with an unshared electron pair. Examples of monovalent onium cations include the following:

[0070] Oxonium cations (such as trimethyloxonium cation, triethyloxonium, and tetramethylenemethyloxonium cation); Pyrilinium cations (such as 4-methylpyrilinium cation and 2,6-diphenylpyrilinium cation); chromenium cations (e.g., 2,4-dimethylchromenium cation); Isochromenium cations (such as 1,3-dimethylisochromenium cation); Ammonium cations [ammonium cation, primary ammonium cations (e.g., n-butylammonium cation), secondary ammonium cations (e.g., diethylammonium cation), tertiary ammonium cations (e.g., triethylammonium cation), quaternary ammonium cations (e.g., tetramethylammonium cation, phenyltrimethylammonium cation, and tetrabutylammonium cation)]; Pyrrolidinium cations (such as N,N-dimethylpyrrolidinium cation and N,N-diethylpyrrolidinium cation); Imidazolinium cations (such as N,N'-dimethylimidazolinium cation and N-ethyl-N'-methylimidazolinium cation); amidinium cations (such as N,N'-dimethyltetrahydropyrimidinium cation, N-benzyl-1,8-diazabicyclo[5.4.0]-7-undecenium cation, and N-benzyl-1,5-diazabicyclo[4.3.0]-5-nonenium cation); Morpholinium cations (such as N,N'-dimethylmorpholinium cation), piperidium cations (such as N,N'-diethylpiperidinium cation); Pyridinium cations (such as N-methylpyridinium cation, N-methoxypyridinium cation, N-butoxypyridinium cation, N-benzyloxypyridinium cation, and N-benzylpyridinium cation). imidazolium cations (such as N,N'-dimethylimidazolium cation and 1-ethyl-3-methylimidazolium cation); Quinolium cations (such as N-methylquinolium cations and N-benzylquinolium cations); isoquinolium cations (e.g., N-methylisoquinolium); Thiazonium cations (e.g., benzylbenzothiazonium cations); Acridium cations (such as benzyl acridium cation and phenacyl acridium cation); diazonium cations (such as phenyldiazonium cation, 2,4,6-triethoxyphenyldiazonium cation, 2,4,6-trihexyloxyphenyldiazonium cation, and 4-anilinophenyldiazonium cation); Guanidinium cations (such as hexamethylguanidinium cation and 2-benzyl-2-tert-butyl-1,1,3,3-tetramethylguanidinium cation). Phosphonium cations [tertiary phosphonium cations (triphenylphosphonium cation, tri-tert-butylphosphonium cation, etc.) and quaternary phosphonium cations (tetraphenylphosphonium cation, tetra-p-tolylphosphonium cation, triphenylbenzylphosphonium cation, triphenylbutyl cation, tetraethylphosphonium cation, tetrabutylphosphonium cation, etc.)]. Sulfonium cations {triphenylsulfonium cation, 4-(phenylthio)phenyldiphenylsulfonium cation, bis[4-(diphenylsulfonio)phenyl]sulfide, 4-hydroxyphenylmethylbenzylsulfonium cation, etc.}; sulfoxonium cations (e.g., triphenylsulfoxonium); thianthrenium cations [such as 5-(4-methoxyphenyl)thianthrenium, 5-phenylthianthrenium, and 5-trilylthianthrenium cations]; Thiophenium cations (e.g., 2-naphthyltetrahydrothiophenium); Iodonium cations [diphenyliodonium cation, di-p-tolyliodonium cation, 4-isopropylphenyl(p-tolyl)iodonium cation, etc.].

[0071] Among the above onium cations, sulfonium cations, iodonium cations, and diazonium cations are preferred in terms of photoresponsiveness.

[0072] Specific examples of preferred axial ligands L1 and L2 represented by formula (3) containing a sulfonium cation include the following.

[0073] [ka]

[0074] Specific examples of preferred axial ligands L1 and L2 represented by formula (3) containing an iodonium cation include the following.

[0075] [ka]

[0076] Specific examples of preferred axial ligands L1 and L2 represented by formula (3) containing a diazonium cation include the following.

[0077] [ka]

[0078] The photoacid generator (target product) represented by general formula (1) of the present invention can be produced by known methods. The target compound can be obtained by synthesizing a metal complex precursor (a) having an aromatic heterocyclic compound with the desired light-absorbing moiety as a cyclic ligand, and an axial ligand precursor (b) containing an onium structure and the desired anion, and then combining these. The production method is shown by the following chemical formula as an example. (Here, the aromatic heterocyclic compound is porphyrin.) The metal complex precursor (a) can be produced by various known methods. (Methods for synthesizing porphyrin and phthalocyanine compounds can be found, for example, in "The Porphyrin Handbook, Vols. 1-10, Academic Press (2000) and Vols. 11-20, (2003)" by Karl M. Kadis H, Kevin M. Smith, and Roger Guilard.)

[0079] [ka]

[0080] (In the formula, M is the same as the central metal M and represents the valence m. X represents a halogen atom and has the same number of halogen atoms as the valence of the metal M. L 3 and L 4 represents a halogen atom or a hydroxy group. [Onium] is the same as A in formula (3), and X1 is the same as X1 in formula (3).

[0081] When the photoacid generator (target product) represented by general formula (2) of the present invention is a cationic metal complex, the target compound can be obtained by combining the cationic metal complex precursor (a') with the axial ligand precursor (b) containing an onium structure and having the target anion. In this process, to introduce the counter anion X2 of the central metal cation, the target metal complex is obtained by exchanging the X2 anion in the presence of an equivalent or greater amount of an alkali metal salt, alkaline earth metal salt, or the like, which is the raw material for the X2 anion.

[0082] [ka]

[0083] (In the formula, M is the same as the central metal M and represents the valence m. X represents a halogen atom and has the same number of halogen atoms as the valence of the metal M. L 3 and L 4 represents a halogen atom or a hydroxy group; [Onium] is the same as A in formula (3); X1 is the same as X1 in formula (3); M' represents an alkali metal, an alkaline earth metal, or an alkyl group; and X2 is the same as X2 in formula (2).

[0084] The onium cation structure used in the axial ligand precursor (b) of the present invention can be prepared by a metathesis method. The metathesis method is described in, for example, Shin Jikken Kagaku Koza (New Experimental Chemistry Lectures), Vol. 14-I (1978, Maruzen), p. 448; Advance in Polymer Science, 62, 1-48 (1984); Shin Jikken Kagaku Koza (New Experimental Chemistry Lectures), Vol. 14-III (1978, Maruzen), pp. 1838-1846; Organic Sulfur Chemistry (Synthetic Reactions, 1982, Kagaku Dojin), Chapter 8, pp. 237-280; Japan Chemical Journal, 87, (5), 74 (1966); Japanese Patent Application Laid-Open Nos. 64-45357, 61-212554, 61-100557, 5-4996, 7-82244, 7-82245, 58-210904, and 6-184170. First, the F of the onium cation is reacted with the cation. - , Cl - , Br - , I - Halogen ion salts such as;OH - Salt; ClO4 - Salt; FSO3 - , ClSO3 - , CH3SO3 - , C6H5SO3 - , CF3SO3 - Salts with sulfonic acid ions such as HSO4 - , SO4 2- Salts with sulfate ions such as HCO3 - , CO3 2- , and salts with carbonate ions such as H2PO4 - , HPO4 2- , PO43- Salts with phosphate ions such as phosphate ions are prepared, and then metathesis is carried out by adding these to a solvent or aqueous solution containing a stoichiometric amount or more of an alkali metal salt, alkaline earth metal salt, or quaternary ammonium salt of the anion that constitutes the target onium salt, and, if necessary, other anion components such as KPF6, KBF4, or NaB(CF5)4. Water or an organic solvent can be used as the solvent. Organic solvents include hydrocarbons (e.g., hexane, heptane, toluene, xylene), cyclic ethers (e.g., tetrahydrofuran and dioxane), chlorinated solvents (e.g., chloroform and dichloromethane), alcohols (e.g., methanol, ethanol, and isopropyl alcohol), ketones (e.g., acetone, methyl ethyl ketone, and methyl isobutyl ketone), nitriles (e.g., acetonitrile), and polar organic solvents (e.g., dimethyl sulfoxide, dimethylformamide, and N-methylpyrrolidone). These solvents can be used alone or in combination.

[0085] The desired photoacid generator thus obtained can be purified, if necessary, by recrystallization or washing with water or a solvent. Purification by recrystallization can be achieved by dissolving the target photoacid generator in a small amount of organic solvent, and then separating the photoacid generator from the organic solvent by adding a poor solvent directly (or after concentrating) to the organic solvent solution containing the target photoacid generator to precipitate the target photoacid generator. Poor solvents that can be used here include linear ethers (e.g., diethyl ether and dipropyl ether), esters (e.g., ethyl acetate and butyl acetate), aliphatic hydrocarbons (e.g., hexane and cyclohexane), and aromatic hydrocarbons (e.g., toluene and xylene). Purification can also be achieved by utilizing temperature-dependent differences in solubility. Purification can be achieved by recrystallization (a method utilizing differences in solubility due to cooling, a method involving precipitation by adding a poor solvent, or a combination of these). If the photoacid generator is oily (i.e., does not crystallize), it can be purified by washing the oil with water or a poor solvent.

[0086] The structure of the photoacid generator thus obtained can be analyzed by a general analytical method, for example, 1 H, 13 C.19 F, 31 It can be identified by nuclear magnetic resonance spectroscopy such as P, infrared absorption spectroscopy, or elemental analysis.

[0087] The photoacid generator of the present invention may contain other conventionally known photoacid generators in addition to the compounds listed above, if necessary. When other photoacid generators are contained, the content (mol %) of the other photoacid generators relative to the number of moles of the photoacid generator of the present invention is preferably 0.1 to 100, more preferably 0.5 to 50.

[0088] Other photoacid generators include conventionally known ones such as onium salts (sulfonium, iodonium, selenium, ammonium, phosphonium, etc.) and salts of transition metal complex ions and anions.

[0089] The photoacid generator of the present invention may be dissolved in advance in a solvent that does not inhibit polymerization, crosslinking, deprotection reactions, etc., in order to facilitate dissolution in a composition containing a cationically polymerizable compound.

[0090] Examples of the solvent include carbonates such as propylene carbonate, ethylene carbonate, 1,2-butylene carbonate, dimethyl carbonate, and diethyl carbonate; ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone, and 2-heptanone; and monomethyl ethers, monoethyl ethers, monopropyl ethers, monobutyl ethers, and monophenyl ethers of ethylene glycol, ethylene glycol monoacetate, diethylene glycol, diethylene glycol monoacetate, propylene glycol, propylene glycol monoacetate, dipropylene glycol, and dipropylene glycol monoacetate. polyhydric alcohols such as ethanol and derivatives thereof; cyclic ethers such as dioxane; esters such as ethyl formate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl pyruvate, ethyl ethoxyacetate, methyl methoxypropionate, ethyl ethoxypropionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 2-hydroxy-3-methylbutanoate, 3-methoxybutyl acetate, and 3-methyl-3-methoxybutyl acetate; and aromatic hydrocarbons such as toluene and xylene.

[0091] When a solvent is used, the proportion of the solvent used is preferably 15 to 1000 parts by weight, more preferably 30 to 500 parts by weight, relative to 100 parts by weight of the photoacid generator of the present invention. The solvents used may be used alone or in combination of two or more kinds.

[0092] The photosensitive composition of the present invention comprises the above-mentioned photoacid generator and a cationically polymerizable compound.

[0093] Examples of the cationically polymerizable compound that is a component of the photosensitive composition include cyclic ethers (epoxides, oxetanes, etc.), ethylenically unsaturated compounds (vinyl ethers, styrenes, etc.), bicycloorthoesters, spiroorthocarbonates, and spiroorthoesters (see JP-A Nos. 11-060996, 09-302269, 2003-026993, 2002-206017, 11-349895, 10-212343, 2000-119306, 10-67812, 2000-186071, 08-85775, 08-134405, 2008 -20838, JP 2008-20839, JP 2008-20841, JP 2008-26660, JP 2008-26644, JP 2007-277327, "Photopolymer Handbook" edited by the Photopolymer Forum (1989, Industrial Research Institute), "UV / EB Curing Technology" edited by the General Technology Center (1982, General Technology Center), "UV / EB Curing Materials" edited by the RadTech Research Group (1992, CMC), "Causes of Curing Failure and Inhibition in UV Curing and Countermeasures" edited by the Technical Information Association (2003, Technical Information Association), Color Materials, 68, (5), 286-293 (1995), Fine Chemicals, 29, (19), 5-14 (2000), etc.

[0094] As the epoxide, known epoxides can be used, including aromatic epoxides, alicyclic epoxides and aliphatic epoxides.

[0095] Examples of aromatic epoxides include glycidyl ethers of mono- or polyhydric phenols having at least one aromatic ring (phenol, bisphenol A, phenol novolak, and alkylene oxide adducts thereof).

[0096] Examples of alicyclic epoxides include compounds obtained by epoxidizing a compound having at least one cyclohexene or cyclopentene ring with an oxidizing agent (e.g., 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate).

[0097] Examples of aliphatic epoxides include polyglycidyl ethers of aliphatic polyhydric alcohols or their alkylene oxide adducts (1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, etc.), polyglycidyl esters of aliphatic polybasic acids (diglycidyl tetrahydrophthalate, etc.), and epoxidized products of long-chain unsaturated compounds (epoxidized soybean oil, epoxidized polybutadiene, etc.).

[0098] As the oxetane, known oxetanes can be used, and examples thereof include 3-ethyl-3-hydroxymethyloxetane, 2-ethylhexyl(3-ethyl-3-oxetanylmethyl)ether, 2-hydroxyethyl(3-ethyl-3-oxetanylmethyl)ether, 2-hydroxypropyl(3-ethyl-3-oxetanylmethyl)ether, 1,4-bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene, oxetanylsilsesquioxetane, and phenol novolac oxetane.

[0099] As the ethylenically unsaturated compound, known cationically polymerizable monomers can be used, including aliphatic monovinyl ethers, aromatic monovinyl ethers, polyfunctional vinyl ethers, styrene, and cationically polymerizable nitrogen-containing monomers.

[0100] Examples of the aliphatic monovinyl ether include methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, and cyclohexyl vinyl ether.

[0101] Examples of aromatic monovinyl ethers include 2-phenoxyethyl vinyl ether, phenyl vinyl ether, and p-methoxyphenyl vinyl ether.

[0102] Examples of polyfunctional vinyl ethers include butanediol-1,4-divinyl ether and triethylene glycol divinyl ether.

[0103] Examples of the styrene include styrene, α-methylstyrene, p-methoxystyrene, and p-tert-butoxystyrene.

[0104] Examples of the cationically polymerizable nitrogen-containing monomer include vinyl monomers such as N-vinylcarbazole and N-vinylpyrrolidone, and monofunctional and polyfunctional aziridine monomers such as ethyl 3-(1-aziridyl)propionate, neopentyl glycol bis(3-(1-aziridyl)propionate), trimethylolpropane tris(3-(2-methyl-1-aziridyl)propionate), and pentaerythritol tetrakis(3-(1-aziridyl)propionate) ester.

[0105] Examples of bicyclo orthoesters include 1-phenyl-4-ethyl-2,6,7-trioxabicyclo[2.2.2]octane and 1-ethyl-4-hydroxymethyl-2,6,7-trioxabicyclo-[2.2.2]octane.

[0106] Examples of spiro orthocarbonates include 1,5,7,11-tetraoxaspiro[5.5]undecane and 3,9-dibenzyl-1,5,7,11-tetraoxaspiro[5.5]undecane.

[0107] Examples of spiro orthoesters include 1,4,6-trioxaspiro[4.4]nonane, 2-methyl-1,4,6-trioxaspiro[4.4]nonane, and 1,4,6-trioxaspiro[4.5]decane.

[0108] Furthermore, polyorganosiloxanes having at least one cationically polymerizable group per molecule can be used (e.g., those described in JP-A Nos. 2001-348482, 2000-281965, 2007-242828, and 2008-195931, Journal of Polym. Sci., Part A, Polym. Chem., Vol. 28, 497 (1990), etc.). These polyorganosiloxanes may be linear, branched, or cyclic, or may be mixtures of these.

[0109] Among these cationically polymerizable compounds, epoxides, oxetanes, and vinyl ethers are preferred, epoxides and oxetanes are more preferred, and alicyclic epoxides and oxetanes are particularly preferred. These cationically polymerizable compounds may be used alone or in combination of two or more.

[0110] The content of the photoacid generator of the present invention in the photosensitive composition is preferably 0.05 to 20 parts by weight, more preferably 0.1 to 10 parts by weight, per 100 parts by weight of the cationically polymerizable compound. This range ensures more sufficient polymerization of the cationically polymerizable compound, resulting in better physical properties of the cured product. The content is determined by taking into consideration various factors, such as the properties of the cationically polymerizable compound, the type of light (light source, wavelength, etc.), the amount of irradiation, temperature, curing time, humidity, and coating thickness, and is not limited to the above range.

[0111] In the photosensitive composition of the present invention, the content of the cationically polymerizable compound is 70% by weight to 99.9% by weight, preferably 80% by weight to 99.5% by weight, and more preferably 90% by weight to 99% by weight, based on the total weight of the photoacid generator and the cationically polymerizable compound. Two or more types of cationically polymerizable compounds may be used in combination.

[0112] The photosensitive composition of the present invention may contain, if necessary, known additives (pigments, fillers, conductive particles, antistatic agents, flame retardants, antifoaming agents, flow control agents, light stabilizers, antioxidants, adhesion imparting agents, ion scavengers, coloration inhibitors, solvents, non-reactive resins, radically polymerizable compounds, etc.).

[0113] The photosensitive composition of the present invention may contain other additives (J) that are commonly used to control the appearance and physical properties of the cured product of the photosensitive composition. Examples of the other additives (J) include colorants (Ja), metal oxide particles (Jb), and metal particles (Jc).

[0114] As the colorant (Ja) in the present invention, pigments such as inorganic pigments and organic pigments and dyes that have conventionally been used in paints, inks, etc. can be used.

[0115] Examples of inorganic pigments include yellow lead, zinc yellow, iron blue, barium sulfate, cadmium red, titanium oxide, zinc white, red iron oxide, alumina, calcium carbonate, ultramarine, carbon black, graphite, and titanium black.

[0116] Examples of organic pigments include soluble azo pigments such as β-naphthols, β-oxynaphthoic acid anilides, acetoacetate anilides, and pyrazolones; insoluble azo pigments such as β-naphthols, β-oxynaphthoic acid, β-oxynaphthoic acid anilides, acetoacetate anilide monoazos, acetoacetate anilide disazos, and pyrazolones; and polycyclic or heterocyclic compounds such as isocindolinones, quinacridones, dioxandines, perinones, and perylenes.

[0117] Specific examples of dyes include yellow dyes, aryl or heteryl azo dyes having phenols, naphthols, anilines, pyrazolones, pyridones, or open-chain active methylene compounds as coupling components, azomethine dyes having open-chain active methylene compounds as coupling components, methine dyes such as benzylidene dyes and monomethine oxonol dyes, quinone dyes such as naphthoquinone dyes and anthraquinone dyes, quinophthalone dyes, nitro, nitroso dyes, acridine dyes, and acridinone dyes.

[0118] Examples of magenta dyes include aryl or heteryl azo dyes having phenols, naphthols, anilines, pyrazolones, pyridones, pyrazolotriazoles, closed-ring active methylene compounds or heterocycles (pyrrole, imidazole, thiophene, thiazole derivatives, etc.) as a coupling component; azomethine dyes having pyrazolones or pyrazolotriazoles as a coupling component, methine dyes such as arylidene dyes, styryl dyes, merocyanine dyes and oxonol dyes; carbonium dyes such as diphenylmethane dyes, triphenylmethane dyes and xanthene dyes; quinone dyes such as naphthoquinone, anthraquinone and anthrapyridone; and condensed polycyclic dyes such as dioxazine dyes.

[0119] Cyan dyes include azomethine dyes such as indoaniline dyes and indophenol dyes, polymethine dyes such as cyanine dyes, oxonol dyes and merocyanine dyes, carbonium dyes such as diphenylmethane dyes, triphenylmethane dyes and xanthene dyes, phthalocyanine dyes, anthraquinone dyes, aryl or heteryl azo dyes having phenols, naphthols, anilines, pyrrolopyrimidinone or pyrrolotriazinone derivatives as coupling components (CI Direct Blue 14, etc.), and indigo and thioindigo dyes.

[0120] From the viewpoint of the image sharpness of the coating film, the particle size of the colorant (Ja) is preferably an average particle size of 0.01 μm to 2.0 μm, more preferably 0.01 μm to 1.0 μm.

[0121] The amount of the colorant (Ja) added is not particularly limited, but is preferably 1 to 60% by weight based on the total weight of the photosensitive composition.

[0122] When a pigment is used, it is preferable to add a pigment dispersant to improve the dispersibility of the pigment and the storage stability of the photosensitive composition. Examples of pigment dispersants include pigment dispersants manufactured by BYK (e.g., Anti-Terra-U, Disperbyk-101, 103, 106, 110, 161, 162, 164, 166, 167, 168, 170, 174, 182, 184, and 2020), pigment dispersants manufactured by Ajinomoto Fine-Techno Co., Inc. (e.g., Ajisper PB711, PB821, PB814, PN411, and PA111), and pigment dispersants manufactured by The Lubrizol Corporation (e.g., Solsperses 5000, 12000, 32000, 33000, and 39000). These pigment dispersants may be used alone or in combination. The amount of pigment dispersant added is not particularly limited, but is preferably in the range of 0.1 to 10% by weight in the photosensitive composition.

[0123] As the filler, known fillers can be used, such as fused silica, crystalline silica, calcium carbonate, aluminum oxide, titanium oxide, niobium oxide, barium titanate, aluminum hydroxide, zirconium oxide, magnesium carbonate, mica, talc, calcium silicate, and lithium aluminum silicate.

[0124] When a filler is contained, the content of the filler is preferably 50 to 600,000 parts by weight, and more preferably 300 to 200,000 parts by weight, relative to 100 parts of the acid generator.

[0125] As the conductive particles, known conductive particles can be used, including metal particles such as Ni, Ag, Au, Cu, Pd, Pb, Sn, Fe, Ni, and Al, plated metal particles obtained by further plating these metal particles with a metal, plated resin particles obtained by plating resin particles with a metal, and particles of conductive materials such as carbon.

[0126] When conductive particles are contained, the content of the conductive particles is preferably 50 to 30,000 parts by weight, and more preferably 100 to 20,000 parts by weight, relative to 100 parts of the acid generator.

[0127] As the antistatic agent, known antistatic agents can be used, and examples thereof include nonionic antistatic agents, anionic antistatic agents, cationic antistatic agents, amphoteric antistatic agents, and polymeric antistatic agents.

[0128] When an antistatic agent is contained, the content of the antistatic agent is preferably 0.1 to 20,000 parts by weight, and more preferably 0.6 to 5,000 parts by weight, relative to 100 parts of the photoacid generator.

[0129] As the flame retardant, known flame retardants can be used, and examples thereof include inorganic flame retardants {antimony trioxide, antimony pentoxide, tin oxide, tin hydroxide, molybdenum oxide, zinc borate, barium metaborate, red phosphorus, aluminum hydroxide, magnesium hydroxide, calcium aluminate, etc.}; bromine flame retardants {tetrabromophthalic anhydride, hexabromobenzene, decabromobiphenyl ether, etc.}; and phosphate ester flame retardants {tris(tribromophenyl)phosphate, etc.}.

[0130] When a flame retardant is contained, the content of the flame retardant is preferably 0.5 to 40,000 parts by weight, and more preferably 5 to 10,000 parts by weight, per 100 parts of the photoacid generator.

[0131] As the defoaming agent, known defoaming agents can be used, and examples thereof include alcohol defoaming agents, metal soap defoaming agents, phosphate ester defoaming agents, fatty acid ester defoaming agents, polyether defoaming agents, silicone defoaming agents, and mineral oil defoaming agents.

[0132] As the flow modifier, known flow modifiers can be used, and examples thereof include hydrogenated castor oil, oxidized polyethylene, organic bentonite, colloidal silica, amide wax, metal soap, and acrylic ester polymer. As the light stabilizer, known light stabilizers can be used, and examples thereof include ultraviolet absorbing stabilizers (benzotriazole, benzophenone, salicylate, cyanoacrylate, and derivatives thereof, etc.); radical scavenging stabilizers (hindered amines, etc.); and quenching stabilizers (nickel complexes, etc.). As the antioxidant, known antioxidants can be used, and examples thereof include phenol-based antioxidants (monophenol-based, bisphenol-based, polymeric phenol-based, etc.), sulfur-based antioxidants, and phosphorus-based antioxidants. As the adhesion promoter, known adhesion promoters can be used, and examples thereof include coupling agents, silane coupling agents, and titanium coupling agents. As the ion scavenger, known ion scavenger can be used, and examples thereof include organic aluminum (alkoxy aluminum, phenoxy aluminum, etc.). As the coloring inhibitor, known coloring inhibitors can be used, and generally, antioxidants are effective, and examples thereof include phenol-based antioxidants (monophenol-based, bisphenol-based, polymeric phenol-based, etc.), sulfur-based antioxidants, and phosphorus-based antioxidants, but they are almost ineffective in preventing coloring during heat resistance tests at high temperatures.

[0133] When an antifoaming agent, a flow control agent, a light stabilizer, an antioxidant, an adhesion imparting agent, an ion scavenger, or a coloring inhibitor is contained, the content of each is preferably 0.1 to 20,000 parts by weight, and more preferably 0.5 to 5,000 parts by weight, relative to 100 parts of the photoacid generator.

[0134] There are no limitations on the solvent as long as it can be used to dissolve the cationically polymerizable compound and adjust the viscosity of the photocurable composition, and the solvents listed above as solvents for the photoacid generator can be used.

[0135] When a solvent is contained, the content of the solvent is preferably 50 to 2,000,000 parts by weight, and more preferably 200 to 500,000 parts by weight, relative to 100 parts of the photoacid generator.

[0136] Examples of non-reactive resins include polyester, polyvinyl acetate, polyvinyl chloride, polybutadiene, polycarbonate, polystyrene, polyvinyl ether, polyvinyl butyral, polybutene, hydrogenated styrene-butadiene block copolymer, (meth)acrylic acid ester copolymer, polyurethane, etc. The number average molecular weight of these resins is preferably 1,000 to 500,000, more preferably 5,000 to 100,000 (the number average molecular weight is a value measured by a general method such as GPC).

[0137] When a non-reactive resin is contained, the content of the non-reactive resin is preferably 5 to 400,000 parts by weight, and more preferably 50 to 150,000 parts by weight, relative to 100 parts of the photoacid generator.

[0138] When a non-reactive resin is contained, it is desirable to dissolve the non-reactive resin in a solvent in advance so that the non-reactive resin can be easily dissolved in the cationically polymerizable compound or the like.

[0139] Examples of radical polymerizable compounds that can be used include known radical polymerizable compounds such as those described in "Photopolymer Handbook" edited by the Photopolymer Forum (1989, Industrial Research Institute), "UV / EB Curing Technology" edited by the General Technology Center (1982, General Technology Center), "UV / EB Curing Materials" edited by the RadTech Research Group (1992, CMC), and "Causes of Curing Failure and Inhibition in UV Curing and Countermeasures Therefor" edited by the Technical Information Association (2003, Technical Information Association), and include monofunctional monomers, bifunctional monomers, polyfunctional monomers, epoxy (meth)acrylates, polyester (meth)acrylates, and urethane (meth)acrylates.

[0140] When a radical polymerizable compound is contained, the content of the radical polymerizable compound is preferably 5 to 400,000 parts by weight, and more preferably 50 to 150,000 parts by weight, relative to 100 parts of the photoacid generator.

[0141] When a radically polymerizable compound is contained, it is preferable to use a radical polymerization initiator that initiates polymerization by heat or light in order to increase the molecular weight of the compound by radical polymerization.

[0142] As the radical polymerization initiator, known radical polymerization initiators can be used, including thermal radical polymerization initiators (organic peroxides, azo compounds, etc.) and photoradical polymerization initiators (acetophenone-based initiators, benzophenone-based initiators, Michler's ketone-based initiators, benzoin-based initiators, thioxanthone-based initiators, acylphosphine-based initiators, etc.).

[0143] When a radical polymerization initiator is contained, the content of the radical polymerization initiator is preferably 0.01 to 20 parts by weight, more preferably 0.1 to 10 parts by weight, based on 100 parts of the radical polymerizable compound.

[0144] The photosensitive composition of the present invention can be prepared by uniformly mixing and dissolving the cationically polymerizable compound, the acid generator, and, if necessary, the additives at room temperature (about 20 to 30°C) or, if necessary, under heating (about 40 to 90°C), or further by kneading them using a three-roll mill or the like.

[0145] The photosensitive composition of the present invention can be used with a light source capable of irradiating energy rays in the visible to infrared range, such as an argon ion laser, a helium cadmium laser, a helium neon laser, a krypton ion laser, various semiconductor lasers, a xenon lamp, or an LED light source. Depending on the application, in addition to commonly used high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, and high-power metal halide lamps can also be used, since they emit energy rays of 400 nm or more.

[0146] The light irradiation time is affected by the intensity of the light source and the light transmittance of the photocurable composition, but 0.1 to 10 seconds at room temperature (approximately 20 to 30°C) is sufficient. However, if the light transmittance is low or the film thickness of the photocurable composition is thick, it may be preferable to use a longer irradiation time. Most photocurable compositions cure by cationic polymerization within 0.1 seconds to several minutes after light irradiation, but if necessary, they can be post-cured by heating at room temperature (approximately 20 to 30°C) to 200°C for several seconds to several hours after light irradiation.

[0147] The photosensitive composition of the present invention can be applied to a substrate by known coating methods such as spin coating, roll coating, and spray coating, as well as known printing methods such as lithographic printing, carton printing, metal printing, offset printing, screen printing, and gravure printing, depending on the application. In addition, the composition can also be applied by an inkjet method that continuously ejects fine droplets. [Example]

[0148] The present invention will be further explained below with reference to examples, but is not intended to be limited thereto. Unless otherwise specified, % means % by weight.

[0149] Production Example 1 Synthesis of Metal Complex Precursor (a-1) Synthesis of octaethylporphyrinatosilicon(IV) dichloride (a-1) The title compound (a-1) was synthesized from octaethylporphyrin and tetrachlorosilane according to JW Buchler, et al., Chem. Ber. 1973, 106, 2710.

[0150] Production Example 2 Synthesis of Metal Complex Precursor (a-3) Synthesis of dichlorotetraphenylporphyrinatoantimony(V) bromide (a-3) The title compound (a-3) was synthesized from tetraphenylporphyrin and antimony trichloride based on YM Idemori, et. al., Journal of Biological Inorganic Chemistry, 2015, 20, 771.

[0151] Production Example 3 Synthesis of metal complex precursor (a-6) Synthesis of tetrakis(pentafluorophenyl)porphyrinatosilicon(IV) dichloride. The title compound (a-6) was synthesized in the same manner as in Production Example 1, except that tetrakis(pentafluorophenyl)porphyrin was used in place of octaethylporphyrin.

[0152] Production Example 4 Synthesis of Metal Complex Precursor (a-8) Synthesis of phthalocyanatogermanium(IV) dichloride. A reaction vessel was charged with 150 g of n-pentanol, 23 g of 1,2-dicyanobenzene, and 10 g of germanium tetrachloride, and then 27 g of DBU (1,8-diazabicyclo[5.4.0]-7-undecene) was added and mixed. The mixture was heated to 140°C and reacted under reflux for 12 hours. After cooling to room temperature, the reaction mixture was gradually added dropwise to 1500 g of methanol / water (1 / 2 by weight) while stirring, yielding a slurry. This was filtered, and the residue was washed five times with 100 g of methanol / water (1 / 2 by weight) and dried, yielding 18.9 g. 1 H-NMR confirmed that this dark blue solid was the metal complex precursor (a-8).

[0153] The structure of the metal complex precursor (a) is shown below: All of the metal complex precursors used except for those in the above production examples were reagents purchased from Aldrich.

[0154] [ka]

[0155] Preparation Example 5: Synthesis of axial ligand precursor (b-1 / PF6) (1) Intermediate-1 (b-1 / Cl): Synthesis of 3,5-dimethyl-4-hydroxyphenyldiphenylsulfonium chloride salt 7.3 g of 2,6-dimethylphenol, 50 g of methanesulfonic acid, and 7 g of diphosphorus pentoxide were added to a reaction vessel and stirred. 10 g of diphenyl sulfoxide was added and the mixture was allowed to react at 45°C for 6 hours. The reaction mixture was gradually added to 100 mL of 20% brine while cooling in an ice bath and stirring. 100 mL of dichloromethane was then added and the mixture was stirred for 1 hour. After allowing to stand, the aqueous layer was removed by separation, and the organic layer was washed five times with 50 mL of water and concentrated. Recrystallization was carried out from acetone to obtain 15.2 g of a white solid. 1 H-NMR confirmed that this white solid was (b-1 / Cl). (2) Synthesis of axial ligand precursor (b-1 / PF6) A reaction vessel was charged with 4.3 g of (b-1 / Cl), 20 mL of THF, 1.5 g of potassium carbonate, and 1.7 g of 2-(2-hydroxyethoxy)ethyl bromide, and the mixture was allowed to react at 60°C for 6 hours. After the reaction, the reaction mixture was poured into an aqueous solution prepared by dissolving 62.0 g of KPF in 50 mL of water. The mixture was stirred for 1 hour, extracted with 100 mL of dichloromethane, and the aqueous layer was removed by separation. The organic layer was washed five times with 50 mL of water, and then concentrated. Recrystallization from dichloromethane-hexane yielded 3.2 g of a white solid (60% yield). 1 H, 19 F and 31 P-NMR confirmed that this white solid was the axial ligand precursor (b-1 / PF6).

[0156] Preparation Example 6 Synthesis of axial ligand precursor (b-1 / SbF6) The same procedure as in Production Example 5(2) was followed, except that 63.1 g of KSbF was used instead of 62.0 g of KPF, to give 6.3 g of a white solid (yield 72%). 1 H, 19 F-NMR confirmed that this white solid was the axial ligand precursor (b-1 / SbF6).

[0157] Preparation Example 7 Synthesis of axial ligand precursor (b-1 / B(C6F5)4) The same procedure as in Production Example 5(2) was followed, except that 47.7 g of NaB(C6F5) (dissolved in 100 mL of water) was used instead of 62.0 g of KPF, to obtain 6.3 g of a pale yellow solid (yield: 59%). 1 H, 19 F-NMR confirmed that this pale yellow solid was the axial ligand precursor (b-1 / B(C6F5)4).

[0158] Preparation Example 8 Synthesis of axial ligand precursor (b-1 / (C2F5)3PF3) The same procedure as in Production Example 5(2) was followed, except that 35.3 g of K(C2F5)3PF was used instead of 62.0 g of KPF, to give 5.1 g of a pale yellow solid (yield 61%). 1 H, 19 F and 31 P-NMR confirmed that this pale yellow solid was the axial ligand precursor (b-1 / (C2F5)3PF3).

[0159] Preparation Example 9 Synthesis of axial ligand precursor (b-1 / Ga(C6F5)4) The same procedure as in Production Example 5(2) was followed, except that 48.4 g of NaGa(C6F5) (dissolved in 100 mL of water) was used instead of 62.0 g of KPF, to obtain 6.2 g of a white solid (yield 55%). 1 H, 19 F-NMR confirmed that this white solid was the axial ligand precursor (b-1 / Ga(C6F5)4).

[0160] Preparation Example 10 Axial Ligand Precursor (b-1 / Al(O t- Synthesis of C4F9)4) In Production Example 5(2), LiAl(O t- According to the method described in Production Example 5(2), except for using 10.7 g of C4F9 (dissolved in 100 mL of water), 6.0 g of a white solid was obtained (yield 44%). 1 H, 19 F-NMR analysis showed that this white solid was an axial ligand precursor (b-1 / Al(O t- It was confirmed that the compound was C4F9)4).

[0161] Preparation Example 11 Synthesis of axial ligand precursor (b-1 / C(CF3SO2)3) The same procedure as in Production Example 5(2) was followed, except that 34.9 g of KC(CF3SO2) was used instead of 62.0 g of KPF, to give 4.9 g of a white solid (yield 61%). 1 H, 19 F-NMR confirmed that this white solid was the axial ligand precursor (b-1 / C(CF3SO2)3).

[0162] Preparation Example 12: Synthesis of axial ligand precursor (b-2 / PF6) (1) Intermediate-2: Synthesis of 4-{3-(hydroxydimethylsilyl)propyl}phenyldiphenylsulfonium triflate (b-2 / OTf) A reaction vessel was charged with 8.1 g of diphenyl sulfoxide and 100 mL of dichloromethane and cooled to -10°C in an ice bath. 13.0 g of trifluoromethanesulfonic anhydride was added dropwise thereto so that the temperature did not exceed 0°C. 8.8 g of 3-(ethoxydimethylsilyl)propylbenzene was then added dropwise thereto at 0°C or below. After the addition, the temperature was gradually raised and the mixture was stirred at room temperature for 1 hour. The reaction solution was added dropwise to 50 mL of 5% aqueous sodium bicarbonate solution cooled in an ice bath with stirring. After allowing to stand, the aqueous layer was removed by separation. The organic layer was washed five times with water and concentrated. The resulting crude crystals were recrystallized from dichloromethane-cyclohexane to yield 12.1 g of a pale yellow solid. 1 This white solid was identified as (b-2 / OTf) by H-NMR. (2) Synthesis of axial ligand precursor (b-2 / PF6) 5.3 g of (b-2 / OTf) was added to a reaction vessel and dissolved in 100 mL of dichloromethane. An aqueous solution of 62.0 g of KPF dissolved in 50 mL of water was added and stirred for 6 hours. The aqueous layer was removed by separation. The organic layer was washed five times with 50 mL of water and concentrated. Recrystallization from dichloromethane-hexane yielded 3.4 g of a pale yellow solid (65% yield). 1 H, 19 F and 31 P-NMR confirmed that this pale yellow solid was the axial ligand precursor (b-2 / PF6).

[0163] Preparation Example 13 Synthesis of axial ligand precursor (b-2 / (C2F5)3PF3) The same procedure as in Production Example 12(2) was followed, except that 35.3 g of K(C2F5)3PF was used instead of 62.0 g of KPF, to give 4.9 g of a pale yellow solid (yield 58%). 1 H, 19 F and 31 P-NMR confirmed that this pale yellow solid was the axial ligand precursor (b-2 / (C2F5)3PF3).

[0164] Preparation Example 14 Synthesis of axial ligand precursor (b-2 / SbF6) The same procedure as in Production Example 12(2) was followed, except that 63.1 g of KSbF was used instead of 62.0 g of KPF, to give 4.2 g of a pale yellow solid (yield 68%). 1 H, 19 F-NMR confirmed that this pale yellow solid was the axial ligand precursor (b-2 / SbF6).

[0165] Preparation Example 15: Synthesis of axial ligand precursor (b-3 / Ga(C6F5)4) (1) Intermediate-3: Synthesis of 4-carboxyphenyldiphenylsulfonium triflate 10 g of 4-iodobenzoic acid was added to a reaction vessel (A) and dissolved in 150 mL of THF. 1.8 g of sodium hydride was added to the mixture. The mixture was stirred for 10 minutes and then cooled to -40°C. 30 mL of a 15% THF solution of diisopropylmagnesium bromide was added dropwise to the mixture. Stirring was continued at -10°C for 3 hours. 16 g of diphenyl sulfoxide was added to a separate reaction vessel (B) and dissolved in 50 mL of THF. The mixture was cooled to -40°C and 15 g of trimethylsilyl trifluoromethanesulfonate was added dropwise to the mixture. Stirring was continued at -40°C for 30 minutes and then transferred to the reaction vessel (A) via a tube. The mixture was stirred at -20°C for 3 hours and then cooled to -70°C. 100 mL of 40% aqueous hydrobromic acid was added to the mixture. The mixture was warmed to room temperature, and 300 mL of diethyl ether and 200 mL of 40% aqueous hydrobromic acid were added. The mixture was stirred for 1 hour and then allowed to stand. The aqueous layer was separated and extracted with diethyl ether and dichloromethane, and the combined organic layer was concentrated. The extract was purified by silica gel column chromatography to obtain 15 g of a white solid. 1 This white solid was identified as Intermediate-3 by 1 H-NMR. (2) Intermediate-4: Synthesis of 4-[N-{(3-(dimethylhydroxysilyl)propyl)}carbamoyl]phenyldiphenylsulfonium triflate (b-3 / OTf)

[0166] [ka]

[0167] 4.5 g of (Intermediate-3) and 30 mL of DMF were added to a reaction vessel, and 3.8 g of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride was further added thereto. This was stirred for 1 hour, and 1.5 g of 3-aminopropyldimethylethoxysilane was added dropwise thereto. After the dropwise addition, the mixture was stirred for 12 hours, and then poured into 100 mL of water. Extraction was performed with 50 mL of dichloromethane, and the organic layer was washed with 1N hydrochloric acid, and then washed with water five times and concentrated. The obtained crude crystals were used as they were as Intermediate-4. Note that, 1 H-NMR confirmed that the main component was intermediate-4 (b-3 / OTf). (3) Axial ligand precursor (b-3 / Ga(C6F5)4) The procedure of Production Example 12(2) was followed, except that 5.3 g of (b-2 / OTf) was replaced with 5.7 g of (b-3 / OTf) and 48.4 g of NaGa(CF) (dissolved in 100 mL of water) was used instead of 62.0 g of KPF, to obtain 6.3 g of a pale yellow solid (yield: 54%). 1 H, 19 F and 31 P-NMR confirmed that this pale yellow solid was the axial ligand precursor (b-3 / Ga(C6F5)4).

[0168] Preparation Example 16 Axial Ligand Precursor (b-4 / B(C6F5)4) (1) Intermediate-5: Synthesis of (3-phenylpropynyl)dimethylethoxysilane A reaction vessel was charged with 6.4 g of dimethylethoxyethynylsilane and 500 mL of THF and cooled to -78°C. 37 mL of a 15% n-butyllithium hexane solution was added dropwise. The mixture was stirred for 1 hour, and then 9.4 g of benzyl bromide (diluted with 50 mL of THF) was added dropwise. After the addition, the temperature was raised to room temperature and the mixture was stirred for a further 6 hours. 30 mL of a 10% aqueous ammonium chloride solution was slowly added to terminate the reaction, and the reaction solution was added to 400 mL of water. The mixture was extracted five times with 100 mL of diethyl ether, and the organic layer was washed three times with water. The mixture was concentrated using an evaporator to obtain 9.5 g of a yellow oil. The oil obtained was used as is as intermediate-5. Note that, 1 H-NMR confirmed that the main component was intermediate-5. (2) Intermediate-6: Synthesis of 4-{3-(hydroxydimethylsilyl)-1-propynyl}phenyldiphenylsulfonium triflate (b-4 / OTf) According to the method described in Production Example 12(1), except that 8.7 g of (Intermediate-5) was used instead of 8.8 g of 3-(ethoxydimethylsilyl)propylbenzene, 10.8 g of a pale yellow solid was obtained. 1 This white solid was identified as (b-4 / OTf) by H-NMR. (3) Axial Ligand Precursor (b-4 / B(C6F5)4) According to the method described in Production Example 12(2), except that 5.3 g of (b-2 / OTf) was replaced with 5.2 g of (b-4 / OTf) and 62.0 g of KPF was replaced with 47.7 g of NaB(CF) (dissolved in 100 mL of water), 10.8 g of a pale yellow solid was obtained. 1 H-NMR confirmed that this pale yellow solid was the axial ligand precursor (b-4 / B(C6F5)4).

[0169] Preparation Example 17 Axial Ligand Precursor (b-5 / Ga(C6F5)4) (1) Intermediate-7: Synthesis of (3-carboxypropyl-1-one-phenyl)diphenylsulfonium chloride A reaction vessel was charged with 9.0 g of triphenylsulfonium chloride, 50 mL of dichloromethane, and 4.0 g of aluminum chloride and stirred. This was cooled in an ice bath, and 9.0 g of succinic anhydride was added dropwise. The mixture was then stirred at room temperature for 8 hours, and the reaction solution was poured into 100 mL of ice water. An additional 50 mL of dichloromethane was added, and the mixture was stirred for another hour. After allowing to stand, the aqueous layer was removed, and the organic layer was washed five times with water and then concentrated. The mixture was purified by silica gel column chromatography, yielding 13.8 g of a white solid. 1 This white solid was identified as Intermediate-7 by 1 H-NMR. (2) Synthesis of Intermediate-8 (b-5 / Cl)

[0170] [ka]

[0171] Crude crystals were obtained in accordance with the method described in Production Example 15(2), except that 4.0 g of (Intermediate-7) was used instead of 4.5 g of (Intermediate-3). 1 H-NMR confirmed that the main component was intermediate-8 (b-5 / Cl). (3) Axial Ligand Precursor (b-5 / Ga(C6F5)4) The same procedure as in Production Example 12(2) was followed, except that 5.3 g of (b-2 / OTf) was replaced with 5.1 g of (b-5 / Cl) and 48.4 g of NaGa(CF) (dissolved in 100 mL of water) instead of 62.0 g of KPF, to obtain 7.3 g of a pale yellow solid (yield: 60%). 1 H, 19 F-NMR confirmed that this pale yellow solid was the axial ligand precursor (b-5 / Ga(C6F5)4).

[0172] Preparation Example 18: Synthesis of axial ligand precursor (b-6 / (C2F5)3PF3) (1) Intermediate 9: Synthesis of 4-(4-phenyl-1,3-butadiynyl)phenyldimethylethoxysilane 2.8 g of 4-(4-phenyl-1,3-butadiynyl)-1-bromobenzene and 20 mL of THF were added to a reaction vessel, dissolved, and cooled to -78°C. 8 mL of a 15% n-butyllithium hexane solution was added dropwise. The mixture was stirred for 1 hour, and then 1.4 g of chlorodimethylethoxysilane (diluted with 10 mL of THF) was added dropwise. After the addition, the temperature was raised to room temperature and the mixture was stirred for a further 6 hours. Under ice cooling, the reaction mixture was gradually added to 20 mL of a 10% aqueous ammonium chloride solution and stirred. Extraction was carried out with 50 mL of hexane, and the organic layer was washed three times with water. The mixture was concentrated using an evaporator to obtain 2.8 g of a yellow oil. The obtained oil was used as is as intermediate-9. Note that, 1 H-NMR confirmed that the main component was intermediate-9. (2) Intermediate-10: Synthesis of 4-{4-(p-dimethylhydroxysilyl)phenyl-1,3-butadiynyl}phenyldiphenylsulfonium triflate (b-6 / OTf) According to the method described in Production Example 12(1), except that 8.8 g of 3-(ethoxydimethylsilyl)propylbenzene was replaced with 12.2 g of (Intermediate-9), 12.8 g of a pale yellow solid was obtained. 1 This pale yellow solid was identified as (b-6 / OTf) by H-NMR. (3) Synthesis of axial ligand precursor (b-6 / (C2F5)3PF3) According to the method described in Production Example 12(2), except that 5.3 g of (b-2 / OTf) was replaced with 6.1 g of (b-6 / OTf) and 62.0 g of KPF was replaced with 35.3 g of K(C2F5)3PF, 6.4 g of a pale yellow solid was obtained. 1 H, 19 F and 31 P-NMR confirmed that this pale yellow solid was the axial ligand precursor (b-6 / (C2F5)3PF3).

[0173] Preparation Example 19 Axial Ligand Precursor (b-7 / Ga(C6F5)4) (1) Intermediate-11: Synthesis of biphenyldimethylethoxysilane According to the same method as in Production Example 17(1), except that 2.8 g of 4-(4-phenyl-1,3-butadiynyl)-1-bromobenzene was replaced with 2.3 g of 4-bromobiphenyl, 2.4 g of a pale yellow oil was obtained. The obtained oil was used as it was as Intermediate-11. 1 H-NMR confirmed that the main component was intermediate-11. (2) Intermediate-12: Synthesis of 4-{4'-(dimethylhydroxysilyl)phenyl}phenyldiphenylsulfonium triflate (b-7 / OTf) According to the method described in Production Example 12(1), except that 8.8 g of 3-(ethoxydimethylsilyl)propylbenzene was replaced with 10.3 g of (Intermediate-11), 15.8 g of a white solid was obtained. 1 This white solid was identified as (b-7 / OTf) by H-NMR. (3) Synthesis of axial ligand precursor (b-7 / Ga(C6F5)4) According to the method described in Production Example 12(2), except that 5.3 g of (b-2 / OTf) was replaced with 6.1 g of (b-7 / OTf) and 62.0 g of KPF was replaced with 48.4 g of NaGa(CF) (dissolved in 100 mL of water), 7.0 g of a pale yellow solid was obtained. 1 H and 19 F-NMR confirmed that this pale yellow solid was the axial ligand precursor (b-7 / (Ga(C6F5)4).

[0174] Preparation Example 20 Axial Ligand Precursor (b-8 / C2F5)3PF3) (1) Intermediate-13: Synthesis of 4-(ethoxydimethylsilyl)stilbene According to the same method as in Production Example 18(1), except that 2.8 g of 4-(4-phenyl-1,3-butadiynyl)-1-bromobenzene was replaced with 2.6 g of 4-bromostilbene, 2.7 g of a pale yellow oil was obtained. The obtained pale yellow oil was used as it was as Intermediate-13. 1 H-NMR confirmed that the main component was intermediate-13. (2) Intermediate-14: Synthesis of 4-[1-{p-(dimethylhydroxysilyl)phenyl}ethenyl)]phenyldiphenylsulfonium triflate (b-8 / OTf) According to the method described in Production Example 12(1), except that 8.8 g of 3-(ethoxydimethylsilyl)propylbenzene was used in place of 11.3 g of (Intermediate-13), 14.1 g of a pale yellow solid was obtained. 1 This pale yellow solid was identified as (b-8 / OTf) by 1 H-NMR. (3) Synthesis of axial ligand precursor (b-8 / (C2F5)3PF3) According to the method described in Production Example 12(2), except that 5.3 g of (b-2 / OTf) was replaced with 5.9 g of (b-8 / OTf) and 62.0 g of KPF was replaced with 35.3 g of K(C2F5)3PF, 5.2 g of a pale yellow solid was obtained. 1 H, 19 F and 31 P-NMR confirmed that this pale yellow solid was the axial ligand precursor (b-8 / (C2F5)3PF3).

[0175] Preparation Example 21 Axial Ligand Precursor (b-9 / Al(O t- C4F9)4) (1) Intermediate-15: Synthesis of (2-methoxy-4-hydroxyphenyl)phenyliodonium chloride 22 g of iodosylbenzene, 12.4 g of 3-methoxyphenol, 700 g of glacial acetic acid, and 70 g of acetic anhydride were dissolved and mixed in a reaction vessel and cooled in an ice bath. 12 g of concentrated sulfuric acid was added dropwise so that the temperature did not exceed 5°C, and the reaction was continued at room temperature for an additional 3 hours. The reaction solution was gradually added to 200 mL of 20% brine while cooling in an ice bath and stirring. 100 mL of dichloromethane was added and the mixture was stirred for 1 hour. After allowing to stand, the aqueous layer was removed by separation, and the organic layer was washed five times with 50 mL of water and concentrated. The product was separated and purified by column chromatography, yielding 10.3 g of a white solid. 1 This white solid was identified as (Intermediate-15) by 1 H-NMR. (2) Intermediate-16: Synthesis of {2-methoxy-4-(2-hydroxyethoxy)ethyl}phenylphenyliodonium chloride (b-9 / Cl) 3.3 g of (Intermediate-15), 20 mL of THF, 1.5 g of potassium carbonate, and 1.7 g of 2-(2-hydroxyethoxy)ethyl bromide were added to a reaction vessel and reacted at room temperature for 18 hours. The reaction solution was concentrated using an evaporator, and the resulting oil was dissolved in 50 mL of dichloromethane. The mixture was washed five times with 50 mL of water, and the organic layer was concentrated. Recrystallization from dichloromethane-hexane yielded 3.8 g of a white solid. 1 H-NMR confirmed that this white solid was (b-9 / Cl). (3) Axial ligand precursor (b-9 / Al(O t- Synthesis of C4F9)4) In Production Example 12(2), 5.3 g of (b-2 / OTf) was replaced with 4.5 g of (b-9 / Cl) and 2.0 g of KPF, and LiAl(O t- According to the method described in Production Example 12(2), except for using 10.7 g of C4F9 (dissolved in 100 mL of water), 7.6 g of a pale yellow solid was obtained (yield 55%). 1 H, 19 F-NMR analysis revealed that this pale yellow solid was an axial ligand precursor (b-9 / Al(O t- It was confirmed that the compound was C4F9)4).

[0176] Preparation Example 22 Axial Ligand Precursor (b-9 / (C2F5)3PF3) The same procedure as in Production Example 12(2) was followed, except that 5.3 g of (b-2 / OTf) was replaced with 4.5 g of (b-9 / Cl) and 35.3 g of K(C2F5)3PF were used instead of 62.0 g of KPF, to obtain 5.2 g of a pale yellow solid (yield 61%). 1 H, 19 F and 31 P-NMR confirmed that this pale yellow solid was the axial ligand precursor (b-9 / (C2F5)3PF3).

[0177] Preparation Example 23 Axial Ligand Precursor (b-9 / (Ga(C6F5)4) The same procedure as in Production Example 12(2) was followed, except that 5.3 g of (b-2 / OTf) was replaced with 4.5 g of (b-9 / Cl) and 62.0 g of KPF was replaced with 48.4 g of NaGa(CF) (dissolved in 100 mL of water), to obtain 5.5 g of a pale yellow solid (yield: 48%). 1 H, 19 F-NMR confirmed that this pale yellow solid was the axial ligand precursor (b-9 / (Ga(C6F5)4).

[0178] Preparation Example 24 Axial Ligand Precursor (b-9 / B(C6F5)4) The same procedure as in Production Example 12(2) was followed, except that 5.3 g of (b-2 / OTf) was replaced with 4.5 g of (b-9 / Cl) and 62.0 g of KPF was replaced with 47.7 g of NaB(CF) (dissolved in 100 mL of water), to obtain 5.8 g of a pale yellow solid (yield: 53%). 1 H, 19 F-NMR confirmed that this pale yellow solid was the axial ligand precursor (b-9 / (B(C6F5)4).

[0179] Preparation Example 25 Axial Ligand Precursor (b-10 / Al(O t- C4F9)4) (1) Intermediate-17: Synthesis of (2,6-dimethoxy-4-hydroxyphenyl)phenyliodonium chloride The same procedure as in Production Example 21(1) was followed, except that 15.4 g of 3,5-dimethoxyphenol was used instead of 12.4 g of 3-methoxyphenol, to give 29.5 g of a white solid. 1 This white solid was identified as (Intermediate-17) by 1 H-NMR. (2) Axial ligand precursor (b-10 / Al(O t- Synthesis of C4F9)4) 3.6 g of (Intermediate-17), 20 mL of THF, 1.5 g of potassium carbonate, and 2.1 g of 2-(2-hydroxyethoxyethoxy)ethyl bromide were added to a reaction vessel and reacted at room temperature for 18 hours. The reaction solution was previously treated with LiAl(O t- This was added to 100 mL of water (10.7 g) and stirred for another hour, followed by extraction with 50 mL of dichloromethane. The aqueous layer was removed by separation, and the organic layer was washed five times with water and then concentrated. Recrystallization from dichloromethane-hexane yielded 7.6 g of a pale yellow solid (52% yield). 1 H, 19 F-NMR analysis revealed that this pale yellow solid was an axial ligand precursor (b-10 / Al(O t- It was confirmed that the compound was C4F9)4).

[0180] Preparation Example 26 Axial Ligand Precursor (b-11 / (C2F5)3PF3) A reaction vessel was charged with 2.6 g of 4-t-butyliodobenzene, 3.3 g of 3-(ethoxydimethylsilyl)propylbenzene, 30 mL of dichloromethane, and 50 mL of trifluoroacetic acid and dissolved. The mixture was heated to 40°C, and 2.7 g of potassium persulfate was added in small portions. After 20 hours of reaction, the reaction mixture was poured into 100 mL of cold water. 100 mL of dichloromethane was added and the mixture was stirred for 1 hour. After allowing to stand, the aqueous layer was removed, and an aqueous solution of 5.3 g of K(C2F5)3PF3 dissolved in 50 mL of water was added and stirred for 1 hour. After allowing to stand, the aqueous layer was removed, and the organic layer was washed five times with water and concentrated. The resulting oil was purified with dichloromethane-cyclohexane to give 4.5 g of a pale yellow solid (47% yield). 1 H, 19 F and 31P-NMR confirmed that this pale yellow solid was the axial ligand precursor (b-11 / (C2F5)3PF3).

[0181] Preparation Example 27 Axial Ligand Precursor (b-12 / (C2F5)3PF3) (1) Intermediate-18: Synthesis of (4-carboxyphenyl)(4-t-amylphenyl)iodonium triflate In a reaction vessel, 2.5 g of 4-iodobenzoic acid and 3.3 g of m-chloroperbenzoic acid (65%) were dissolved in 30 mL of dichloromethane. 1.6 g of t-amylbenzene was added and the mixture was cooled to 0°C. 3.0 g of trifluoromethanesulfonic acid was added dropwise so that the temperature did not exceed 5°C. The mixture was gradually warmed to room temperature and stirred at room temperature for 2 hours. The reaction solution was concentrated under reduced pressure, 50 mL of diethyl ether was added, and the mixture was allowed to stand at -10°C to precipitate a solid. 3.5 g of a white solid was obtained by filtration. 1 This white solid was identified as (Intermediate-18) by 1 H-NMR. (2) Synthesis of Intermediate-19 (b-12 / OTf)

[0182] [ka]

[0183] Intermediate-19 was obtained according to the method described in Production Example 15(2), except that 4.5 g of (Intermediate-3) was replaced with 5.4 g of (Intermediate-18). 1 H-NMR confirmed that the main component was intermediate-19 (b-12 / OTf). (3) Axial Ligand Precursor (b-12 / (C2F5)3PF3) The procedure of Production Example 12(2) was followed, except that 5.3 g of (b-2 / OTf) was replaced with 6.6 g of (b-12 / OTf) and 62.0 g of KPF was replaced with 35.3 g of K(C2F5)3PF, to obtain 5.6 g of a pale yellow solid (yield 59%). 1 H, 19 F and 31P-NMR confirmed that this pale yellow solid was the axial ligand precursor (b-12 / (C2F5)3PF3).

[0184] Preparation Example 28 Axial Ligand Precursor (b-13 / (C2F5)3PF3) (1) Intermediate-20: Synthesis of 4-(hydroxyethoxy)ethyl-2,6-methoxyaniline 1.7 g of 2,6-dimethoxy-4-hydroxyaniline, 20 mL of THF, 1.5 g of potassium carbonate, and 1.7 g of 2-(2-hydroxyethoxy)ethyl bromide were added to a reaction vessel and reacted at 60°C for 1 hour. The mixture was concentrated using an evaporator, and 10 mL of dichloromethane was added. The organic layer was washed five times with water and concentrated, yielding 2.2 g of a pale yellow oil. 1 1 H-NMR confirmed that this pale yellow oil was (Intermediate-20). (2) Axial ligand precursor (b-13 / (C2F5)3PF3) A reaction vessel was charged with 2.6 g of (Intermediate-20), 10 mL of water, and 2 mL of 35% hydrochloric acid, and the mixture was cooled in a salt-ice bath while stirring. At 0°C, an aqueous solution of 0.7 g of sodium nitrite dissolved in 5 mL of water was slowly added with stirring. The mixture was stirred at 0°C for 1 hour. While maintaining the temperature, an aqueous solution of 5.3 g of K(C2F5)3PF3 dissolved in 50 mL of water was added, and the mixture was stirred for an additional 6 hours. 50 mL of dichloromethane was added to the mixture for extraction, and the aqueous layer was removed by separation. The mixture was washed five times with water and concentrated on an evaporator. Crystallization from diethyl ether yielded 2.9 g of a pale yellow solid (41% yield). 1 H, 19 F and 31 P-NMR confirmed that this pale yellow solid was the axial ligand precursor (b-13 / (C2F5)3PF3).

[0185] Preparation Example 29 Axial Ligand Precursor (b-13 / Ga(C6F5)4) The same procedure as in Production Example 28(2) was followed, except that 48.4 g of NaGa(C6F5) (dissolved in 100 mL of water) was used instead of 35.3 g of K(C2F5)3PF, to obtain 3.7 g of a pale yellow solid (yield 37%). 1 H,19 F-NMR confirmed that this pale yellow solid was the axial ligand precursor (b-13 / Ga(C6F5)4).

[0186] Preparation Example 30 Axial Ligand Precursor (b-14 / (C2F5)3PF3) (1) Intermediate 21: Synthesis of 4-(hydroxyethoxyethoxy)ethyl-2,6-methoxyaniline The procedure of Production Example 28(1) was followed, except that 2.1 g of 2-(2-hydroxyethoxyethoxy)ethyl bromide was used instead of 1.7 g of 2-(2-hydroxyethoxy)ethyl bromide, to give 2.5 g of a pale yellow oil. 1 1 H-NMR confirmed that this pale yellow oil was (Intermediate-21). (2) Axial Ligand Precursor (b-14 / (C2F5)3PF3) According to the same method as in Production Example 28(2), except that 2.6 g of (Intermediate-20) was replaced with 3.0 g of (Intermediate-21), 3.7 g of a pale yellow solid was obtained (yield 40%). 1 H, 19 F and 31 P-NMR confirmed that this pale yellow solid was the axial ligand precursor (b-14 / (C2F5)3PF3).

[0187] Preparation Example 31 Axial Ligand Precursor (b-15 / C(CF3SO2)3) (1) Intermediate-22: Synthesis of 2-methoxy-4-(isopropoxydimethylsilylpropyl)aniline A reaction vessel was charged with 1.6 g of 2-methoxy-4-allylaniline, 0.01 g of 1,3-divinyltetramethyldisiloxane platinum complex (0.1 M xylene solution), and 5 mL of toluene, and then 1.2 g of isopropoxydimethylsilane was added thereto and the reaction was carried out for 12 hours at 100° C. The solvent was distilled off and the mixture was purified by silica gel column chromatography to obtain 2.8 g of a pale yellow oil. 1 1 H-NMR confirmed that this pale yellow oil was (Intermediate-22). (2) Axial ligand precursor (b-15 / C(CF3SO2)3) In Production Example 28(2), 2.6 g of (Intermediate-20) was replaced with 2.8 g of (Intermediate-22), According to the method described in Production Example 28(2), except for using 4.9 g of KC(CF3SO2) instead of 35.3 g of K(C2F5)3PF, 2.9 g of a pale yellow solid was obtained (yield 44%). 1 H, 19 F-NMR confirmed that this pale yellow solid was the axial ligand precursor (b-15 / C(CF3SO2)3).

[0188] Examples 1 to 53 (Synthesis of Photoacid Generators of the Present Invention) The photoacid generators of the present invention were synthesized based on the following synthesis methods (I to III). The structures of the photoacid generators (abbreviated as PAG) synthesized in Examples 1 to 53 and the synthesis methods used are shown in Table 1.

[0189] Synthesis method (I) (metal complexes with two axial ligands) Examples 1 to 21, 32 to 41, 46 to 53 A metal complex precursor (a) and an axial ligand precursor (b / X1 - ) were mixed in an acetonitrile solvent at a molar ratio of 1:2 at room temperature, and the mixture was reacted for 6 hours while blowing in nitrogen. The acetonitrile was then distilled off under reduced pressure to obtain the target product (photoacid generator).

[0190] Synthesis method (II) (Cationic metal complex with two axial ligands and counter anion X2 - (if you have) Examples 30, 31, 42 to 45 In a reaction vessel, a metal complex precursor (a) and an axial ligand precursor (b / X1 - ) were mixed in a molar ratio of 1:2 in acetonitrile solvent at room temperature, and reacted for 6 hours while blowing in nitrogen. After acetonitrile was distilled off under reduced pressure, the mixture was dissolved in dichloromethane. - An aqueous solution of an alkali metal salt (lithium, sodium, or potassium salt) of the above was added and stirred for 1 hour. After standing, the aqueous layer was removed, and the organic layer was washed with water five times and concentrated. The target product (photoacid generator) was obtained by purifying with dichloromethane-hexane.

[0191] Synthesis method (III) (Metal complexes with one axial ligand) Examples 22 to 29 The metal complex precursor (a) and the axial ligand precursor (b-2 / X1) synthesized in Production Example 12 were placed in a reaction vessel. - ) were mixed in a molar ratio of 1:1 in acetonitrile solvent at room temperature, and the reaction was carried out for 6 hours while blowing in nitrogen. The acetonitrile was then distilled off under reduced pressure to obtain the target product (photoacid generator).

[0192] [Table 1]

[0193] (evaluation) <Examples 54 to 126 and Comparative Examples 1 to 14> [Preparation of Photosensitive Composition-1] 100 g of a cationically polymerizable compound (C) and the acid generators of the present invention (PAG-1 to PAG-53) were uniformly mixed to prepare photosensitive compositions (Q-1) to (Q-146) of the present invention. Similarly, 100 g of a cationically polymerizable compound (C), comparative acid generators (H-1 to H-3), and sensitizer (B) were uniformly mixed to prepare comparative photosensitive resin compositions (Q'-1) to (Q'-14). The types and amounts of the raw materials used are shown in Tables 2 to 7.

[0194] [Ingredients used] PAG-1 to PAG-53 (photoacid generators listed in Table 1) H-1: CPI-210S (manufactured by San-Apro) H-2: Di(tert-butylphenyl)iodonium hexafluorophosphate (Tokyo Chemical Industry Co., Ltd.) H-3: 4-Isopropyl-4'-methyldiphenyliodonium tetrakis(pentafluorophenyl)borate (Tokyo Chemical Industry Co., Ltd.) B-1: Tetraphenylporphyrin (Tokyo Chemical Industry Co., Ltd.) B-2: Phthalocyanine (Tokyo Chemical Industry Co., Ltd.) C-1: Product name: Celoxide 2021P (manufactured by Daicel) C-2: Product name jER828 (Mitsubishi Chemical) C-3: Product name OXT-221 (manufactured by Toagosei) C-4: Product name: ETERNACOLL OXBP (manufactured by Ube Industries; this product name is a registered trademark) C-5: Product name THI-DE (manufactured by Eneos)

[0195] [Curability] Curing test: The photosensitive composition of the present invention and the comparative photosensitive resin composition were applied to a glass substrate (76 mm × 52 mm) using an applicator (40 μm), and a curing test was carried out by exposing the composition to light under the following conditions using an irradiation device, LIGHTNINGCURE Spot Light Source LC8 (manufactured by Hamamatsu Photonics KK) as the light source. Curing-1: Infrared transmission filter (HOYA) R64 (cuts below 620 nm) Curing-2: Infrared transmission filter (HOYA) R72 (cuts below 700 nm) Thereafter, the curability was evaluated by the following evaluation method, and the results are shown in Tables 2 to 7. Curability rating: ◎ There is no tack on the surface, so it will not get scratched even if you scratch it with your fingernails. ○ There is no tack on the surface, but it can be scratched by fingernails. △ Tack remains on the surface. × It remains liquid and does not harden.

[0196] [Table 2]

[0197] [Table 3]

[0198] [Table 4]

[0199] [Table 5]

[0200] [Table 6]

[0201] [Table 7]

[0202] As shown in Tables 2 to 7, Examples 54 to 146 and Comparative Examples 1 to 14 demonstrate that photosensitive compositions containing the photoacid generators of the present invention exhibit superior curability when exposed to light in the visible to infrared range compared to comparative photosensitive compositions. As shown in Examples 54 to 146 and Comparative Examples 1 to 14, the photoacid generators of the present invention have an onium salt structure in the axial ligand that serves as the acid-generating moiety. This axial ligand of the metal allows the photoacid generators of the present invention to be in close proximity to the aromatic heterocyclic compound, which is a cyclic ligand and also serves as the light-absorbing moiety, within the same molecule, thereby generating acid very efficiently. In the comparative examples, a cyclic compound with a similar structure was added separately as a sensitizer, but the curability was poor compared to the examples, suggesting poor acid generation efficiency. Furthermore, as shown in Examples 86 to 105 and Examples 127 to 146, similar curability was obtained regardless of the type of cationically polymerizable compound.

[0203] <Examples 147 to 158: Examples of photosensitive compositions containing additive (J)> [Preparation of Photosensitive Composition-2] As additives, 30 g of titanium oxide (Ja-1, manufactured by Ishihara Sangyo Kaisha, Ltd., "Tipake R-930") or 30 g of Direct Blue 14 (Ja-2, manufactured by Tokyo Chemical Industry Co., Ltd.) were added to each of them, along with 3 g of a pigment dispersant (manufactured by Lubrizol Corporation, "Solsperse 32000"), 60 g of a cationically polymerizable compound (C-1), and 1 g of a photoacid generator of the present invention. These were then kneaded in a ball mill at 25°C for 3 hours to produce photosensitive compositions (Q-94) to (Q-105) of the present invention. The coating curability (Curability-3 and 4) was evaluated by the following method, and the results are shown in Table 8.

[0204] [Curability] Curability-3 and 4: These photosensitive compositions were applied to a surface-treated 100 μm thick PET (polyethylene terephthalate) film [Cosmoshine A4300 manufactured by Toyobo Co., Ltd.] using a bar coater to a film thickness of 20 μm (Curability-3) and 100 μm (Curability-4). Exposure was carried out using a LIGHTNINGCURE spot light source LC8 (manufactured by Hamamatsu Photonics KK) as the light source, and the curability was evaluated using the following evaluation method. Curability rating: ◎ There is no tack on the surface, so it will not get scratched even if you scratch it with your fingernails. ○ There is no tack on the surface, but it can be scratched by fingernails. △ Tack remains on the surface. × It remains liquid and does not harden.

[0205] [Table 8]

[0206] The results in Table 8 show that the photosensitive composition of the present invention can be cured efficiently even when a high concentration of a substance such as a colorant that attenuates or blocks irradiated light is present. For comparison, H-3 was used as the acid generator and B-2 as the sensitizer instead of the photoacid generator of the present invention, but no cured product was obtained. [Industrial Applicability]

[0207] The photosensitive composition of the present invention utilizes light (particularly in the visible to infrared region) to produce paints, coating agents, various coating materials (hard coats, stain-resistant coatings, anti-fogging coatings, contact-resistant coatings, optical fibers, etc.), backside treatment agents for adhesive tapes, release coating materials for release sheets for adhesive labels (release paper, release plastic films, release metal foils, etc.), printing plates, dental materials (dental compounds, dental composites), inkjet inks, positive resists (for forming connection terminals and wiring patterns in the manufacture of electronic parts such as circuit boards, CSPs, and MEMS elements), resist films, liquid resists, negative resists (for surface protection films for transparent electrodes (ITO, IZO, GZO) for semiconductor elements and FPDs, interlayer insulating films, permanent film materials such as planarizing films, etc.), MEMS resists, positive photosensitive materials, negative photosensitive materials, various adhesives, etc. It is suitable for use in adhesives (temporary fixing agents for various electronic components, adhesives for HDDs, adhesives for pickup lenses, adhesives for functional films for FPDs (deflectors, anti-reflection films, etc.), insulating films for circuit formation and semiconductor encapsulation, anisotropic conductive adhesives (ACA), films (ACF), pastes (ACP), etc.), holographic resins, FPD materials (color filters, black matrices, partition materials, photospacers, ribs, alignment films for liquid crystal displays, FPD sealants, etc.), optical components, molding materials (for construction materials, optical components, lenses), casting materials, putty, glass fiber impregnating agents, fillers, sealants, chip encapsulants such as flip chips and COFs, package encapsulants such as CSPs and BGAs, optical semiconductor (LED) encapsulants, optical waveguide materials, nanoimprint materials, materials for stereolithography, and materials for micro stereolithography.

Claims

1. A photoacid generator comprising a metal complex having a ring structure in which five-membered aromatic heterocyclic compounds are connected directly or through π-conjugation, the ring structure being a ligand, the central metal having one or two axial ligands, the axial ligands having an onium salt structure, and the metal complex being represented by general formula (1) or general formula (2). 【Chemistry 1】 [In formula (1), R 1 to R 8 are substituents on the aromatic heterocycle, and R 1 and R 2 , R 3 and R 4 , R 5 and R 6 , and R 7 and R 8 may be bonded to each other to form a condensed polycyclic aromatic structure; Y may be a nitrogen atom, a carbon atom, or may be directly bonded, and if it is a carbon atom, hydrogen or an aromatic hydrocarbon having 6 to 14 carbon atoms is substituted on the carbon atom; M is selected from the group consisting of Al, Ga, In, Si, Ge, Sn, Fe, Ti, Co, and Mn; L 1 and L 2 are axial ligands represented by formula (3) that coordinate to the metal; and when M is Al, Ga, In, Fe, Co, or Mn, only L 1 is present.] 【Chemistry 2】 [Formula (2) represents a case where the central metal M is cationic, R 1 to R 8 , Y, L 1 and L 2 are the same as in formula (1), M is selected from the group consisting of P, Sb and Bi, and X 2 − represents a monovalent counter anion corresponding to the central metal cation.] 【Transformation 3】 [In formula (3), D represents an oxygen atom or a sulfur atom; E represents an alkylene having 1 to 8 carbon atoms, an alkenylene having 2 to 8 carbon atoms, an alkynylene having 2 to 8 carbon atoms, or an arylene having 6 to 14 carbon atoms, and may contain an ether group, a sulfide group, a ketone group, an amide group, an ester group, a thioester group, a urea group, a sulfone group, a silyl group, or a phenylene group in the main chain; A + represents a monovalent onium cation which is a sulfonium cation, a diazonium cation, or an iodonium cation; and X 1 − represents a monovalent counter anion corresponding to the onium cation.]

2. 2. The photoacid generator according to claim 1, wherein the ligand forming the ring structure is a porphyrin or a phthalocyanine.

3. A photosensitive composition comprising the photoacid generator according to claim 1 or 2 and a cationically polymerizable compound.

4. A cured product obtained by curing the photosensitive composition according to claim 3.

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