[go: up one dir, main page]

WO2021065796A1 - Composition durcissable, matériau durci et procédé de formation d'un matériau durci - Google Patents

Composition durcissable, matériau durci et procédé de formation d'un matériau durci Download PDF

Info

Publication number
WO2021065796A1
WO2021065796A1 PCT/JP2020/036621 JP2020036621W WO2021065796A1 WO 2021065796 A1 WO2021065796 A1 WO 2021065796A1 JP 2020036621 W JP2020036621 W JP 2020036621W WO 2021065796 A1 WO2021065796 A1 WO 2021065796A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
formula
represented
alkyl
groups
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2020/036621
Other languages
English (en)
Japanese (ja)
Inventor
媛▲青▼ 張
大 塩田
和也 染谷
二郎 引田
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Tokyo Ohka Kogyo Co Ltd
Original Assignee
Tokyo Ohka Kogyo Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Tokyo Ohka Kogyo Co Ltd filed Critical Tokyo Ohka Kogyo Co Ltd
Priority to KR1020227014570A priority Critical patent/KR102765016B1/ko
Priority to CN202080068095.4A priority patent/CN114502613A/zh
Publication of WO2021065796A1 publication Critical patent/WO2021065796A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
    • C08G59/687—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used containing sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins

Definitions

  • the present invention relates to a curable composition containing a cationic curing agent (A) and a cationically curable compound (B), a cured product of the curable composition, and a method for forming a cured product using the curable composition. ..
  • cationically polymerizable curable compositions containing a cationically polymerizable compound such as an epoxy compound as a curable component have been used for various purposes.
  • Such a curable composition includes, for example, a cationically polymerizable compound containing an aromatic ring-containing alicyclic epoxy compound, a cationically polymerizable compound other than the aromatic ring-containing alicyclic epoxy compound, and a thermocationic polymerization initiator.
  • Thermosetting compositions are known (see Patent Document 1). By using such a curable composition, it is possible to form a cured product having a high glass transition temperature, which is less likely to yellow even when heated to a high temperature, and has excellent substrate adhesion.
  • a high temperature may be required for curing or a long time may be required for curing.
  • Such a defect can be solved by using an onium salt-based photoacid generator.
  • an onium salt-based photoacid generator when a curable composition containing an onium salt-based photoacid generator and a cationically curable compound is cured by exposure, there is a problem that the cured product is often colored during curing.
  • the present invention has been made in view of the above problems, and is a cationically curable curable composition capable of suppressing coloring of a cured product at the time of curing and having good curability, and the curable composition. It is an object of the present invention to provide a cured product of the above and a method for forming a cured product using the curable composition.
  • the present inventors have a photoacid generator (A1) composed of an onium salt having a cation portion having a specific structure in a curable composition containing a cationic curing agent (A) and a cationic curing compound (B).
  • A1 a photoacid generator
  • A2 thermoacid generator
  • A2 a gallium-containing anion having a specific structure as an anion portion in combination. ..
  • the present invention provides the following.
  • a first aspect of the present invention comprises a cationic curing agent (A) and a cationic curing compound (B).
  • the cationic curing agent (A) contains a photoacid generator (A1) and a thermoacid generator (A2).
  • the photoacid generator (A1) is an onium salt having a cation moiety represented by the following formula (ai).
  • the thermoacid generator (A2) is a curable composition which is an onium salt having an anion portion represented by the following formula (Ai). (R a1 ) t + 1 -R a2 + ...
  • Ra1 is an independently monovalent organic group
  • Ra2 is an element having a valence t of groups 15 to 17 in the Periodic Table of the Elements according to the IUPAC notation.
  • At least one of R a1 is an aryl group which may have a substituent.
  • R A1 4 -Ga - ⁇
  • RA1 is a phenyl group or a perfluoroalkyl group which may independently have one or more substituents.
  • the second aspect of the present invention is a cured product of the curable composition according to the first aspect.
  • a third aspect of the present invention is a method for forming a cured product, which comprises exposing and heating the curable composition according to the first aspect.
  • a cationically curable curable composition capable of suppressing coloration of a cured product at the time of curing and having good curability, a cured product of the curable composition, and the curable composition.
  • a method for forming a cured product using the above can be provided.
  • the curable composition contains a cationic curing agent (A) and a cationic curing compound (B).
  • the cationic curing agent (A) contains a photoacid generator (A1) and a thermoacid generator (A2).
  • the photoacid generator (A1) is an onium salt having a cation moiety represented by the following formula (ai). (R a1 ) t + 1 -R a2 + ... (ai) (In the formula (ai), Ra1 is an independently monovalent organic group, and Ra2 is an element having a valence t of groups 15 to 17 in the Periodic Table of the Elements according to the IUPAC notation.
  • thermoacid generator (A2) is an onium salt having an anion portion represented by the following formula (Ai).
  • (R A1) 4 -Ga - ⁇ (Ai) In the formula (Ai), RA1 is a phenyl group or a perfluoroalkyl group which may independently have one or more substituents.
  • thermoacid generator (A2) when the thermoacid generator (A2) is decomposed by heating, a substance that causes coloration due to the color-causing substance generated by the decomposition of the photoacid generator (A1) is not generated, or the thermoacid is generated. It is considered that the decomposition product of the generator (A2) exerts some action on the color-causing substance, thereby suppressing the coloring of the cured product at the time of curing.
  • the cation-curable compound (B) described later is a compound that gives a colorless and transparent cured product, it is suitable for optical applications by combining the above-mentioned cation-curing agent (A) and the cation-curable compound (B). It is possible to form a highly colorless and transparent cured product.
  • the photoacid generator (A1) is an onium salt having a cation moiety represented by the following formula (ai).
  • the anion portion constituting the onium salt as the photoacid generator (A1) is not particularly limited as long as it does not impair the object of the present invention.
  • (R a1 ) t + 1 -R a2 + ... (ai) (In the formula (ai), Ra1 is an independently monovalent organic group, and Ra2 is an element having a valence t of groups 15 to 17 in the Periodic Table of the Elements according to the IUPAC notation. At least one of R a1 is an aryl group which may have a substituent.)
  • Ra 1 in the formula (ai) which is a cation part represents an organic group bonded to Ra 2.
  • the organic group is preferably a carbon atom-containing group, from one or more carbon atoms and one or more atoms selected from the group consisting of H, O, S, Se, N, B, P, Si, and halogen atoms. Is more preferred.
  • the number of carbon atoms of the carbon atom-containing group is not particularly limited, and is preferably 1 or more and 50 or less, and more preferably 1 or more and 20 or less.
  • a plurality of R a1 when R a1 is existing in plural numbers may be the same or different.
  • Ra 1 includes an aryl group (aromatic hydrocarbon group) having 6 to 14 carbon atoms which may have a substituent and an alkyl group having 1 to 18 carbon atoms which may have a substituent. , It may have an aralkyl group having 7 or more and 12 or less carbon atoms which may have a substituent, an alkenyl group which may have a substituent and may have 2 or more and 18 or less carbon atoms, and a substituent ring group. Examples thereof include an alkynyl group having 2 or more and 18 or less carbon atoms.
  • Ra 1 includes an aryl group having 6 to 14 carbon atoms and an alkyl group having 1 to 18 carbon atoms.
  • An alkenyl group having 2 to 18 carbon atoms and an alkynyl group having 2 to 18 carbon atoms are preferable.
  • Examples of the substituent that the aryl group, aralkyl group, alkyl group, alkenyl group, and alkynyl group as R a1 may have include an alkyl group having 1 to 18 carbon atoms and 1 to 18 carbon atoms.
  • Alkyl halide group aliphatic cyclic group having 3 to 18 carbon atoms, aliphatic aliphatic ring group having 3 to 18 carbon atoms, alkenyl group having 2 to 18 carbon atoms, 2 carbon atoms Alkinyl group with 18 or more carbon atoms, aryl group with 6 to 14 carbon atoms, nitro group, hydroxyl group, cyano group, alkoxy group with 1 to 18 carbon atoms, aryloxy group with 6 to 14 carbon atoms, carbon An aliphatic acyl group having 2 to 19 atoms, an aromatic acyl group having 7 to 15 carbon atoms, an aliphatic acyloxy group having 2 to 19 carbon atoms, and an aromatic acyloxy group having 7 to 15 carbon atoms.
  • An alkylthio group having 1 to 18 carbon atoms, an arylthio group having 6 to 14 carbon atoms, and 1 or 2 hydrogen atoms bonded to a nitrogen atom are substituted with hydrocarbon groups having 1 to 18 carbon atoms. Examples thereof include an amino group and a halogen atom.
  • an alkyl group, an alkyl halide group, an aliphatic cyclic group, a halogenated aliphatic cyclic group, an alkoxy group, an aryloxy group, an aliphatic acyl group, an aromatic acyl group, and an aliphatic acyloxy are preferable.
  • a group, an aromatic acyloxy group, an alkylthio group, an arylthio group, and an amino group which may be substituted with a hydrocarbon group are preferable.
  • alkyl group when an aryl group, an aralkyl group, an alkyl group, an alkenyl group, and the substituent which may be possessed by the alkynyl group is an alkyl group, preferred examples of the alkyl group include a methyl group, an ethyl radical, n -Propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n Linear alkoxy groups such as -tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, and n-octadecyl group; isopropyl group, isobut
  • R a1 when an aryl group, an aralkyl group, an alkyl group, an alkenyl group, and the substituent which may be possessed by the alkynyl group is a halogenated alkyl group, preferred examples of the halogenated alkyl group, trifluoromethyl Group, trichloromethyl group, pentafluoroethyl group, 2,2,2-trichloroethyl group, 2,2,2-trifluoroethyl group, 1,1-difluoroethyl group, heptafluoro-n-propyl group, 1, 1-difluoro-n-propyl group, 3,3,3-trifluoro-n-propyl group, nonafluoro-n-butyl group, 3,3,4,5,4-pentafluoro-n-butyl group, perfluoro Linear alkyl halides such as -n-pentyl group and perfluoro-n-oct
  • an aryl group, an aralkyl group, an alkyl group, an alkenyl group, and the substituent which may be possessed by the alkynyl group is an aliphatic cyclic group
  • preferred examples of the aliphatic cyclic group, a cycloalkyl examples thereof include a propyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and an adamantyl group.
  • an aryl group, an aralkyl group, an alkyl group, when an alkenyl group, and the substituent which may be possessed alkynyl group is a halogenated aliphatic cyclic group, a halogenated aliphatic cyclic group
  • Preferred examples thereof include a pentafluorocyclopropyl group, a nonafluorocyclobutyl group, a perfluorocyclopentyl group, a perfluorocyclohexyl group, a perfluoroadamantyl group and the like.
  • an aryl group if an aralkyl group, an alkyl group, an alkenyl group, and the substituent which may be possessed by the alkynyl group is an alkoxy group
  • preferred examples of the alkoxy group include a methoxy group, an ethoxy radical, n -Propyloxy group, n-butyloxy group, n-pentyloxy group, n-hexyloxy group, n-octyloxy group, n-nonyloxy group, n-decyloxy group, n-undecyloxy group, n-dodecyloxy group , N-Tridecyloxy group, n-tetradecyloxy group, n-pentadecyloxy group, n-hexadecyloxy group, n-heptadecyloxy group, n-octadecyloxy group and other linear alk
  • R a1 when an aryl group, an aralkyl group, an alkyl group, an alkenyl group, and the substituent which may be possessed by an alkynyl group an aryl group, preferred examples of the aryloxy group, a phenoxy group, alpha- Examples thereof include a naphthyloxy group, a ⁇ -naphthyloxy group, a biphenyl-4-yloxy group, a biphenyl-3-yloxy group, a biphenyl-2-yloxy group, an anthryloxy group, a phenanthryloxy group and the like.
  • R a1 when an aryl group, an aralkyl group, an alkyl group, an alkenyl group, and the substituent which may be possessed by the alkynyl group is an aliphatic acyl group, preferred examples of the aliphatic acyl group, an acetyl group, Examples thereof include a propanoyl group, a butanoyl group, a pentanoyl group, a hexanoyl group, a heptanoil group, an octanoyl group and the like.
  • R a1 when an aryl group, an aralkyl group, an alkyl group, an alkenyl group, and the substituent which may be possessed by the alkynyl group is an aromatic acyl group, preferred examples of the aromatic acyl group, a benzoyl group, Examples thereof include ⁇ -naphthoyl group, ⁇ -naphthoyl group, biphenyl-4-ylcarbonyl group, biphenyl-3-ylcarbonyl group, biphenyl-2-ylcarbonyl group, anthrylcarbonyl group, phenanthrylcarbonyl group and the like.
  • R a1 when an aryl group, an aralkyl group, an alkyl group, an alkenyl group, and the substituent which may be possessed by the alkynyl group is an aliphatic acyloxy group, preferred examples of the aliphatic acyloxy group, acetyloxy group , Propanoyloxy group, butanoyloxy group, pentanoyloxy group, hexanoyloxy group, heptanoiloxy group, octanoyloxy group and the like.
  • an aryl group, an aralkyl group, the alkyl group, alkenyl group, and the substituent which may be possessed by the alkynyl group is an aromatic acyloxy group, preferred examples of the aromatic acyloxy groups, benzoyloxy groups , ⁇ -naphthoyloxy group, ⁇ -naphthoyloxy group, biphenyl-4-ylcarbonyloxy group, biphenyl-3-ylcarbonyloxy group, biphenyl-2-ylcarbonyloxy group, anthrylcarbonyloxy group, and Fe Examples thereof include a nantrilcarbonyloxy group.
  • the above-mentioned alkoxy group, or a group in which an oxygen atom in a group suitable as an aryloxy group is replaced with a sulfur atom can be mentioned.
  • the amino group which may be used are an amino group, a methylamino group, an ethylamino group, an n-propylamino group, a dimethylamino group, a diethylamino group, a methylethylamino group and a di-n-propylamino group.
  • the piperidino group and the like are an amino group, a methylamino group, an ethylamino group, an n-propylamino group, a dimethylamino group, a diethylamino group, a methylethylamino group and a di-n-propylamino group.
  • R a1 when an aryl group, an aralkyl group, an alkyl group, an alkenyl group, and the substituent which may be possessed by the alkynyl group is a halogen atom, the preferred examples of the halogen atom, fluorine atom, chlorine atom, Examples include a bromine atom and an iodine atom.
  • an alkyl halide group having 1 or more and 8 or less carbon atoms, a halogen atom, a nitro group, and a cyano group are preferable in that the activity of the photoacid generator (A1) is high, and carbon is preferable.
  • a fluorinated alkyl group having 1 or more and 8 or less atoms is more preferable.
  • R a1 there are a plurality, the plurality of R a1 may form a ring together with R a2.
  • the rings formed by the plurality of R a1 and R a2 have -O-, -S-, -SO-, -SO 2- , -NH-, -CO-, -COO-, in the ring structure. It may contain more bonds selected from the group consisting of and -CONH-.
  • R a2 in formula (ai) is an element of valence t 15 to Group 17 of the Periodic Table (IUPAC notation).
  • R a2 15 to Group 17 element of Group of the Periodic Table of the Elements (IUPAC notation)
  • R a2 combines with the organic group R a1 to form an onium ion.
  • Periodic Table of 15 to Group 17 Group elements (IUPAC notation) preferred elements as R a2 is S (sulfur), N (nitrogen), I (iodine), and P (phosphorus).
  • Corresponding onium ions include sulfonium ions, ammonium ions, iodonium ions, and phosphonium ions. These are preferred because they are stable and easy to handle. Sulfonium ions and iodonium ions are more preferable, and sulfonium ions are particularly preferable, because they are excellent in cationic polymerization performance and cross-linking reaction performance. That is, in the above formula (ai), it is preferable that Ra2 is sulfur and t is 2.
  • sulfonium ion examples include triphenylsulfonium, tri-p-tolylsulfonium, tri-o-tolylsulfonium, tris (4-methoxyphenyl) sulfonium, 1-naphthyldiphenylsulfonium, 2-naphthyldiphenylsulfonium, and tris (4).
  • ammonium ions include tetraalkylammoniums such as tetramethylammonium, ethyltrimethylammonium, diethyldimethylammonium, triethylmethylammonium, and tetraethylammonium; N, N-dimethylpyrrolidinium, N-ethyl-N-methylpyrroli.
  • pyrrolidiniums such as N, N-diethylpyrrolidinium; N, N'-dimethylimidazolinium, N, N'-diethylimidazolinium, N-ethyl-N'-methylimidazolinium, 1, Imidazolinium such as 3,4-trimethylimidazolinium and 1,2,3,4-tetramethylimidazolinium; tetrahydropyrimidinium such as N, N'-dimethyltetrahydropyrimidinium; N, N' -Morholinium such as dimethylmorpholinium; piperidinium such as N, N'-diethylpiperidinium; pyridinium such as N-methylpyridinium, N-benzylpyridinium, and N-phenacylpyridium; N, N'-dimethylimidazole Imidazolium such as ammonium; quinolium such as N-methylquinolium, N-benzylquinolium
  • phosphonium ions include tetraaryls such as tetraphenylphosphonium, tetra-p-tolylphosphonium, tetrakis (2-methoxyphenyl) phosphonium, tetrakis (3-methoxyphenyl) phosphonium, and tetrakis (4-methoxyphenyl) phosphonium.
  • Triarylphosphoniums such as Triphenylbenzylphosphoniums, Triphenylphenacylphosphoniums, Triphenylmethylphosphoniums, and Triphenylbutylphosphoniums; Examples thereof include silphosphonium and tetraalkylphosphoniums such as tributylphenacilphosphonium.
  • iodonium ions include diphenyl iodonium, di-p-tolyl iodonium, bis (4-dodecylphenyl) iodonium, bis (4-methoxyphenyl) iodonium, (4-octyloxyphenyl) phenyl iodonium, and bis (4-dodecylphenyl) iodonium.
  • Examples thereof include iodonium ions such as decyloxy) phenyliodonium, 4- (2-hydroxytetradecyloxy) phenylphenyliodonium, 4-isopropylphenyl (p-tolyl) iodonium, and 4-isobutylphenyl (p-tolyl) iodonium.
  • iodonium ions such as decyloxy) phenyliodonium, 4- (2-hydroxytetradecyloxy) phenylphenyliodonium, 4-isopropylphenyl (p-tolyl) iodonium, and 4-isobutylphenyl (p-tolyl) iodonium.
  • Examples of the photoacid generator (A1) include a gallium-containing onium salt having an anion moiety represented by the following formula (aiii) and a boron-containing onium salt having an anion moiety represented by the following formula (aiii). Be done.
  • R a3 , R a4 , R a5 , and R a6 are each independently a hydrocarbon group which may have a substituent or a heterocycle which may have a substituent.
  • R a7 , R a8 , R a9 , and R a10 are each independently a hydrocarbon group which may have a substituent or a heterocycle which may have a substituent.
  • the number of carbon atoms in the hydrocarbon group or heterocyclic group as R a3 ⁇ R a6 in the formula (aii) is not particularly limited, but is preferably 1 or more and 50 or less, more preferably 1 to 30, 1 to 20 Especially preferable.
  • Specific examples of the hydrocarbon groups as R a3 to Ra 6 include a linear or branched alkyl group, a linear or branched alkenyl group, a linear or branched alkynyl group, and an aromatic group. Examples thereof include group hydrocarbon groups, alicyclic hydrocarbon groups, and aralkyl groups.
  • R a3 at least one of ⁇ R a6 is an aromatic group which may have a substituent
  • R a3 ⁇ aromatic also have three or more substituents of R a6 It is more preferably a group, and it is particularly preferable that all of Ra3 to Ra6 are aromatic groups which may have a substituent.
  • the hydrocarbon group as R a3 to R a6 or the heterocyclic group may have, an alkyl halide group having 1 to 18 carbon atoms and a halogenated group having 3 to 18 carbon atoms
  • the hydrocarbon group as R a3 to R a6 is an aromatic hydrocarbon group
  • the aromatic hydrocarbon group is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, and an alkenyl group having 2 to 18 carbon atoms. And it may be substituted with one or more substituents selected from the group consisting of alkynyl groups having 2 or more and 18 or less carbon atoms.
  • the number of substituents is not particularly limited, and may be 1 or 2 or more. When the number of substituents is plural, the plurality of substituents may be the same or different.
  • R a3 to R a6 are alkyl groups include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-octyl group, and the like.
  • n-nonyl group n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, Linear alkyl groups such as n-nonadecil group and n-icosyl group; isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, isopentyl group, neopentyl group, tert-pentyl group, isohexyl group, 2-ethylhexyl Examples thereof include a group and a branched alkyl group such as a 1,1,3,3-tetramethylbutyl group.
  • R a3 to R a6 are an alkenyl group or an alkynyl group include an alkenyl group corresponding to the above-mentioned group suitable as an alkyl group and an alkynyl group.
  • R a3 to R a6 are aromatic hydrocarbon groups are a phenyl group, an ⁇ -naphthyl group, a ⁇ -naphthyl group, a biphenyl-4-yl group, a biphenyl-3-yl group, and a biphenyl-2.
  • -Il group, anthryl group, phenyl group and the like can be mentioned.
  • R a3 to R a6 are alicyclic hydrocarbon groups include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclopentyl group, cyclooctyl group, cyclononyl group, cyclodecyl group and the like.
  • Cycloalkyl groups examples include crosslinked aliphatic cyclic hydrocarbon groups such as norbornyl group, adamantyl group, tricyclodecyl group, and pinanyl group.
  • R a3 to R a6 are aralkyl groups include a benzyl group, a phenethyl group, an ⁇ -naphthylmethyl group, a ⁇ -naphthylmethyl group, an ⁇ -naphthylethyl group, a ⁇ -naphthylethyl group and the like. Can be mentioned.
  • R a3 to R a6 are heterocyclic groups include a thienyl group, a furanyl group, a selenophenyl group, a pyranyl group, a pyrrolyl group, an oxazolyl group, a thiazolyl group, a pyridyl group, a pyrimidyl group and a pyrazinyl group.
  • Indrill group benzofuranyl group, benzothienyl group, quinolyl group, isoquinolyl group, quinoxalinyl group, quinazolinyl group, carbazolyl group, acridinyl group, phenothiazine group, phenazinyl group, xanthenyl group, thianthrenyl group, phenoxadinyl group, phenoxatinyl group, Examples thereof include a chromanyl group, an isochromanyl group, a dibenzothienyl group, a xanthonyl group, a thioxanthonyl group, and a dibenzofuranyl group.
  • R a7 to R a10 in the formula (aiii) include groups similar to those described above for R a3 to R a6 in the formula (aiii).
  • Tetrakis (4-nonafluorobiphenyl) gallium anion Tetrakis (1-heptafluoronaphthyl) gallium anion, Tetrakis (pentafluorophenyl) gallium anion, Tetrakis (3,4,5-trifluorophenyl) gallate anion, Tetrakis (2-nonaphenylbiphenyl) gallium anion, Tetrakis (2-heptafluoronaphthyl) gallium anion, Tetrakis (7-nonafluoroanthril) gallium anion, Tetrakis (4'-(methoxy) octafluorobiphenyl) gallium anion, Tetrakis (2,4,6-tris (trifluoromethyl) phenyl) gallium anion, Tetrakis (3,5-bis (trifluoromethyl) pheny
  • Tetrakis (4-nonafluorobiphenyl) boron anion Tetrakis (1-heptafluoronaphthyl) boron anion, Tetrakis (pentafluorophenyl) boron anion, Tetrakis (3,4,5-trifluorophenyl) boron anion, Tetrakis (2-nonaphenylbiphenyl) boron anion, Tetrakis (2-heptafluoronaphthyl) boron anion, Tetrakis (7-nonafluoroanthril) boron anion, Tetrakis (4'-(methoxy) octafluorobiphenyl) boron anion, Tetrakis (2,4,6-tris (trifluoromethyl) phenyl) boron anion, Tetrakis (3,5-bis (
  • the photoacid generator (A1) has a cation portion represented by the following formula (a1).
  • the onium salt as the photoacid generator (A1) has a cation portion represented by the formula (a1)
  • the sensitivity of the photoacid generator (A1) is excellent.
  • the onium salt as the photoacid generator (A1) contains a cation portion represented by the following formula (a1), the curing of the cation-curable compound (B) described later can be easily promoted satisfactorily.
  • R 1 and R 2 are independently a group represented by the alkyl group or the following formula may be substituted with a halogen atom (a2), R 1 and R 2 are bonded to each other Then, a ring may be formed together with the sulfur atom in the formula, R 3 represents a group represented by the following formula (a3) or a group represented by the following formula (a4), and A 1 represents S, O, Or Se, but R 1 and R 2 are not alkyl groups that may be substituted with halogen atoms at the same time.
  • ring Z 1 represents an aromatic hydrocarbon ring
  • R 4 is an alkyl group, a hydroxy group, an alkoxy group, an alkylcarbonyl group, an alkoxycarbonyl group or an acyloxy group which may be substituted with a halogen atom.
  • R 5 is hydroxy group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, arylthio group, an acyloxy group, an arylthio group, an alkylthio group, an aryl group, Heterocyclic hydrocarbon group, aryloxy group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, hydroxy (poly) alkyleneoxy group, optionally substituted amino group, cyano group, nitro group, or An alkylene group which may be substituted with a halogen atom or a group represented by the following formula (a5) is shown, and R 6 is a hydroxy group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbony
  • Arylthiocarbonyl group asyloxy group, arylthio group, alkylthio group, aryl group, heterocyclic hydrocarbon group, aryloxy group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, hydroxy (poly) alkylene
  • R 7 and R 8 are independently hydroxy group, alkoxy group, alkylcarbonyl group, arylcarbonyl group, alkoxycarbonyl group, aryloxycarbonyl group, arylthiocarbonyl group, asyloxy group, arylthio group, Alkylthio group, aryl group, heterocyclic hydrocarbon group, aryloxy group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, hydroxy (poly) alkyleneoxy group, optionally substituted amino group, cyano Indicates an alkylene group that may be substituted with a group, a nitro group, or a halogen atom, or a group represented by the following formula (a5), and R 9 and R 10 are independently substituted alkyl groups that may be substituted with a halogen atom.
  • a group or a group represented by the above formula (a2) may be shown, and R 9 and R 10 may be bonded to each other to form a ring together with the sulfur atom in the formula, and A 3 is a single bond, S, O, indicates sulfinyl group, or a carbonyl group, X - represents a monovalent anion, n2 represents 0 or 1, provided that, R 9 and R 10, simultaneously, in the alkyl group which may be substituted with a halogen atom Absent.)
  • ring Z 2 represents an aromatic hydrocarbon ring
  • R 11 is an alkyl group, a hydroxy group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, or an alkoxycarbonyl which may be substituted with a halogen atom.
  • ring Z 3 represents an aromatic hydrocarbon ring
  • R 12 is an alkyl group, a hydroxy group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group or an alkoxycarbonyl which may be substituted with a halogen atom.
  • R 1 and R 2 are a group represented by the formula (a2).
  • R 1 and R 2 may be the same or different from each other.
  • the ring formed may be a 3 to 10-membered ring including the sulfur atom. It is preferably a 5- to 7-membered ring, more preferably.
  • the ring formed may be a polycycle, preferably a polycycle in which a 5- to 7-membered ring is condensed.
  • R 3 is preferably a group represented by the above formula (a3).
  • a 1 is preferably S or O, and more preferably S.
  • R 4 is an alkyl group which may be substituted with a halogen atom, a hydroxy group, an alkylcarbonyl group, a thienylcarbonyl group, a furanylcarbonyl group, a selenophylcarbonyl group, or an amino which may be substituted. It is preferably a group or a nitro group, and more preferably an alkyl group, an alkylcarbonyl group, or a thienylcarbonyl group which may be substituted with a halogen atom.
  • m1 may be selected depending on the species of the ring Z 1, for example, 0 to 4 integer, there preferably 0 to 3 of an integer, more preferably 0 to 2 integer You may.
  • R 5 may be an alkylene group; a hydroxy group, an optionally substituted amino group, or an alkylene group substituted with a nitro group; or a group represented by the above formula (a5). It is preferable that the group is represented by the above formula (a5).
  • R 6 may be an alkyl group; a hydroxy group, an optionally substituted amino group, or an alkyl group substituted with a nitro group; or a group represented by the above formula (a6). It is preferable that the group is represented by the above formula (a6).
  • a 2 is preferably S or O, and more preferably S.
  • n1 is preferably 0.
  • R 7 and R 8 are independently represented by an alkylene group; an alkylene group substituted with a hydroxy group, an optionally substituted amino group, or a nitro group; or the above formula (a5). It is preferably a group, and more preferably a group represented by the above formula (a5). R 7 and R 8 may be the same or different from each other. In the above formula (a4), it is preferable that both R 9 and R 10 are groups represented by the above formula (a2). R 9 and R 10 may be the same or different from each other.
  • the ring formed when R 9 and R 10 are bonded to each other to form a ring together with the sulfur atom in the formula, the ring formed may be a 3 to 10-membered ring including the sulfur atom. It is preferably a 5- to 7-membered ring, more preferably.
  • the ring formed may be a polycycle, preferably a polycycle in which a 5- to 7-membered ring is condensed.
  • a 3 is preferably S or O, more preferably S.
  • n2 is preferably 0.
  • R 11 is preferably an alkyl group which may be substituted with a halogen atom, a hydroxy group, an amino group which may be substituted, or a nitro group, and is substituted with a halogen atom. It is more preferable that it is a good alkyl group.
  • m2 can be selected according to the type of ring Z 2 , and is, for example, an integer of 0 or more and 4 or less, preferably an integer of 0 or more and 3 or less, and more preferably an integer of 0 or more and 2 or less. You may.
  • R 12 is an alkyl group which may be substituted with a halogen atom, a hydroxy group, an alkylcarbonyl group, a thienylcarbonyl group, a furanylcarbonyl group, a selenophylcarbonyl group, or an amino which may be substituted. It is preferably a group or a nitro group, and more preferably an alkyl group, an alkylcarbonyl group, or a thienylcarbonyl group which may be substituted with a halogen atom.
  • m3 may be selected depending on the type of ring Z 3, for example, 0 to 4 integer, there preferably 0 to 3 of an integer, more preferably 0 to 2 integer You may.
  • the counter anion of the cation portion represented by the above formula (a1) irradiates the sulfonium salt having the cation portion represented by the formula (a1) with active energy rays (visible light, ultraviolet rays, electron beams, X-rays, etc.). It is a monovalent anion corresponding to the acid generated by the above.
  • Preferred examples of the counter anion of the cation portion represented by the formula (a1) include an anion portion represented by the above formula (aiii) and an anion portion represented by the formula (aiii).
  • the counter anion of the cation portion represented by the formula (a1) other monovalent polyatomic anions are also preferably mentioned, and MY a ⁇ , (Rf) b PF 6-b ⁇ , R x1 c BY. 4-c -, R x1 c GaY 4-c -, R x2 SO 3 -, (R x2 SO 2) 3 C -, or (R x2 SO 2) 2 N - anion represented by is more preferable.
  • the counter anion of the cation portion represented by the formula (a1) may be a halogen anion, and examples thereof include fluoride ion, chloride ion, bromide ion, and iodide ion.
  • M represents a phosphorus atom, a boron atom, or an antimony atom.
  • Y represents a halogen atom (preferably a fluorine atom).
  • Rf represents an alkyl group in which 80 mol% or more of hydrogen atoms are substituted with fluorine atoms (an alkyl group having 1 to 8 carbon atoms is preferable).
  • Alkyl groups to be converted to Rf by fluorine substitution include linear alkyl groups (methyl, ethyl, propyl, butyl, pentyl, octyl, etc.), branched alkyl groups (isopropyl, isobutyl, sec-butyl, tert-butyl, etc.) and cyclo.
  • Alkyl groups cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc. and the like can be mentioned.
  • the ratio of hydrogen atoms of these alkyl groups substituted with fluorine atoms in Rf is preferably 80 mol% or more, more preferably 90, based on the number of moles of hydrogen atoms possessed by the original alkyl group. % Or more, particularly preferably 100%.
  • the substitution ratio by the fluorine atom is in these preferable ranges, the photosensitivity of the sulfonium salt (Q) is further improved.
  • Rf particularly preferred Rf, CF 3 -, CF 3 CF 2 -, (CF 3) 2 CF -, CF 3 CF 2 CF 2 -, CF 3 CF 2 CF 2 -, (CF 3) 2 CFCF 2 - , CF 3 CF 2 (CF 3 ) CF - and (CF 3) 3 C - and the like.
  • the b Rfs are independent of each other and may therefore be the same or different from each other.
  • P represents a phosphorus atom and F represents a fluorine atom.
  • R x1 represents a phenyl group in which a part of a hydrogen atom is substituted with at least one element or an electron-withdrawing group.
  • Examples of such one element include a halogen atom and include a fluorine atom, a chlorine atom, a bromine atom and the like.
  • Examples of the electron attracting group include a trifluoromethyl group, a nitro group and a cyano group. Of these, a phenyl group in which at least one hydrogen atom is substituted with a fluorine atom or a trifluoromethyl group is preferable.
  • the c R x1s are independent of each other and may therefore be the same or different from each other.
  • B represents a boron atom and Ga represents a gallium atom.
  • R x2 represents an alkyl group having 1 to 20 carbon atoms, a fluoroalkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, and the alkyl group and fluoroalkyl group are linear. , Branched chain or cyclic, and the alkyl group, fluoroalkyl group, or aryl group may be unsubstituted or have a substituent. Examples of the substituent include a hydroxy group, an amino group which may be substituted (for example, a group exemplified in the following description relating to the above formulas (a2) to (a6)), a nitro group and the like. Be done.
  • the carbon chain in the alkyl group, fluoroalkyl group or aryl group represented by R x2 may have a hetero atom such as an oxygen atom, a nitrogen atom or a sulfur atom.
  • the carbon chain in the alkyl group or fluoroalkyl group represented by R x2 is a divalent functional group (for example, ether bond, carbonyl bond, ester bond, amino bond, amide bond, imide bond, sulfonyl bond, sulfonylamide). It may have a bond, a sulfonylimide bond, a urethane bond, etc.).
  • the alkyl group, fluoroalkyl group or aryl group represented by R x2 has the above-mentioned substituent, hetero atom or functional group
  • the number of the above-mentioned substituent, hetero atom or functional group may be one. There may be two or more.
  • S represents a sulfur atom
  • O represents an oxygen atom
  • C represents a carbon atom
  • N represents a nitrogen atom
  • a represents an integer of 4 or more and 6 or less.
  • b is preferably an integer of 1 or more and 5 or less, more preferably an integer of 2 or more and 4 or less, and particularly preferably 2 or 3.
  • c is preferably an integer of 1 or more and 4 or less, and more preferably 4.
  • (Rf) b PF 6-b - as the anion represented by the, (CF 3 CF 2) 2 PF 4 -, (CF 3 CF 2) 3 PF 3 -, ((CF 3) 2 CF) 2 PF 4 -, ((CF 3) 2 CF) 3 PF 3 -, (CF 3 CF 2 CF 2) 2 PF 4 -, (CF 3 CF 2 CF 2) 3 PF 3 -, ((CF 3) 2 CFCF 2) 2 PF 4 -, ((CF 3) 2 CFCF 2) 3 PF 3 -, (CF 3 CF 2 CF 2 CF 2) 2 PF 4 - or (CF 3 CF 2 CF 2 CF 2) 3 PF 3 - Table with Examples thereof include anions to be produced.
  • (CF 3 CF 2) 3 PF 3 -, (CF 3 CF 2 CF 2) 3 PF 3 -, ((CF 3) 2 CF) 3 PF 3 -, ((CF 3) 2 CF) 2 PF 4 -, ((CF 3 ) 2 CFCF 2) 3 PF 3 - , or ((CF 3) 2 CFCF 2 ) 2 PF 4 - anion represented by are preferred.
  • R x1 c BY 4-c - As the anion represented by, preferably R x1 c BY 4-c - (In the formula, R x 1 represents a phenyl group in which at least a part of the hydrogen atom is substituted with a halogen atom or an electron attractant group, Y represents a halogen atom, and c represents an integer of 1 or more and 4 or less.)
  • R x 1 represents a phenyl group in which at least a part of the hydrogen atom is substituted with a halogen atom or an electron attractant group
  • Y represents a halogen atom
  • c represents an integer of 1 or more and 4 or less.
  • R x2 SO 3 - as the anion represented by, trifluoromethanesulfonic acid anion, pentafluoroethanesulfonate anion, heptafluoropropanesulfonate acid anion, nonafluorobutanesulfonic acid anion, pentafluorophenyl sulfonate anion, p- toluene
  • examples thereof include sulfonic acid anion, benzenesulfonic acid anion, camphor sulfonic acid anion, methanesulfonic acid anion, ethanesulfonic acid anion, propanesulfonic acid anion and butanesulfonic acid anion.
  • trifluoromethanesulfonic acid anion nonafluorobutanesulfonic acid anion, methanesulfonic acid anion, butanesulfonic acid anion, camphorsulfonic acid anion, benzenesulfonic acid anion or p-toluenesulfonic acid anion are preferable.
  • MY a -, (Rf) b PF 6-b -, R x1 c BY 4-c -, R x1 c GaY 4-c - and (R x2 SO 2 ) 3 C - anion is preferably represented by, SbF 6 -, PF 6 - , (CF 3 CF 2) 3 PF 3 -, (C 6 F 5) 4 B -, ((CF 3) 2 C 6 H 3) 4 B -, (C 6 F 5) 4 Ga -, ((CF 3) 2 C 6 H 3) 4 Ga - and (CF 3 SO 2) 3 C - , more preferably, R x1 c BY 4- c - is more preferred.
  • the aromatic hydrocarbon ring includes a benzene ring, a condensed polycyclic aromatic hydrocarbon ring [for example, a condensed bicyclic hydrocarbon ring (for example, naphthalene).
  • a condensed polycyclic aromatic hydrocarbon ring for example, a condensed bicyclic hydrocarbon ring (for example, naphthalene).
  • C 8-20 fused bicyclic hydrocarbon ring such as ring, preferably C 10-16 condensed dicyclic hydrocarbon ring, condensed tricyclic aromatic hydrocarbon ring (for example, anthracene ring, phenanthrene ring, etc.) and the like.
  • Condensation 2 to 4 ring-type aromatic hydrocarbon ring and the like.
  • the aromatic hydrocarbon ring is preferably a benzene ring or a naphthalene ring, and more preferably a benzene ring.
  • examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • the alkyl group is a linear alkyl group (methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-octyl, n) having 1 to 18 carbon atoms.
  • n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, etc. branched-chain alkyl groups with 3 to 18 carbon atoms (isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, etc.) , Tert-pentyl, isohexyl, isooctadecyl, etc.), and cycloalkyl groups having 3 to 18 carbon atoms (cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 4-decylcyclohexyl, etc.) and the like.
  • the alkyl group optionally substituted with a halogen atom means an alkyl group and an alkyl group substituted with a halogen atom. ..
  • the alkyl group substituted with a halogen atom include the above-mentioned linear alkyl group, branched chain alkyl group, or group in which at least one hydrogen atom in the cycloalkyl group is substituted with a halogen atom (monofluoromethyl, difluoromethyl, tri). Fluoromethyl, etc.) and the like.
  • a trifluoromethyl group is particularly preferred, for R 4 , R 6 , R 11 or R 12 .
  • the alkoxy group is a linear or branched-chain alkoxy group (methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert) having 1 to 18 carbon atoms. -Butoxy, hexyloxy, decyloxy, dodecyloxy, octadecyloxy, etc.) and the like.
  • the alkyl group in the alkylcarbonyl group includes the above-mentioned linear alkyl group having 1 or more and 18 or less carbon atoms, a branched alkyl group having 3 or more and 18 or less carbon atoms, or a carbon atom.
  • Cycloalkyl groups having a number of 3 to 18 are mentioned, and examples of the alkylcarbonyl group include linear, branched or cyclic alkylcarbonyl groups having 2 to 18 carbon atoms (acetyl, propionyl, butanoyl, 2-methyl).
  • examples of the arylcarbonyl group include arylcarbonyl groups (benzoyl, naphthoyl, etc.) having 7 or more and 11 or less carbon atoms.
  • alkoxycarbonyl group a linear or branched alkoxycarbonyl group having 2 to 19 carbon atoms (methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, Isobutoxycarbonyl, sec-butoxycarbonyl, tert-butoxycarbonyl, octyloxycarbonyl, tetradecyloxycarbonyl, octadecyloxycarbonyl, etc.) and the like.
  • examples of the aryloxycarbonyl group include an aryloxycarbonyl group having 7 to 11 carbon atoms (phenoxycarbonyl, naphthoxycarbonyl, etc.) and the like.
  • examples of the arylthiocarbonyl group include arylthiocarbonyl groups having 7 or more and 11 or less carbon atoms (phenylthiocarbonyl, naphthoxythiocarbonyl, etc.) and the like.
  • asyloxy group a linear or branched asyloxy group having 2 to 19 carbon atoms (acetoxy, ethylcarbonyloxy, propylcarbonyloxy, isopropylcarbonyloxy, butylcarbonyloxy, Isobutylcarbonyloxy, sec-butylcarbonyloxy, tert-butylcarbonyloxy, octylcarbonyloxy, tetradecylcarbonyloxy, octadecylcarbonyloxy, etc.) and the like.
  • the arylthio group includes an arylthio group having 6 to 20 carbon atoms (phenylthio, 2-methylphenylthio, 3-methylphenylthio, 4-methylphenylthio, 2-chlorophenyl).
  • the alkylthio group is a linear or branched alkylthio group having 1 to 18 carbon atoms (methylthio, ethylthio, propylthio, isopropylthio, butylthio, isobutylthio, sec-butylthio, etc. tert-butylthio, pentilthio, isopentilthio, neopentylthio, tert-pentylthio, octylthio, decylthio, dodecylthio, isooctadecylthio, etc.) and the like.
  • examples of the aryl group include an aryl group having 6 to 10 carbon atoms (phenyl, trill, dimethylphenyl, naphthyl, etc.) and the like.
  • the heterocyclic aliphatic hydrocarbon group includes heterocyclic hydrocarbon groups (pyrrolidinyl, tetrahydrofuranyl, tetrahydrothienyl, piperidinyl) having 2 or more and 20 or less carbon atoms (preferably 4 or more and 20 or less). , Tetrahydropyranyl, tetrahydrothiopyranyl, morpholinyl, etc.) and the like.
  • the heterocyclic hydrocarbon group includes heterocyclic hydrocarbon groups having 4 to 20 carbon atoms (thienyl, furanyl, selenophenyl, pyranyl, pyrrolyl, oxazolyl, thiazolyl, etc.).
  • examples of the aryloxy group include aryloxy groups having 6 or more and 10 or less carbon atoms (phenoxy, naphthyloxy, etc.).
  • the alkylsulfinyl group is a linear or branched sulfinyl group having 1 to 18 carbon atoms (methylsulfinyl, ethylsulfinyl, propylsulfinyl, isopropylsulfinyl, butylsulfinyl, isobutylsulfinyl).
  • examples of the arylsulfinyl group include arylsulfinyl groups having 6 to 10 carbon atoms (phenylsulfinyl, tolylsulfinyl, naphthylsulfinyl, etc.) and the like.
  • the alkylsulfonyl group includes a linear or branched alkylsulfonyl group having 1 to 18 carbon atoms (methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, butylsulfonyl, isobutyl).
  • examples of the arylsulfonyl group include arylsulfonyl groups having 6 to 10 carbon atoms (phenylsulfonyl, tosylsulfonyl (tosyl group), naphthylsulfonyl, etc.).
  • the hydroxy (poly) alkyleneoxy group is HO (AO) q- (in the formula, AO independently represents an ethyleneoxy group and / or a propyleneoxy group, and q is 1).
  • AO independently represents an ethyleneoxy group and / or a propyleneoxy group, and q is 1).
  • a hydroxy (poly) alkyleneoxy group represented by (representing an integer of 5 or less) can be mentioned.
  • the amino groups that may be substituted include an amino group (-NH 2 ) and a substituted amino group having 1 or more and 15 or less carbon atoms (methylamino, dimethylamino, ethylamino, etc.).
  • the alkylene group is a linear or branched alkylene group (methylene group, 1,2-ethylene group, 1,1-ethylene group, propane) having 1 to 18 carbon atoms.
  • -1,3-diyl group propane-1,2-diyl group, propane-1,1-diyl group, propane-2,2-diyl group, butane-1,4-diyl group, butane-1,3- Diyl group, butane-1,2-diyl group, butane-1,1-diyl group, butane-2,2-diyl group, butane-2,3-diyl group, pentane-1,5-diyl group, pentane- 1,4-diyl group, hexane-1,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, 2-ethylhex
  • the sulfonium salt having a cation moiety represented by the formula (a1) can be synthesized, for example, according to the following scheme. Specifically, a compound represented by the following formula (b2) is reacted with 1-fluoro-2-methyl-4-nitrobenzene represented by the following formula (b1) in the presence of a base such as potassium hydroxide. Then, a nitro compound represented by the following formula (b3) is obtained, and then reduction is carried out in the presence of reducing iron to obtain an amine compound represented by the following formula (b4).
  • nitrite e.g., sodium nitrite
  • this diazo compound cuprous halide represented by CuX'(wherein X'indicates a halogen atom such as a bromine atom; the same applies hereinafter), and hydrogen halide represented by HX'.
  • the mixture is mixed and the reaction is allowed to proceed to obtain a halide represented by the following formula (b5).
  • a Grignard reagent is prepared from this halide and magnesium, and then the Grignard reagent is reacted with a sulfoxide compound represented by the following formula (b6) in the presence of chlorotrimethylsilane, and represented by the following formula (b7).
  • the sulfonium salt to be obtained can be obtained.
  • Mb + X The sulfonium salt "- (wherein, Mb + is a metal cation, for example, represents an alkali metal cation such as potassium ion, X" - the X - 1 monovalent anion represented by (wherein, A sulfonium salt represented by the following formula (b8) can be obtained by reacting with a salt represented by) represented by)) to exchange salts.
  • R 1 ⁇ R 3 and A 1 are the same as those in the formula (a1).
  • Specific examples of the cation portion represented by the above formula (a1) include the following cation portions.
  • Specific examples of the anion portion with respect to the cation portion represented by the above formula (a1) include conventionally known anion portions such as the anion portion mentioned above.
  • the sulfonium salt having a cation moiety represented by the above formula (a1) can be synthesized according to the above scheme (in the scheme, X ⁇ represents a counter anion), and if necessary, further salt exchange can be performed to further salt exchange the cation moiety.
  • the cation portion represented by the following formula is more preferable.
  • thermoacid generator (A2) is an onium salt having an anion portion represented by the following formula (Ai). (R A1) 4 -Ga - ⁇ (Ai) (In the formula (Ai), RA1 is a phenyl group or a perfluoroalkyl group which may independently have one or more substituents.)
  • R A1 in the formula (Ai) is 1 or more may have a substituent group phenyl group or a perfluoroalkyl group.
  • RA1 is a phenyl group
  • the substituent that the phenyl group may have is not particularly limited as long as it does not impair the object of the present invention.
  • the substituent that the phenyl group may have include a perfluoroalkyl group, a perfluoroalkoxy group, a nitro group, a cyano group, an acyl group, and a halogen atom.
  • the phenyl group represented by R A1 has plural substituents, the plurality of substituents may be the same or different.
  • the number of carbon atoms of the perfluoroalkyl group as a substituent on the phenyl group is preferably 1 or more and 8 or less, and more preferably 1 or more and 4 or less.
  • Specific examples of the perfluoroalkyl group as a substituent on the phenyl group include a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, a nonafluorobutyl group, a perfluoropentyl group, a perfluorooctyl group and the like.
  • a branched perfluoroalkyl group such as a linear perfluoroalkyl group, a heptafluoroisopropyl group, a nonafluoroisobutyl group, a nonafluoro-sec-butyl group, and a nonafluoro-tert-butyl group, a perfluorocyclopropyl group, and a perfluorocyclo.
  • Examples thereof include a perfluorocycloalkyl group such as a butyl group, a perfluorocyclopentyl group, and a perfluorocyclohexyl group.
  • the number of carbon atoms of the perfluoroalkoxy group as a substituent on the phenyl group is preferably 1 or more and 8 or less, and more preferably 1 or more and 4 or less.
  • Specific examples of the perfluoroalkoxy group as a substituent on the phenyl group include a trifluoromethoxy group, a pentafluoroethoxy group, a heptafluoropropyloxy group, a nonafluorobutyloxy group, a perfluoropentyloxy group, and a perfluorooctyl group.
  • Examples thereof include a linear perfluoroalkoxy group such as an oxy group, and a branched perfluoroalkoxy group such as a heptafluoroisopropyloxy group, a nonafluoroisobutyloxy group, a nonafluoro-sec-butyloxy group, and a nonafluoro-tert-butyloxy group.
  • a linear perfluoroalkoxy group such as an oxy group
  • a branched perfluoroalkoxy group such as a heptafluoroisopropyloxy group, a nonafluoroisobutyloxy group, a nonafluoro-sec-butyloxy group, and a nonafluoro-tert-butyloxy group.
  • RA1 is a perfluoroalkyl group
  • preferred examples of the perfluoroalkyl group are the same as those of the perfluoroalkyl group as a substituent on the phenyl group.
  • thermal acid generator (A2) From the viewpoint of cationic polymerization performance of thermal acid generator (A2), at least one of R A1, perfluoroalkyl group, and at least one substituted phenyl group with a group selected from the group consisting of fluorine atoms preferably there, all R A1 is a perfluoroalkyl group, and more preferably 1 or more substituted phenyl group with a group selected from the group consisting of fluorine atom.
  • R A1 is pentafluorophenyl group, trifluorophenyl group, tetrafluorophenyl group, (trifluoromethyl) phenyl group, bis (trifluoromethyl) phenyl group, (pentafluoroethyl) phenyl group, a bis (Pentafluoroethyl) phenyl group, fluoro (trifluoromethyl) phenyl group, fluorobis (trifluoromethyl) phenyl group, fluoro (pentafluoroethyl) phenyl group, fluorobis (pentafluoroethyl) phenyl group, pentachlorophenyl group, Trichlorophenyl group, tetrachlorophenyl group, (trichloromethyl) phenyl group, bis (trichloromethyl) phenyl group, (pentachloroethyl) phenyl group, (
  • anion portion represented by the formula (Ai) include the following anions.
  • R A01 is a monovalent organic group
  • D is, 15 to Group 17 Group valence of the Periodic Table of the Elements (IUPAC notation) is an element of u
  • R A02 is , An alkyl group which may have a substituent or an aralkyl group which may have a substituent.
  • RA02 is an alkyl group which may have a substituent
  • at least RA01. one is an alkyl group which may have a substituent .
  • u is 1 to 3 integer multiple of R A01 may be the same or different, and combining a plurality of R A01 D May form a ring with.
  • D in the formula (Aii) is an element having a valence u in groups 15 to 17 of the Periodic Table of the Elements (IUPAC notation). D is the same as Ra 2 in the above formula (ai). D binds to an organic group RA01 and a benzyl group optionally substituted with RA02 to form an onium ion. Of the elements of Groups 15 to 17 of the Periodic Table of the Elements (IUPAC notation), S (sulfur), N (nitrogen), I (iodine), and P (phosphorus) are preferable.
  • Corresponding onium ions are sulfonium ion, ammonium ion, iodonium ion, and phosphonium ion, which are preferable because they are stable and easy to handle. Sulfonium ions and iodonium ions are more preferable, and sulfonium ions are even more preferable, in terms of excellent cationic polymerization performance and cross-linking reaction performance.
  • R A01 represents an organic group bonded to D, a plurality of R A01 in the case of R A01 is existing in plural numbers may be the same or different.
  • the organic group is preferably a carbon atom-containing group, from one or more carbon atoms and one or more atoms selected from the group consisting of H, O, S, Se, N, B, P, Si, and halogen atoms. Is more preferred.
  • the number of carbon atoms of the carbon atom-containing group is not particularly limited, and is preferably 1 or more and 50 or less, and more preferably 1 or more and 20 or less.
  • RA01 includes aromatic hydrocarbon groups having 6 to 14 carbon atoms, alkyl groups having 1 to 18 carbon atoms, alkenyl groups having 2 to 18 carbon atoms, and 2 to 18 carbon atoms. Alkinyl groups can be mentioned.
  • Aromatic hydrocarbon group as R A01, an alkyl group, the alkenyl and alkynyl groups include the same groups as previously described for R a1 in formula (ai).
  • RA01 is an aromatic hydrocarbon group, it may have a substituent, and the substituents include a hydroxyl group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group and an allyl.
  • Luciocarbonyl group asyloxy group, arylthio group, alkylthio group, aryl group, heterocyclic hydrocarbon group, aryloxy group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, hydroxy (poly) alkyleneoxy group , A silyl group which may be substituted, an amino group which may be substituted, a halogen atom and the like. Further, in the equation (Aii), if R A01 there are a plurality, the plurality of R A01 may form a ring together with D.
  • the rings formed by the plurality of RA01s and D have -O-, -S-, -SO-, -SO 2- , -NH-, -CO-, -COO-, and-in the intervening structure. It may contain more bonds than selected from the group consisting of CONH-.
  • alkyl group as R A02 is a methyl group, an ethyl group, n- propyl group, n- butyl group, n- pentyl group, n- octyl group, n- decyl radical, n -Linear alkyl groups with 1 to 18 carbon atoms such as dodecyl group, n-tetradecyl group, n-hexadecyl group and n-octadecyl group, isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, isopentyl A branched alkyl group having 3 to 18 carbon atoms such as a group, a neopentyl group, a tert-pentyl group, an isohexyl group and an isooctadecyl group, and a cyclopropyl group,
  • Examples thereof include cycloalkyl groups having 3 or more and 18 or less carbon atoms such as groups.
  • R A02 is an alkyl group which may have a substituent
  • at least one of R A01 is a alkyl group which may have a substituent.
  • specific examples of the aralkyl group as R A02 are benzyl group, 1-naphthylmethyl group, and 2-naphthylmethyl groups, substituted with an aryl group having 10 or less carbon atoms having 6 or more Examples thereof include lower alkyl groups.
  • R A02 is 2, such as methyl benzyl group, an aryl group having not more than 10 good 6 or more carbon atoms which may have a substituent Examples thereof include a substituted lower alkyl group.
  • R A02 is preferably an aralkyl group which may have a substituent, more preferably a cation moiety represented by the following formula (Aiii).
  • R A01 is a monovalent organic group
  • D is an element of Group 15 to 17 Group valency u periodic table of elements according to IUPAC notation
  • R A03 is 1 It is an organic group of valence
  • u is an integer of 1 or more and 3 or less
  • v is an integer of 0 or more and 5 or less.
  • the monovalent organic group R A03 preferably a carbon atom-containing group, one or more carbon atoms, and H, O, S, Se, N, B, P, Si, and halogen atoms A group consisting of one or more atoms selected from the group consisting of is more preferred.
  • the number of carbon atoms of the carbon atom-containing group is not particularly limited, and is preferably 1 or more and 50 or less, and more preferably 1 or more and 20 or less.
  • the monovalent organic group of RA03 is particularly preferably an alkyl group.
  • the alkyl group as R A03 include the same groups as the alkyl group described in R A02 of formula (Aii).
  • v is preferably 0 or 1.
  • D is sulfur and the cation represented by the formula (Aii) is a sulfonium ion. That is, it is preferable that D is sulfur and u is 2.
  • Specific examples of the cation part represented by the formula (Aii) or the formula (Aii) will be given. In the specific example below, D'is an S atom or a Se atom, preferably an S atom.
  • the content of the cationic curing agent (A) in the curable composition is 0.01 part by mass with respect to 100 parts by mass of the cationic curing compound (B) in terms of the balance between the curability and the physical properties of the cured product. 5 parts by mass or more is preferable, 0.05 parts by mass or more and 3 parts by mass or less is more preferable, and 0.1 parts by mass or more and 2 parts by mass or less is particularly preferable.
  • the cationic curing agent (A) may contain a cationic curing agent other than the photoacid generator (A1) and the thermoacid generator (A2) as long as the object of the present invention is not impaired.
  • the total ratio of the mass of the photoacid generator (A1) and the mass of the thermoacid generator (A2) to the mass of the cationic curing agent (A) is preferably 70% by mass or more, more preferably 80% by mass or more. , 90% by mass or more is more preferable, and 100% by mass is particularly preferable.
  • the ratio of is preferably 50% by mass or less, and more preferably 30% by mass or less.
  • the lower limit is not particularly limited, but in terms of chemical resistance and process margin, 10% by mass or more is preferable, 15% by mass or more is more preferable, and 20% by mass or more is further preferable.
  • ⁇ Conic curable compound (B)> As the cationically curable compound (B), various compounds conventionally known as cationically curable compounds can be used. By curing the cationically curable compound (B) with the above-mentioned (B) cationic curing agent (A), a well-cured cured product having excellent solvent resistance can be formed, and coloring of the cured product can be suppressed.
  • a compound represented by the following formula (b1) can be mentioned.
  • W 1 and W 2 are independently represented by the following formula (b2): It is a group represented by In formula (b2), ring Z represents an aromatic hydrocarbon ring, X B represents a single bond or a group represented by —S—, RB1 is a single bond, and an alkylene having 1 or more and 4 or less carbon atoms.
  • R B1 is an alkylene group, an oxygen atom in the alkylene group is bonded with the ring Z
  • R B2 is a monovalent hydrocarbon Group, hydroxyl group, group represented by -OR 4a , group represented by -SR 4b , acyl group, alkoxycarbonyl group, halogen atom, nitro group, cyano group, mercapto group, carboxy group, amino group, carbamoyl group, -NHR
  • the hydrogen atom bonded to the carbon atom contained in the group is represented by a monovalent hydrocarbon group, a hydroxyl group, or -OR 4a.
  • m indicates an integer of 0 or more
  • R 3 indicates an integer of 0 or more.
  • Ring Y 1 and ring Y 2 denote the same or different aromatic hydrocarbon ring
  • R represents a single bond
  • methylene group which may have a substituent may have a substituent
  • 2 carbon atoms Indicates an ethylene group which may contain a hetero atom in between, a group represented by -O-, a group represented by -NH-, or a group represented by -S-
  • R 3a and R 3b are independently cyano groups and halogens. It represents an atom or a monovalent hydrocarbon group, and n1 and n2 independently represent an integer of 0 or more and 4 or less.
  • the ring Z is, for example, a benzene ring, a fused polycyclic aromatic hydrocarbon ring [for example, a fused bicyclic hydrocarbon ring (for example, a C8-20 fused dicyclic ring such as a naphthalene ring). Condensed 2-4 ring aromatic hydrocarbons such as formal hydrocarbon rings, preferably C 10-16 fused bicyclic hydrocarbon rings), fused tricyclic aromatic hydrocarbon rings (eg, anthracene rings, phenanthrene rings, etc.) Hydrogen ring] and the like.
  • a fused polycyclic aromatic hydrocarbon ring for example, a fused bicyclic hydrocarbon ring (for example, a C8-20 fused dicyclic ring such as a naphthalene ring). Condensed 2-4 ring aromatic hydrocarbons such as formal hydrocarbon rings, preferably C 10-16 fused bicyclic hydrocarbon rings), fused tricyclic aromatic hydrocarbon rings (eg, anthracene rings,
  • Ring Z is preferably a benzene ring or a naphthalene ring, and more preferably a naphthalene ring. Since W 1 and W 2 in the formula (b1) are independently represented by the following formula (b2), W 1 and W 2 each include a ring Z.
  • the ring Z contained in W 1 and the ring Z contained in W 2 may be the same or different. For example, one ring may be a benzene ring, the other ring may be a naphthalene ring, or the like. It is particularly preferable that the ring of is also a naphthalene ring.
  • substitution position of the ring Z bonded via a X B to the carbon atom to which both W 1 and W 2 are directly connected is not particularly limited.
  • the group corresponding to the ring Z bonded to the carbon atom may be a 1-naphthyl group, a 2-naphthyl group, or the like.
  • X B independently represents a single bond or a group represented by —S—, and is typically a single bond.
  • examples of R B1 for example, a single bond; methylene group, ethylene group, trimethylene group (-CH 2 CH 2 CH 2 - ), propylene (-CH 2 CH (CH 3) -), An alkylene group having 1 or more and 4 or less carbon atoms such as a butane-1,2-diyl group; carbon such as a methyleneoxy group, an ethyleneoxy group, and a propyleneoxy group (-CH 2 CH (CH 3 ) -O-).
  • Examples thereof include an alkyleneoxy group having 1 or more and 4 or less atoms, and a single bond; a C 2-4 alkylene group (particularly, a C 2-3 alkylene group such as an ethylene group or a propylene group); a C 2-4 alkyleneoxy group. (In particular, a C 2-3 alkylene group such as an ethyleneoxy group or a propyleneoxy group) is preferable, and a single bond is more preferable.
  • RB1 is an alkyleneoxy group, the oxygen atom in the alkyleneoxy group is bonded to the ring Z.
  • W 1 and W 2 in the formula (b1) are independently represented by the formula (b2), W 1 and W 2 each include R B1 which is a divalent group. ..
  • the R B1 contained in R B1 and W 2 included in W 1 may be the same or may be different.
  • the RB2 is, for example, a C 1-12 alkyl group such as an alkyl group (for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, etc., preferably a C 1-8 alkyl group. , More preferably C 1-6 alkyl group, etc.), cycloalkyl group (C 5-10 cycloalkyl group such as cyclohexyl group, preferably C 5-8 cycloalkyl group, more preferably C 5-6 cycloalkyl group, etc.
  • an alkyl group for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, etc., preferably a C 1-8 alkyl group.
  • cycloalkyl group C 5-10 cycloalkyl group such as cyclohexyl group, preferably C 5-8 cycloal
  • Aryl group for example, C 6-14 aryl group such as phenyl group, trill group, xsilyl group, naphthyl group, preferably C 6-10 aryl group, more preferably C 6-8 aryl group, etc.
  • Alkoxy group for example, C 6-14 aryl group such as phenyl group, trill group, xsilyl group, naphthyl group, preferably C 6-10 aryl group, more preferably C 6-8 aryl group, etc.
  • Monovalent hydrocarbon groups such as (C 6-10aryl- C 1-4 alkyl groups such as benzyl group and phenethyl group); hydroxyl groups; C 1 such as alkoxy groups (methoxy group, ethoxy group, propoxy group, butoxy group, etc.) -12 Alkoxy groups, preferably C 1-8 alkoxy groups, more preferably C 1-6 alkoxy groups, etc.), cycloalkoxy groups (C 5-10 cycloalkoxy groups such as cyclohexyloxy groups), aryloxy groups (phenoxy).
  • C 6-10aryl- C 1-4 alkyl groups such as benzyl group and phenethyl group
  • hydroxyl groups C 1 such as alkoxy groups (methoxy group, ethoxy group, propoxy group, butoxy group, etc.) -12 Alkoxy groups, preferably C 1-8 alkoxy groups, more preferably C 1-6 alkoxy groups, etc.), cycloalkoxy groups (C 5-10 cycl
  • C 6-10 aryloxy groups such as groups
  • an aralkyl group e.g., group [wherein represented by -OR 4a of C 6-10 aryl -C 1-4 alkyl group) such as a benzyloxy group, R 4a represents a monovalent hydrocarbon group (such as the above-exemplified monovalent hydrocarbon group).
  • Alkylthio group (C 1-12 alkyl thio group such as methyl thio group, ethyl thio group, propyl thio group, butyl thio group, preferably C 1-8 alkyl thio group, more preferably C 1-6 alkyl thio group, etc.), cycloalkyl thio group ( C 5-10 cycloalkylthio group such as cyclohexylthio group), arylthio group (C 6-10 arylthio group such as phenylthio group), aralkylthio group (for example, C 6-10aryl- C 1-4 such as benzylthio group) Alkylthio group) and other groups represented by -SR 4b [In the formula, R 4b represents a monovalent hydrocarbon group (such as the above-exemplified monovalent hydrocarbon group).
  • Acyl group (C 1-6 acyl group such as acetyl group); alkoxycarbonyl group (C 1-4 alkoxy-carbonyl group such as methoxycarbonyl group); halogen atom (fluorine atom, chlorine atom, bromine atom, etc.) Iodine atom, etc.); Nitro group; Cyan group; Mercapto group; Carboxy group; Amino group; Carbamoyl group; Alkylamino group (methylamino group, ethylamino group, propylamino group, butylamino group, etc.
  • C 1-12 alkylamino Group preferably C 1-8 alkylamino group, more preferably C 1-6 alkylamino group, etc.
  • cycloalkylamino group C 5-10 cycloalkylamino group such as cyclohexylamino group
  • arylamino group preferably C 5-10 cycloalkylamino group, etc.
  • arylamino group A group represented by -NHR 4c such as a C 6-10 arylamino group such as a phenylamino group
  • an aralkylamino group for example, a C 6-10aryl- C 1-4 alkylamino group such as a benzylamino group
  • R 4c represents a monovalent hydrocarbon group (such as the above-exemplified monovalent hydrocarbon group). ]; Dialkylamino group (dimethylamino group, diethylamino group, dipropylamino group, dibutylamino group and other di (C 1-12 alkyl) amino group, preferably di (C 1-8 alkyl) amino group, more preferably.
  • R 4d independently represents a monovalent group (such as the above-exemplified monovalent group).
  • at least a part of the hydrogen atom bonded to the carbon atom contained in the group represented by -N (R 4d ) 2 is the above monovalent hydrocarbon group, hydroxyl group, group represented by -OR 4a , -SR 4b .
  • alkoxyaryl group eg, C 1-4 alkoxy C 6-10 aryl group such as methoxyphenyl group
  • alkoxycarbonylaryl Groups for example, C 1-4 alkoxy-carbonyl C 6-10 aryl groups such as methoxycarbonylphenyl group and ethoxycarbonylphenyl group
  • RB2 is typically a monovalent hydrocarbon group, a group represented by -OR 4a , a group represented by -SR 4b , an acyl group, an alkoxycarbonyl group, a halogen atom, a nitro group, and a cyano group.
  • -NHR 4c the group represented by -N (R 4d ) 2 , and the like may be used.
  • Preferred RB2s include monovalent hydrocarbon groups [eg, alkyl groups (eg, C 1-6 alkyl groups), cycloalkyl groups (eg, C 5-8 cycloalkyl groups), aryl groups (eg, C 6-). 10 aryl group), aralkyl group (for example, C 6-8 aryl-C 1-2 alkyl group), etc.], alkoxy group (C 1-4 alkoxy group, etc.) and the like.
  • R 2a and R 2b are monovalent hydrocarbons such as alkyl groups [C 1-4 alkyl groups (particularly methyl groups)] and aryl groups [for example, C 6-10 aryl groups (particularly phenyl groups)]. It is preferably a group (particularly an alkyl group).
  • the plurality of RB2s may be different from each other or may be the same. Further, the R B2 included in R B2 and W 2 included in W 1, it may be the same or may be different.
  • the number m of RB2 can be selected according to the type of ring Z, and may be, for example, 0 or more and 4 or less, preferably 0 or more and 3 or less, and more preferably 0 or more and 2 or less. .. Note that m in W 1 and m in W 2 may be the same or different.
  • R 3 is a hydrogen atom, a vinyl group, a thiran-2-ylmethyl group, or a glycidyl group. Both W 1 and W 2 do not have a hydrogen atom as R 3.
  • the vinyloxy group, the thiran-2-ylmethyl group, and the glycidyl group are all cationically polymerizable functional groups. Therefore, the compound represented by the formula (b1) is a cationically polymerizable compound having 1 or 2 cationically polymerizable functional groups.
  • the R 3 contained in R 3 and W 2 included in W 1, as long as both are not hydrogen atoms, may be the same or may be different.
  • the ring Y 1 and the ring Y 2 include, for example, a benzene ring, a condensed polycyclic aromatic hydrocarbon ring [for example, a fused bicyclic hydrocarbon ring (for example, C 8 such as a naphthalene ring). Condensation 2-4 of -20 fused bicyclic hydrocarbon rings, preferably C 10-16 fused bicyclic hydrocarbon rings), fused tricyclic aromatic hydrocarbon rings (eg, anthracene rings, phenanthrene rings, etc.) Cyclic aromatic hydrocarbon ring] and the like.
  • a condensed polycyclic aromatic hydrocarbon ring for example, a fused bicyclic hydrocarbon ring (for example, C 8 such as a naphthalene ring). Condensation 2-4 of -20 fused bicyclic hydrocarbon rings, preferably C 10-16 fused bicyclic hydrocarbon rings), fused tricyclic aromatic hydrocarbon rings (eg, anthracene rings, phenanthrene
  • Ring Y 1 and ring Y 2 is preferably a benzene ring or a naphthalene ring, more preferably a benzene ring.
  • the ring Y 1 and the ring Y 2 may be the same or different.
  • one ring may be a benzene ring, the other ring may be a naphthalene ring, or the like.
  • R is a single bond, a methylene group which may have a substituent, an ethylene group which may have a substituent and may contain a hetero atom between two carbon atoms, —O. It represents a group represented by-, a group represented by -NH-, or a group represented by -S-, and is typically a single bond.
  • a cyano group for example, a cyano group, a halogen atom (fluorine atom, chlorine atom, bromine atom, etc.), a monovalent hydrocarbon group [for example, an alkyl group (methyl group, ethyl group, propyl group, isopropyl group, etc., C 1-6 alkyl group such as butyl group and t-butyl group), aryl group (C 6-10 aryl group such as phenyl group), etc.] and the like, and examples of the hetero atom include an oxygen atom and a nitrogen atom. , Sulfur atom, silicon atom and the like.
  • R 3a and R 3b are usually non-reactive substituents such as a cyano group, a halogen atom (fluorine atom, chlorine atom, bromine atom, etc.) and a monovalent hydrocarbon group [for example.
  • a cyano group, a halogen atom (fluorine atom, chlorine atom, bromine atom, etc.) and a monovalent hydrocarbon group for example.
  • An alkyl group, an aryl group (C 6-10 aryl group such as a phenyl group), etc.] and the like can be mentioned, and a cyano group or an alkyl group is preferable, and an alkyl group is particularly preferable.
  • alkyl group examples include C 1-6 alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group and t-butyl group (for example, C 1-4 alkyl group, particularly methyl group) and the like. ..
  • R 3a When n1 is an integer of 2 or more, R 3a may be different from each other or may be the same. Further, when n2 is an integer of 2 or more, R 3b may be different from each other or may be the same. Further, R 3a and R 3b may be the same or different. Further, the bonding position (replacement position) of R 3a and R 3b with respect to the ring Y 1 and the ring Y 2 is not particularly limited.
  • the preferred substitution numbers n1 and n2 are 0 or 1, especially 0. Note that n1 and n2 may be the same or different from each other.
  • the compound represented by the above formula (b1) has high reactivity because it has a cationically polymerizable functional group while maintaining excellent optical and thermal properties.
  • the compound represented by the above formula (b1) has a fluorene skeleton, and further has optical and thermal properties. Excellent.
  • the compound represented by the above formula (b1) gives a cured product having high hardness and is preferable as a base material component in the composition.
  • Preferred examples of the cationically polymerizable compound other than the compound represented by the formula (b1) include a vinyl ether compound containing a vinyloxy group, an epoxy compound containing an epoxy group, and an episulfide compound containing an episulfide group.
  • vinyl ether compounds, epoxy compounds, and episulfide compounds will be described.
  • the vinyl ether compound as the cationically curable compound (B) other than the compound represented by the formula (b1) is not particularly limited as long as it has a vinyloxy group and is cationically polymerizable.
  • the vinyl ether compound used in combination with the compound represented by the formula (b1) may or may not contain an aromatic group. From the viewpoint of good thermal decomposition resistance of the cured product, the vinyl ether compound used in combination with the compound represented by the formula (b1) is preferably a compound having a vinyloxy group bonded to an aromatic group.
  • Suitable specific examples of the vinyl ether compound that can be used together with the compound represented by the formula (b1) include vinylphenyl ether, 4-vinyloxytoluene, 3-vinyloxytoluene, 2-vinyloxytoluene, and 1-vinyloxy-.
  • epoxy compound examples include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, and bisphenol AD type epoxy resin. , Naphthalene type epoxy resin, biphenyl type epoxy resin and other bifunctional epoxy resins; phenol novolac type epoxy resin, brominated phenol novolac type epoxy resin, orthocresol novolac type epoxy resin, bisphenol A novolac type epoxy resin, and bisphenol AD novolac.
  • Novolac epoxy resin such as type epoxy resin; ring-type aliphatic epoxy resin such as epoxidized product of dicyclopentadiene type phenol resin; aromatic epoxy resin such as epoxidized product of naphthalene type phenol resin; glycidyl ester of dimer acid, and triglycidyl ester Glycidyl ester type epoxy resins such as tetraglycidyl aminodiphenylmethane, triglycidyl-p-aminophenol, tetraglycidyl metaxylylene diamine, and glycidyl amine type epoxy resins such as tetraglycidyl bisaminomethylcyclohexane; Cyclic epoxy resin; fluoroglycinol triglycidyl ether, trihydroxybiphenyl triglycidyl ether, trihydroxyphenylmethane triglycidyl ether, glycerin triglycidyl
  • an oligomer-type or polymer-type polyfunctional epoxy compound can also be preferably used as the cationically curable compound (B).
  • Typical examples are phenol novolac type epoxy compound, brominated phenol novolac type epoxy compound, orthocresol novolac type epoxy compound, xylenol novolac type epoxy compound, naphthol novolac type epoxy compound, bisphenol A novolac type epoxy compound, bisphenol AD novolac type.
  • examples thereof include type epoxy compounds, epoxies of dicyclopentadiene type phenol resin, and epoxies of naphthalene type phenol resin.
  • a suitable epoxy compound is a polyfunctional alicyclic epoxy compound having an alicyclic epoxy group.
  • the cationically curable compound (B) contains an alicyclic epoxy compound, it is easy to form a cured product having excellent transparency by using the curable composition.
  • alicyclic epoxy compound examples include 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-meth-dioxane and bis (3,4-epoxycyclohexylmethyl) adipate.
  • the alicyclic epoxy compounds represented by the following formulas (b01-1) to (b01-5) are preferable because they give a cured product having high hardness.
  • Z 01 represents a single bond or a linking group (a divalent group having one or more atoms).
  • R b01 to R b018 are independent hydrogen atoms, halogen atoms, and halogen atoms, respectively. It is a group selected from the group consisting of organic groups.
  • linking group Z 01 examples include divalent hydrocarbon groups, -O-, -O-CO-, -S-, -SO-, -SO 2- , -CBr 2- , and -C (CBr 3 ). Examples thereof include a divalent group selected from the group consisting of 2- , -C (CF 3 ) 2- , and -R b019 -O-CO-, and a group to which a plurality of these are bonded.
  • Examples of the divalent hydrocarbon group as the linking group Z 01 include a linear or branched alkylene group having 1 to 18 carbon atoms and a divalent alicyclic hydrocarbon group. Can be done.
  • Examples of the linear or branched alkylene group having 1 or more and 18 or less carbon atoms include a methylene group, a methylmethylene group, a dimethylmethylene group, a dimethylene group, a trimethylene group and the like.
  • Examples of the divalent alicyclic hydrocarbon group include 1,2-cyclopentylene group, 1,3-cyclopentylene group, cyclopentylidene group, 1,2-cyclohexylene group and 1,3-.
  • Examples thereof include a cycloalkylene group (including a cycloalkylidene group) such as a cyclohexylene group, a 1,4-cyclohexylene group and a cyclohexylidene group.
  • a cycloalkylene group including a cycloalkylidene group
  • examples thereof include a cycloalkylene group (including a cycloalkylidene group) such as a cyclohexylene group, a 1,4-cyclohexylene group and a cyclohexylidene group.
  • R b019 is an alkylene group having 1 or more carbon atoms and 8 or less carbon atoms, and is preferably a methylene group or an ethylene group.
  • R b01 to R b018 are groups selected from the group consisting of a hydrogen atom, a halogen atom, and an organic group.
  • R b02 and R b010 may be bonded to each other.
  • R B013 and R B016 good .m b1 be bonded to each other to form a ring is 0 or 1.
  • Compounds are preferred.
  • R b01 to R b012 are groups selected from the group consisting of a hydrogen atom, a halogen atom, and an organic group.
  • R b02 and R b010 are bonded to each other to form a ring. May be formed.
  • R b01 to R b010 are groups selected from the group consisting of a hydrogen atom, a halogen atom, and an organic group. R b02 and R b08 may be bonded to each other. )
  • R b01 to R b012 are groups selected from the group consisting of a hydrogen atom, a halogen atom, and an organic group. R b02 and R b010 may be bonded to each other. )
  • R b01 to R b012 are groups selected from the group consisting of a hydrogen atom, a halogen atom, and an organic group.
  • R b01 to R b018 are organic groups
  • the organic group is not particularly limited as long as it does not impair the object of the present invention, and even if it is a hydrocarbon group.
  • halogen atoms include chlorine atom, bromine atom, iodine atom, fluorine atom and the like.
  • Examples of the organic group include a hydrocarbon group, a group consisting of a carbon atom, a hydrogen atom, and an oxygen atom, a halogenated hydrocarbon group, a group consisting of a carbon atom, an oxygen atom, and a halogen atom, a carbon atom, and a hydrogen atom. , Oxygen atom, and a group consisting of a halogen atom are preferable.
  • the organic group is a hydrocarbon group
  • the hydrocarbon group may be an aromatic hydrocarbon group, an aliphatic hydrocarbon group, or a group containing an aromatic skeleton and an aliphatic skeleton.
  • the number of carbon atoms of the organic group is preferably 1 or more and 20 or less, more preferably 1 or more and 10 or less, and particularly preferably 1 or more and 5 or less.
  • hydrocarbon group examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group and n-hexyl group.
  • halogenated hydrocarbon group examples include chloromethyl group, dichloromethyl group, trichloromethyl group, bromomethyl group, dibromomethyl group, tribromomethyl group, fluoromethyl group, difluoromethyl group, trifluoromethyl group, 2,2.
  • 2-Trifluoroethyl group pentafluoroethyl group, heptafluoropropyl group, perfluorobutyl group, and perfluoropentyl group, perfluorohexyl group, perfluoroheptyl group, perfluorooctyl group, perfluorononyl group, and Chain alkyl group halides such as perfluorodecyl group; 2-chlorocyclohexyl group, 3-chlorocyclohexyl group, 4-chlorocyclohexyl group, 2,4-dichlorocyclohexyl group, 2-bromocyclohexyl group, 3-bromocyclohexyl group , And cycloalkyl halide groups such as 4-bromocyclohexyl group; 2-chlorophenyl group, 3-chlorophenyl group, 4-chlorophenyl group, 2,3-dichlorophenyl group,
  • Specific examples of the group consisting of a carbon atom, a hydrogen atom, and an oxygen atom are hydroxy chains such as a hydroxymethyl group, a 2-hydroxyethyl group, a 3-hydroxy-n-propyl group, and a 4-hydroxy-n-butyl group.
  • Alkyl group such as 2-hydroxycyclohexyl group, 3-hydroxycyclohexyl group, and 4-hydroxycyclohexyl group; 2-hydroxyphenyl group, 3-hydroxyphenyl group, 4-hydroxyphenyl group, 2,3 -Hydroxyaryl groups such as -dihydroxyphenyl group, 2,4-dihydroxyphenyl group, 2,5-dihydroxyphenyl group, 2,6-dihydroxyphenyl group, 3,4-dihydroxyphenyl group, and 3,5-dihydroxyphenyl group.
  • Hydroxyaralkyl groups such as 2-hydroxyphenylmethyl group, 3-hydroxyphenylmethyl group, and 4-hydroxyphenylmethyl group; methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butyloxy group, isobutyloxy Group, sec-butyloxy group, tert-butyloxy group, n-pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, 2-ethylhexyloxy group, n-nonyloxy group, n-decyloxy Group, n-undecyloxy group, n-tridecyloxy group, n-tetradecyloxy group, n-pentadecyloxy group, n-hexadecyloxy group, n-heptadecyloxy group, n-octadecyloxy group, Chain
  • An aliphatic acyl group such as a group, a heptanoid group, an octanoyl group, a nonanoyl group, and a decanoyyl group; an aromatic acyl group such as a benzoyl group, an ⁇ -naphthoyl group, and a ⁇ -naphthoyl group; a methoxycarbonyl group, an ethoxycarbonyl group, n -Propoxycarbonyl group, n-butyloxycarbonyl group, n-pentyloxycarbonyl group, n-hexylcarbonyl group, n-heptyloxycarbonyl group, n-octyloxycarbonyl group, n-nonyloxycarbonyl group, and n-decyl Chain alkyloxycarbonyl groups such as oxycarbonyl groups; aryloxycarbonyl groups such as phenoxycarbonyl groups
  • R b01 to R b018 are preferably groups independently selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 or more and 5 or less carbon atoms, and an alkoxy group having 1 or more and 5 or less carbon atoms.
  • R b01 to R b018 are hydrogen atoms because it is easy to form a cured film having excellent mechanical properties.
  • R b01 ⁇ R b018 are the same as R b01 ⁇ R b018 in formula (b01-1).
  • R b02 and R b010 when R b02 and R b010 are combined with each other, in the formula (b01-2), when R b013 and R b016 are combined with each other, and in the formula (b01-2).
  • examples of the divalent group formed when R b02 and R b08 are bonded to each other include -CH 2- and -C (CH 3 ) 2- .
  • alicyclic epoxy compounds represented by the formula (b01-1) specific examples of suitable compounds are the following formulas (b01-1a), formula (b01-1b), and formula (b01-1c).
  • alicyclic epoxy compounds represented by the formula (b01-2) specific examples of suitable compounds are the alicyclic epoxy represented by the following formula (b01-2a) and the following formula (b01-2b). Examples include compounds.
  • alicyclic epoxy compounds represented by the formula (b01-3) specific examples include S spiro [3-oxatricyclo [3.2.1.0 2,4 ] octane-6. , 2'-Oxylan] and the like.
  • alicyclic epoxy compounds represented by the formula (b01-4) specific examples include 4-vinylcyclohexenedioxide, dipentenedioxide, limonendioxide, and 1-methyl-4- (3).
  • -Methyloxylan-2-yl) -7-oxabicyclo [4.1.0] heptane and the like can be mentioned.
  • alicyclic epoxy compounds represented by the formula (b01-5) specific examples include 1,2,5,6-diepoxycyclooctane and the like.
  • X b1 , X b2 , and X b3 are organic groups that may independently contain a hydrogen atom or an epoxy group, respectively, and are X b1 , X b2 , and X b3.
  • the total number of epoxy groups contained in is 2 or more.
  • E 1 to E 3 are an epoxy group, an oxetanyl group, an ethylenically unsaturated group, an alkoxysilyl group, an isocyanate group, and a blocked isocyanate.
  • E 1 ⁇ E 3 is an epoxy group And at least one selected from the group consisting of oxetanyl groups.
  • each group is a group represented by the following formula (b1-IIa).
  • the groups represented by the plurality of formulas (b1-IIa) bound to one compound are preferably the same group.
  • C b is an epoxy group.
  • L and C b may be bonded to form a cyclic structure.
  • the linear, branched or cyclic alkylene group as L is preferably an alkylene group having 1 or more and 10 or less carbon atoms
  • the arylene group as L is preferably an arylene group.
  • An arylene group having 5 or more and 10 or less carbon atoms is preferable.
  • a group consisting of a combination of at least one of O)-and NH- is preferable.
  • examples of the compound represented by the formula (b1-II) include, but are not limited to, an epoxy compound having an oxylanyl group or an alicyclic epoxy group.
  • siloxane compound having two or more glycidyl groups in the molecule
  • siloxane compound can be suitably used as the cationically curable compound (B).
  • the siloxane compound is a compound having a siloxane skeleton composed of a siloxane bond (Si—O—Si) and two or more glycidyl groups in the molecule.
  • Examples of the siloxane skeleton in the siloxane compound include a cyclic siloxane skeleton and a cage-type or ladder-type polysilsesquioxane skeleton.
  • cyclic siloxane a compound having a cyclic siloxane skeleton represented by the following formula (b1-III) (hereinafter, may be referred to as “cyclic siloxane”) is preferable.
  • R b24 , and R b25 is a monovalent group or an alkyl group containing an epoxy group.
  • x1 in the formula (b1-III) indicates an integer of 3 or more.
  • R b24, R b25 in the compound represented by the formula (b1-III) may be the same or different.
  • the plurality of R b24s may be the same or different.
  • the plurality of R b25s may be the same or different.
  • the alkyl group has, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, or the like having 1 or more and 18 or less carbon atoms (preferably 1 or more and 6 or less carbon atoms, and particularly preferably 1 or more carbon atoms. 3 or less) Linear or branched alkyl groups can be mentioned.
  • X1 in the formula (b1-III) represents an integer of 3 or more, and among them, an integer of 3 or more and 6 or less is preferable in terms of excellent cross-linking reactivity when forming a cured film.
  • the number of epoxy groups contained in the molecule of the siloxane compound is 2 or more, and from the viewpoint of excellent cross-linking reactivity when forming a cured film, 2 or more and 6 or less are preferable, and 2 or more and 4 or less are particularly preferable. Is.
  • Examples of the monovalent group containing an epoxy group, alicyclic epoxy group, and -D B -O-R glycidyl ether group represented by b26 [D B represents an alkylene group, R b26 is a glycidyl group ] Is preferable, the alicyclic epoxy group is more preferable, and the alicyclic epoxy group represented by the following formula (b1-IIIa) or the following formula (b1-IIIb) is further preferable.
  • the D B (alkylene group) for example, methylene group, methylmethylene group, dimethylmethylene group, a dimethylene group, a linear or branched alkylene group having carbon atoms is 1 to 18, such as trimethylene group And so on.
  • D 1 and D 2 each independently represent an alkylene group, and ms represents an integer of 0 or more and 2 or less.
  • the curable composition is described in JP-A-2008-248169 as a cationic curable compound (B), in addition to the siloxane compound represented by the formula (b1-III), an alicyclic epoxy group-containing cyclic siloxane.
  • a cationic curable compound represented by the formula (b1-III)
  • an alicyclic epoxy group-containing cyclic siloxane Contains an alicyclic epoxy group-containing silicone resin and a compound having a siloxane skeleton such as an organopolysilsesquioxane resin having at least two epoxy functional groups in one molecule described in JP-A-2008-19422. You may be doing it.
  • examples of the siloxane compound include cyclic siloxanes having two or more glycidyl groups in the molecule, which are represented by the following formulas.
  • examples of the siloxane compound include trade names "X-40-2670", “X-40-2701”, “X-40-2728", “X-40-2738", and "X-40-2740".
  • Commercially available products such as (above, manufactured by Shin-Etsu Chemical Co., Ltd.) can be used.
  • the curable composition includes, if necessary, a cross-linking agent (including, for example, P1 and P2 described later), a sensitizer, a surfactant, a thermal polymerization inhibitor, a defoaming agent, a silane coupling agent, and a coloring agent.
  • Additives such as agents (pigments, dyes), inorganic fillers, and organic fillers can be contained.
  • conventionally known additives can be used.
  • the curable composition is substantially composed of a non-polymer component, a polymer (known thermosetting resin such as epoxy resin, thermoplastic resin, alkali-soluble resin, etc.) is used as long as the effect of the present invention is not impaired. ) May be included.
  • the content of the polymer is, for example, 0% by mass or more and 5% by mass or less with respect to the total solid content of the curable composition.
  • the sensitizer a known sensitizer that has been conventionally used in combination with various cationic polymerization initiators can be used without particular limitation.
  • Specific examples of the sensitizer include anthracene, 9,10-dibutoxyanthracene, 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, and 9,10-.
  • Anthracene compounds such as dipropoxyanthracene; pyrene; 1,2-benzanthracene; perylene; tetracene; coronen; thioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone and 2,4-diethyl Thioxanthone compounds such as thioxanthone; phenothracene compounds such as phenothracene, N-methylphenanthrene, N-ethylphenanthrene, and N-phenylphenanthrene; xanthone; 1-naphthol, 2-naphthol, 1-methoxynaphthrene, 2-methoxynaphthalene, 1, Naphthalene compounds such as 4-dihydroxynaphthalene and 4-methoxy-1-naphthol; dimethoxyacetophenone
  • sensitizers may be used in combination of two or more.
  • the amount of the sensitizer used is not particularly limited, but is preferably 1 part by mass or more and 300 parts by mass or less, and more preferably 5 parts by mass or more and 200 parts by mass or less with respect to 100 parts by mass of the energy-sensitive curing agent (A).
  • A energy-sensitive curing agent
  • the surfactant examples include anionic, cationic and nonionic compounds
  • examples of the thermal polymerization inhibitor include hydroquinone and hydroquinone monoethyl ether
  • examples of the defoaming agent examples include silicone and fluorine. Examples include compounds.
  • the curable composition is a polymerizable compound other than the aromatic vinyl ether compound (B), such as a vinyl ether compound or an epoxy compound having no vinyloxy group on the aromatic group, as long as the object of the present invention is not impaired. May include.
  • an epoxy group-containing fluorene compound in the curable composition.
  • a compound represented by the following formula (P1) containing 9,9-bis (glycidyloxynaphthyl) fluorenes is more preferable.
  • ring Z P1 is a condensed polycyclic aromatic hydrocarbon ring
  • RP1 and RP2 are substituents
  • RP3 is a hydrogen atom or a methyl group
  • k1 is an integer of 0 or more and 4 or less.
  • k2 is an integer of 0 or more, and k3 is an integer of 1 or more.
  • the fused polycyclic aromatic hydrocarbon ring represented by ring Z P1 is a fused bicyclic hydrocarbon ring (for example, a C8 to C20 fused bicyclic ring such as an inden ring or a naphthalene ring).
  • a fused bicyclic hydrocarbon ring for example, a C8 to C20 fused bicyclic ring such as an inden ring or a naphthalene ring.
  • examples thereof include a hydrocarbon ring, preferably a C10 to C16 fused bicyclic hydrocarbon ring), a condensed tricyclic hydrocarbon ring (for example, an anthracene ring, a phenanthrene ring, etc.) and the like. ..
  • Preferred condensed polycyclic aromatic hydrocarbon rings include naphthalene rings, anthracene rings and the like, and naphthalene rings are particularly preferable.
  • the two rings Z P1 substituted at the 9-position of fluorene may be the same or different rings, and usually may be the same ring.
  • the substitution position of the ring Z P1 to be substituted at the 9-position of fluorene is not particularly limited.
  • the naphthyl group substituted at the 9-position of fluorene may be a 1-naphthyl group, a 2-naphthyl group or the like. In particular, it is preferably a 2-naphthyl group.
  • R P1 as the substituent represented by R P1, for example, a cyano group, a halogen atom (fluorine atom, a chlorine atom, a bromine atom), a hydrocarbon group [e.g., an alkyl group, an aryl group Non-reactive substituents such as (C6 to C10 aryl groups such as phenyl group), etc.] are mentioned, and in particular, they are often halogen atoms, cyano groups or alkyl groups (particularly alkyl groups).
  • alkyl group examples include C1-C6 alkyl groups (for example, C1-C4 alkyl groups, particularly methyl groups) such as methyl group, ethyl group, propyl group, isopropyl group, butyl group and t-butyl group.
  • RP1s may be different from each other or may be the same.
  • R P1 is replaced with two benzene rings constituting the fluorene (or fluorene skeleton) may be the same or may be different.
  • the bonding position of R P1 for benzene ring constituting the fluorene (substitution position) is not particularly limited.
  • the preferred k1 is 0 or 1, especially 0. In the two benzene rings constituting fluorene, k1 may be the same or different from each other.
  • the R P2 to be substituted with the ring Z P1 is, for example, a C1 to C12 alkyl group such as an alkyl group (for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, etc., preferably a C1 to C8 alkyl group, more preferably Is a C1-C6 alkyl group, etc.), a cycloalkyl group (for example, a C5-C8 cycloalkyl group such as a cyclohexyl group, preferably a C5-C6 cycloalkyl group, etc.), an aryl group (for example, a phenyl group, a trill group, a xsilyl group).
  • an alkyl group for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, etc
  • C6-C14 aryl group such as, preferably C6-C10 aryl group, more preferably C6-C8 aryl group, etc., aralkyl group (for example, C6-C10 aryl group such as benzyl group, phenethyl group and C1-C4 alkyl group.
  • a hydrocarbon group such as an aralkyl group formed by bonding with and an alkoxy group (for example, a C1 to C8 alkoxy group such as a methoxy group, preferably a C1 to C6 alkoxy group), a cycloalkyl group (C5 to C10 cycloalkyl).
  • RP4 indicates a hydrocarbon group (the above-exemplified hydrocarbon group, etc.).
  • Groups such as alkylthio groups (eg, C1-C8 alkylthio groups such as methylthio groups, preferably C1-C6 alkylthio groups, etc.)-SR P4 (in the formula, RP4 is the same as above); acyl groups (eg, the same as above); C1-C6 acyl group such as acetyl group); Alkoxycarbonyl group (for example, alkoxycarbonyl group formed by bonding C1-C4 alkoxy group such as methoxycarbonyl group and carbonyl group); Halogen atom (fluorine atom, chlorine) Atomic, bromine atom, iodine atom, etc.); hydroxy group; nitro group; cyano group
  • RP2 is preferably a hydrocarbon group, an alkoxy group, a cycloalkoxy group, an aryloxy group, an aralkyloxy group, an acyl group, a halogen atom, a nitro group, a cyano group, a substituted amino group and the like, and in particular.
  • Preferred RP2s are hydrocarbon groups [eg, alkyl groups (eg, C1-C6 alkyl groups)], alkoxy groups (C1-C4 alkoxy groups, etc.), halogen atoms (fluorine atoms, chlorine atoms, bromine atoms, iodine atoms). Etc.) etc.
  • RP2 may be different from each other or may be the same.
  • R P2 may be the same or different.
  • the preferred k2 may be 0 or more and 8 or less, preferably 0 or more and 6 or less (for example, 1 or more and 5 or less), more preferably 0 or more and 4 or less, and particularly 0 or more and 2 or less (for example, 0 or 1). Good.
  • k2 may be the same as or different from each other.
  • RP3 is a hydrogen atom or a methyl group, and preferably RP3 is a hydrogen atom.
  • k3 may be 1 or more, for example, 1 or more and 4 or less, preferably 1 or more and 3 or less, more preferably 1 or 2, and particularly 1 or more. It should be noted that k3 may be the same or different in each ring Z P1 , and is usually the same in many cases.
  • the substitution position of the epoxy group-containing group is not particularly limited, and it may be substituted at an appropriate substitution position of the ring Z P1.
  • the epoxy group-containing group is at least substituted with a hydrocarbon ring (for example, the 5-position, 6-position of the naphthalene ring, etc.) different from the hydrocarbon ring bonded to the 9-position of fluorene in the condensed polycyclic hydrocarbon ring. In many cases.
  • Specific compounds represented by the above formula (P1) include, for example, 9,9-bis (glycidyloxynaphthyl) fluorene [for example, 9,9-bis (6-glycidyloxy-2-naphthyl) fluorene, 9 , 9-Bis (5-glycidyloxy-1-naphthyl) fluorene, etc.] and the like, wherein k3 is 1 in the above formula (P1).
  • the hydroxyl group-containing fluorene compound in the curable composition.
  • R P1 , R P2 , Z P1 , k1, k2, and k3 are the same as those in the formula (P1).
  • the curable composition preferably contains a solvent (S) for the purpose of adjusting the coatability and viscosity.
  • a solvent for the purpose of adjusting the coatability and viscosity.
  • an organic solvent is typically used.
  • the type of the organic solvent is not particularly limited as long as the components contained in the energy-sensitive composition can be uniformly dissolved or dispersed.
  • the curable composition contains the solvent (S)
  • the solid content concentration of the curable composition is, for example, 0.1% by mass or more and 50% by mass or less, preferably 0.5% by mass or more and 30% by mass or less. Is. Within the above range, the coatability and operability are improved.
  • the organic solvent that can be used as the solvent (S) are ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, and diethylene glycol mono.
  • Ethyl ether diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether , Dipropylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol (Poly) alkylene glycol monoalkyl ethers such as monoethyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol mono
  • the curable composition may contain a high boiling point solvent as long as the effects of the present invention are not impaired.
  • the high boiling point solvent is a solvent having a boiling point of 180 ° C. or higher under atmospheric pressure.
  • the high boiling point solvent may be appropriately selected from hydrocarbons, alcohols, ketones, esters, ethers, chlorine-based solvents and the like.
  • 1-octanol, 2-ethylhexanol, 1-nonanol, 1-decanol, 1-undecanol ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,5-hexanediol, 2,4-Heptanediol, 2-ethyl-1,3-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, glycerin, n-nonyl acetate, monohexyl ether, ethylene glycol mono-2-ethylhexyl Ether, ethylene glycol monophenyl ether, ethylene glycol monobenzyl
  • the content of the high boiling point solvent may be adjusted in the range of, for example, 0% by mass or more and 25% by mass or less, preferably 0% by mass or more and 10% by mass or less, based on the entire solvent component.
  • a curable composition can be produced by uniformly mixing each of the components described above in a predetermined ratio. If desired, the curable composition may be filtered using a filter with openings of the desired size to remove insoluble foreign matter.
  • the method for forming the cured product is not particularly limited as long as it can cure the above-mentioned curable composition formed into a desired shape.
  • the curable composition comprises a photoacid generator (A1) and a thermoacid generator (A2). Therefore, usually, when forming a cured product, the curable composition is exposed and heated.
  • the shape of the molded product of the cured composition is not particularly limited, but a film is preferable because it is easy to apply heat uniformly to the molded product and it is easy to uniformly irradiate the molded product with exposure light.
  • a curable composition is applied onto a substrate such as a glass substrate to form a coating film.
  • the coating method include a method using a contact transfer type coating device such as a roll coater, a reverse coater, and a bar coater, and a non-contact type coating device such as a spinner (rotary coating device), a slit coater, and a curtain flow coater.
  • the curable composition is applied by a printing method such as an inkjet method or a screen printing method to form a coating film patterned in a desired shape. You may.
  • the volatile component such as the solvent (S) is removed to dry the coating film.
  • the drying method is not particularly limited, but for example, it is dried under reduced pressure at room temperature using a vacuum drying device (VCD), and then to a temperature of 80 ° C. or higher and 120 ° C. or lower, preferably 90 ° C. or higher and 100 ° C. or lower on a hot plate. A method of drying for a time within the range of 60 seconds or more and 120 seconds or less can be mentioned. After forming the coating film in this way, the coating film is exposed and heated. The exposure is performed by irradiating an active energy ray such as an excimer laser beam.
  • Energy dose to be irradiated may differ depending on the composition of the curable composition, for example, preferably from 10 mJ / cm 2 or more 2000 mJ / cm 2 or less, 30 mJ / cm 2 or more 1500 mJ / cm 2 and more preferably less, 50 mJ / cm 2 or more 1200 mJ / cm 2 or less is more preferable.
  • the temperature at the time of heating is not particularly limited, and is preferably 120 ° C. or higher and 280 ° C. or lower, more preferably 150 ° C. or higher and 260 ° C. or lower, and particularly preferably 200 ° C. or higher and 250 ° C. or lower.
  • the heating time is typically preferably 1 minute or more and 60 minutes or less, more preferably 10 minutes or more and 50 minutes or less, and particularly preferably 20 minutes or more and 40 minutes or less.
  • the epoxy group content measured by the following method is preferably 1.8 or less, more preferably 0.8 or more and 1.3 or less. is there.
  • the above-mentioned epoxy group content is determined by measuring the area of the peak representing the epoxy group obtained by measuring the cured product with a Fourier transform infrared spectroscopy (FT-IR) apparatus and also measuring it with an FT-IR apparatus. It is a value divided by the area of the peak representing the epoxide.
  • FT-IR Fourier transform infrared spectroscopy
  • the cured product formed as described above, particularly the cured film, is suitably used for a display panel for an image display device and OLED lighting.
  • A1-1, A1-2, A1-3, and A1-4 were used as the above-mentioned photoacid generator (A1).
  • A1-1 and A1-2 were used as the above-mentioned photoacid generator (A1).
  • the structures of A1-1 and A1-2 are described below.
  • A1-3 is composed of a cation portion composed of a triarylsulfonium cation different from the cation portion contained in A1-1 and A1-2, and an anion portion composed of an anion portion of the same type as the anion portion contained in A1-1 and A1-2. Is a sulfonium salt.
  • A1-4 has a cation portion of the cation of the same kind provided in A1-3, (C 6 F 5) 4 Ga - is composed of an anion portion represented by sulfonium salt. (C 6 F 5) 4 Ga - In, C 6 F 5 is a pentafluorophenyl group.
  • A2-1, A2-2, and A2-3 were used as the above-mentioned thermal acid generator (A2). The structures of A2-2 and A2-3 are described below.
  • A2-1 is a sulfonium salt composed of a cation portion contained in A2-2 and A2-3 and an anion portion contained in A1-4.
  • the type and amount of the cationic curing agent (A) shown in Table 1 and 99 parts by mass of the cationic curing compound (B) were uniformly added to propylene glycol monomethyl ether acetate so that the solid content concentration was 20% by mass.
  • To obtain a curable composition of each Example and Comparative Example Using the obtained curable composition, the appearance, coloring, solvent resistance, and epoxy group content of the cured product of the curable composition were evaluated according to the following method. The results of these evaluations are shown in Table 1. However, there are some examples in which the coloring and the epoxy group content have not been partially measured.
  • ⁇ Appearance of cured product> The curable compositions of each Example and Comparative Example were applied onto a glass substrate with a spin coater, and then heated at 100 ° C. for 120 seconds to form a coating film. The entire surface of the formed coating film was exposed at an exposure amount of 1000 mJ / cm 2. Next, the exposed coating film was heated at 230 ° C. for 20 minutes to form a cured film (thickness: about 1 ⁇ m) as a cured product. The formed cured film was visually observed to confirm whether it was transparent or yellowish due to coloring.
  • ⁇ Epoxy group content> The cured film formed by the same method as the appearance evaluation of the cured product was measured by a Fourier transform infrared spectroscopy (FT-IR) apparatus. Based on the measurement result, the value represented by the value obtained by dividing the area of the peak representing the epoxy group by the area of the peak representing benzene also measured by the FT-IR apparatus was calculated as the epoxy group content. The smaller the epoxy group content value, the more the curing of the cationically curable compound (B) is progressing.
  • FT-IR Fourier transform infrared spectroscopy
  • the curable composition of the example containing the epoxy compound of the above gives a cured film that is less colored, transparent, and has excellent solvent resistance, and that curing proceeds satisfactorily by exposure and heating.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Epoxy Resins (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

L'invention concerne une composition durcissable par voie cationique dans laquelle la suppression de la décoloration d'un matériau durci pendant le durcissement et une bonne aptitude au durcissement peuvent toutes deux être obtenues en même temps, un matériau durci obtenu à partir de ladite composition durcissable, et un procédé de formation d'un matériau durci mettant en oeuvre ladite composition durcissable.　L'invention concerne également une composition durcissable comprenant un agent de durcissement cationique (A) et un composé durcissable par voie cationique (B), l'agent de durcissement cationique utilisé comprenant une association d'un générateur de photoacide (A1) comprenant un sel d'onium ayant une partie cationique qui possède une structure spécifique, et d'un générateur d'acide thermique (A2) ayant comme partie anionique un anion contenant du gallium qui possède une structure spécifique.
PCT/JP2020/036621 2019-10-02 2020-09-28 Composition durcissable, matériau durci et procédé de formation d'un matériau durci Ceased WO2021065796A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
KR1020227014570A KR102765016B1 (ko) 2019-10-02 2020-09-28 경화성 조성물, 경화물, 및 경화물의 형성 방법
CN202080068095.4A CN114502613A (zh) 2019-10-02 2020-09-28 固化性组合物、固化物及固化物的形成方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2019-182545 2019-10-02
JP2019182545A JP7295768B2 (ja) 2019-10-02 2019-10-02 硬化性組成物、硬化物、及び硬化物の形成方法

Publications (1)

Publication Number Publication Date
WO2021065796A1 true WO2021065796A1 (fr) 2021-04-08

Family

ID=75338331

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2020/036621 Ceased WO2021065796A1 (fr) 2019-10-02 2020-09-28 Composition durcissable, matériau durci et procédé de formation d'un matériau durci

Country Status (5)

Country Link
JP (1) JP7295768B2 (fr)
KR (1) KR102765016B1 (fr)
CN (1) CN114502613A (fr)
TW (1) TWI858148B (fr)
WO (1) WO2021065796A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2023024144A (ja) * 2021-08-06 2023-02-16 東京応化工業株式会社 硬化性組成物、硬化物、硬化膜、表示パネル、及び硬化物の製造方法
WO2025142521A1 (fr) * 2023-12-27 2025-07-03 日産化学株式会社 Composition durcissable par voie cationique

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2025105092A1 (fr) * 2023-11-17 2025-05-22 パナソニックＩｐマネジメント株式会社 Composition de résine pour guide d'ondes optiques, et film sec, guide d'ondes optique et substrat de boîtier de semi-conducteur l'utilisant

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017173765A (ja) * 2016-03-25 2017-09-28 東京応化工業株式会社 着色感光性組成物、それによって得られる着色硬化物、表示素子及び着色硬化物の製造方法
JP2017179330A (ja) * 2016-03-25 2017-10-05 東京応化工業株式会社 エネルギー感受性組成物、硬化物及び硬化物の製造方法
WO2018020974A1 (fr) * 2016-07-28 2018-02-01 サンアプロ株式会社 Sel de sulfonium, générateur de chaleur ou de photo-acide, composition thermodurcissable ou photodurcissable, et produit durci correspondant
WO2018110297A1 (fr) * 2016-12-12 2018-06-21 株式会社Adeka Composition

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5699080B2 (ja) * 2009-08-03 2015-04-08 サンアプロ株式会社 光酸発生剤，光硬化性組成物，及びその硬化体
JP2014156522A (ja) 2013-02-15 2014-08-28 Toyo Ink Sc Holdings Co Ltd 熱硬化性組成物
JP6331526B2 (ja) * 2014-03-14 2018-05-30 オムロン株式会社 樹脂組成物およびその硬化物
WO2016047784A1 (fr) * 2014-09-26 2016-03-31 東京応化工業株式会社 Sel de sulfonium, générateur photo-acide, et composition photosensible
JP6708382B2 (ja) * 2015-09-03 2020-06-10 サンアプロ株式会社 硬化性組成物及びそれを用いた硬化体
US10683266B2 (en) * 2016-06-29 2020-06-16 San Apro Ltd. Sulfonium salt, photoacid generator, photocurable composition, and cured product thereof
US11306212B2 (en) * 2017-05-24 2022-04-19 Toray Industries, Inc. Transparent resin composition, transparent coating film and transparent resin-coated glass substrate
JP6935260B2 (ja) * 2017-07-31 2021-09-15 東京応化工業株式会社 硬化性組成物、硬化膜、表示パネル又はｏｌｅｄ照明、並びに硬化物の製造方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017173765A (ja) * 2016-03-25 2017-09-28 東京応化工業株式会社 着色感光性組成物、それによって得られる着色硬化物、表示素子及び着色硬化物の製造方法
JP2017179330A (ja) * 2016-03-25 2017-10-05 東京応化工業株式会社 エネルギー感受性組成物、硬化物及び硬化物の製造方法
WO2018020974A1 (fr) * 2016-07-28 2018-02-01 サンアプロ株式会社 Sel de sulfonium, générateur de chaleur ou de photo-acide, composition thermodurcissable ou photodurcissable, et produit durci correspondant
WO2018110297A1 (fr) * 2016-12-12 2018-06-21 株式会社Adeka Composition

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2023024144A (ja) * 2021-08-06 2023-02-16 東京応化工業株式会社 硬化性組成物、硬化物、硬化膜、表示パネル、及び硬化物の製造方法
JP7767053B2 (ja) 2021-08-06 2025-11-11 東京応化工業株式会社 硬化性組成物、硬化物及び硬化物の製造方法
WO2025142521A1 (fr) * 2023-12-27 2025-07-03 日産化学株式会社 Composition durcissable par voie cationique

Also Published As

Publication number Publication date
TW202124500A (zh) 2021-07-01
TWI858148B (zh) 2024-10-11
KR102765016B1 (ko) 2025-02-11
JP2021059615A (ja) 2021-04-15
CN114502613A (zh) 2022-05-13
JP7295768B2 (ja) 2023-06-21
KR20220074926A (ko) 2022-06-03

Similar Documents

Publication Publication Date Title
JP6894290B2 (ja) 硬化性組成物、硬化膜、表示パネル、及び硬化物の製造方法
KR102780282B1 (ko) 경화성 조성물, 경화막, 표시 패널 또는 oled 조명, 및 경화물의 제조 방법
TWI791629B (zh) 硬化性組成物、硬化膜，及硬化物之製造方法
JP7100962B2 (ja) 硬化性組成物、硬化物、硬化膜、表示パネル、及び硬化物の製造方法
WO2021065796A1 (fr) Composition durcissable, matériau durci et procédé de formation d'un matériau durci
JP2017173765A (ja) 着色感光性組成物、それによって得られる着色硬化物、表示素子及び着色硬化物の製造方法
US10479879B2 (en) Curable composition, cured product of the curable composition, and method of producing a cured product using the curable composition
JP7767053B2 (ja) 硬化性組成物、硬化物及び硬化物の製造方法
JP7125308B2 (ja) 平坦化膜を具備する基板の製造方法
JP7028743B2 (ja) 平坦化膜を具備する基板の製造方法
JP2021167396A (ja) 積層体の製造方法、マイクロレンズの製造方法、ｃｍｏｓイメージセンサーの製造方法、及び硬化性組成物

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 20872566

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 20227014570

Country of ref document: KR

Kind code of ref document: A

122 Ep: pct application non-entry in european phase

Ref document number: 20872566

Country of ref document: EP

Kind code of ref document: A1