WO2021220919A1 - Procédé de fabrication de microparticules d'oxyde métallique modifiées, procédé de fabrication de dispersion liquide de microparticules d'oxyde métallique modifiées, et procédé de fabrication d'article solide - Google Patents

Procédé de fabrication de microparticules d'oxyde métallique modifiées, procédé de fabrication de dispersion liquide de microparticules d'oxyde métallique modifiées, et procédé de fabrication d'article solide Download PDF

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WO2021220919A1
WO2021220919A1 PCT/JP2021/016227 JP2021016227W WO2021220919A1 WO 2021220919 A1 WO2021220919 A1 WO 2021220919A1 JP 2021016227 W JP2021016227 W JP 2021016227W WO 2021220919 A1 WO2021220919 A1 WO 2021220919A1
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group
metal oxide
oxide fine
aromatic
formula
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PCT/JP2021/016227
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English (en)
Japanese (ja)
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麻祐美 黒子
和也 染谷
大 塩田
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東京応化工業株式会社
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Priority to JP2022517677A priority Critical patent/JPWO2021220919A1/ja
Publication of WO2021220919A1 publication Critical patent/WO2021220919A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
    • C01B13/14—Methods for preparing oxides or hydroxides in general

Definitions

  • the present invention relates to a method for producing modified metal oxide fine particles capable of producing modified metal oxide fine particles having excellent dispersion stability in dispersion liquids having various compositions, and a modified metal containing the modified metal oxide fine particles.
  • the present invention relates to a method for producing an oxide fine particle dispersion and a method for producing a solid article formed by using the modified metal oxide fine particle dispersion.
  • Metal oxide fine particles are widely used as optical materials, electronic component materials, and materials used for processing various articles such as abrasives. Such metal oxide fine particles are often used as a dispersion liquid because they are easy to transport, measure, and handle.
  • a dispersion medium such as an organic solvent
  • the metal oxide fine particles tend to aggregate.
  • the metal oxide fine particles are aggregated in the dispersion medium, it is difficult for the metal oxide fine particles to exert their functions. Therefore, in order to impart good dispersion stability to the metal oxide fine particles with respect to a dispersion medium such as an organic solvent, a surface treatment method for the metal oxide fine particles has been proposed.
  • Patent Document 1 a method of coating at least a part of the surface of the metal oxide fine particles with a carboxylic acid compound having an aromatic structure has been proposed.
  • the metal oxide fine particles surface-treated by the method described in Patent Document 1 may easily aggregate depending on the type of the component contained in the dispersion liquid.
  • the present invention has been made in view of the above problems, and is a method for producing modified metal oxide fine particles capable of producing modified metal oxide fine particles having excellent dispersion stability in dispersion liquids having various compositions. It is an object of the present invention to provide a method for producing a modified metal oxide fine particle dispersion containing the modified metal oxide fine particles, and a method for producing a solid article formed by using the modified metal oxide fine particle dispersion. ..
  • the present inventors prepare the metal oxide fine particles (B) in the presence of the solvent (SI), or disperse the metal oxide fine particles (B) in the presence of the dispersion medium (S-II). And the metal oxide fine particles (B) and the aromatic group-containing carboxylic acid compound (A) and / or the aromatic group-containing carboxylic acid compound (A) in the presence of the solvent (SI) or the dispersion medium (S-II). ), It has been found that the above problems can be solved by using a nitrogen-containing organic solvent as the solvent (SI) or the dispersion medium (S-II) in the method including contacting with the carboxylate derived from). The present invention has been completed. Specifically, the present invention provides the following.
  • a first aspect of the present invention is to prepare the metal oxide fine particles (B) in the presence of a solvent (SI) or to prepare the metal oxide fine particles (B) in the presence of a dispersion medium (S-II).
  • a solvent SI
  • S-II dispersion medium
  • a second aspect of the present invention is to produce modified metal oxide fine particles by the method according to the first aspect.
  • Production of Modified Metal Oxide Fine Particle Dispersion Containing by Mixing Modified Metal Oxide Fine Particles and Base Material Component (C) in Solvent (S) to Obtain Modified Metal Oxide Fine Particle Dispersion The method.
  • a third aspect of the present invention is to produce a modified metal oxide fine particle dispersion by the method according to the second aspect. Molding the modified metal oxide fine particle dispersion liquid according to the shape of the solid article to be formed, A method for producing a solid article, which comprises solidifying a molded modified metal oxide fine particle dispersion by one or more methods selected from the group consisting of drying, curing with moisture, heating, and exposure.
  • a method for producing modified metal oxide fine particles capable of producing modified metal oxide fine particles having excellent dispersion stability in dispersion liquids having various compositions, and a modification containing the modified metal oxide fine particles. It is possible to provide a method for producing a quality metal oxide fine particle dispersion and a method for producing a solid article formed by using the modified metal oxide fine particle dispersion.
  • the method for producing the modified metal oxide fine particles is to prepare the metal oxide fine particles (B) in the presence of the solvent (SI) or to prepare the metal oxide fine particles (S-II) in the presence of the dispersion medium (S-II).
  • the preparation includes mixing or stirring the metal oxide fine particles (B) or its raw material.
  • Dispersion includes disperse the metal oxide fine particles (B) in a dispersed state.
  • the carboxylate derived from the aromatic group-containing carboxylic acid compound (A) and / or the aromatic group-containing carboxylic acid compound (A) is bonded to the surface of the metal oxide fine particles (B). Or it adheres.
  • the metal oxide fine particles (B) When the carboxylate derived from the aromatic group-containing carboxylic acid compound (A) and / or the aromatic group-containing carboxylic acid compound (A) is bonded or adhered to the surface of the metal oxide fine particles (B), the metal oxide fine particles (B) ), The aromatic group is exposed on the surface. As a result, it is considered that the aromatic group exposed on the surface of the metal oxide fine particles stabilizes the dispersion of the modified metal oxide fine particles in the dispersion liquid.
  • the carboxylate is a carboxylic acid anion derived from the aromatic group-containing carboxylic acid compound (A) or an aromatic group-containing carboxylic acid compound (A) that can be bonded or adhered to the surface of the metal oxide fine particles (B). It is salt.
  • X X-ray photoelectron spectrometer
  • the counter cation for the carboxylic acid anion may be an inorganic cation or an organic cation, and an inorganic cation is preferable.
  • the counter cation may be a monovalent cation or a divalent or higher polyvalent cation.
  • the counter cation for the carboxylic acid anion may be an inorganic cation or an organic cation, and an inorganic cation is preferable.
  • the counter cation may be a monovalent cation or a divalent or higher polyvalent cation.
  • the inorganic cation is not particularly limited, but an alkali metal cation such as sodium ion or potassium ion, a cation derived from a metal element contained in the metal oxide fine particles (B), or the like is preferable. Preferred metal elements that can be contained in the metal oxide fine particles (B) will be described later.
  • the (SI) or the dispersion medium (S-II) is not particularly limited as long as it contains a nitrogen-containing organic solvent.
  • a hydrogen bond is formed between the hydroxyl group on the surface of the metal oxide fine particles (B) and the carboxylate derived from the aromatic group-containing carboxylic acid compound (A) and / or the aromatic group-containing carboxylic acid compound (A).
  • the nitrogen-containing organic solvent acts as a buffer and promotes the formation of hydrogen bonds.
  • the metal oxide fine particles (B) are brought into contact with the aromatic group-containing carboxylic acid compound (A) and / or the carboxylate derived from the aromatic group-containing carboxylic acid compound (A) in the nitrogen-containing organic solvent.
  • the carboxylate derived from the aromatic group-containing carboxylic acid compound (A) and / or the aromatic group-containing carboxylic acid compound (A) is likely to be well bonded or adhered to the surface of the metal oxide fine particles (B). (Hereinafter, it may be referred to as a coating).
  • the nitrogen-containing organic solvent is not particularly limited as long as it has a nitrogen atom.
  • the nitrogen-containing organic solvent may be amines such as triethylamine, triisopropylamine, piperidine, piperazine, morpholin, aniline, or a nitrogen-containing aromatic heterocyclic compound such as pyridine or pyrimidine, N, N-dimethyl. It may be a compound having an amide structure such as formamide and N, N-dimethylacetamide. Among these, the bond or adhesion of the carboxylate derived from the aromatic group-containing carboxylic acid compound (A) and / or the aromatic group-containing carboxylic acid compound (A) to the metal oxide fine particles (B) is likely to be promoted. Therefore, a compound having an amide structure is preferable.
  • a preferable example of the compound having an amide structure is a compound represented by the following formula (S1).
  • R S1 and R S2 are each independently an alkyl group having 1 to 3 carbon atoms
  • R S3 is the following formula (S1-1) or the following formula (S1-2): It is a group represented by.
  • R S4 is a hydrogen atom or a hydroxyl group
  • R S5 and R S6 are each independently 1 or more carbon atoms of 3 or less alkyl groups.
  • R S7 and R S8 are each independently a hydrogen atom, or an alkyl group having 1 to 3 carbon atoms.
  • R S3 is a group represented by the formula (S1-1) is, N, N, 2- trimethyl propionamide, N- ethyl, N , 2-Dimethylpropionamide, N, N-diethyl-2-methylpropionamide, N, N, 2-trimethyl-2-hydroxypropionamide, N-ethyl-N, 2-dimethyl-2-hydroxypropionamide, and Examples thereof include N, N-diethyl-2-hydroxy-2-methylpropionamide.
  • R S3 is a group represented by the formula (S1-2) is, N, N, N ', N'- tetramethyl urea, N , N, N', N'-tetraethylurea and the like.
  • N, N, 2-trimethylpropionamide and N, N, N', N'-tetramethylurea are particularly preferable.
  • the compound having an amide structure as preferable examples other than the compound represented by the formula (S1), N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N, N-dimethylformamide, N, N- Examples thereof include diethylformamide, N, N-dimethylacetamide, 1,3-dimethyl-2-imidazolidinone and the like.
  • the compound having an amide structure one type may be used alone, or two or more types may be used in combination.
  • the solvent (SI) or the dispersion medium (S-II) may contain an organic solvent other than the nitrogen-containing organic solvent as long as the object of the present invention is not impaired.
  • the solvent other than the nitrogen-containing organic solvent that the solvent (SI) or the dispersion medium (S-II) may contain include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol-n-propyl ether, and ethylene.
  • Glycol mono-n-butyl ether diethylene glycol monomethyl ether, diethylene glycol monoethyl 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, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono- (Poly) alkylene glycol monoalkyl ethers such as n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol mono
  • the amount of the nitrogen-containing organic solvent used is not particularly limited as long as the desired effect can be obtained.
  • the amount of the nitrogen-containing organic solvent used is not particularly limited, and is typically 10 parts by mass or more with respect to 100 parts by mass of the modified metal oxide fine particles to be produced or the metal oxide fine particles (B) to be dispersed. It is preferably 5000 parts by mass or less, more preferably 20 parts by mass or more and 1000 parts by mass or less, and further preferably 50 parts by mass or more and 500 parts by mass or less.
  • the amount used is not particularly limited, and typically, it is preferably 10 parts by mass or more and 5000 parts by mass or less, and more preferably 50 parts by mass or more and 1000 parts by mass or less with respect to 100 parts by mass of the metal oxide fine particles (B). More preferably, it is 100 parts by mass or more and 500 parts by mass or less.
  • the temperature at which the carboxylate derived from the aromatic group-containing carboxylic acid compound (A) and / or the aromatic group-containing carboxylic acid compound (A) and the metal oxide fine particles (B) are brought into contact with each other is the metal oxide fine particles (A).
  • the temperature is not particularly limited as long as the temperature is such that the carboxylate derived from B), the aromatic group-containing carboxylic acid compound (A) and / or the aromatic group-containing carboxylic acid compound (A) does not deteriorate or decompose due to heating.
  • the temperature at which the carboxylate derived from the aromatic group-containing carboxylic acid compound (A) and / or the aromatic group-containing carboxylic acid compound (A) is brought into contact with the metal oxide fine particles (B) is, for example, ⁇ 20. ° C. or higher and 150 ° C. or lower, preferably ⁇ 10 ° C. or higher and 100 ° C. or lower, and more preferably 20 ° C. or higher and 100 ° C. or lower.
  • the pressure at which the carboxylate derived from the aromatic group-containing carboxylic acid compound (A) and / or the aromatic group-containing carboxylic acid compound (A) is brought into contact with the metal oxide fine particles (B) is under reduced pressure or high pressure. Is preferable, and under reduced pressure is more preferable from the viewpoint of convenience.
  • the time for contacting the carboxylate derived from the aromatic group-containing carboxylic acid compound (A) and / or the aromatic group-containing carboxylic acid compound (A) with the metal oxide fine particles (B) is not particularly limited.
  • the time for contacting the carboxylate derived from the aromatic group-containing carboxylic acid compound (A) and / or the aromatic group-containing carboxylic acid compound (A) with the metal oxide fine particles (B) is, for example, 5 minutes or more 24. It is within an hour, preferably 10 minutes or more and 12 hours or less, and more preferably 30 minutes or more and 6 hours or less.
  • the pH at the time of contacting the carboxylate derived from the aromatic group-containing carboxylic acid compound (A) and / or the aromatic group-containing carboxylic acid compound (A) with the metal oxide fine particles (B) is, for example, 3 or more and 6 or less. Is preferable.
  • the pH may be confirmed with pH test paper or the like.
  • aromatic group-containing carboxylic acid compound (A) and the metal oxide fine particles (B), which are the main materials used in the method for producing the modified metal oxide fine particles, will be described.
  • the aromatic group-containing carboxylic acid compound (A) may be used as a carboxylate derived from the aromatic group-containing carboxylic acid compound (A).
  • the aromatic group-containing carboxylic acid compound (A) is not particularly limited as long as it is a compound having an aromatic group and a carboxy group in the molecule.
  • the aromatic group may be an aromatic hydrocarbon group or an aromatic heterocyclic group, and an aromatic hydrocarbon group is preferable.
  • the aromatic hydrocarbon group is a group obtained by removing one or more hydrogen atoms from a benzene ring, a naphthalene ring, a biphenyl ring, an anthracene ring, a fluorene ring, a dibenzothiophene ring, a stilbene ring, a bisphenol ring, or a phenanthrene ring.
  • Examples include monovalent or divalent or higher polyvalent groups.
  • the carboxylic acid compound can be suitably used as the aromatic group-containing carboxylic acid compound (A).
  • the carboxylic acid compound having the above aromatic structure having a (meth) acryloyl structure can also be suitably used as the aromatic group-containing carboxylic acid compound (A).
  • an aromatic group-containing carboxylic acid compound (A) having a fused ring structure in which an aromatic hydrocarbon ring such as a benzimidazole ring, a carbazole ring, or a quinoline ring is condensed with a heterocycle. Is understood to have an aromatic hydrocarbon group.
  • the aromatic group-containing carboxylic acid compound (A) is a group consisting of a compound represented by the following formula (1), benzoic acid which may have a substituent, and naphthoic acid which may have a substituent. One or more selected is preferable.
  • R 1 and R 2 are independently hydrogen atoms or monovalent organic groups, and R 1 and R 2 may be bonded to each other to form a ring.
  • R 3 is an aromatic group which may have a substituent
  • R 4 Is a methylene group or a single bond.
  • carboxylic acid compound represented by the formula (1) for convenience, only the carboxylic acid compound represented by the formula (1) will be described, but the carboxylate derived from the carboxylic acid compound represented by the formula (1) is also represented by the carboxylic acid compound represented by the formula (1). It can be used for coating in the same manner as above.
  • R 1 and R 2 are independently hydrogen atoms or monovalent organic groups, respectively.
  • the monovalent organic group is not particularly limited.
  • the monovalent organic group may have, for example, an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an aralkyl group which may have a substituent, and a substituent. It may be a good aliphatic heterocyclic group, an aromatic group which may have a substituent, or the like.
  • the number of carbon atoms of the organic group is preferably 1 or more and 40 or less, more preferably 1 or more and 30 or less, further preferably 1 or more and 20 or less, and 1 or more. 10 or less is particularly preferable. Further, R 1 and R 2 may be combined with each other to form a ring.
  • R 1 and R 2 whether R 1 and R 2 are independent hydrogen atoms, alkyl groups which may have a substituent, or aromatic groups which may have a substituent, respectively, R 1 And R 2 are preferably combined to form a ring.
  • the alkyl group may have an ether bond, an ester bond, an amide bond, a sulfide bond, a disulfide bond, or the like in the chain.
  • the number of carbon atoms of the alkyl group as R 1 and R 2 is preferably 1 or more and 40 or less, more preferably 1 or more and 30 or less, further preferably 1 or more and 20 or less, particularly preferably 1 or more and 10 or less, and 1 or more and 5 or less. Is the most preferable.
  • the substituents that the alkyl groups as R 1 and R 2 may have are not particularly limited as long as they do not impair the object of the present invention.
  • Specific examples of the substituent that the alkyl group may have include a hydroxyl group, an alkoxy group, an amino group, a cyano group, a halogen atom and the like.
  • the alkylene group may be a linear alkyl group or a branched chain alkyl group, and a linear alkyl group is preferable.
  • alkyl group as R 1 and R 2 include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group and n-pentyl.
  • isopentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, 2-ethyl-n-hexyl group, 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, n-nonadecil group, and n-icosyl group can be mentioned.
  • the aromatic group which may have a substituent as R 1 and R 2 may be an aromatic hydrocarbon group which may have a substituent or an aromatic heterocyclic group which may have a substituent. good.
  • the type of aromatic hydrocarbon group is not particularly limited as long as the object of the present invention is not impaired.
  • the aromatic hydrocarbon group may be a monocyclic aromatic group, or may be a group formed by condensing two or more aromatic hydrocarbon groups, or two or more aromatic hydrocarbon groups. May be a group formed by bonding with a single bond.
  • a phenyl group, a naphthyl group, a biphenylyl group, an anthryl group, and a phenanthrenyl group are preferable.
  • the type of aromatic heterocyclic group is not particularly limited as long as the object of the present invention is not impaired.
  • the aromatic heterocyclic group may be a monocyclic group or a polycyclic group.
  • a pyridyl group, a fryl group, a thienyl group, an imidazolyl group, a pyrazolyl group, an oxazolyl group, a thiazolyl group, an isooxazolyl group, an isothiazolyl group, a benzoxazolyl group, a benzothiazolyl group, and a benzoimidazolyl group are preferable.
  • Substituents that the phenyl group, polycyclic aromatic hydrocarbon group, or aromatic heterocyclic group may have include a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, and a nitroso group. , Sulfino group, sulfo group, sulfonato group, phosphino group, phosphinyl group, phosphono group, phosphonato group, amino group, ammonio group, and organic group.
  • the plurality of substituents may be the same or different.
  • the substituent of the aromatic group is an organic group
  • examples of the organic group include an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group, an aralkyl group and the like.
  • This organic group may contain a bond or a substituent other than the hydrocarbon group such as a hetero atom in the organic group.
  • the organic group may be linear, branched chain, cyclic, or a combination of these structures.
  • This organic group is usually monovalent, but can be a divalent or higher organic group when forming a cyclic structure or the like.
  • the two substituents bonded on the adjacent carbon atom may be bonded to each other to form a cyclic structure.
  • the cyclic structure include an aliphatic hydrocarbon ring and an aliphatic ring containing a hetero atom.
  • Examples of the bond containing a hetero atom that the organic group may have include ether bond, thioether bond, carbonyl bond, thiocarbonyl bond, ester bond, from the viewpoint of heat resistance of the carboxylic acid compound represented by the formula (1).
  • the type of the substituent other than the hydrocarbon group is not particularly limited as long as the object of the present invention is not impaired.
  • substituents other than the hydrocarbon group include halogen atom, hydroxyl group, mercapto group, sulfide group, cyano group, isocyano group, cyanato group, isocyanato group, thiocyanato group, isothiocyanato group, silyl group, silanol group and alkoxy group.
  • Alkoxycarbonyl group amino group, monoalkylamino group, dialkylaluminum group, monoarylamino group, diarylamino group, carbamoyl group, thiocarbamoyl group, nitro group, nitroso group, carboxylate group, acyl group, acyloxy group, sulfino Examples thereof include a group, a sulfonato group, a phosphino group, a phosphinyl group, a phosphonato group, an alkyl ether group, an alkenyl ether group, an alkyl thio ether group, an alkenyl thio ether group, an aryl ether group, an aryl thio ether group and the like.
  • the hydrogen atom contained in the above substituent may be substituted with a hydrocarbon group. Further, the hydrocarbon group contained in the above-mentioned substituent may be linear, branched chain, or cyclic.
  • the substituent of the phenyl group, polycyclic aromatic hydrocarbon group, or aromatic heterocyclic group includes an alkyl group having 1 to 12 carbon atoms, an aryl group having 1 to 12 carbon atoms, and 1 carbon atom. Alkoxy groups having 12 or more carbon atoms, aryloxy groups having 1 to 12 carbon atoms, arylamino groups having 1 to 12 carbon atoms, and halogen atoms are preferable.
  • R 1 and R 2 may be combined with each other to form a ring.
  • the ring formed by combining R 1 and R 2 is a nitrogen-containing heterocycle.
  • the nitrogen-containing ring contains one or more elements selected from the group consisting of N, S, and O as ring constituent elements.
  • the nitrogen-containing ring may be a monocyclic ring or a polycyclic ring, and a monocyclic ring is preferable.
  • the nitrogen-containing heterocycle is a condensed polycycle in which one or more aliphatic monocycles and one or more aromatic monocycles are condensed, regardless of whether it is an aliphatic ring or an aromatic ring. May be good.
  • Preferable examples of the nitrogen-containing heterocycle formed by combining R 1 and R 2 are piperidine, piperazine, morpholine, pyrrolidine, pyrrole, imidazole, pyrazole, indole, benzimidazole, purine, phenoxazine, and phenoxazine.
  • pyrrolidine, pyrrole, imidazole, and pyrazole are preferable, and imidazole is more preferable. That is, in the formula (1), it is preferable that R 1 and R 2 are combined to form an imidazole ring.
  • the carboxylic acid compound having an imidazole ring formed by combining R 1 and R 2 is excellent in the effect of coating the metal oxide fine particles (B).
  • the nitrogen-containing heterocycle formed by combining R 1 and R 2 may have a substituent.
  • substituents include a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, a nitroso group, a sulfonato group, a phosphino group, a phosphinyl group, a phosphonat group, and an organic group.
  • the number of substituents on the nitrogen-containing heterocycle is not particularly limited. When a plurality of substituents are present on the nitrogen-containing heterocycle, the plurality of substituents may be the same or different from each other.
  • the organic group is the same as the organic group as a substituent when R 1 and R 2 are aromatic groups which may have a substituent. Is.
  • the organic group is preferably an alkyl group, an aromatic hydrocarbon group, and an aromatic heterocyclic group.
  • the alkyl group a linear or branched alkyl group having 1 to 8 carbon atoms is preferable, and a methyl group, an ethyl group, an n-propyl group, and an isopropyl group are more preferable.
  • aromatic hydrocarbon group a phenyl group, a naphthyl group, a biphenylyl group, an anthryl group, and a phenanthrenyl group are preferable, a phenyl group and a naphthyl group are more preferable, and a phenyl group is particularly preferable.
  • a pyridyl group, a fryl group, a thienyl group, an imidazolyl group, a pyrazolyl group, an oxazolyl group, a thiazolyl group, an isooxazolyl group, an isothiazolyl group, a benzoxazolyl group, a benzothiazolyl group and a benzoimidazolyl group are preferable.
  • a frill group and a thienyl group are more preferable.
  • R 3 is an aromatic group which may have a substituent.
  • an aromatic hydrocarbon group which may have a substituent is preferable.
  • the aromatic group which may have a substituent as R 3 is the same as the aromatic group which may have a substituent as R 1 and R 2 .
  • R 4 is a single bond, or a methylene group.
  • the compound represented by the formula (1) is preferably a carboxylic acid compound represented by the following formula (1-1) in that the desired effect by coating can be easily obtained.
  • R 3 is an aromatic group which may have a substituent
  • R 5 is a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, It is a nitroso group, a sulfonat group, a phosphino group, a phosphinyl group, a phosphonato group, or an organic group, and n is an integer of 0 or more and 3 or less.
  • R 3 in the above formula (1-1) is as described above for the formula (1). Further, when R 5 in the formula (1-1) is an organic group, the organic group is used as a substituent when R 1 and R 2 are aromatic groups which may have a substituent. Similar to an organic group. When n is 2 or 3, the plurality of R 5s may be the same or different.
  • the compound represented by the following formula (1-2) is preferable because it can be easily synthesized at low cost.
  • R 5 and n are the same as those in the formula (1-1), and R 6 , R 7 , R 8 , R 9 and R 10 are independently hydrogen atoms, respectively.
  • At least two of R 10 may be combined to form a cyclic structure.
  • R 1 may be combined with R 8 to form a cyclic structure.
  • R 6 , R 7 , R 8 , R 9 , and R 10 are organic groups, the organic groups have R 1 and R 2 in formula (1) as substituents. Similar to organic groups.
  • R 6 , R 7 , R 8 and R 9 are preferably hydrogen atoms from the viewpoint of solubility of the carboxylic acid compound in the solvent.
  • R 6 , R 7 , R 8 , R 9 , and R 10 are preferably the following substituent, and R 10 is particularly preferably the following substituent.
  • R 10 is the following substituent
  • R 6 , R 7 , R 8 and R 9 are preferably hydrogen atoms.
  • -OR 11 R 11 is a hydrogen atom or an organic group.
  • R 11 is an organic group
  • the organic group is the same as the organic group that R 1 and R 2 in the formula (1) have as substituents.
  • an alkyl group is preferable, an alkyl group having 1 or more and 8 or less carbon atoms is more preferable, an alkyl group having 1 or more and 3 or less carbon atoms is particularly preferable, and a methyl group is most preferable.
  • suitable examples of the carboxylic acid compound R 4 is a methylene group in the formula (1) include the following compounds.
  • the substituents in benzoic acid which may have a substituent and naphthoic acid which may have a substituent include alkyl such as methyl group, ethyl group, n-propyl group, isopropyl group and n-butyl group.
  • alkoxy group such as methoxy group, ethoxy group, n-propyloxy group, isopropyloxy group and n-butyloxy group
  • aryl group such as phenyl group, naphthalene-1-yl group and naphthalene-2-yl group
  • Aryloxy groups such as phenoxy group, naphthalene-1-yloxy group, and naphthalene-2-yloxy group
  • Acyloxy groups such as groups; halogen atoms such as fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms; amino groups; nitro groups; alkoxycarbonyl groups such as methoxycarbonyl groups and ethoxycarbonyl groups; 2-methoxyethoxycarbonyl groups, And an alkoxyalkoxycarbonyl group such as a 2-ethoxyethoxycarbonyl group; an acyloxyalkoxycarbonyl group such as a 2-acetoxyethoxycarbonyl group and a 2- (meth) acryloyloxyethoxycarbonyl group and the like.
  • an alkoxycarbonyl group such as a methoxycarbonyl group and an ethoxycarbonyl group
  • an alkoxyalkoxycarbonyl group such as a 2-methoxyethoxycarbonyl group and a 2-ethoxyethoxycarbonyl group
  • a 2-acetoxyethoxycarbonyl group
  • an acyloxyalkoxycarbonyl group such as a 2- (meth) acryloyloxyethoxycarbonyl group is preferred. Since these groups are hydrophilic when compared with the aromatic structure, they are preferable in that the balance between hydrophobicity and hydrophilicity of the modified metal oxide fine particles after treatment is improved.
  • 2- (meth) acryloyloxyethoxycarbonyl group, etc. in that the characteristics of the cured product are improved without causing problems such as aggregation and bleed-out during curing because copolymerization with other compounding components is possible.
  • the acyloxyalkoxycarbonyl group of is more preferred.
  • the benzoic acid which may have a substituent includes, for example, benzoic acid; o-methylbenzoic acid, m-methylbenzoic acid, p-methylbenzoic acid, o-ethylbenzoic acid, m-ethylbenzoic acid, and p.
  • -Alkyl-substituted benzoic acids such as ethyl benzoic acid; phenyl-substituted benzoic acids such as o-phenyl benzoic acid, m-phenyl benzoic acid, and p-phenyl benzoic acid; o-methoxy benzoic acid, m-methoxy benzoic acid, p- Alkoxy-substituted benzoic acids such as methoxybenzoic acid, o-ethoxybenzoic acid, m-ethoxybenzoic acid, and p-ethoxybenzoic acid; phenoxy such as o-phenoxybenzoic acid, m-phenoxybenzoic acid, and p-phenoxybenzoic acid.
  • Substituted benzoic acids acyloxy benzoic acids such as o-acetoxy benzoic acid, m-acetoxy benzoic acid, p-acetoxy benzoic acid, o-benzoyloxy benzoic acid, m-benzoyloxy benzoic acid, and p-benzoyloxy benzoic acid; o -Chlorobenzoic acid, p-chlorobenzoic acid, m-chlorobenzoic acid, o-bromobenzoic acid, m-bromobenzoic acid, p-bromobenzoic acid, o-fluorobenzoic acid, m-fluorobenzoic acid, and p- Halogenized benzoic acids such as fluorobenzoic acid; aminobenzoic acids such as o-aminobenzoic acid, m-aminobenzoic acid, and p-aminobenzoic acid; o-nitrobenzoic acid, m-nitrobenz
  • naphthoic acid examples include 1-naphthoic acid and naphthoic acid such as 2-naphthoic acid; 2-methyl-1-naphthoic acid, 3-methyl-1-naphthoic acid, 4-methyl- 1-naphthoic acid, 5-methyl-1-naphthoic acid, 6-methyl-1-naphthoic acid, 7-methyl-1-naphthoic acid, 8-methyl-1-naphthoic acid, 1-methyl-2-naphthoic acid, 3-Methyl-2-naphthoic acid, 4-methyl-2-naphthoic acid, 5-methyl-2-naphthoic acid, 6-methyl-2-naphthoic acid, 7-methyl-2-naphthoic acid, and 8-methyl- Alkyl naphtho acids such as 2-naphthoic acid; 2-methoxy-1-naph
  • 3-acetoxy-1-naphthoic acid 4-acetoxy-1-naphthoic acid, 5-acetoxy-1-naphthoic acid, 6-acetoxy-1-naphthoic acid, 7-acetoxy-1-naphthoic acid, 8-acetoxy- 1-naphthoic acid, 1-acetoxy-2-naphthoic acid, 3-acetoxy-2-naphthoic acid, 4-acetoxy-2-naphthoic acid, 5-acetoxy-2-naphthoic acid, 6-acetoxy-2-naphthoic acid, Acyloxynaphthoe such as 7-acetoxy-2-naphthoic acid and 8-acetoxy-2-naphthoic acid; 2,6-naphthalenedicarboxylic acid monomethyl ester, 2,7-naphthalenedicarboxylic acid monomethyl ester, 1,4-na
  • the benzenedicarboxylic acid monoester is preferable because it has a high effect of stabilizing the dispersion. Monoesters are more preferred.
  • the benzoic acid, which may have these substituents, and the naphthoic acid, which may have a substituent have a substituent containing a polymerizable unsaturated double bond and an ester bond (-CO-O-). It is more preferable to have the cured product of the modified metal oxide fine particle dispersion liquid containing the polymerizable base material component (C) in that the characteristics are good.
  • An aliphatic carboxylic acid compound can be used together with the aromatic group-containing carboxylic acid compound (A) as long as the object of the present invention is not impaired.
  • Specific examples of the aliphatic carboxylic acid compound include a linear carboxylic acid having 4 or more and 20 or less carbon atoms (a linear aliphatic carboxylic acid, preferably a linear saturated aliphatic carboxylic acid, etc.) and 4 carbon atoms.
  • Branched chain carboxylic acid (branched chain aliphatic carboxylic acid) of 20 or more, cyclic carboxylic acid of 4 or more and 20 or less carbon atoms (alicyclic carboxylic acid, preferably fat having no unsaturated double bond)
  • Carboxylic acids having a carboxylic acid group of (cyclic carboxylic acid, etc.) can be preferably adopted.
  • Specific examples of aliphatic carboxylic acids include linear carboxylic acids such as butyric acid, valeric acid, hexanoic acid, heptanic acid, octanoic acid, nonanoic acid, decanoic acid, dodecanoic acid, tetradecanoic acid, and stearic acid; pivalic acid.
  • Aromatic group-containing carboxylic to the total of the mass of the carboxylate derived from the aromatic group-containing carboxylic acid compound (A) and / or the aromatic group-containing carboxylic acid compound (A) and the mass of the aliphatic carboxylic acid compound.
  • the mass ratio of the carboxylate derived from the acid compound (A) and / or the aromatic group-containing carboxylic acid compound (A) is preferably 70% by mass or more, more preferably 80% by mass or more, and 90% by mass or more. More preferably, 100% by mass is particularly preferable.
  • the amount of the carboxylate derived from the aromatic group-containing carboxylic acid compound (A) and / or the aromatic group-containing carboxylic acid compound (A) used for the surface treatment of the metal oxide fine particles (B) is determined by the amount of the metal oxide fine particles.
  • B With respect to 100 parts by mass, 0.1 parts by mass or more and 300 parts by mass or less is preferable, 0.5 parts by mass or more and 200 parts by mass or less is more preferable, and 1 part by mass or more and 100 parts by mass or less is further preferable.
  • Metal oxide fine particles (B) As the metal oxide fine particles (B), various metal oxide fine particles conventionally used for various purposes can be used without particular limitation.
  • metal oxides such as ZrO 2 fine particles in the high refractive index material, are used as fillers in order to achieve a high refractive index.
  • the shape of the metal oxide fine particles (B) is not particularly limited.
  • the shape of the metal oxide fine particles (B) includes a spherical shape, a granular shape, an elliptical spherical shape, a cubic shape, a rectangular parallelepiped shape, a pyramid shape, a needle shape, a columnar shape, a rod shape, a tubular shape, a flaky shape, a plate shape, and a flaky shape. Examples thereof are spherical, granular, columnar and the like.
  • the type of metal oxide constituting the metal oxide fine particles (B) is not particularly limited as long as the object of the present invention is not impaired.
  • the metal oxide fine particles may be fine particles made of a single metal oxide, or may be fine particles made of two or more kinds of metal oxides. Further, in the production method according to the present invention, one kind of metal oxide fine particles (B) may be used alone, or two or more kinds of metal oxide fine particles (B) may be used in combination.
  • the metal contained in the metal oxide constituting the metal oxide fine particles (B) is selected from the group consisting of, for example, Ag, Cu, In, Sn, Ti, Hf, Al, Zr, Zn, Sn, Ru and Ce. At least one type is preferable. From the viewpoint of providing a metal oxide having a high refractive index, at least one selected from the group consisting of Ti, Al, Zr, Zn, Sn and Ce is preferable among the above metal elements, and Zr is particularly preferable. ..
  • metal oxide constituting the metal oxide fine particles (B) include aluminum oxide (Al 2 O 3 ), titanium oxide (TiO 2 ), hafnium oxide (HfO 2 ), zirconium oxide (ZrO 2 ), and the like.
  • the average particle size of the metal oxide fine particles (B) is not particularly limited as long as the object of the present invention is not impaired.
  • the average particle size of the metal oxide fine particles (B) is, for example, preferably 50 nm or less, more preferably 20 nm or less, further preferably 15 nm or less, and particularly preferably 12 nm or less.
  • the lower limit of the average particle size of the metal oxide fine particles (B) is, for example, 1 nm or more, and may be 2 nm or more.
  • the average particle size of the metal oxide fine particles (B) is a Z average size (Z-Average size) measured using a particle size distribution meter.
  • the particle size of the metal oxide fine particles (B) at a cumulative value of 99.99% in the cumulative particle size volume distribution measured by the dynamic light scattering method is preferably 50 nm or less in terms of high refractive index, for example. , 30 nm or less is more preferable, and 20 nm or less is further preferable. There is no particular lower limit, but it is, for example, 5 nm or more.
  • metal oxide fine particles (B) By coating the metal oxide fine particles (B) as described above, at least a part of the surface becomes an aromatic group-containing carboxylic acid compound (A) and / or an aromatic group-containing carboxylic acid compound (A). Modified metal oxide fine particles coated with the derived carboxylate are obtained.
  • the modified metal oxide fine particles may be coated with another coating agent together with the carboxylate derived from the aromatic group-containing carboxylic acid compound (A) and / or the aromatic group-containing carboxylic acid compound (A). good.
  • the total ratio of the mass of A) and the mass of the carboxylate derived from the aromatic group-containing carboxylic acid compound (A) is not particularly limited and can be appropriately adjusted to be 1% by mass or more and 100% by mass or less.
  • the modified metal obtained after the metal oxide fine particles (B) are coated with the above-mentioned aromatic group-containing carboxylic acid compound (A) and / or carboxylate derived from the aromatic group-containing carboxylic acid compound (A).
  • the surface of the oxide fine particles may be further coated with another coating material, or with a carboxylate derived from the aromatic group-containing carboxylic acid compound (A) and / or the aromatic group-containing carboxylic acid compound (A).
  • the surface of the metal oxide fine particles may be coated with another coating material before being coated.
  • silane compounds (i)-(iii) described below monovinyltrialkoxysilanes such as vinyltrimethoxysilane, vinyltriethoxysilane, and allyltrimethoxysilane; 3-methacryloxypropyl (Meta) acryloxyalkyl monoalkyldialkoxysilanes such as trimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane; 3-acryloxypropyl (Meta) acryloxyalkyltrialkoxysilanes such as trimethoxysilane; non-alicyclic silanes such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxys
  • the coating agent used in the case of further coating after coating with a carboxylate derived from the aromatic group-containing carboxylic acid compound (A) and / or the aromatic group-containing carboxylic acid compound (A) is the following formula (a).
  • the compound represented by ⁇ I) is preferable.
  • the compound represented by the following formula (a-I) is a modified metal oxidation coated with a carboxylate derived from the aromatic group-containing carboxylic acid compound (A) and / or the aromatic group-containing carboxylic acid compound (A). Goodly adheres to or binds to the surface of fine particles.
  • the modified metal oxide fine particles coated with at least a part of the outermost surface of the compound represented by the following formula (a-I) are particularly well stable in dispersion liquids having various compositions as a result of being coated. And disperse.
  • the carboxylate derived from the aromatic group-containing carboxylic acid compound (A) and / or the aromatic group-containing carboxylic acid compound (A) is bonded or adhered to the surface of the metal oxide fine particles (B).
  • the compound represented by the following formula (a-I) has a hydroxyl group or a glycidyl group as W 1 and W 2.
  • the metal oxide fine particles (B) are usually hydrophilic on the surface thereof due to a hydroxyl group and a carboxylate derived from an aromatic group-containing carboxylic acid compound (A) and / or an aromatic group-containing carboxylic acid compound (A).
  • the compound represented by the formula (a-I) has a polycyclic group containing an aromatic ring. Such polycyclic groups are hydrophobic and bulky. Therefore, it is considered that the compound represented by the formula (a-I) adheres to the surface of the modified metal oxide fine particles to form micelle-like coated metal oxide fine particles. As a result, it is considered that the modified metal oxide fine particles to which the compound represented by the formula (a-I) is attached to the surface are well dispersed in the dispersion liquid having various compositions.
  • W 1 and W 2 are independently represented by the following formula (a-II): It is a group represented by In formula (a-II), ring Z represents an aromatic hydrocarbon ring, X represents a single bond or a group represented by —S—, RA1 is a single bond, and the number of carbon atoms is 1 or more and 4 or less.
  • R A1 is an alkylene group, an oxygen atom in the alkylene group is bonded with the ring Z
  • R A2 is a monovalent hydrocarbon Hydrogen 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,- Group represented by NHR 4c , group represented by -N (R 4d ) 2 , sulfo group, or monovalent hydrocarbon group, group represented by -OR 4a , group represented by -SR 4b , acyl group, alkoxycarbonyl At least a part of the hydrogen atom bonded to the carbon atom contained in the group, the group represented by -NHR 4c , or the group represented by -N (R 4d
  • Group represented by -SR 4b acyl group, alkoxycarbonyl group, halogen atom, nitro group, cyano group, mercapto group, carboxy group, amino group, carbamoyl group, group represented by -NHR 4c , -N ( groups represented by R 4d) 2, shows a mesyloxy group, or sulfo-substituted group by group
  • R 4a ⁇ R 4d represents a monovalent hydrocarbon radical independently
  • m represents an integer of 0 or more
  • R A3 Is a hydrogen atom or a glycidyl group
  • 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
  • the ring Z is, for example, a benzene ring, a condensed polycyclic aromatic hydrocarbon ring [for example, a fused bicyclic hydrocarbon ring (for example, a C8-20 condensation of a naphthalene ring or the like).
  • Bicyclic hydrocarbon rings preferably C 10-16 fused bicyclic hydrocarbon rings
  • fused tricyclic aromatic hydrocarbon rings eg, anthracene rings, phenanthrene rings, etc.
  • Group hydrocarbon ring and the like.
  • 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 (a-I) are independently represented by the above formula (a-II), 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.
  • 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 benzene is also a naphthalene ring in terms of making the coating agent hydrophobic or high bending.
  • substitution position of the ring Z bonded to the carbon atom to which both W 1 and W 2 are directly connected via X 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 independently represents a single bond or a group represented by -S-, and is typically a single bond.
  • RA1 has, for example, a single bond; a methylene group, an ethylene group, a trimethylene group, a propylene group, a butane-1,2-diyl group, or the like having 1 or more and 4 or less carbon atoms.
  • RA1 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 (a-I) are independently represented by the above formula (a-II), W 1 and W 2 are divalent groups, respectively. Includes some RA1.
  • the R A1 contained in R A1 and W 2 included in W 1, may be the same or may be different.
  • RA2 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 C 1-8. Alkoxy groups, more preferably C 1-6 alkyl groups, etc.), cycloalkyl groups (C 5-10 cycloalkyl groups such as cyclohexyl groups, preferably C 5-8 cycloalkyl groups, more preferably C 5-6 cycloalkyl groups.
  • alkyl group for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, etc., preferably C 1-8.
  • Alkoxy groups more preferably C 1-6 alkyl groups, etc.
  • cycloalkyl groups C 5-10 cycloalkyl groups such as cyclohexyl groups, preferably C
  • aryl groups eg, C 6-14 aryl groups such as phenyl group, tolyl group, xylyl group, naphthyl group, preferably C 6-10 aryl group, more preferably C 6-8 aryl group, etc.
  • Monovalent hydrocarbon groups such as aralkyl groups (C 6-10 aryl-C 1-4 alkyl groups such as benzyl group and phenethyl group); hydroxyl groups; alkoxy groups (methoxy group, ethoxy group, propoxy group, butoxy group, etc.) C 1-12 alkoxy group, preferably C 1-8 alkoxy group, more preferably C 1-6 alkoxy group, etc.), cycloalkoxy group (C 5-10 cycloalkoxy group such as cyclohexyloxy group), aryloxy group (C 6-10 aryloxy group such as phenoxy group ), group represented by -OR 4a such as aralkyloxy group (for example, C 6-14 aryl
  • 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 such as cyclohexylamino group
  • 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 [formula].
  • R 4c represents a monovalent hydrocarbon group (such as the above-exemplified monovalent hydrocarbon group). ]; Dialkylamino groups (dimethylamino group, diethylamino group, dipropylamino group, dibutylamino group and other di (C 1-12 alkyl) amino groups, preferably di (C 1-8 alkyl) amino groups, more preferably.
  • R4d independently represents a monovalent hydrocarbon group (such as the above-exemplified monovalent hydrocarbon 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
  • RA2 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 RA2s 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 RA2s may be different from each other or may be the same. Further, the R A2 contained in R A2 and W 2 included in W 1, may be the same or may be different.
  • the number m of RA2 can be selected according to the type of ring Z, and is, 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. May be good. Note that m in W 1 and m in W 2 may be the same or different.
  • RA3 is a hydrogen atom or a glycidyl group.
  • the R A3 contained in R A3 and W 2 included in W 1, may be the same or may be different.
  • ring Y 1 and ring Y 2 for example, benzene ring, condensed polycyclic aromatic hydrocarbon ring [e.g., fused bicyclic hydrocarbon ring (e.g., naphthalene ring Condensation of C 8-20 fused bicyclic hydrocarbon rings, preferably C 10-16 condensed bicyclic hydrocarbon rings), condensed tricyclic aromatic hydrocarbon rings (eg, anthracene rings, phenanthrene rings, etc.) 2 To 4-cyclic aromatic hydrocarbon ring] and the like.
  • condensed polycyclic aromatic hydrocarbon ring e.g., fused bicyclic hydrocarbon ring (e.g., naphthalene ring Condensation of C 8-20 fused bicyclic hydrocarbon rings, preferably C 10-16 condensed bicyclic hydrocarbon rings), condensed tricyclic aromatic hydrocarbon rings (eg, anthracene rings, phenanthrene rings, etc.) 2 To 4-cyclic aromatic hydrocarbon ring
  • Ring Y 1 and ring Y 2 is preferably a benzene ring or a naphthalene ring, more preferably a benzene ring.
  • Ring Y 1 and 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. It represents a group represented by -O-, 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
  • a cyano group a halogen atom (fluorine atom, chlorine atom, bromine atom, etc.)
  • a monovalent hydrocarbon group a cyano group, a halogen atom (fluorine atom, chlorine atom, bromine atom, etc.) and a monovalent hydrocarbon group
  • 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 (a-I) retains excellent optical and thermal properties.
  • rings Y 1 and Y 2 are benzene rings and R is a single bond
  • the compound represented by the above formula (a-I) has a fluorene skeleton and has optical and thermal properties. Even better.
  • the coating of the modified metal oxide fine particles is typically carried out by bringing a coating agent such as a compound represented by the formula (aI) into contact with the modified metal oxide fine particles in the presence of an organic solvent. It is said.
  • a coating agent such as a compound represented by the formula (aI)
  • the organic solvent used at the time of coating is not particularly limited as long as the modified metal oxide fine particles can be dispersed and the coating agent is soluble.
  • the organic solvent preferably does not have a hydroxyl group and a carboxy group from the viewpoint that coating with a coating agent can be easily performed.
  • organic solvent examples include (poly) alkylenes such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate.
  • Glycol monoalkyl ether acetates such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone; methyl 3-methoxypropionate, Ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate, N-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl formate, isopentyl acetate, n-butyl prop
  • the amount of the organic solvent used for the coating treatment with the coating agent such as the compound represented by the formula (a-I) is not particularly limited, and is typically based on 100 parts by mass of the modified metal oxide fine particles. , 0.1 part by mass or more and 5000 parts by mass or less is preferable, 50 parts by mass or more and 1000 parts by mass or less is more preferable, and 100 parts by mass or more and 500 parts by mass or less is further preferable.
  • the temperature at which the coating agent such as the compound represented by the formula (a-I) is brought into contact with the modified metal oxide fine particles does not cause deterioration or decomposition of the modified metal oxide fine particles or the coating agent due to heating.
  • the temperature is not particularly limited.
  • the temperature at which the coating agent and the modified metal oxide fine particles are brought into contact is, for example, ⁇ 20 ° C. or higher and 150 ° C. or lower, preferably ⁇ 10 ° C. or higher and 100 ° C. or lower, and more preferably 20 ° C. or higher and 100 ° C. or lower.
  • the pressure at which the coating agent such as the compound represented by the formula (a-I) is brought into contact with the modified metal oxide fine particles is not particularly limited and may be under atmospheric pressure, reduced pressure, or high pressure. From the viewpoint of convenience, it is preferable to use atmospheric pressure or reduced pressure.
  • the time for contacting the dressing such as the compound represented by the formula (a-I) with the modified metal oxide fine particles is not particularly limited.
  • the time for contacting the coating agent and the modified metal oxide fine particles is, for example, 5 minutes or more and 24 hours or less, preferably 10 minutes or more and 12 hours or less, and more preferably 30 minutes or more and 6 hours or less.
  • the pH at the time of contacting the metal oxide fine particles (B) with the coating agent such as the compound represented by the formula (a-I) is preferably 3 or more and 6 or less, for example.
  • the pH may be confirmed with pH test paper or the like.
  • the amount of the compound represented by the formula (a-I) used is, for example, 0.1 part by mass or more and 500 parts by mass or less with respect to 100 parts by mass of the metal oxide fine particles (B). , 0.5 parts by mass or more and 300 parts by mass or less is preferable, 1 part by mass or more and 100 parts by mass or less is more preferable, and 2 parts by mass or more and 20 parts by mass or less is further preferable. Further, the total mass of the carboxylate derived from the aromatic group-containing carboxylic acid compound (A) and / or the aromatic group-containing carboxylic acid compound (A) and the mass of the metal oxide fine particles (B) is 100 parts by mass.
  • the amount of the compound represented by the formula (a-I) used is, for example, 1 part by mass or more and 500 parts by mass or less, preferably 2 parts by mass or more and 300 parts by mass or less, and 5 parts by mass or more and 100 parts by mass or less. Is more preferable. Further, the amount of the compound represented by the formula (a-I) to be used with respect to 1 part by mass of the aromatic group-containing carboxylic acid compound (A) and / or the carboxylate derived from the aromatic group-containing carboxylic acid compound (A).
  • the amount of the compound represented by the formula (a-I) used is the aromatic group-containing carboxylic acid compound (A) and / or. It is preferable that the amount of the carboxylate derived from the aromatic group-containing carboxylic acid compound (A) is greater than or equal to the amount used.
  • the modified metal oxide fine particles obtained by the above method are used for various purposes in a state of being dispersed in a dispersion medium, in a dry state, or in a state of being separated from the dispersion medium by a method such as centrifuge.
  • the modified metal oxide fine particle dispersion liquid contains the above-mentioned modified metal oxide fine particles.
  • the modified metal oxide fine particle dispersion may contain metal oxide fine particles other than the modified metal oxide fine particles.
  • the amount of the above-mentioned modified metal oxide fine particles in the total mass of the modified metal oxide fine particles in the modified metal oxide fine particle dispersion is not particularly limited as long as the object of the present invention is not impaired.
  • the content of the modified metal oxide fine particles is preferably 50% by mass or more, more preferably 70% by mass or more, further preferably 90% by mass or more, and particularly preferably 100% by mass, based on the total mass of the metal oxide fine particles. preferable.
  • the modified metal oxide fine particle dispersion liquid may be a dispersion liquid in which the modified metal oxide fine particles are dispersed in a molten resin or the like, or may be a dispersion liquid in which the modified metal oxide fine particles are dispersed in a solvent. Often, it may be a dispersion liquid in which modified metal oxide fine particles are dispersed in a liquid in which various additive components are dissolved in a solvent. Since the modified metal oxide fine particle dispersion contains the above-mentioned modified metal oxide fine particles as the metal oxide fine particles, the modified metal oxide fine particle dispersion is excellent in dispersion stability. Therefore, the modified metal oxide fine particle dispersion is preferably used in various applications.
  • modified metal oxide fine particle dispersion is not particularly limited.
  • examples of applications of the modified metal oxide fine particle dispersion liquid include a polishing liquid, a sealing composition, a composition for forming a high refractive index film, and the like.
  • the metal oxide fine particle dispersion contains the base material component (C).
  • the amount of the metal oxide fine particles in the modified metal oxide fine particle dispersion liquid is determined by the modified metal oxide fine particle dispersion. It is determined as appropriate in consideration of the use of the liquid.
  • the amount of the metal oxide fine particles is based on 100 parts by mass of the base material component (C) in the modified metal oxide fine particle dispersion liquid. It is preferably 0.1 part by mass or more and 200 parts by mass or less, more preferably 1 part by mass or more and 150 parts by mass or less, and particularly preferably 3 parts by mass or more and 100 parts by mass or less.
  • the upper limit of the amount of the metal oxide fine particles may be 80 parts by mass or less, 50 parts by mass or less, or 30 parts by mass or less with respect to 100 parts by mass of the base material component (C). ..
  • the lower limit of the amount of the metal oxide fine particles may be 5 parts by mass or more, 10 parts by mass or more, or 20 parts by mass or more with respect to 100 parts by mass of the base material component (C). ..
  • the base material component (C) is a formable material capable of producing an article having a desired shape in a modified metal oxide fine particle dispersion as it is by a well-known method such as a melting process, or is exposed, heated, or water. It is a component that imparts shapeability so that an article having a desired shape can be produced by a treatment such as a reaction.
  • the base material component (C) is not particularly limited as long as it is a material capable of imparting desired shapeability to the modified metal oxide fine particle dispersion liquid.
  • the base material component (C) is typically a resin material composed of a polymer compound, which is cured by cross-linking to form a polymer compound by heating or chemical modification such as intramolecular cyclization by heating.
  • Heat-curable materials, photopolymerizable compounds that can be cured by exposure, hydrolysis-condensable silane compounds that are hydrolyzed by moisture in the composition or atmosphere, and the like are used.
  • Hydrolyzable condensable silane compounds include tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, methyltriethoxylan, ethyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, and dimethyldimethoxy. Examples thereof include alkoxysilane compounds such as silane, diethyldimethoxysilane, dimethyldiethoxysilane, diethyldiethoxysilane, diphenyldimethoxysilane, and diphenyldiethoxysilane.
  • the hydrolyzable condensable silane compound may be a partially hydrolyzed condensate of these silane compounds.
  • the modified metal oxide fine particle dispersion liquid has the following formula (b-01) as the base material component (C) in that it easily forms an article having a high refractive index, particularly a high refractive index film.
  • W 01 and W 02 are independently described in the following formula (b-02): It is a group represented by In formula (b-02), ring Z 01 represents an aromatic hydrocarbon ring, X 01 represents a single bond or a group represented by —S—, R 01 is a single bond, and the number of carbon atoms is 1 or more and 4 or less.
  • R 01 When an alkylene group or an alkyleneoxy group having 1 or more and 4 or less carbon atoms and R 01 is an alkyleneoxy group, the oxygen atom in the alkyleneoxy group is bonded to the ring Z 01, and R 01 is monovalent.
  • the group shown the group represented by -SR 4B , the acyl group, the alkoxycarbonyl group, the halogen atom, the nitro group, the cyano group, the mercapto group, the carboxy group, the amino group, the carbamoyl group, the group represented by -NHR 4C , -N.
  • R 4D Indicates a group represented by 2 , a mesyloxy group, or a group substituted with a sulfo group
  • R 4A to R 4D independently indicate a monovalent hydrocarbon group
  • M indicates an integer of 0 or more
  • R 03 is a hydrogen atom, a vinyl group, a thiran-2-ylmethyl group, a glycidyl group, or a (meth) acryloyl group.
  • Both W 01 and W 02 do not have a hydrogen atom as R 03, Ring Y 01 and ring Y 02 show the same or different aromatic hydrocarbon rings, and R 00 is a single bond, may have a methylene group having a substituent, may have a substituent, and may have two carbons.
  • An ethylene group which may contain a hetero atom between atoms, a group represented by -O-, a group represented by -NH-, or a group represented by -S-, and R 3A and R 3B are independently cyano groups. It represents a halogen atom or a monovalent hydrocarbon group, and N1 and N2 independently represent integers from 0 to 4. ) It is also preferable to include a compound represented by.
  • the compound represented by the above formula (b-01) can be thermoset or photocured by being used in combination with a curing agent, if necessary.
  • the ring Z 01 is, for example, a benzene ring, a condensed polycyclic aromatic hydrocarbon ring [for example, a fused bicyclic hydrocarbon ring (for example, a naphthalene ring or the like, C 8-20). Fused 2-4 ring type such as fused bicyclic hydrocarbon ring, preferably C 10-16 fused bicyclic hydrocarbon ring), fused tricyclic aromatic hydrocarbon ring (eg, anthracene ring, phenanthrene ring, etc.) Aromatic hydrocarbon ring] and the like.
  • a condensed polycyclic aromatic hydrocarbon ring for example, a fused bicyclic hydrocarbon ring (for example, a naphthalene ring or the like, C 8-20).
  • Fused 2-4 ring type such as fused bicyclic hydrocarbon ring, preferably C 10-16 fused bicyclic hydrocarbon ring), fused tricyclic aromatic hydrocarbon ring (eg, anthracene
  • Ring Z 01 is preferably a benzene ring or a naphthalene ring, and more preferably a naphthalene ring. Since W 01 and W 02 in the formula (b-01) are independently represented by the above formula (b-02), W 01 and W 02 each include a ring Z 01. .. The ring Z 01 contained in the ring Z 01 and W 02 included in the W 01, may be the same or different, for example, one ring is a benzene ring, although other ring may be a naphthalene ring, , It is particularly preferable that each ring is a naphthalene ring.
  • substitution position of the ring Z 01 bonded to the carbon atom to which both W 01 and W 02 are directly connected via X 01 is not particularly limited.
  • the group corresponding to ring Z 01 bonded to the carbon atom may be a 1-naphthyl group, a 2-naphthyl group, or the like.
  • X 01 independently represents a single bond or a group represented by -S-, and is typically a single bond.
  • R 01 for example, a single bond; a methylene group, an ethylene group, a trimethylene group, a propylene group, a butane-1,2-diyl group, or the like has a carbon atom number of 1 or more and 4 or less.
  • R 01 is an alkyleneoxy group
  • the oxygen atom in the alkyleneoxy group is bonded to the ring Z 01.
  • W 01 and W 02 in the formula (b-01) are independently represented by the above formula (b-02)
  • W 01 and W 02 are divalent groups, respectively. Includes some R 01.
  • the R 01 that is included in the R 01 and W 02 to be included in the W 01 may be the same or may be different.
  • R 02 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 C 1-8. Alkoxy groups, more preferably C 1-6 alkyl groups, etc.), cycloalkyl groups (C 5-10 cycloalkyl groups such as cyclohexyl groups, preferably C 5-8 cycloalkyl groups, more preferably C 5-6 cycloalkyl groups.
  • an alkyl group for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, etc., preferably C 1-8.
  • Alkoxy groups more preferably C 1-6 alkyl groups, etc.
  • cycloalkyl groups C 5-10 cycloalkyl groups such as cyclohexyl groups, preferably C
  • aryl groups eg, C 6-14 aryl groups such as phenyl group, tolyl group, xylyl group, naphthyl group, preferably C 6-10 aryl group, more preferably C 6-8 aryl group, etc.
  • Monovalent hydrocarbon groups such as aralkyl groups (C 6-10 aryl-C 1-4 alkyl groups such as benzyl group and phenethyl group); hydroxyl groups; alkoxy groups (methoxy group, ethoxy group, propoxy group, butoxy group, etc.) C 1-12 alkoxy group, preferably C 1-8 alkoxy group, more preferably C 1-6 alkoxy group, etc.), cycloalkoxy group (C 5-10 cycloalkoxy group such as cyclohexyloxy group), aryloxy group (C 6-10 aryloxy group such as phenoxy group ), group represented by -OR 4A such as aralkyloxy group (for example, C 6-14 aryl
  • 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)
  • a group represented by -SR 4B such as (alkylthio group) [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.
  • R 4C represents a monovalent hydrocarbon group (such as the above-exemplified monovalent hydrocarbon group).
  • Dialkylamino groups dimethylamino group, diethylamino group, dipropylamino group, dibutylamino group and other di (C 1-12 alkyl) amino groups, preferably di (C 1-8 alkyl) amino groups, more preferably.
  • R 4D independently represents a monovalent hydrocarbon group (such as the above-exemplified monovalent hydrocarbon group).
  • 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
  • R 02 is 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.
  • the group represented by -NHR 4C , the group represented by -N (R 4D ) 2 , and the like may be used.
  • R 02s 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 02 is a monovalent hydrocarbon group (particularly, C 1-4 alkyl group (particularly methyl group), etc.], aryl group [for example, C 6-10 aryl group (particularly phenyl group), etc.] and the like.
  • Alkyl group is preferable.
  • the plurality of R 02s may be different from each other or may be the same.
  • the R 02 contained in R 02 and W 2 included in W 01 it may be the same or may be different.
  • the number M of R 02 can be selected according to the type of ring Z 01 , and is, 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. You may.
  • the M in W 01 and the M in W 02 may be the same or different.
  • R 03 is a hydrogen atom, a vinyl group, a thiran-2-ylmethyl group, a glycidyl group, or a (meth) acryloyl group. Both W 01 and W 02 do not have a hydrogen atom as R 03.
  • 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 (b-01) and having a vinyl group, a thiran-2-ylmethyl group, or a glycidyl group as R 03 is a cationically polymerizable compound.
  • the compound represented by the formula (b-01) and having a (meth) acryloyl group as R 03 is a radically polymerizable compound.
  • the R 03 contained in R 03 and W 02 included in the W 01 may be the same or may be different.
  • the R 03 contained in R 03 and W 02 included in the W 01, both a vinyl group is preferably from thiirane-2-ylmethyl group, or a glycidyl group, both a vinyl group, thiirane-2 More preferably, it is the same group selected from the group consisting of an ylmethyl group and a glycidyl group. Further, it is also preferable that both R 03 contained in W 01 and R 03 contained in W 02 are (meth) acryloyl groups.
  • a vinyl group, a glycidyl group, or a (meth) acryloyl group is preferable because the compound represented by the formula (b-01) can be easily synthesized and obtained. Since a curable modified metal oxide fine particle dispersion can be prepared while reducing the types of components, the compound represented by the formula (b-01) includes a vinyl group, a thiran-2-ylmethyl group, and a group. It is preferable to have only a group selected from glycidyl groups as a reactive group or only a (meth) acryloyl group as a reactive group.
  • the ring Y 01 and the ring Y 02 include, for example, a benzene ring, a condensed polycyclic aromatic hydrocarbon ring [for example, a condensed bicyclic hydrocarbon ring (for example, a naphthalene ring, etc.). Condensation of C 8-20 fused bicyclic hydrocarbon rings, preferably C 10-16 condensed bicyclic hydrocarbon rings), condensed tricyclic aromatic hydrocarbon rings (eg, anthracene rings, phenanthrene rings, etc.) 2 To 4-cyclic aromatic hydrocarbon ring] and the like.
  • a condensed polycyclic aromatic hydrocarbon ring for example, a condensed bicyclic hydrocarbon ring (for example, a naphthalene ring, etc.). Condensation of C 8-20 fused bicyclic hydrocarbon rings, preferably C 10-16 condensed bicyclic hydrocarbon rings), condensed tricyclic aromatic hydrocarbon rings (eg, anthracene rings,
  • Ring Y 01 and ring Y 02 are preferably benzene rings or naphthalene rings, and more preferably benzene rings.
  • the ring Y 01 and the ring Y 02 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 00 is a single bond, a methylene group which may have a substituent, or an ethylene group which may contain a hetero atom between two carbon atoms. , -O-, -NH-, or -S-, 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., A butyl group, a C 1-6 alkyl group such as a tert-butyl group), an aryl group (C 6-10 aryl group such as a phenyl group), etc.] and the like can be mentioned.
  • 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
  • a cyano group a halogen atom (fluorine atom, chlorine atom, bromine atom, etc.) and a monovalent hydrocarbon group
  • a cyano group or an alkyl group is preferable, and an alkyl group is particularly preferable.
  • alkyl group examples include a C 1-6 alkyl group (for example, a C 1-4 alkyl group, particularly a methyl group) such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group and a tert-butyl group. ..
  • N1 is an integer of 2 or more
  • R 3A may be different from each other or may be the same.
  • N2 is an integer of 2 or more
  • R 3B may be different from each other or may be the same.
  • R 3A and R 3B may be the same or different.
  • the bonding position (replacement position) of R 3A and R 3B with respect to the ring Y 01 and the ring Y 02 is not particularly limited.
  • the preferred substitution numbers N1 and N2 are 0 or 1, especially 0. N1 and N2 may be the same or different from each other.
  • the compound represented by the above formula (b-01) 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 (b-01) has a fluorene skeleton, and has optical properties and thermal properties. Even better in characteristics.
  • the compound represented by the above formula (b-01) gives a cured product having high hardness and is preferable as the base material component (C) in the modified metal oxide fine particle dispersion liquid.
  • the resin material include polyacetal resin, polyamide resin, polycarbonate resin, polyester resin (polybutylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, polyarylate, etc.), FR-AS resin, FR.
  • ABS resin polyphenylene oxide resin, polyphenylene sulfide resin, polysulfone resin, polyethersulfone resin, polyether ether ketone resin, fluororesin, polyimide resin, polyamideimide resin, polyamidebismaleimide resin, polyether Imid resin, polybenzoxazole resin, polybenzothiazole resin, polybenzoimidazole resin, silicone resin, BT resin, polymethylpentene, ultrahigh molecular weight polyethylene, FR-polypropylene, (meth) acrylic resin (for example, polymethylmethacrylate, etc.) , And polystyrene and the like.
  • a modified metal oxide fine particle dispersion liquid in which a predetermined amount of the metal oxide fine particles containing the above-mentioned modified metal oxide fine particles is blended with the resin material has been conventionally used.
  • a membrane is preferable as the form of the article produced by using the modified metal oxide fine particle dispersion liquid.
  • the modified metal oxide fine particle dispersion liquid may be a melt or a solution.
  • Examples of the film forming method include a melt processing method such as a T-die method (casting method), an inflation method, and a pressing method, a casting method using a solution, an inkjet method, a spin coating method, and the like.
  • a melt processing method such as a T-die method (casting method), an inflation method, and a pressing method
  • a casting method using a solution such as an inkjet method, a spin coating method, and the like.
  • a liquid containing a resin material and metal oxide fine particles is applied or spilled onto a substrate to form a film, and then, if necessary, a method such as heating from the film is used.
  • a metal oxide fine particle-containing film is formed.
  • the metal oxide fine particle-containing film obtained by using the modified metal oxide fine particle dispersion may be subjected to a stretching treatment such as uniaxial stretching or biaxial stretching, if necessary.
  • the modified metal oxide fine particle dispersion liquid is, if necessary, an antioxidant, an ultraviolet absorber, a flame retardant, a mold release agent, a plasticizer, and metal oxidation. It may contain a filler other than fine particles and an additive such as a reinforcing material.
  • the modified metal oxide fine particle dispersion is a composition for casting, the modified metal oxide fine particle dispersion may contain a solvent. The type of solvent is appropriately selected according to the type of resin material.
  • thermosetting material examples include precursor materials of various thermosetting resins that have been widely used in the past.
  • specific examples of the thermosetting resin include phenol resin, epoxy resin, oxetane resin, melamine resin, urea resin, unsaturated polyester resin, alkyd resin, polyurethane resin, polyimide resin, polybenzoxasol resin, polybenzimidazole resin and the like. Can be mentioned.
  • a resin that causes an intramolecular aromatic ring formation reaction and / or an intramolecular cross-linking reaction by heating is also preferably used as a thermosetting material.
  • a resin that causes an intramolecular aromatic ring formation reaction and / or an intramolecular cross-linking reaction by heating is also referred to as a precursor resin.
  • thermosetting material a precursor material particularly suitable as the base material component (C).
  • epoxy resin precursor As the epoxy resin precursor, various conventionally known epoxy compounds can be used.
  • the modified metal oxide fine particle dispersion can be used as a thermosetting composition by using a curing agent or a curing accelerator in combination with an epoxy resin precursor, if necessary. Can be.
  • a photosensitive curing agent and an epoxy resin precursor in combination in the modified metal oxide fine particle dispersion a photosensitive composition capable of photocuring the modified metal oxide fine particle dispersion can be obtained. You can also do it.
  • the molecular weight of the epoxy compound as the epoxy resin precursor is not particularly limited.
  • epoxy compounds a polyfunctional epoxy compound having two or more epoxy groups in the molecule is preferable because it is easy to form a metal oxide fine particle-containing film having excellent heat resistance, chemical resistance, mechanical properties and the like.
  • the epoxy resin precursor can be used alone or in combination of two or more.
  • the polyfunctional epoxy compound is not particularly limited as long as it is a bifunctional or higher functional epoxy compound.
  • Examples of polyfunctional epoxy compounds include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD type epoxy resin, naphthalene type epoxy resin, tetrabrom bisphenol A type epoxy resin, and biphenyl type epoxy.
  • Bifunctional epoxy resin such as resin; glycidyl ester type epoxy resin such as dimer acid glycidyl ester and triglycidyl ester; tetraglycidyl aminodiphenylmethane, triglycidyl-p-aminophenol, tetraglycidyl metaxylylene diamine, and tetraglycidyl bisamino.
  • Glycidylamine type epoxy resin such as methylcyclohexane; Hydantin type epoxy resin such as 1,3-diglycidyl-5-methyl-5-ethylhydantin; Hydroquinone type epoxy resin; Fluorene type epoxy resin; Epoxy resin; fluoroglycinol triglycidyl ether, trihydroxybiphenyl triglycidyl ether, trihydroxyphenylmethane triglycidyl ether, glycerin triglycidyl ether, 2- [4- (2,3-epoxypropoxy) phenyl] -2- [4 -[1,1-Bis [4- (2,3-epoxypropoxy) phenyl] ethyl] phenyl] propane and 1,3-bis [4- [1- [4- (2,3-epoxypropoxy) phenyl] ] -1- [4- [1- [4- (2,3-Epoxypropoxy)
  • Examples of commercially available polyfunctional epoxy compounds include JER Coat 828, 1001, 801N, 806, 807, 152, 604, 630, 871, YX8000, YX8034, YX4000 manufactured by Japan Epoxy Resin, and Epicron 830 manufactured by DIC. , EXA835LV, HP4032D, HP820, EP4100 series, EP4000 series, EPU series manufactured by ADEKA Co., Ltd., Serokiside series manufactured by Daicel (2021, 2021P, 2083, 2085, 3000, etc.), Epoxy series, EHPE series, new Nittetsu Chemical Co., Ltd.
  • An alicyclic epoxy compound is also preferable as a polyfunctional epoxy compound in that it gives a cured product having high hardness.
  • Specific examples of the alicyclic epoxy compound 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 (a01-1) to (a01-5) are preferable because they give a cured product having a high hardness.
  • Z 01 represents a single bond or a linking group (a divalent group having one or more atoms).
  • R a01 to R a018 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 ). 2 -, - C (CF 3 ) 2 -, and -R a019 -O-CO- 2 divalent group and which are selected from the group consisting of these can be exemplified a plurality bonded group.
  • Examples of the divalent hydrocarbon group as the linking group Z include a linear or branched alkylene group having 1 to 18 carbon atoms and a divalent alicyclic hydrocarbon group. can.
  • 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 a019 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 a01 to R a018 are groups selected from the group consisting of a hydrogen atom, a halogen atom, and an organic group.
  • R a02 and R a010 may be bonded to each other.
  • R A013 and R A016 good .m a1 be bonded to each other to form a ring is 0 or 1.
  • Compounds are preferred.
  • R a01 to R a012 are groups selected from the group consisting of a hydrogen atom, a halogen atom, and an organic group.
  • R a02 and R a010 are bonded to each other to form a ring. May be formed.
  • R a01 to R a010 are groups selected from the group consisting of a hydrogen atom, a halogen atom, and an organic group.
  • R a02 and R a08 may be bonded to each other.
  • R a01 to R a012 are groups selected from the group consisting of a hydrogen atom, a halogen atom, and an organic group.
  • R a02 and R a010 may be bonded to each other.
  • R a01 to R a012 are groups selected from the group consisting of a hydrogen atom, a halogen atom, and an organic group.
  • R a01 to R a018 are organic groups
  • the organic group is not particularly limited as long as the object of the present invention is not impaired, and even if it is a hydrocarbon group.
  • halogen atoms include chlorine atom, bromine atom, iodine atom, fluorine atom and the like.
  • the organic group includes 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, and a carbon atom and a hydrogen atom.
  • An oxygen atom, and a group consisting of a halogen atom are preferable.
  • 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 groups 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 Halogen chain alkyl group 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 halides such as 4-bromocyclohexyl group; 2-chlorophenyl group, 3-chlorophenyl group, 4-chlorophenyl group, 2,3-dichlorophenyl group,
  • Aryl halide groups such as groups and 4-fluorophenyl groups; 2-chlorophenylmethyl group, 3-chlorophenylmethyl group, 4-chlorophenylmethyl group, 2-bromophenylmethyl group, 3-bromophenylmethyl group, 4-bromophenyl It is a halogenated aralkyl group such as a methyl group, a 2-fluorophenylmethyl group, a 3-fluorophenylmethyl group, and a 4-fluorophenylmethyl 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 a01 to R a018 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 a01 to R a018 are hydrogen atoms because it is easy to form a cured film having excellent mechanical properties.
  • R a01 ⁇ R a018 is the same as R a01 ⁇ R a018 in formula (a01-1).
  • examples of the divalent group formed when R a02 and R a08 are bonded to each other include -CH 2- and -C (CH 3 ) 2- .
  • alicyclic epoxy compounds represented by the formula (a01-1) specific examples of suitable compounds are the following formulas (a01-1a), formula (a01-1b), and formula (a01-1c).
  • alicyclic epoxy compounds represented by the formula (a01-2) specific examples of suitable compounds are the alicyclic epoxy represented by the following formula (a01-2a) and the following formula (a01-2b). Examples include compounds.
  • alicyclic epoxy compounds represented by the formula (a01-3) 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 (a01-4) specific examples include 4-vinylcyclohexenedioxide, dipentenedioxide, limonene dioxide, 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 (a01-5) specific examples include 1,2,5,6-diepoxycyclooctane and the like.
  • a compound represented by the following formula (a1-I) can be suitably used as an epoxy resin precursor.
  • X a1 , X a2 , and X a3 are organic groups that may independently contain a hydrogen atom or an epoxy group, respectively, and are X a1 , X a2 , and X a3.
  • 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 (a1-IIa).
  • the groups represented by the plurality of formulas (a1-IIa) bound to one compound are preferably the same group.
  • C a is an epoxy group in. the formula (a1-IIa), may form a ring structure by bonding with L and C a.
  • 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 (a1-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 or alicyclic epoxy groups in the molecule
  • siloxane compound a siloxane compound having two or more glycidyl groups or alicyclic epoxy groups in the molecule
  • the siloxane compound is a compound having a siloxane skeleton composed of a siloxane bond (Si—O—Si) and two or more glycidyl groups or alicyclic epoxy 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 (a1-III) (hereinafter, may be referred to as “cyclic siloxane”) is preferable.
  • Ra24 and Ra25 represent a monovalent group or an alkyl group containing an epoxy group.
  • x1 in the formula (a1-III) indicates an integer of 3 or more.
  • Ra24 and Ra25 in the compound represented by the formula (a1-III) may be the same or different.
  • the plurality of Ra 24s may be the same or different.
  • the plurality of Ra 25s may be the same or different.
  • alkyl group examples include a linear or branched alkyl group having 1 or more and 18 or less carbon atoms such as a methyl group, an ethyl group, a propyl group and an isopropyl group.
  • the number of carbon atoms of the alkyl group is preferably 1 or more and 6 or less, and particularly preferably 1 or more and 3 or less.
  • X1 in the formula (a1-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.
  • the monovalent group containing the epoxy group includes an alicyclic epoxy group and a glycidyl ether group represented by —DOR a26 [D represents an alkylene group and R a26 represents a glycidyl group].
  • the alicyclic epoxy group is more preferable, and the alicyclic epoxy group represented by the following formula (a1-IIIa) or the following formula (a1-IIIb) is further preferable.
  • the D (alkylene group) include a linear or branched alkylene group having 1 or more and 18 or less carbon atoms such as a methylene group, a methylmethylene group, a dimethylmethylene group, a dimethylene group and a trimethylene group. Can be mentioned.
  • 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 modified metal oxide fine particle dispersion liquid is described in JP-A-2008-248169 as an epoxy resin precursor, in addition to the siloxane compound represented by the formula (a1-III), an alicyclic epoxy group-containing cyclic siloxane.
  • a compound having a siloxane skeleton such as an alicyclic epoxy group-containing silicone resin and an organopolysilsesquioxane resin having at least two epoxy functional groups in one molecule described in JP-A-2008-19422. It may be contained.
  • examples of the siloxane compound include cyclic siloxanes having two or more glycidyl groups or alicyclic epoxy 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.
  • a precursor resin which is a resin that causes an intramolecular aromatic ring formation reaction and / or an intramolecular cross-linking reaction by heating is preferable. Further, a precursor resin that gives a cured product by firing is also preferable as a base material component (CD).
  • the structure of the molecular chain constituting the resin becomes rigid, and a metal oxide fine particle-containing film having excellent heat resistance and mechanical properties can be formed.
  • preferred reactions include, for example, the reactions represented by the following formulas (I) to (VI).
  • the reaction in the following formula is only an example of the aroma ring forming reaction, and the structure of the resin used as the base material component (C) that causes an intramolecular aroma ring forming reaction by heating is described in the following formula. It is not limited to the structure of the precursor polymer shown in.
  • a resin having a group selected from a hydroxyl group, a carboxylic acid anhydride group, a carboxy group, and an epoxy group in the molecule According to the cross-linking reaction between molecules, the molecular chains constituting the resin are cross-linked with each other to form a three-dimensional cross-linked structure. Therefore, when a resin having a group selected from a hydroxyl group, a carboxylic acid anhydride group, a carboxy group, and an epoxy group in the molecule, which causes a cross-linking reaction by heating, is used as the base material component (C), it has heat resistance. And a metal oxide fine particle-containing film having excellent mechanical properties can be obtained.
  • the action of the dehydration condensate agent causes cross-linking between molecules contained in the resin due to dehydration condensation between the hydroxyl groups. Further, since the hydroxyl group contains an active hydrogen atom and is highly reactive, it reacts with various cross-linking agents to give a cured product containing the cross-linked resin.
  • the carboxy groups generated by the hydrolysis of the acid anhydride group are dehydrated and condensed by the action of the dehydration condensing agent to crosslink.
  • the acid anhydride group itself is also highly reactive, for example, by using a cross-linking agent such as a polyol having two or more hydroxyl groups and a polyamine having two or more amino groups, a cured product containing the cross-linked resin can be obtained. give.
  • the action of the dehydration condensing agent causes cross-linking between the molecules contained in the resin by dehydration condensation between the carboxy groups. It is also possible to carry out cross-linking using a cross-linking agent having a functional group capable of reacting with a carboxy group such as an isocyanate group.
  • a well-known curing accelerator or the like is used to cause cross-linking between the molecules contained in the resin due to a heavy addition reaction between the epoxy groups.
  • the resin having a carboxylic acid anhydride group in the molecule has an unsaturated double bond containing one or more monomers selected from maleic acid anhydride, citraconic acid anhydride, and itaconic acid anhydride.
  • a copolymer obtained by polymerizing a mixture of monomers is preferable.
  • a styrene-maleic acid copolymer is preferable.
  • Examples of the resin having a carboxy group in the molecule include a resin obtained by hydrolyzing an acid anhydride group in the resin having a carboxylic acid anhydride group in the molecule, (meth) acrylic acid, crotonic acid, and malein.
  • the epoxy group-containing resin having an epoxy group in the molecule will be described in detail later.
  • Benzoxazole precursors polybenzothiazole precursors, polybenzoimidazole precursors, styrene-maleic acid copolymers, and epoxy group-containing resins are preferred.
  • polyimide resin precursor examples include polyamic acid, which is formed in the presence of an imidizing agent after forming a film of a modified metal oxide fine particle dispersion containing polyamic acid as a base material component (C). When the formed film is heated, a metal oxide fine particle-containing film containing a polyimide resin and having excellent heat resistance is formed.
  • the molecular weight of the polyamic acid is preferably 5,000 or more and 30,000 or less, and more preferably 10,000 or more and 20,000 or less, as a mass average molecular weight.
  • Suitable polyamic acids include, for example, polyamic acids composed of structural units represented by the following formula (A1).
  • R a020 is a tetravalent organic group
  • R A021 represents a divalent organic group
  • n a is the number of repetitions of structural units represented by the formula (A1).
  • the number of carbon atoms of R a020 and R a021 is preferably 2 or more and 50 or less, and more preferably 2 or more and 30 or less.
  • R a020 and R a021 may be an aliphatic group, an aromatic group, or a group combining these structures, respectively.
  • the tetravalent aromatic group is the same as that of Ra022 described later.
  • R a020 and R a021 may contain a halogen atom, an oxygen atom, and a sulfur atom in addition to the carbon atom and the hydrogen atom.
  • R a020 and R a021 contain an oxygen atom, a nitrogen atom, or a sulfur atom
  • the oxygen atom, the nitrogen atom, or the sulfur atom is a nitrogen-containing heterocyclic group
  • -CONH-, -NH-, -N N-
  • Polyamic acid is usually prepared by reacting a tetracarboxylic dianhydride component with a diamine component.
  • a method for producing a tetracarboxylic dianhydride component, a diamine component, and a polyamic acid used for preparing a polyamic acid will be described.
  • the tetracarboxylic dianhydride component which is a raw material for synthesizing the polyamic acid, is not particularly limited as long as it can form the polyamic acid by reacting with the diamine component.
  • the tetracarboxylic dianhydride component can be appropriately selected from the tetracarboxylic dianhydride components that have been conventionally used as a raw material for synthesizing polyamic acids.
  • the tetracarboxylic acid dianhydride component may be aromatic tetracarboxylic acid dianhydride or aliphatic tetracarboxylic acid dianhydride, and for example, tetra represented by the following formula (a1-01).
  • Carous acid dianhydride is mentioned, and aromatic tetracarboxylic acid dianhydride is preferable. Two or more kinds of tetracarboxylic dianhydride components may be used in combination. (In the formula (a1-01), R a020 is the same as R A020 of formula (A1).)
  • aromatic tetracarboxylic acid dianhydrides include pyromellitic acid dianhydrides, 3,3', 4,4'-biphenyltetracarboxylic acid dianhydrides, 2,3,3', 4'. -Biphenyltetracarboxylic acid dianhydride, 3,3', 4,4'-benzophenone tetracarboxylic acid dianhydride, 4,4'-oxydiphthalic anhydride, and 3,3', 4,4'-diphenylsulfone Examples thereof include tetracarboxylic acid dianhydride. Among these, 3,3', 4,4'-biphenyltetracarboxylic dianhydride and pyromellitic dianhydride are preferable from the viewpoint of price, availability and the like.
  • the diamine component which is a raw material for synthesizing the polyamic acid, is not particularly limited as long as the polyamic acid can be formed by reacting with the tetracarboxylic dianhydride component.
  • the diamine component can be appropriately selected from diamines conventionally used as a synthetic raw material for polyamic acids.
  • a diamine component represented by the following formula (a1-02) or a diamine giving Y d described later can be used.
  • the diamine component may be an aromatic diamine or an aliphatic diamine, but an aromatic diamine is preferable. Two or more kinds of diamine components may be used in combination. (In the formula (a1-02), R a021 is the same as R A021 of formula (A1).)
  • aromatic diamines include p-phenylenediamine, m-phenylenediamine, 2,4-diaminotoluene, 4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis ( Trifluoromethyl) biphenyl, 3,3'-diaminodiphenyl sulphon, 4,4'-diaminodiphenyl sulphon, 4,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3 , 4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-amino) Phenoxy) benz
  • p-phenylenediamine, m-phenylenediamine, 2,4-diaminotoluene, and 4,4'-diaminodiphenyl ether are preferable from the viewpoint of price, availability, and the like.
  • a polyamic acid can be obtained by reacting the tetracarboxylic dianhydride component and the diamine component described above in a solvent capable of dissolving both of them.
  • the amount of the tetracarboxylic dianhydride component and the diamine component used in synthesizing the polyamic acid is not particularly limited. It is preferable to use 0.50 mol or more and 1.50 mol or less of the diamine component, more preferably 0.60 mol or more and 1.30 mol or less, and 0.70 mol or less, with respect to 1 mol of the tetracarboxylic acid dianhydride component. It is particularly preferable to use more than 1 mol and 1.20 mol or less.
  • Solvents that can be used for the synthesis of polyamic acids include, for example, N, N, N', N'-tetramethylurea, N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide.
  • Hexamethylphosphoramide, 1,3-dimethyl-2-imidazolidinone, and aprotic polar organic solvents such as ⁇ -butyrolactone, diethylene glycol dialkyl ether, ethylene glycol monoalkyl ether acetate, diethylene glycol monoalkyl ether acetate, Examples thereof include glycol ethers such as propylene glycol monoalkyl ether acetate and propylene glycol monoalkyl ether propionate. Two or more of these solvents can be used in combination. Among these, it is preferable to use N, N, N', N'-tetramethylurea.
  • the amount of the solvent used when synthesizing the polyamic acid is not particularly limited as long as the polyamic acid having a desired molecular weight can be synthesized.
  • the amount of the solvent used is preferably 100 parts by mass or more and 4000 parts by mass or less, preferably 150 parts by mass or more, with respect to 100 parts by mass in total of the amount of the tetracarboxylic dianhydride component and the amount of the diamine component. More preferably, it is 2000 parts by mass or less.
  • the temperature at which the tetracarboxylic dianhydride component and the diamine component are reacted is not particularly limited as long as the reaction proceeds well.
  • the reaction temperature of the tetracarboxylic dianhydride component and the diamine component is preferably ⁇ 5 ° C. or higher and 150 ° C. or lower, more preferably 0 ° C. or higher and 120 ° C. or lower, and particularly preferably 0 ° C. or higher and 70 ° C. or lower. preferable.
  • the time for reacting the tetracarboxylic dianhydride component with the diamine component varies depending on the reaction temperature, but is typically preferably 1 hour or more and 50 hours or less, and more preferably 2 hours or more and 40 hours or less. It is particularly preferable that the time is 5 hours or more and 30 hours or less.
  • a polyamic acid solution or paste can be obtained.
  • a solution or paste may be used as it is for the preparation of the modified metal oxide fine particle dispersion.
  • the solid polyamic acid obtained by removing the solvent from the solution or paste of the polyamic acid may be used for the preparation of the modified metal oxide fine particle dispersion.
  • Polybenzoxazole precursors are typically produced by reacting an aromatic diaminediol with a dicarbonyl compound of a particular structure.
  • aromatic diamine diol the dicarbonyl compound, the solvent used for the synthesis of the polybenzoxazole precursor, and the method for producing the polybenzoxazole precursor will be described.
  • aromatic diamine diol As the aromatic diamine diol, an aromatic diamine diol conventionally used for the synthesis of polybenzoxazole can be used without particular limitation. As the aromatic diamine diol, it is preferable to use a compound represented by the following formula (a02). The aromatic diamine diol may be used alone or in combination of two or more.
  • R a022 is a tetravalent organic group containing one or more aromatic rings, and is a combination of two sets of amino groups and a hydroxyl group contained in the aromatic diamine diol represented by the formula (a02). In each combination, the amino group and the hydroxyl group are bonded to two adjacent carbon atoms on the aromatic ring contained in Ra022.
  • R a022 is a tetravalent organic group containing one or more aromatic rings, and the number of carbon atoms thereof is preferably 6 or more and 50 or less, and more preferably 6 or more and 30 or less.
  • R a022 may be an aromatic group, and two or more aromatic groups contain an aliphatic hydrocarbon group, a halogenated aliphatic hydrocarbon group, or a heteroatom such as an oxygen atom, a sulfur atom, and a nitrogen atom. It may be a group attached via a binding that contains.
  • the aromatic ring contained in Ra022 may be an aromatic heterocycle.
  • the aromatic ring bonded to the amino group and the hydroxyl group in Ra022 is preferably a benzene ring.
  • the ring bonded to the amino group and the hydroxyl group in R a022 is a fused ring containing two or more rings, the ring bonded to the amino group and the hydroxyl group in the condensed ring is preferably a benzene ring.
  • R a022 include groups represented by the following formulas (a02-1) to (a02-9).
  • X 01 is an alkylene group having 1 to 10 carbon atoms, a fluorinated alkylene group having 1 to 10 carbon atoms, -O-, -S- , -SO-, -SO 2 -, -CO-, -COO-, -CONH-, and one selected from the group consisting of a single bond.
  • Y 01 is the same, respectively. However, it may be different, and is one selected from the group consisting of -CH 2- , -O-, -S-, -SO-, -SO 2-, -CO-, and a single bond.
  • the groups represented by the above formulas (a02-1) to (a02-9) may have one or more substituents on the aromatic ring.
  • the substituent are a fluorine atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a fluorinated alkyl group having 1 to 6 carbon atoms, and a carbon atom number.
  • a fluorinated alkoxy group of 1 or more and 6 or less is preferable.
  • the substituent is a fluorinated alkyl group or a fluorinated alkoxy group, it is preferably a perfluoroalkyl group or a perfluoroalkoxy group.
  • Specific examples of the compound represented by the above formula (a02) include 2,4-diamino-1,5-benzenediol, 2,5-diamino-1,4-benzenediol, and 2,5-diamino-3-. Fluoro-1,4-benzenediol, 2,5-diamino-3,6-difluoro-1,4-benzenediol, 2,6-diamino-1,5-dihydroxynaphthalene, 1,5-diamino-2,6 -Dihydroxynaphthalene, 2,6-diamino-3,7-dihydroxynaphthalene, 1,6-diamino-2,5-dihydroxynaphthalene, 4,4'-diamino-3,3'-dihydroxybiphenyl, 3,3'- Diamino-4,4'-dihydroxybiphenyl, 2,3'-diamino-3,2'-dihydroxybiphenyl,
  • a dicarbonyl compound As a raw material for synthesizing the polybenzoxazole precursor, a dicarbonyl compound represented by the following formula (a03) is used together with the aromatic diamine diol described above.
  • a polybenzoxazole precursor can be obtained by condensing the above-mentioned aromatic diaminediol with the dicarbonyl compound represented by the following formula (a03).
  • R A023 represents a divalent organic group
  • a 0 represents a hydrogen atom or a halogen atom.
  • R a023 in the formula (a03) may be an aromatic group, an aliphatic group, or a group in which an aromatic group and an aliphatic group are combined.
  • Ra023 is preferably a group containing an aromatic group and / or an alicyclic group from the viewpoint of good heat resistance, mechanical properties, chemical resistance and the like of the obtained polybenzoxazole resin.
  • the aromatic group contained in Ra023 may be an aromatic hydrocarbon group or an aromatic heterocyclic group.
  • Ra 023 may contain a halogen atom, an oxygen atom, and a sulfur atom in addition to the carbon atom and the hydrogen atom.
  • R a023 contains an oxygen atom, a nitrogen atom, or a sulfur atom
  • one of the two A 0 is a hydrogen atom, but the other may be a halogen atom, or the two A are both hydrogen atoms, two A 0 is a both a halogen atom Is preferable.
  • a 0 is a halogen atom, chlorine, bromine, and iodine are preferable as A 0, and chlorine is more preferable.
  • a dialdehyde compound in which two A 0s are both hydrogen atoms is used as the dicarbonyl compound represented by the formula (a03)
  • a polybenzoxazole precursor represented by the following formula (A2) is produced.
  • R a022 and R a023 are the same as those in the formula (a02) and the formula (a03)
  • n 1 is the number of repetitions of the unit represented by the formula (A2).
  • dialdehyde compound and the dicarboxylic acid dihalide which are suitable compounds as the dicarbonyl compound, will be described.
  • dialdehyde compound used as a raw material for the polybenzoxazole precursor is a compound represented by the following formula (a02-I).
  • One type of dialdehyde compound may be used alone, or two or more types may be used in combination.
  • R a023 is the same as the formula (a03).
  • Examples of the aromatic group or aromatic ring-containing group suitable as Ra203 in the formula (a2-I) include the following groups.
  • X 02 is an alkylene group having 1 or more and 10 or less carbon atoms, a fluorinated alkylene group having 1 or more and 10 or less carbon atoms, -O-, -S-, -SO-, -SO 2- , -CO -, - COO -, - CONH-, and if one is a .
  • X 02 selected from the group consisting of a single bond is more, a plurality of X 02 good be the same or different .
  • Y 02 Are the same or different, respectively, and are selected from the group consisting of -CH 2- , -O-, -S-, -SO-, -SO 2- , -CO-, and a single bond.
  • P 0 and q 0 are integers from 0 to 3, respectively.
  • Examples of the alicyclic group or the alicyclic-containing group suitable as R a023 in the formula (a2-I) include the following groups.
  • X 02 is an alkylene group having 1 or more and 10 or less carbon atoms, a fluorinated alkylene group having 1 or more and 10 or less carbon atoms, -O-, -S-, -SO-, -SO 2- , -CO -, - COO -, - CONH-, and if it is one selected from the group consisting of single bond .
  • X 02 is a plurality, the plurality of X 2 are optionally be the same or different .
  • Y 02 Are the same or different, respectively, and are selected from the group consisting of -CH 2- , -O-, -S-, -SO-, -SO 2- , -CO-, and a single bond.
  • .Z 0 is the, -CH 2 -, - CH 2 CH 2 -, and
  • the aromatic ring or alicyclic ring contained in the group suitable as Ra023 may have one or more substituents on the ring.
  • the substituent are a fluorine atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a fluorinated alkyl group having 1 to 6 carbon atoms, and a carbon atom number.
  • a fluorinated alkoxy group of 1 or more and 6 or less is preferable.
  • the substituent is a fluorinated alkyl group or a fluorinated alkoxy group, it is preferably a perfluoroalkyl group or a perfluoroalkoxy group.
  • dialdehyde compound represented by the formula (a2-I) is an aromatic dialdehyde
  • suitable examples thereof include benzenedialdehydes, pyridinedialdehydes, pyrazinedialdehydes, pyrimidindialdehydes, and naphthalene.
  • benzenedialdehydes include phthalaldehyde, isophthalaldehyde, terephthalaldehyde, 3-fluorophthalaldehyde, 4-fluorophthalaldehyde, 2-fluoroisophthalaldehyde, 4-fluoroisophthalaldehyde, 5-fluoroisophthalaldehyde, 2 -Fluoroterephthalaldehyde, 3-trifluoromethylphthalaldehyde, 4-trifluoromethylphthalaldehyde, 2-trifluoromethylisophthalaldehyde, 4-trifluoromethylisophthalaldehyde, 5-trifluoromethylisophthalaldehyde, 2-trifluoromethyl Examples thereof include terephthalaldehyde, 3,4,5,6-tetrafluorophthalaldehyde, 2,4,5,6-tetrafluoroisophthalaldehyde, and 2,3,5,6-tetrafluoroterephthal
  • pyridine dialdehydes include pyridine-2,3-dialdehyde, pyridine-3,4-dialdehyde, and pyridine-3,5-dialdehyde.
  • pyrazine dialdehydes include pyrazine-2,3-dialdehyde, pyrazine-2,5-dialdehyde, pyrazine-2,6-dialdehyde and the like.
  • pyrimidine dialdehydes include pyrimidine-2,4-dialdehyde, pyrimidine-4,5-dialdehyde, pyrimidine-4,6-dialdehyde and the like.
  • naphthalenedialdehydes include naphthalene-1,5-dialdehyde, naphthalene-1,6-dialdehyde, naphthalene-2,6-dialdehyde, naphthalene-3,7-dialdehyde, 2,3.
  • biphenyldialdehydes include biphenyl-2,2'-dialdehyde, biphenyl-2,4'-dialdehyde, biphenyl-3,3'-dialdehyde, biphenyl-4,4'-dialdehyde, 6,6'-difluorobiphenyl-3,4'-dialdehyde, 6,6'-difluorobiphenyl-2,4'-dialdehyde, 6,6'-difluorobiphenyl-3,3'-dialdehyde, 6,6 6'-difluorobiphenyl-3,4'-dialdehyde, 6,6'-difluorobiphenyl-4,4'-dialdehyde, 6,6'-ditrifluoromethylbiphenyl-2,2'-dialdehyde, 6, 6'-ditrifluoromethylbiphenyl-2,4'-dialdehyde, 6,6'-ditrifluoromethylbiphen
  • diphenyl ether dialdehydes include diphenyl ether-2,4'-dialdehyde, diphenyl ether-3,3'-dialdehyde, diphenyl ether-3,4'-dialdehyde, and diphenyl ether-4,4'-dialdehyde. And so on.
  • diphenylsulfone dialdehydes include diphenylsulfone-3,3'-dialdehyde, diphenylsulfone-3,4'-dialdehyde, diphenylsulfone-4,4'-dialdehyde and the like.
  • diphenylsulfide dialdehydes include diphenylsulfide-3,3'-dialdehyde, diphenylsulfide-3,4'-dialdehyde, diphenylsulfide-4,4'-dialdehyde and the like.
  • diphenylketone dialdehydes include diphenylketone-3,3'-dialdehyde, diphenylketone-3,4'-dialdehyde, diphenylketone-4,4'-dialdehyde and the like.
  • bis (formylphenoxy) benzenes include 1,3-bis (3-formylphenoxy) benzene, 1,4-bis (3-formylphenoxy) benzene, and 1,4-bis (4-formylphenoxy). ) Benzene and the like.
  • [1,4-phenylenebis (1-methylethylidene)] bisbenzaldehydes include 3,3'-[1,4-phenylenebis (1-methylethylidene)] bisbenzaldehyde, 3,4'-. Examples thereof include [1,4-phenylenebis (1-methylethylidene)] bisbenzaldehyde, and 4,4'-[1,4-phenylenebis (1-methylethylidene)] bisbenzaldehyde.
  • 2,2-bis [4- (formylphenoxy) phenyl] propane examples include 2,2-bis [4- (2-formylphenoxy) phenyl] propane and 2,2-bis [4- (3).
  • -Formyl phenoxy) phenyl] propane, 2,2-bis [4- (4-formyl phenoxy) phenyl] propane, 2,2-bis [4- (3-formyl phenoxy) phenyl] hexafluoropropane, and 2,2 -Bis [4- (4-formylphenoxy) phenyl] hexafluoropropane and the like can be mentioned.
  • bis [4- (formylphenoxy) phenyl] sulfides include bis [4- (3-formylphenoxy) phenyl] sulfide and bis [4- (4-formylphenoxy) phenyl] sulfide. ..
  • bis [4- (formylphenoxy) phenyl] sulfone include bis [4- (3-formylphenoxy) phenyl] sulfone and bis [4- (4-formylphenoxy) phenyl] sulfone. ..
  • fluorene-containing aldehyde examples include fluorene-2,6-dialdehyde, fluorene-2,7-dialdehyde, dibenzofuran-3,7-dialdehyde, 9,9-bis (4-formylphenyl) fluorene, and the like. Examples thereof include 9,9-bis (3-formylphenyl) fluorene and 9- (3-formylphenyl) -9- (4'-formylphenyl) fluorene.
  • diphenylalcandialdehyde or diphenylfluoroalcandialdehyde represented by the following formula can also be suitably used as an aromatic dialdehyde compound.
  • a compound having an imide bond represented by the following formula can also be suitably used as an aromatic dialdehyde compound.
  • dicarbonyl compound represented by the formula (a2-I) is an alicyclic dialdehyde containing an alicyclic group
  • suitable examples thereof include cyclohexane-1,4-dialdehyde and cyclohexane-1,3.
  • isophthalaldehyde is preferable because it is easy to synthesize and obtain, and it is easy to obtain a polybenzoxazole precursor that gives a polybenzoxazole resin having excellent heat resistance and mechanical properties.
  • the dicarboxylic acid dihalide used as a raw material for the polybenzoxazole precursor is a compound represented by the following formula (a2-II).
  • a2-II dicarboxylic acid dihalide
  • one type may be used alone, or two or more types may be used in combination.
  • R a023 is the same as the formula (a03), and Hal is a halogen atom.
  • a suitable compound as the compound represented by the formula (a2-II) as a suitable example of the dialdehyde compound, a compound in which the two aldehyde groups of the above-mentioned compound are replaced with a halocarbonyl group, preferably a chlorocarbonyl group. Can be mentioned.
  • terephthalic acid dichloride is selected because it is easy to synthesize and obtain, and it is easy to obtain a polybenzoxazole precursor that gives a polybenzoxazole resin having excellent heat resistance and mechanical properties. preferable.
  • the solvent used for preparing the polyimide resin precursor or the polybenzoxazole precursor is not particularly limited, and can be appropriately selected from the solvents conventionally used for preparing the polyimide resin precursor or the polybenzoxazole precursor.
  • As the solvent used for preparing the polyimide resin precursor or the polybenzoxazole precursor it is preferable to use a solvent containing the compound represented by the above formula (S01).
  • the polybenzoxazole precursor is synthesized using a solvent containing the compound represented by the above formula (S01), even when the polybenzoxazole precursor is heat-treated at a low temperature, the polybenzoxazole precursor is heated. It is possible to produce a polybenzoxazole resin having excellent mechanical properties such as tensile elongation and chemical resistance while suppressing a decrease in transparency due to coloring of the resin.
  • N, N, 2-trimethylpropionamide and N, N, N', N'-tetramethylurea are particularly preferable.
  • the boiling point of N, N, 2-trimethylpropionamide under atmospheric pressure is 175 ° C
  • the boiling point of N, N, N', N'-tetramethylurea under atmospheric pressure is 177 ° C.
  • N, N, 2-trimethylpropionamide, and N, N, N', N'-tetramethylurea can dissolve aromatic diaminediols, dicarbonyl compounds, and the polybenzoxazole precursors produced. It has a relatively low boiling point in various solvents.
  • a polybenzoxazole precursor synthesized using a solvent containing at least one selected from N, N, 2-trimethylpropionamide and N, N, N', N'-tetramethylurea is used.
  • the solvent is unlikely to remain in the produced polybenzoxazole resin when the polybenzoxazole precursor is heated, and the tensile elongation of the obtained polybenzoxazole resin is unlikely to decrease. ..
  • N, N, 2-trimethylpropionamide, and N, N, N', N'-tetramethylurea are substances of very high concern under the REACH regulation in the EU (European Union). It is also useful in that it is a substance with low toxicity, as it is not designated as a substance of very high concern (Substance of Very High Concern).
  • the content of the compound represented by the formula (S01) in the solvent is preferably 70% by mass or more, preferably 80% by mass. % Or more is more preferable, 90% by mass or more is particularly preferable, and 100% by mass is most preferable.
  • examples of the organic solvent that can be used together with the compound represented by the formula (S01) include N, N-dimethylformamide, N, N-dimethylacetamide, and the like.
  • Nitrogen-containing polar solvents such as N-methyl-2-pyrrolidone, hexamethylphosphoramide, 1,3-dimethyl-2-imidazolidinone; ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and isophorone; ⁇ -butyrolactone , ⁇ -Valerolactone, ⁇ -Valerolactone, ⁇ -caprolactone, ⁇ -caprolactone, ⁇ -methyl- ⁇ -butyrolactone, ethyl lactate, methyl acetate, ethyl acetate, and esters such as -n-butyl acetate; dioxane, and Cyclic ether
  • the polybenzoxazole precursor is produced by reacting the above-mentioned aromatic diaminediol with a dicarbonyl compound in a solvent according to a well-known method.
  • a production method when the dicarbonyl compound is a dialdehyde compound and a production method when the dicarbonyl compound is a dicarboxylic acid halide will be described.
  • the reaction between aromatic diaminediol and dialdehyde compound is a Schiff base formation reaction and can be carried out according to a well-known method.
  • the reaction temperature is not particularly limited, but is usually preferably 20 ° C. or higher and 200 ° C. or lower, more preferably 20 ° C. or higher and 160 ° C. or lower, and particularly preferably 100 ° C. or higher and 160 ° C. or lower.
  • the reaction between the aromatic diaminediol and the dialdehyde compound may be carried out while adding an entrainer to the solvent and reflux dehydration.
  • the entrainer is not particularly limited, and is appropriately selected from an organic solvent that forms an azeotropic mixture with water and forms a two-phase system with water at room temperature.
  • Preferable examples of entrainers include esters such as isobutyl acetate, allyl acetate, -n-propyl propionate, isopropyl propionate, -n-butyl propionate, and isobutyl propionate; dichloromethyl ether, ethyl isoamyl ether, and the like.
  • Ethers Ketones such as ethylpropyl ketone
  • Aromatic hydrocarbons such as toluene.
  • the reaction time between the aromatic diaminediol and the dialdehyde compound is not particularly limited, but is typically about 2 hours or more and 72 hours or less.
  • the amount of the dialdehyde compound used in producing the polybenzoxazole precursor is preferably 0.5 mol or more and 1.5 mol or less, and 0.7 mol or more and 1.3 mol, based on 1 mol of the aromatic diamine diol. More preferably, the molar amount or less.
  • the amount of the solvent used is not particularly limited as long as the reaction between the aromatic diaminediol and the dialdehyde compound proceeds well.
  • a solvent having a mass of 1 to 40 times or more, preferably 1.5 to 20 times or less the total mass of the aromatic diamine diol and the mass of the dialdehyde compound is used. ..
  • the reaction between the aromatic diaminediol and the dialdehyde compound is carried out until the number average molecular weight of the produced polybenzoxazole precursor is preferably 1000 or more and 20000 or less, and more preferably 1200 or more and 5000 or less.
  • reaction temperature for reacting aromatic diaminediol and dicarboxylic acid dihalide is not particularly limited, but is usually preferably -20 ° C or higher and 150 ° C or lower, and -10 ° C or higher and 150 ° C. The following is more preferable, and -5 ° C. or higher and 70 ° C. or lower is particularly preferable.
  • Hydrogen halides are by-produced in the reaction of aromatic diaminediols with dicarboxylic acid dihalides.
  • an organic base such as triethylamine, pyridine, and N, N-dimethyl-4-aminopyridine, or an alkali metal hydroxide such as sodium hydroxide and potassium hydroxide is used as a reaction solution. A small amount may be added therein.
  • the reaction time between the aromatic diaminediol and the dicarboxylic acid dihalide is not particularly limited, but is typically about 2 hours or more and 72 hours or less.
  • the amount of dicarboxylic acid dihalide used in producing a polybenzoxazole precursor is preferably 0.5 mol or more and 1.5 mol or less, and 0.7 mol or more and 1.3 mol, based on 1 mol of aromatic diaminediol. More preferably, the molar amount or less.
  • the amount of the solvent used is not particularly limited as long as the reaction between the aromatic diaminediol and the dicarboxylic acid dihalide proceeds well.
  • a solvent having a mass of 1 to 40 times, preferably 1.5 to 20 times or less the total mass of the aromatic diamine diol and the mass of the dicarboxylic acid dihalide is used. ..
  • the reaction between the aromatic diaminediol and the dicarboxylic acid dihalide is carried out until the number average molecular weight of the produced polybenzoxazole precursor is preferably 1000 or more and 20000 or less, and more preferably 1200 or more and 5000 or less.
  • a solution of the polybenzoxazole precursor can be obtained by the method described above.
  • the solution of the polybenzoxazole precursor may be used as it is.
  • Polybenzoxazole obtained by removing at least a part of the solvent from the solution of the polybenzoxazole precursor at a low temperature under reduced pressure so as not to convert the polybenzoxazole precursor into the polybenzoxazole resin.
  • the precursor paste or solid can also be used to prepare the modified metal oxide fine particle dispersion.
  • Polybenzothiazole precursors are typically produced by reacting an aromatic diaminedithiol with a dicarbonyl compound of a particular structure.
  • aromatic diaminedithiol a compound in which the hydroxyl group of the aromatic diaminediol used in the synthesis of the polybenzoxal precursor is replaced with a mercapto group can be used.
  • dicarbonyl compound a compound similar to the dicarbonyl compound used for the synthesis of the polybenzoxazole precursor can be used.
  • reaction method When synthesizing a polybenzothiazole precursor by reacting an aromatic diaminedithiol with a dicarbonyl compound, the reaction method, reaction conditions, etc. are as follows. Is the same as the case of synthesizing.
  • Polybenzimidazole precursors are typically produced by reacting an aromatic tetraamine with a dicarboxylic acid dihalide.
  • aromatic tetraamine a compound in which the hydroxyl group of the aromatic diaminediol used in the synthesis of the polybenzoxazole precursor is replaced with an amino group can be used.
  • dicarboxylic acid dihalide a compound similar to the dicarboxylic acid dihalide used for the synthesis of the polybenzoxazole precursor can be used.
  • reaction method When synthesizing a polybenzimidazole precursor by reacting an aromatic tetraamine with a dicarboxylic acid dihalide, the reaction method, reaction conditions, etc. are as follows. It is the same as the case of synthesizing.
  • the type of styrene-maleic acid copolymer is not particularly limited as long as it does not impair the object of the present invention.
  • the copolymerization ratio (mass ratio) of styrene / maleic acid in the styrene-maleic acid copolymer is preferably 1/9 or more and 9/1 or less, more preferably 2/8 or more and 8/1 or less, and 1/1 or more. 8/1 or less is particularly preferable.
  • the molecular weight of the styrene-maleic acid copolymer is not particularly limited, but the polystyrene-equivalent mass average molecular weight is preferably 1000 or more and 100,000 or less, and more preferably 5000 or more and 12000 or less.
  • Epoxy group-containing resin When the epoxy group-containing resin is used as the base material component (C), the modified metal oxide fine particle dispersion liquid formed into a desired shape is heated in the presence of a curing agent or a curing accelerator as needed. , The epoxy groups of the epoxy group-containing resin are crosslinked. As a result, a cured product having excellent heat resistance and mechanical properties can be obtained.
  • the epoxy group-containing resin is not particularly limited as long as it is a resin composed of molecules having an epoxy group.
  • the epoxy group-containing resin may be a polymer obtained by polymerizing a monomer having an epoxy group or a monomer mixture containing a monomer having an epoxy group.
  • the epoxy group-containing resin is a resin in which an epoxy group is introduced into a polymer having a reactive functional group such as a hydroxyl group, a carboxy group, or an amino group by using a compound having an epoxy group such as epichlorohydrin. You may. Since it is easy to obtain, prepare, adjust the amount of epoxy groups in the polymer, etc., the polymer having an epoxy group is a single amount containing a monomer having an epoxy group or a monomer having an epoxy group. A polymer obtained by polymerizing a body mixture is preferable.
  • Preferred examples of the epoxy group-containing resin are novolak epoxy resins such as 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 type epoxy resin.
  • a ring-type aliphatic epoxy resin such as an epoxie of a dicyclopentadiene type phenol resin; an aromatic epoxy resin such as an epoxie of a naphthalene type phenol resin can be mentioned.
  • the homopolymer of the (meth) acrylic acid ester having an epoxy group is easy to prepare and the physical properties of the metal oxide fine particle-containing film can be easily adjusted.
  • a copolymer of a (meth) acrylic acid ester having an epoxy group and another monomer is preferable.
  • the (meth) acrylic acid ester having an epoxy group is a (meth) acrylic acid ester having an alicyclic epoxy group, which will be described later, even if it is a (meth) acrylic acid ester having a chain aliphatic epoxy group. There may be. Further, the (meth) acrylic acid ester having an epoxy group may contain an aromatic group. Among the (meth) acrylic acid esters having an epoxy group, an aliphatic (meth) acrylic acid ester having a chain aliphatic epoxy group and an aliphatic (meth) acrylic acid ester having an alicyclic epoxy group are preferable.
  • Aliphatic (meth) acrylic acid esters having an alicyclic epoxy group are more preferable, and from the viewpoint of patterning properties, an aliphatic (meth) having an alicyclic epoxy group having a polycyclic structure in the ring structure of the alicyclic epoxy group ( Meta) epoxides are more preferred.
  • Examples of (meth) acrylic acid esters containing an aromatic group and having an epoxy group include 4-glycidyloxyphenyl (meth) acrylate, 3-glycidyloxyphenyl (meth) acrylate, and 2-glycidyloxyphenyl (meth) acrylate. , 4-Glysidyloxyphenylmethyl (meth) acrylate, 3-glycidyloxyphenylmethyl (meth) acrylate, 2-glycidyloxyphenylmethyl (meth) acrylate and the like.
  • Examples of aliphatic (meth) acrylic acid esters having a chain aliphatic epoxy group include ester groups (-O-CO-) such as epoxyalkyl (meth) acrylates and epoxyalkyloxyalkyl (meth) acrylates. ), A (meth) acrylic acid ester in which a chain aliphatic epoxy group is bonded to an oxy group (—O—) can be mentioned.
  • the chain aliphatic epoxy group contained in such a (meth) acrylic acid ester may contain one or more oxy groups (—O—) in the chain.
  • the number of carbon atoms of the chain aliphatic epoxy group is not particularly limited, but is preferably 3 or more and 20 or less, more preferably 3 or more and 15 or less, and particularly preferably 3 or more and 10 or less.
  • aliphatic (meth) acrylic acid ester having a chain aliphatic epoxy group examples include glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, 6, Epoxyalkyl (meth) acrylates such as 7-epoxyheptyl (meth) acrylate; 2-glycidyloxyethyl (meth) acrylate, 3-glycidyloxy-n-propyl (meth) acrylate, 4-glycidyloxy-n-butyl (meth).
  • aliphatic (meth) acrylic acid ester having an alicyclic epoxy group examples include compounds represented by the following formulas (a05-1) to (a05-15).
  • the compounds represented by the following formulas (a05-1) to (a05-5) are preferable, and the compounds represented by the following formulas (a05-1) to (a05-2) are more preferable.
  • the binding site of the oxygen atom of the ester group to the alicyclic is not limited to the position shown here, and may contain a partial position isomer.
  • R a032 represents a hydrogen atom or a methyl group
  • R a033 represents a divalent aliphatic saturated hydrocarbon group having 1 or more and 6 or less carbon atoms
  • R a034 represents 2 having 1 or more and 10 or less carbon atoms. It indicates a valent hydrocarbon group
  • t 0 indicates an integer of 0 or more and 10 or less.
  • a linear or branched alkylene group for example, a methylene group, an ethylene group, a propylene group, a tetramethylene group, an ethylethylene group, a pentamethylene group, or a hexamethylene group is preferable.
  • R a034 for example, a methylene group, an ethylene group, a propylene group, a tetramethylene group, an ethylethylene group, a pentamethylene group, a hexamethylene group, a phenylene group and a cyclohexylene group are preferable.
  • the polymer having an epoxy group either a homopolymer of a (meth) acrylic acid ester having an epoxy group or a copolymer of a (meth) acrylic acid ester having an epoxy group and another monomer is used.
  • the content of the unit derived from the (meth) acrylic acid ester having an epoxy group in the polymer having an epoxy group is, for example, 1% by mass or more and 100% by mass or less, and 10% by mass or more. 90% by mass or less is preferable, 30% by mass or more and 80% by mass or less is more preferable, and 50% by mass or more and 75% by mass or less is particularly preferable.
  • the polymer having an epoxy group is a copolymer of a (meth) acrylic acid ester having an epoxy group and another monomer
  • the other monomer has an unsaturated carboxylic acid and an epoxy group.
  • examples thereof include (meth) acrylic acid esters, (meth) acrylamides, allyl compounds, vinyl ethers, vinyl esters, styrenes and the like. These compounds can be used alone or in combination of two or more.
  • It has an epoxy group from the viewpoint of storage stability of the modified metal oxide fine particle dispersion and chemical resistance to alkalis of articles such as films formed by using the modified metal oxide fine particle dispersion (meth).
  • the copolymer of the acrylic acid ester and the other monomer preferably does not contain a unit derived from the unsaturated carboxylic acid.
  • unsaturated carboxylic acids include (meth) acrylic acid; (meth) acrylic acid amide; crotonic acid; maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, and anhydrides of these dicarboxylic acids.
  • Examples of (meth) acrylic acid esters having no epoxy group include direct methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, amyl (meth) acrylate, and tert-octyl (meth) acrylate. Chained or branched alkyl (meth) acrylates; chloroethyl (meth) acrylates, 2,2-dimethylhydroxypropyl (meth) acrylates, 2-hydroxyethyl (meth) acrylates, trimethylolpropane mono (meth) acrylates, benzyls.
  • Examples thereof include (meth) acrylates and furfuryl (meth) acrylates; (meth) acrylic acid esters having a group having an alicyclic skeleton.
  • the (meth) acrylic acid esters having no epoxy group the (meth) acrylic acid ester having a group having an alicyclic skeleton is preferable.
  • the alicyclic group constituting the alicyclic skeleton may be monocyclic or polycyclic.
  • the monocyclic alicyclic group include a cyclopentyl group and a cyclohexyl group.
  • the polycyclic alicyclic group include a norbornyl group, an isobornyl group, a tricyclononyl group, a tricyclodecyl group, a tetracyclododecyl group and the like.
  • Examples of the (meth) acrylic acid ester having a group having an alicyclic skeleton include compounds represented by the following formulas (a06-1) to (a06-8). Among these, the compounds represented by the following formulas (a06-3) to (a06-8) are preferable, and the compounds represented by the following formulas (a06-3) or (a06-4) are more preferable.
  • R a035 represents a hydrogen atom or a methyl group
  • Ra 036 represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms
  • R a037 represents a hydrogen atom or a carbon atom number. Indicates an alkyl group of 1 or more and 5 or less.
  • R a036 a single bond, a linear or branched alkylene group, for example, a methylene group, an ethylene group, a propylene group, a tetramethylene group, an ethylethylene group, a pentamethylene group, or a hexamethylene group is preferable.
  • R a037 a methyl group and an ethyl group are preferable.
  • Examples of (meth) acrylamides include (meth) acrylamide, N-alkyl (meth) acrylamide, N-aryl (meth) acrylamide, N, N-dialkyl (meth) acrylamide, N, N-aryl (meth) acrylamide. , N-Methyl-N-phenyl (meth) acrylamide, N-hydroxyethyl-N-methyl (meth) acrylamide and the like.
  • allyl compounds include allyl esters such as allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, allyl lactate; allyloxyethanol; And so on.
  • allyl esters such as allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, allyl lactate; allyloxyethanol; And so on.
  • vinyl ethers examples include hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethyl hexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl ether, 2-ethylbutyl vinyl ether, and hydroxy.
  • Aliphatic vinyl ethers such as ethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether; vinyl phenyl ether, vinyl trill ether, vinyl chlorophenyl ether, vinyl-2,4 -Vinyl aryl ethers such as dichlorophenyl ethers, vinyl naphthyl ethers and vinyl anthranyl ethers; and the like.
  • vinyl esters include vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl barate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxyacetate, vinyl butoxyacetate, vinyl.
  • vinyl esters include phenylacetate, vinylacetate acetate, vinyl lactate, vinyl- ⁇ -phenylbutyrate, vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, vinyl naphthoate and the like.
  • styrenes examples include styrene; methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, isopropylstyrene, butylstyrene, hexylstyrene, cyclohexylstyrene, decylstyrene, benzylstyrene, chloromethylstyrene, trifluoromethylstyrene.
  • Alkylstyrene such as ethoxymethylstyrene and acetoxymethylstyrene; alkoxystyrene such as methoxystyrene, 4-methoxy-3-methylstyrene and dimethoxystyrene; chlorostyrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromo Examples thereof include styrene, dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene, halostyrene such as 2-bromo-4-trifluoromethylstyrene and 4-fluoro-3-trifluoromethylstyrene; and the like.
  • the molecular weight of the epoxy group-containing resin is not particularly limited as long as it does not impair the object of the present invention, but the polystyrene-equivalent mass average molecular weight is preferably 3,000 or more and 30,000 or less, and 5,000 or more and 15,000 or less. More preferred.
  • a resin that forms a cured film by firing is also preferable as the precursor resin as the base material component (C).
  • the resin that forms a cured film by firing include a silicon-containing resin.
  • Preferred examples of the silicon-containing resin include one or more selected from a siloxane resin and polysilane.
  • the modified metal oxide fine particle dispersion liquid is, if necessary, a curing agent, a curing accelerator, and a dehydration condensation. It may contain additives such as agents, antioxidants, UV absorbers, flame retardants, mold release agents, plasticizers, fillers, and reinforcing materials. Further, in order to facilitate film formation, the modified metal oxide fine particle dispersion liquid preferably contains a solvent. The type of solvent is appropriately selected according to the type of thermosetting material.
  • the non-energy-sensitive composition containing the non-thermosetting resin as the base material component (C) and the heat-curable material as the base material component (C) described above are used.
  • a photosensitive composition known as a so-called photoresist composition is also preferable. Since it is easy to form an article such as a film containing metal oxide fine particles that are well dispersed and that contains metal oxide fine particles having excellent heat resistance and chemical resistance, the modified metal oxide fine particle dispersion liquid is used. It is preferably an energy-sensitive composition having heat sensitivity and / or photosensitivity.
  • a modified metal oxide fine particle dispersion liquid which is an energy-sensitive composition can be obtained.
  • Conventionally known energy-sensitive compositions include various thermosetting or photocurable compounds, alkali-soluble resins, resins whose solubility in alkali is increased by exposure, and the like as a base material component (C). Is done.
  • the photosensitive modified metal oxide fine particle dispersion liquid may be a negative type photosensitive composition that is insoluble in the developing solution by exposure, and may be a positive type photosensitive composition that is solubilized in the developing solution by exposure. It may be a composition.
  • a suitable energy-sensitive composition and a silicon-containing resin composition which is a preferable example of a composition containing a resin that forms a cured film by firing will be described.
  • the energy-sensitive composition of the first aspect is a metal containing a modified metal oxide fine particle together with an alkali-soluble resin, a photopolymerizable compound, and a photopolymerization initiator. It is a negative type photosensitive composition containing oxide fine particles and an organic solvent.
  • the alkali-soluble resin and the photopolymerizable compound correspond to the base material component (C).
  • the energy-sensitive composition of the first aspect may contain (meth) acrylic resin obtained by polymerizing (meth) acrylic acid, (meth) acrylic acid ester, or the like as an alkali-soluble resin as described later. be.
  • (meth) acrylic resin obtained by polymerizing (meth) acrylic acid, (meth) acrylic acid ester, or the like as an alkali-soluble resin as described later.
  • the metal oxide fine particles subjected to the coating treatment as described in Patent Document 1 are blended in the composition containing the (meth) acrylic resin, the metal oxide fine particles may not be dispersed well. However, the above-mentioned modified metal oxide fine particles are likely to be stably dispersed even in a composition containing a (meth) acrylic resin.
  • the alkali-soluble resin in the energy-sensitive composition of the first aspect is not particularly limited, and conventionally known alkali-soluble resins can be used.
  • This alkali-soluble resin may have an ethylenically unsaturated group or may not have an ethylenically unsaturated group.
  • the alkali-soluble resin is a resin solution having a resin concentration of 20% by mass (solvent: propylene glycol monomethyl ether acetate) to form a resin film having a thickness of 1 ⁇ m on the substrate and having a thickness of 2.38% by mass.
  • TMAH tetramethylammonium hydroxide
  • alkali-soluble resin having an ethylenically unsaturated group for example, a resin obtained by further reacting a reaction product of an epoxy compound and an unsaturated carboxylic acid with a polybasic acid anhydride can be used.
  • the resin represented by the following formula (a-1) is preferable.
  • the resin represented by this formula (a-1) is preferable in that it has high photocurability.
  • X a represents a group represented by the following formula (a-2).
  • R a1 independently represents a hydrogen atom, a hydrocarbon group having 1 or more and 6 or less carbon atoms, or a halogen atom
  • R a2 independently represents a hydrogen atom or a methyl group.
  • W a represents a group represented by a single bond or the following formula (a-3).
  • Y a represents the residue obtained by removing dicarboxylic acid anhydride from the acid anhydride group (-CO-O-CO-).
  • dicarboxylic acid anhydrides are phthalic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, chlorendic anhydride, methyltetrahydro.
  • examples thereof include phthalic anhydride and glutaric anhydride.
  • Z a represents a residue obtained by removing two acid anhydride groups from a tetracarboxylic acid dianhydride.
  • tetracarboxylic acid dianhydride examples include pyromellitic acid dianhydride, benzophenone tetracarboxylic acid dianhydride, biphenyltetracarboxylic acid dianhydride, biphenyl ether tetracarboxylic acid dianhydride and the like.
  • m represents an integer of 0 or more and 20 or less.
  • a polyester (meth) obtained by reacting a (meth) acrylic acid with a polyester prepolymer obtained by condensing a polyhydric alcohol with a monobasic acid or a polybasic acid.
  • Acrylic Polyurethane (meth) acrylate obtained by reacting a polyol with a compound having two isocyanate groups and then reacting with (meth) acrylic acid; bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S-type epoxy resin, phenol or cresol novolac type epoxy resin, resol type epoxy resin, triphenol methane type epoxy resin, polycarboxylic acid polyglycidyl ester, polyol polyglycidyl ester, aliphatic or alicyclic epoxy resin, amine epoxy resin, An epoxy (meth) acrylate resin obtained by reacting an epoxy resin such as a dihydroxybenzene type epoxy resin with (meth) acrylic acid can also be used.
  • (meth) acrylic acid means both acrylic acid and methacrylic acid.
  • (meth) acrylate” means both acrylate and methacrylate.
  • the alkali-soluble resin having no ethylenically unsaturated group a resin obtained by copolymerizing an unsaturated carboxylic acid with another unsaturated compound can be used.
  • the other unsaturated compound it is preferable to use at least one selected from an epoxy group-containing unsaturated compound and an alicyclic group-containing unsaturated compound.
  • Examples of the unsaturated carboxylic acid include monocarboxylic acids such as (meth) acrylic acid and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid and itaconic acid; and anhydrides of these dicarboxylic acids; Be done.
  • (meth) acrylic acid and maleic anhydride are preferable from the viewpoints of copolymerizability, alkali solubility of the obtained resin, easy availability, and the like.
  • These unsaturated carboxylic acids can be used alone or in combination of two or more.
  • Examples of the epoxy group-containing unsaturated compound include an epoxy group-containing unsaturated compound having no alicyclic group and an epoxy group-containing unsaturated compound having an alicyclic group.
  • Examples of the epoxy group-containing unsaturated compound having an alicyclic group include compounds represented by the above formulas (a05-1) to (a05-15).
  • Examples of the epoxy group-containing unsaturated compound having no alicyclic group include glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, and 6,7-epoxyheptyl ( Epoxyalkyl (meth) acrylates such as meta) acrylates; 2-glycidyloxyethyl (meth) acrylates, 3-glycidyloxy-n-propyl (meth) acrylates, 4-glycidyloxy-n-butyl (meth) acrylates, 5- Epoxyalkyloxyalkyl (meth) acrylates such as glycidyloxy-n-pentyl (meth) acrylate, 6-glycidyloxy-n-hexyl (meth) acrylate; glycidyl ⁇ -ethylacrylate, glycidyl ⁇ -n-propylacrylate,
  • glycidyl (meth) acrylate 2-methylglycidyl (meth) acrylate, 6,7-epoxyheptyl (meth) acrylate, o-vinylbenzyl from the viewpoint of copolymerization reactivity, strength of resin after curing, etc.
  • Glysidyl ethers, m-vinylbenzyl glycidyl ethers, and p-vinylbenzyl glycidyl ethers are preferred.
  • These epoxy group-containing unsaturated compounds can be used alone or in combination of two or more.
  • the alicyclic group-containing unsaturated compound is not particularly limited as long as it is an unsaturated compound having an alicyclic group.
  • the alicyclic group may be monocyclic or polycyclic. Examples of the monocyclic alicyclic group include a cyclopentyl group and a cyclohexyl group. Examples of the polycyclic alicyclic group include an adamantyl group, a norbornyl group, an isobornyl group, a tricyclononyl group, a tricyclodecyl group, a tetracyclododecyl group and the like. Specifically, examples of the alicyclic group-containing unsaturated compound include compounds represented by the above-mentioned formulas (a06-1) to (a06-8).
  • a compound other than the above with respect to the unsaturated carboxylic acid examples include (meth) acrylic acid esters, (meth) acrylamides, allyl compounds, vinyl ethers, vinyl esters, styrenes, maleimides and the like. These compounds can be used alone or in combination of two or more.
  • good examples of (meth) acrylamides, allyl compounds, vinyl ethers, vinyl esters, and styrenes are those of (meth) acrylic acid esters with epoxy groups and other monomers. This is the same as the preferred examples for (meth) acrylamides, allyl compounds, vinyl ethers, vinyl esters, and styrenes described for polymers.
  • (meth) acrylic acid esters examples include linear chains such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, amyl (meth) acrylate, and tert-octyl (meth) acrylate.
  • maleimides examples include N-methylmaleimide, N-ethylmaleimide, Nn-propylmaleimide, N-isopropylmaleimide, Nn-butylmaleimide, Nn-pentylmaleimide, and Nn-.
  • Maleimide N-substituted with an alkyl group having 1 to 10 carbon atoms such as hexyl maleimide; an alicyclic group having 3 to 20 carbon atoms such as N-cyclopentylmaleimide, N-cyclohexylmaleimide, and N-cycloheptylmaleimide.
  • N-substituted maleimide N-arylmaleimide N-substituted with an aryl group having 6 to 20 carbon atoms such as N-phenylmaleimide, N- ⁇ -naphthylmaleimide, and N- ⁇ -naphthylmaleimide; N-benzyl.
  • Examples thereof include N-aralkylmaleimide N-substituted with an aralkyl group having 7 or more and 20 or less carbon atoms such as maleimide and N-phenethylmaleimide.
  • a copolymer having at least a structural unit derived from an unsaturated carboxylic acid and a structural unit having a polymerizable site with a photopolymerizable compound described later, or a structural unit derived from an unsaturated carboxylic acid and an epoxy group can also be suitably used as the alkali-soluble resin.
  • these alkali-soluble resins it is possible to form a metal oxide fine particle-containing film having excellent mechanical strength and adhesion to a substrate.
  • the copolymer having a structural unit having a polymerizable site with the above-mentioned photopolymerizable compound includes the above-mentioned (meth) acrylic acid esters, (meth) acrylamides, allyl compounds, vinyl ethers, vinyl esters, and styrenes. , And one or more structural units derived from polymers and the like.
  • the structural unit having a polymerizable moiety with the photopolymerizable compound preferably has an ethylenically unsaturated group as the polymerizable moiety with the photopolymerizable compound.
  • a copolymer having such a structural unit can be prepared by reacting at least a part of carboxy groups contained in an unsaturated carboxylic acid homopolymer with an epoxy group-containing unsaturated compound. Alternatively, the unsaturated carboxylic acid can be reacted with at least a part of the epoxy group in the polymer having the structural unit derived from the unsaturated carboxylic acid and the structural unit derived from the unsaturated compound containing an epoxy group.
  • a copolymer having a structural unit having a polymerizable site with a photopolymerizable compound can be prepared.
  • the proportion of the structural unit derived from the unsaturated carboxylic acid in the alkali-soluble resin is preferably 3% by mass or more and 25% by mass or less, and more preferably 5% by mass or more and 25% by mass or less.
  • the proportion of the structural unit derived from the epoxy group-containing unsaturated compound is preferably 30% by mass or more and 95% by mass or less, and more preferably 50% by mass or more and 90% by mass or less.
  • the proportion of the structural unit derived from the alicyclic group-containing unsaturated compound is preferably 1% by mass or more and 30% by mass or less, and more preferably 3% by mass or more and 25% by mass or less. It is more preferably mass% or more and 20 mass% or less.
  • the adhesiveness of the cured product of the energy-sensitive composition of the first aspect to the substrate and the energy-sensitive composition of the first aspect can be adjusted while making the alkali solubility of the obtained resin appropriate.
  • the strength after curing can be increased.
  • the mass average molecular weight of the alkali-soluble resin is preferably 1000 or more and 40,000 or less, and more preferably 2000 or more and 30,000 or less. Within the above range, sufficient heat resistance and film strength can be obtained while obtaining good developability.
  • the content of the alkali-soluble resin is preferably 5% by mass or more and 80% by mass or less, and more preferably 15% by mass or more and 50% by mass or less, based on the solid content of the photosensitive composition of the first aspect. preferable. Within the above range, the developability tends to be easily balanced.
  • the photopolymerizable compound in the energy-sensitive composition of the first aspect includes a monofunctional monomer and a polyfunctional monomer.
  • the monofunctional monomer include (meth) acrylamide, methylol (meth) acrylamide, methoxymethyl (meth) acrylamide, ethoxymethyl (meth) acrylamide, propoxymethyl (meth) acrylamide, butoxymethoxymethyl (meth) acrylamide, and N-methylol ( Meta) acrylamide, N-hydroxymethyl (meth) acrylamide, (meth) acrylic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, crotonic acid, 2-acrylamide- 2-Methylpropanesulfonic acid, tert-butylacrylamide sulfonic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth)
  • the content of the photopolymerizable compound is preferably 1% by mass or more and 30% by mass or less, and 5% by mass or more and 20% by mass or less, based on the solid content of the energy-sensitive composition of the first aspect. Is more preferable. Within the above range, it tends to be easy to balance sensitivity, developability, and resolution.
  • the photopolymerization initiator in the energy-sensitive composition of the first aspect is not particularly limited, and a conventionally known photopolymerization initiator can be used.
  • photopolymerization initiator 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2- Hydroxy-2-methyl-1-propane-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4-dodecylphenyl) -2-hydroxy-2 -Methylpropan-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one, bis (4-dimethylaminophenyl) ketone, 2-methyl-1- [4- (methylthio) phenyl]- 2-Morphorinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane-1-one, etanone, 1- [9-ethyl-6- (2-methyl) Benzoyl)
  • an oxime ester-based photopolymerization initiator in terms of sensitivity.
  • particularly preferable compounds are O-acetyl-1- [6- (2-methylbenzoyl) -9-ethyl-9H-carbazole-3-yl] etanone oxime and etanone. , 1- [9-ethyl-6- (pyrrole-2-ylcarbonyl) -9H-carbazol-3-yl], 1- (O-acetyloxime), and 1,2-octanedione, 1- [4- (Phenylthio)-, 2- (O-benzoyloxime)].
  • R c1 is a group selected from the group consisting of a monovalent organic group, an amino group, a halogen, a nitro group, and a cyano group.
  • n1 is an integer of 0 or more and 4 or less
  • n2 is 0 or 1
  • R c2 is a phenyl group which may have a substituent or a carbazolyl group which may have a substituent.
  • R c3 is a hydrogen atom or an alkyl group having 1 or more and 6 or less carbon atoms.
  • R c1 is not particularly limited as long as it does not interfere with the object of the present invention, and is appropriately selected from various organic groups.
  • R c1 is an organic group include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, a saturated aliphatic acyloxy group, an alkoxycarbonyl group and a substituent.
  • n1 is an integer of 2 or more and 4 or less
  • R c1 may be the same or different. Further, the number of carbon atoms of the substituent does not include the number of carbon atoms of the substituent further possessed by the substituent.
  • R c1 is an alkyl group
  • the number of carbon atoms is preferably 1 or more and 20 or less, and more preferably 1 or more and 6 or less.
  • R c1 is an alkyl group, it may be a straight chain or a branched chain.
  • Specific examples of the case where R c1 is an alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group and an n-pentyl group.
  • R c1 is an alkyl group
  • the alkyl group may contain an ether bond (—O—) in the carbon chain.
  • alkyl group having an ether bond in the carbon chain examples include a methoxyethyl group, an ethoxyethyl group, a methoxyethoxyethyl group, an ethoxyethoxyethyl group, a propyloxyethoxyethyl group, a methoxypropyl group and the like.
  • R c1 is an alkoxy group
  • the number of carbon atoms is preferably 1 or more and 20 or less, and more preferably 1 or more and 6 or less.
  • R c1 is an alkoxy group, it may be a straight chain or a branched chain.
  • Specific examples of the case where R c1 is an alkoxy group include a methoxy group, an ethoxy group, an n-propyloxy group, an isopropyloxy group, an n-butyloxy group, an isobutyloxy group, a sec-butyloxy group, a tert-butyloxy group and n.
  • -Pentyloxy group isopentyloxy group, sec-pentyloxy group, tert-pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, isooctyloxy group, sec-octyloxy group , Trt-octyloxy group, n-nonyloxy group, isononyloxy group, n-decyloxy group, isodecyloxy group and the like.
  • R c1 is an alkoxy group
  • the alkoxy group may contain an ether bond (—O—) in the carbon chain.
  • alkoxy group having an ether bond in the carbon chain examples include methoxyethoxy group, ethoxyethoxy group, methoxyethoxyethoxy group, ethoxyethoxyethoxy group, propyloxyethoxyethoxy group, methoxypropyloxy group and the like.
  • R c1 is a cycloalkyl group or a cycloalkoxy group
  • the number of carbon atoms is preferably 3 or more and 10 or less, and more preferably 3 or more and 6 or less.
  • Specific examples of the case where R c1 is a cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group and the like.
  • R c1 is a cycloalkoxy group
  • R c1 is a cycloalkoxy group
  • R c1 is a cycloalkoxy group
  • R c1 is a saturated aliphatic acyl group or a saturated aliphatic acyloxy group
  • the number of carbon atoms is preferably 2 or more and 20 or less, and more preferably 2 or more and 7 or less.
  • Specific examples of the case where R c1 is a saturated aliphatic acyl group include an acetyl group, a propanoyl group, an n-butanoyl group, a 2-methylpropanoyl group, an n-pentanoyl group, a 2,2-dimethylpropanoyl group and n.
  • n-Hexanoyl group n-heptanoyl group, n-octanoyl group, n-nonanoyl group, n-decanoyl group, n-undecanoyl group, n-dodecanoyl group, n-tridecanoyl group, n-tetradecanoyl group, n-pentadeca
  • Examples thereof include a noyl group and an n-hexadecanoyl group.
  • R c1 is a saturated aliphatic acyloxy group
  • R c1 is a saturated aliphatic acyloxy group
  • R c1 is a saturated aliphatic acyloxy group
  • R c1 is a saturated aliphatic acyloxy group
  • R c1 is a saturated aliphatic acyloxy group
  • R c1 is an alkoxycarbonyl group
  • the number of carbon atoms is preferably 2 or more and 20 or less, and more preferably 2 or more and 7 or less.
  • Specific examples of the case where R c1 is an alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, an n-propyloxycarbonyl group, an isopropyloxycarbonyl group, an n-butyloxycarbonyl group, an isobutyloxycarbonyl group, and sec-butyl.
  • R c1 is a phenylalkyl group
  • the number of carbon atoms is preferably 7 or more and 20 or less, and more preferably 7 or more and 10 or less.
  • R c1 is a naphthylalkyl group
  • the number of carbon atoms is preferably 11 or more and 20 or less, and more preferably 11 or more and 14 or less.
  • Specific examples of the case where R c1 is a phenylalkyl group include a benzyl group, a 2-phenylethyl group, a 3-phenylpropyl group, and a 4-phenylbutyl group.
  • R c1 is a naphthylalkyl group
  • Rc1 is a phenylalkyl group or a naphthylalkyl group
  • Rc1 may further have a substituent on the phenyl group or the naphthyl group.
  • R c1 is a heterocyclyl group
  • the heterocyclyl group is a 5- or 6-membered monocycle containing one or more N, S, O, or the monocycles are fused together, or the monocycle and the benzene ring are condensed.
  • Heterocyclyl group When the heterocyclyl group is a fused ring, the number of monocycles constituting the fused ring is up to 3.
  • heterocycle constituting such a heterocyclyl group examples include furan, thiophene, pyrrol, oxazole, isoxazole, thiazole, thiadiazol, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, pyridazine, benzofuran, benzothiophene, and indol.
  • examples thereof include isoindole, indridin, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalazine, cinnoline, and quinoxalin.
  • R c1 is a heterocyclyl group
  • the heterocyclyl group may further have a substituent.
  • R c1 is an amino group substituted with 1 or 2 organic groups
  • suitable examples of the organic group are an alkyl group having 1 to 20 carbon atoms and a cycloalkyl group having 3 to 10 carbon atoms.
  • a phenylalkyl group of 20 or less, a naphthyl group which may have a substituent, a naphthoyl group which may have a substituent, a naphthylalkyl group which may have a substituent and has 11 or more and 20 or less carbon atoms, and Heterocyclyl groups and the like can be mentioned. Specific examples of these suitable organic groups are the same as for R c1 .
  • amino group substituted with the organic group 1 or 2 include a methylamino group, an ethylamino group, a diethylamino group, an n-propylamino group, a din-propylamino group, an isopropylamino group, and an n-.
  • the substituents include an alkyl group having 1 to 6 carbon atoms and an alkoxy group having 1 to 6 carbon atoms.
  • Examples thereof include a monoalkylamino group having, a dialkylamino group having an alkyl group having 1 or more and 6 or less carbon atoms, a morpholin-1-yl group, a piperazine-1-yl group, a halogen, a nitro group, a cyano group and the like.
  • the number of the substituent is not limited as long as the object of the present invention is not impaired, but is preferably 1 or more and 4 or less.
  • the phenyl group, the naphthyl group, and the heterocyclyl group contained in R c1 have a plurality of substituents, the plurality of substituents may be the same or different.
  • alkyl groups having 1 or more and 6 or less carbon atoms and 1 carbon atom have carbon atoms because they are chemically stable, have few steric obstacles, and facilitate the synthesis of oxime ester compounds.
  • a group selected from the group consisting of an alkoxy group having 6 or more carbon atoms and a saturated aliphatic acyl group having 2 to 7 carbon atoms is preferable, an alkyl having 1 to 6 carbon atoms is more preferable, and a methyl group is particularly preferable. ..
  • Position R c1 is bonded to the phenyl group, the phenyl group R c1 are attached the position of the bond to the main chain of the phenyl group and the oxime ester compound as a 1-position, if the 2-position of the position of the methyl group
  • the 4th or 5th position is preferable, and the 5th position is more preferable.
  • n1 is preferably an integer of 0 or more and 3 or less, more preferably an integer of 0 or more and 2 or less, and particularly preferably 0 or 1.
  • R c2 is a phenyl group which may have a substituent or a carbazolyl group which may have a substituent.
  • R c2 is a carbazolyl group which may have a substituent
  • the nitrogen atom on the carbazolyl group may be substituted with an alkyl group having 1 or more and 6 or less carbon atoms.
  • the substituent contained in the phenyl group or the carbazolyl group is not particularly limited as long as it does not impair the object of the present invention.
  • suitable substituents that the phenyl group or carbazolyl group may have on the carbon atom include an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and a carbon atom.
  • It may have a naphthoyloxy group, a naphthylalkyl group having 11 or more and 20 or less carbon atoms which may have a substituent, a heterocyclyl group which may have a substituent, and a heterocyclylcarbonyl which may have a substituent.
  • Examples thereof include an amino group substituted with a group, an amino group, 1 or 2 organic groups, a morpholin-1-yl group, a piperazine-1-yl group, a halogen, a nitro group, a cyano group and the like.
  • R c2 is a carbazolyl group
  • suitable substituents that the carbazolyl group may have on the nitrogen atom include an alkyl group having 1 to 20 carbon atoms and a cyclo having 3 to 10 carbon atoms.
  • Examples thereof include a heterocyclylcarbonyl group which may have a substituent.
  • an alkyl group having 1 to 20 carbon atoms is preferable, an alkyl group having 1 to 6 carbon atoms is more preferable, and an ethyl group is particularly preferable.
  • substituents which the phenyl group or the carbazolyl group may have are an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, an alkoxycarbonyl group, a saturated aliphatic acyloxy group, and a substituent.
  • substituents which may have groups, naphthylalkyl groups which may have substituents, heterocyclyl groups which may have substituents, and amino groups substituted with one or two organic groups. , R c1 .
  • R c2 an alkyl having 1 to 6 carbon atoms as an example of a substituent when the phenyl group, the naphthyl group, and the heterocyclyl group contained in the substituent of the phenyl group or the carbazolyl group further have a substituent.
  • alkoxy group with 1 to 6 carbon atoms saturated aliphatic acyl group with 2 to 7 carbon atoms
  • alkoxycarbonyl group with 2 to 7 carbon atoms saturated aliphatic acyl group with 2 to 7 carbon atoms It is selected from the group consisting of an acyloxy group; a phenyl group; a naphthyl group; a benzoyl group; a naphthoyl group; an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, and a phenyl group.
  • a benzoyl group substituted with a group; a monoalkylamino group having an alkyl group having 1 to 6 carbon atoms; a dialkylamino group having an alkyl group having 1 to 6 carbon atoms; a morpholin-1-yl group; piperazin- 1-Il group; halogen; nitro group; cyano group can be mentioned.
  • the phenyl group, the naphthyl group, and the heterocyclyl group contained in the substituent of the phenyl group or the carbazolyl group further have a substituent, the number of the substituent is not limited as long as the object of the present invention is not impaired. It is preferably 1 or more and 4 or less.
  • the phenyl group, the naphthyl group, and the heterocyclyl group have a plurality of substituents, the plurality of substituents may be the same or different.
  • R c2 the group represented by the following formula (c2) or (c3) is preferable, and the group represented by the following formula (c2) is more preferable, from the viewpoint that a photopolymerization initiator having excellent sensitivity can be easily obtained.
  • R c4 is a group selected from the group consisting of a monovalent organic group, an amino group, a halogen, a nitro group, and a cyano group, A is S or O, and n3 is an integer of 0 or more and 4 or less. Is.
  • R c5 and R c6 are monovalent organic groups, respectively.
  • R c4 in the formula (c2) is an organic group
  • it can be selected from various organic groups as long as the object of the present invention is not impaired.
  • a preferred example of the case where R c4 is an organic group in the formula (c2) is an alkyl group having 1 or more and 6 or less carbon atoms; an alkoxy group having 1 or more and 6 or less carbon atoms; and 2 or more and 7 or less carbon atoms.
  • Saturated aliphatic acyl group alkoxycarbonyl group having 2 to 7 carbon atoms; saturated aliphatic acyloxy group having 2 to 7 carbon atoms; phenyl group; naphthyl group; benzoyl group; naphthoyl group; 1 to 6 carbon atoms
  • R c4 it is substituted with a group selected from the group consisting of a benzoyl group; a naphthoyl group; an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazine-1-yl group, and a phenyl group.
  • the benzoyl group; nitro group is preferable, and the benzoyl group; naphthoyl group; 2-methylphenylcarbonyl group; 4- (piperazin-1-yl) phenylcarbonyl group; 4- (phenyl) phenylcarbonyl group is more preferable.
  • n3 is preferably an integer of 0 or more and 3 or less, more preferably an integer of 0 or more and 2 or less, and particularly preferably 0 or 1. If n3 is 1, binding position of R c4, to the bond to the phenyl group R c4 is bonded is bonded to an oxygen atom or a sulfur atom, it is preferably in the para position.
  • R c5 in the formula (c3) can be selected from various organic groups as long as the object of the present invention is not impaired.
  • R c5 are an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a saturated aliphatic acyl group having 2 to 20 carbon atoms, and 2 carbon atoms. It may have an alkoxycarbonyl group of 20 or more, a phenyl group which may have a substituent, a benzoyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, and a substituent.
  • a phenylalkyl group having 7 to 20 carbon atoms a naphthyl group which may have a substituent, a naphthoyl group which may have a substituent, a naphthoxycarbonyl group which may have a substituent, and a substituent.
  • Examples thereof include a naphthylalkyl group having 11 or more and 20 or less carbon atoms, a heterocyclyl group which may have a substituent, and a heterocyclylcarbonyl group which may have a substituent.
  • an alkyl group having 1 to 20 carbon atoms is preferable, an alkyl group having 1 to 6 carbon atoms is more preferable, and an ethyl group is particularly preferable.
  • R c6 in the formula (c3) is not particularly limited as long as it does not impair the object of the present invention, and can be selected from various organic groups.
  • a group suitable as R c6 include an alkyl group having 1 to 20 carbon atoms, a phenyl group which may have a substituent, a naphthyl group which may have a substituent, and a substituent.
  • Examples include heterocyclyl groups which may be used. Among these groups, a phenyl group which may have a substituent is more preferable as R c6, and a 2-methylphenyl group is particularly preferable.
  • the substituent includes an alkyl group having 1 to 6 carbon atoms and 1 carbon atom.
  • the phenyl group, naphthyl group, and heterocyclyl group contained in R c4 , R c5 , or R c6 further have a substituent, the number of the substituent is not limited as long as the object of the present invention is not impaired. It is preferably 1 or more and 4 or less.
  • the plurality of substituents may be the same or different.
  • R c3 in the formula (c1) is a hydrogen atom or an alkyl group having 1 or more and 6 or less carbon atoms.
  • R c3 a methyl group or an ethyl group is preferable, and a methyl group is more preferable.
  • PI-1 to PI-42 are particularly suitable compounds.
  • An oxime ester compound represented by the following formula (c4) is also preferable as a photopolymerization initiator.
  • R c7 is a hydrogen atom, a nitro group or a monovalent organic group
  • R c8 and R c9 are a chain alkyl group which may have a substituent and a cyclic organic group which may have a substituent, respectively. It is a group or a hydrogen atom, and R c8 and R c9 may be bonded to each other to form a ring
  • R c10 is a monovalent organic group
  • R c11 has a hydrogen atom and a substituent. It is an alkyl group having 1 or more and 11 or less carbon atoms, or an aryl group which may have a substituent, n4 is an integer of 0 or more and 4 or less, and n5 is 0 or 1.
  • the oxime compound for producing the oxime ester compound of the formula (c4) the compound represented by the following formula (c5) is suitable.
  • R c7 is a hydrogen atom, a nitro group or a monovalent organic group.
  • R c7 is attached to a 6-membered aromatic ring on the fluorene ring in the formula (c4), which is different from the 6-membered aromatic ring attached to the group represented by ⁇ (CO) n5-.
  • the binding position of R c7 with respect to the fluorene ring is not particularly limited.
  • the compound represented by the formula (c4) has 1 or more R c7 , one of the 1 or more R c7 is a fluorene ring because the compound represented by the formula (c4) can be easily synthesized. It is preferable to bind to the 2-position of the inside. If R c7 is more, a plurality of R c7 is independently in may be the same or different.
  • R c7 is not particularly limited as long as it does not interfere with the object of the present invention, and is appropriately selected from various organic groups.
  • R c7 is an organic group include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, a saturated aliphatic acyloxy group, an alkoxycarbonyl group and a substituent.
  • It has a naphthoxycarbonyl group which may have a substituent, a naphthyloxy group which may have a substituent, a naphthylalkyl group which may have a substituent, a heterocyclyl group which may have a substituent, and a substituent.
  • a naphthoxycarbonyl group which may have a substituent
  • a naphthyloxy group which may have a substituent
  • a naphthylalkyl group which may have a substituent
  • a heterocyclyl group which may have a substituent
  • a substituent include a heterocyclylcarbonyl group, an amino group substituted with one or two organic groups, a morpholin-1-yl group, a piperazine-1-yl group and the like.
  • R c7 is an alkyl group
  • the number of carbon atoms of the alkyl group is preferably 1 or more and 20 or less, and more preferably 1 or more and 6 or less.
  • R c7 is an alkyl group, it may be a straight chain or a branched chain.
  • Specific examples of the case where R c7 is an alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group and an n-pentyl group.
  • R c7 is an alkyl group
  • the alkyl group may contain an ether bond (—O—) in the carbon chain.
  • alkyl group having an ether bond in the carbon chain examples include a methoxyethyl group, an ethoxyethyl group, a methoxyethoxyethyl group, an ethoxyethoxyethyl group, a propyloxyethoxyethyl group, a methoxypropyl group and the like.
  • R c7 is an alkoxy group
  • the number of carbon atoms of the alkoxy group is preferably 1 or more and 20 or less, and more preferably 1 or more and 6 or less.
  • R c7 is an alkoxy group, it may be a straight chain or a branched chain.
  • Specific examples of the case where R c7 is an alkoxy group include a methoxy group, an ethoxy group, an n-propyloxy group, an isopropyloxy group, an n-butyloxy group, an isobutyloxy group, a sec-butyloxy group, a tert-butyloxy group and n.
  • -Pentyloxy group isopentyloxy group, sec-pentyloxy group, tert-pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, isooctyloxy group, sec-octyloxy group , Trt-octyloxy group, n-nonyloxy group, isononyloxy group, n-decyloxy group, isodecyloxy group and the like.
  • R c7 is an alkoxy group
  • the alkoxy group may contain an ether bond (—O—) in the carbon chain.
  • alkoxy group having an ether bond in the carbon chain examples include methoxyethoxy group, ethoxyethoxy group, methoxyethoxyethoxy group, ethoxyethoxyethoxy group, propyloxyethoxyethoxy group, methoxypropyloxy group and the like.
  • R c7 is a cycloalkyl group or a cycloalkoxy group
  • the number of carbon atoms of the cycloalkyl group or cycloalkoxy group is preferably 3 or more and 10 or less, and more preferably 3 or more and 6 or less.
  • Specific examples of the case where R c7 is a cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group and the like.
  • R c7 is a cycloalkoxy group
  • R c7 is a cycloalkoxy group
  • R c7 is a cycloalkoxy group
  • R c7 is a saturated aliphatic acyl group or a saturated aliphatic acyloxy group
  • the number of carbon atoms of the saturated aliphatic acyl group or the saturated aliphatic acyloxy group is preferably 2 or more and 21 or less, and more preferably 2 or more and 7 or less.
  • Specific examples of the case where R c7 is a saturated aliphatic acyl group include an acetyl group, a propanoyl group, an n-butanoyl group, a 2-methylpropanoyl group, an n-pentanoyl group, a 2,2-dimethylpropanoyl group and n.
  • n-Hexanoyl group n-heptanoyl group, n-octanoyl group, n-nonanoyl group, n-decanoyl group, n-undecanoyl group, n-dodecanoyl group, n-tridecanoyl group, n-tetradecanoyl group, n-pentadeca
  • Examples thereof include a noyl group and an n-hexadecanoyl group.
  • R c7 is a saturated aliphatic acyloxy group
  • R c7 is a saturated aliphatic acyloxy group
  • R c7 is a saturated aliphatic acyloxy group
  • R c7 is a saturated aliphatic acyloxy group
  • R c7 is a saturated aliphatic acyloxy group
  • R c7 is an alkoxycarbonyl group
  • the number of carbon atoms of the alkoxycarbonyl group is preferably 2 or more and 20 or less, and more preferably 2 or more and 7 or less.
  • Specific examples of the case where R c7 is an alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, an n-propyloxycarbonyl group, an isopropyloxycarbonyl group, an n-butyloxycarbonyl group, an isobutyloxycarbonyl group, and sec-butyl.
  • R c7 is a phenylalkyl group
  • the number of carbon atoms of the phenylalkyl group is preferably 7 or more and 20 or less, and more preferably 7 or more and 10 or less.
  • R c7 is a naphthylalkyl group
  • the number of carbon atoms of the naphthylalkyl group is preferably 11 or more and 20 or less, and more preferably 11 or more and 14 or less.
  • Specific examples of the case where R c7 is a phenylalkyl group include a benzyl group, a 2-phenylethyl group, a 3-phenylpropyl group, and a 4-phenylbutyl group.
  • R c7 is a naphthylalkyl group
  • Rc7 is a naphthylalkyl group
  • Rc7 may further have a substituent on the phenyl group or the naphthyl group.
  • R c7 is a heterocyclyl group
  • the heterocyclyl group is a 5- or 6-membered monocycle containing one or more N, S, O, or the monocycles are fused together, or the monocycle and the benzene ring are condensed.
  • Heterocyclyl group When the heterocyclyl group is a fused ring, the number of monocycles constituting the fused ring is up to 3.
  • the heterocyclyl group may be an aromatic group (heteroaryl group) or a non-aromatic group.
  • heterocycle constituting such a heterocyclyl group examples include furan, thiophene, pyrrol, oxazole, isooxazole, thiazole, thiadiazol, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, pyridazine, benzofuran, benzothiophene, and indol.
  • Examples thereof include isoindole, indridin, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalazine, cinnoline, quinoxaline, piperidine, piperazine, morpholine, tetrahydropyran, and tetrahydrofuran.
  • R c7 is a heterocyclyl group
  • the heterocyclyl group may further have a substituent.
  • R c7 is a heterocyclyl carbonyl group
  • the heterocyclyl group contained in the heterocyclyl carbonyl group is the same as when R c7 is a heterocyclyl group.
  • R c7 is an amino group substituted with 1 or 2 organic groups
  • suitable examples of the organic group are an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, and the like.
  • phenylalkyl groups which may have substituents
  • naphthoyl groups which may have substituents
  • naphthylalkyl groups which may have substituents and have 11 to 20 carbon atoms, and heterocyclyl.
  • the group etc. can be mentioned.
  • Specific examples of these suitable organic groups are the same as for R c7 .
  • Specific examples of the amino group substituted with the organic group 1 or 2 include a methylamino group, an ethylamino group, a diethylamino group, an n-propylamino group, a din-propylamino group, an isopropylamino group, and an n-.
  • the substituents include an alkyl group having 1 to 6 carbon atoms and an alkoxy group having 1 to 6 carbon atoms.
  • Examples thereof include a monoalkylamino group having, a dialkylamino group having an alkyl group having 1 or more and 6 or less carbon atoms, a morpholin-1-yl group, a piperazine-1-yl group, a halogen, a nitro group, a cyano group and the like.
  • the number of the substituent is not limited as long as the object of the present invention is not impaired, but is preferably 1 or more and 4 or less.
  • the phenyl group, the naphthyl group, and the heterocyclyl group contained in R c7 have a plurality of substituents, the plurality of substituents may be the same or different.
  • R c7 a nitro group or a group represented by R c12- CO- tends to improve the sensitivity and is preferable.
  • R c12 is not particularly limited as long as it does not interfere with the object of the present invention, and can be selected from various organic groups. Examples of a suitable group as R c12 include an alkyl group having 1 to 20 carbon atoms, a phenyl group which may have a substituent, a naphthyl group which may have a substituent, and a substituent. Heterocyclyl groups may be mentioned.
  • R c12 2-methylphenyl group, thiophen-2-yl group, and ⁇ -naphthyl group are particularly preferable as R c12.
  • R c7 is a hydrogen atom
  • the transparency tends to be good, which is preferable.
  • R c7 is a hydrogen atom
  • R c10 is a group represented by the formula (c4a) or (c4b) described later, the transparency tends to be better.
  • R c8 and R c9 are a chain alkyl group which may have a substituent, a cyclic organic group which may have a substituent, or a hydrogen atom, respectively.
  • R c8 and R c9 may be coupled to each other to form a ring.
  • a chain alkyl group which may have a substituent is preferable.
  • the chain alkyl group may be a linear alkyl group or a branched alkyl group.
  • R c8 and R c9 are chain alkyl groups having no substituent
  • the number of carbon atoms of the chain alkyl 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 6 or less.
  • Specific examples of cases where R c8 and R c9 are chain alkyl groups include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group.
  • N-Pentyl group Isopentyl group, sec-Pentyl group, tert-Pentyl group, n-Hexyl group, n-Heptyl group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, n-nonyl Examples thereof include a group, an isononyl group, an n-decyl group, and an isodecyl group.
  • R c8 and R c9 are alkyl groups, the alkyl group may contain an ether bond (—O—) in the carbon chain.
  • alkyl group having an ether bond in the carbon chain examples include a methoxyethyl group, an ethoxyethyl group, a methoxyethoxyethyl group, an ethoxyethoxyethyl group, a propyloxyethoxyethyl group, a methoxypropyl group and the like.
  • R c8 and R c9 are chain alkyl groups having a substituent
  • the number of carbon atoms of the chain alkyl 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 6 or less. ..
  • the number of carbon atoms of the substituent is not included in the number of carbon atoms of the chain alkyl group.
  • the chain alkyl group having a substituent is preferably linear.
  • the substituent that the alkyl group may have is not particularly limited as long as it does not impair the object of the present invention.
  • the substituent include a cyano group, a halogen atom, a cyclic organic group, and an alkoxycarbonyl group.
  • the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Among these, a fluorine atom, a chlorine atom and a bromine atom are preferable.
  • the cyclic organic group include a cycloalkyl group, an aromatic hydrocarbon group, and a heterocyclyl group. Specific examples of the cycloalkyl group are the same as in the preferred example when R c7 is a cycloalkyl group.
  • the aromatic hydrocarbon group include a phenyl group, a naphthyl group, a biphenylyl group, an anthryl group, a phenanthryl group and the like.
  • Specific examples of the heterocyclyl group are the same as in the preferred example when R c7 is a heterocyclyl group.
  • R c7 is an alkoxycarbonyl group
  • the alkoxy group contained in the alkoxycarbonyl group may be linear or branched, preferably linear.
  • the number of carbon atoms of the alkoxy group contained in the alkoxycarbonyl group is preferably 1 or more and 10 or less, and more preferably 1 or more and 6 or less.
  • the number of the substituents is not particularly limited.
  • the number of preferred substituents depends on the number of carbon atoms in the chain alkyl group.
  • the number of substituents is typically 1 or more and 20 or less, preferably 1 or more and 10 or less, and more preferably 1 or more and 6 or less.
  • the cyclic organic group may be an alicyclic group or an aromatic group.
  • the cyclic organic group include an aliphatic cyclic hydrocarbon group, an aromatic hydrocarbon group, and a heterocyclyl group.
  • R c8 and R c9 are cyclic organic groups, the substituents that the cyclic organic group may have are the same as when R c8 and R c9 are chain alkyl groups.
  • R c8 and R c9 are aromatic hydrocarbon groups
  • the group is formed by condensing a plurality of benzene rings.
  • the aromatic hydrocarbon group is a phenyl group or a group formed by bonding or condensing a plurality of benzene rings
  • the number of rings of the benzene ring contained in the aromatic hydrocarbon group is not particularly limited. 3 or less is preferable, 2 or less is more preferable, and 1 is particularly preferable.
  • Preferred specific examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, a biphenylyl group, an anthryl group, a phenanthryl group and the like.
  • R c8 and R c9 are aliphatic cyclic hydrocarbon groups
  • the aliphatic cyclic hydrocarbon group may be monocyclic or polycyclic.
  • the number of carbon atoms of the aliphatic cyclic hydrocarbon group is not particularly limited, but is preferably 3 or more and 20 or less, and more preferably 3 or more and 10 or less.
  • Examples of monocyclic cyclic hydrocarbon groups include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, norbornyl group, isobornyl group, tricyclononyl group, tricyclodecyl group, Examples thereof include a tetracyclododecyl group and an adamantyl group.
  • the heterocyclyl group is a 5- or 6-membered monocycle containing one or more N, S, O, such monocyclic rings, or such monocyclic and benzene rings. Is a heterocyclyl group condensed with.
  • the heterocyclyl group is a fused ring, the number of monocycles constituting the fused ring is up to 3.
  • the heterocyclyl group may be an aromatic group (heteroaryl group) or a non-aromatic group.
  • heterocycle constituting such a heterocyclyl group examples include furan, thiophene, pyrrol, oxazole, isooxazole, thiazole, thiadiazol, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, pyridazine, benzofuran, benzothiophene, and indol.
  • Examples thereof include isoindole, indridin, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalazine, cinnoline, quinoxaline, piperidine, piperazine, morpholine, tetrahydropyran, and tetrahydrofuran.
  • R c8 and R c9 may be coupled to each other to form a ring.
  • the group consisting of the ring formed by R c8 and R c9 is preferably a cycloalkylidene group.
  • the ring constituting the cycloalkylidene group is preferably a 5-membered ring or a 6-membered ring, and more preferably a 5-membered ring.
  • the cycloalkylidene group may be condensed with one or more other rings.
  • rings that may be fused with a cycloalkylene group include a benzene ring, a naphthalene ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a furan ring, a thiophene ring, a pyrrole ring, and a pyridine. Rings, pyrazine rings, pyrimidine rings and the like can be mentioned.
  • R c8 and R c9 examples include groups represented by the formula -A 1 -A 2.
  • a 1 is a linear alkylene group and A 2 is an alkoxy group, a cyano group, a halogen atom, an alkyl halide group, a cyclic organic group, or an alkoxycarbonyl group.
  • the number of carbon atoms of the linear alkylene group of A 1 is preferably 1 or more and 10 or less, and more preferably 1 or more and 6 or less.
  • a 2 is an alkoxy group
  • the alkoxy group may be linear or branched, preferably linear.
  • the number of carbon atoms of the alkoxy group is preferably 1 or more and 10 or less, and more preferably 1 or more and 6 or less.
  • a 2 is a halogen atom, a fluorine atom, a chlorine atom, a bromine atom and an iodine atom are preferable, and a fluorine atom, a chlorine atom and a bromine atom are more preferable.
  • the halogen atom contained in the alkyl halide group is preferably a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and more preferably a fluorine atom, a chlorine atom or a bromine atom.
  • the alkyl halide group may be linear or branched, preferably linear.
  • a 2 is a cyclic organic group
  • examples of the cyclic organic group are the same as those of the cyclic organic group that R c8 and R c9 have as substituents.
  • a 2 is an alkoxycarbonyl group
  • examples of alkoxycarbonyl groups are similar to the alkoxycarbonyl groups that R c8 and R c9 have as substituents.
  • R c8 and R c9 are alkyl groups such as ethyl group, n-propyl group, n-butyl group, n-hexyl group, n-heptyl group, and n-octyl group; 2-methoxyethyl.
  • Alkyl group 2-cyclohexylethyl group, 3-cyclohexyl-n-propyl group, 4-cyclohexyl-n-butyl group, 5-cyclohexyl-n-pentyl group, 6-cyclohexyl-n-hexyl group, 7-cyclohexyl-n -Heptyl group, 8-cyclohexyl-n-octyl group, 2-cyclopentylethyl group, 3-cyclopentyl-n-propyl group, 4-cyclopentyl-n-butyl group, 5-cyclopentyl-n-pentyl group, 6-cyclopentyl- Cycloalkylalkyl groups such as n-hexyl group, 7-cyclopentyl-n-heptyl group, and 8-cyclopentyl-n-octyl group; 2-methoxycarbonylethyl group, 3-methoxycarbonyl-n-propyl
  • R c8 and R c9 the preferred groups among the above are ethyl group, n-propyl group, n-butyl group, n-pentyl group, 2-methoxyethyl group, 2-cyanoethyl group, 2-phenylethyl group, 2-Cyclohexylethyl group, 2-methoxycarbonylethyl group, 2-chloroethyl group, 2-bromoethyl group, 3,3,3-trifluoropropyl group, and 3,3,4,5,5,5-hepta It is a fluoro-n-pentyl group.
  • R c10 examples include alkyl groups, alkoxy groups, cycloalkyl groups, cycloalkoxy groups, saturated aliphatic acyl groups, alkoxycarbonyl groups, saturated aliphatic acyloxy groups and substituents , as in R c7.
  • Examples thereof include a heterocyclylcarbonyl group which may have a group, an amino group substituted with one or two organic groups, a morpholin-1-yl group, a piperazine-1-yl group and the like. Specific examples of these groups are similar to those described for R c7. Further, as R c10 , a cycloalkylalkyl group, a phenoxyalkyl group which may have a substituent on the aromatic ring, and a phenylthioalkyl group which may have a substituent on the aromatic ring are also preferable.
  • the substituents that the phenoxyalkyl group and the phenylthioalkyl group may have are the same as the substituents that the phenyl group contained in R c7 may have.
  • R c10 includes an alkyl group, a cycloalkyl group, a phenyl group which may have a substituent, or a cycloalkylalkyl group, and a phenylthio which may have a substituent on the aromatic ring.
  • Alkyl groups are preferred.
  • the alkyl group an alkyl group having 1 to 20 carbon atoms is preferable, an alkyl group having 1 to 8 carbon atoms is more preferable, an alkyl group having 1 to 4 carbon atoms is particularly preferable, and a methyl group is the most preferable. preferable.
  • a methylphenyl group is preferable, and a 2-methylphenyl group is more preferable.
  • the number of carbon atoms of the cycloalkyl group contained in the cycloalkylalkyl group is preferably 5 or more and 10 or less, more preferably 5 or more and 8 or less, and particularly preferably 5 or 6.
  • the number of carbon atoms of the alkylene group contained in the cycloalkylalkyl group is preferably 1 or more and 8 or less, more preferably 1 or more and 4 or less, and particularly preferably 2.
  • a cyclopentylethyl group is preferable.
  • the number of carbon atoms of the alkylene group contained in the phenylthioalkyl group which may have a substituent on the aromatic ring is preferably 1 or more and 8 or less, more preferably 1 or more and 4 or less, and particularly preferably 2.
  • a 2- (4-chlorophenylthio) ethyl group is preferable.
  • a 3 is a divalent organic group, preferably a divalent hydrocarbon group, and preferably an alkylene group.
  • a 4 is a monovalent organic group, preferably a monovalent hydrocarbon group.
  • the alkylene group may be linear or branched, preferably linear.
  • the number of carbon atoms of the alkylene group is preferably 1 or more and 10 or less, more preferably 1 or more and 6 or less, and particularly preferably 1 or more and 4 or less.
  • a 4 the number 1 to 10 alkyl group carbon atoms, having 7 or more carbon atoms and 20 or less aralkyl group, and an aromatic hydrocarbon group having 6 to 20 carbon atoms.
  • Specific preferable examples of A 4 is methyl group, ethyl group, n- propyl group, an isopropyl group, n- butyl group, isobutyl group, sec- butyl group, tert- butyl group, n- pentyl group, n- hexyl Examples thereof include a group, a phenyl group, a naphthyl group, a benzyl group, a phenethyl group, an ⁇ -naphthylmethyl group, a ⁇ -naphthylmethyl group and the like.
  • Preferable specific examples of the group represented by -A 3- CO-O-A 4 are 2-methoxycarbonylethyl group, 2-ethoxycarbonylethyl group, 2-n-propyloxycarbonylethyl group, 2-n. -Butyloxycarbonylethyl group, 2-n-pentyloxycarbonylethyl group, 2-n-hexyloxycarbonylethyl group, 2-benzyloxycarbonylethyl group, 2-phenoxycarbonylethyl group, 3-methoxycarbonyl-n-propyl Group, 3-ethoxycarbonyl-n-propyl group, 3-n-propyloxycarbonyl-n-propyl group, 3-n-butyloxycarbonyl-n-propyl group, 3-n-pentyloxycarbonyl-n-propyl group , 3-n-hexyloxycarbonyl-n-propyl group, 3-benzyloxycarbonyl-n-propyl group,
  • R c10 preferably a group represented by the following formula (C4a) or (C4b).
  • R c13 and R c14 are organic groups, respectively, n6 is an integer of 0 or more and 4 or less, and R c13 and R c14 are present at adjacent positions on the benzene ring.
  • R c13 and R c14 may be combined with each other to form a ring, n7 is an integer of 1 or less and 8 or less, n8 is an integer of 1 or more and 5 or less, and n9 is 0 or more (n8 + 3). It is the following integer, and R c15 is an organic group.
  • Examples of organic groups for R c13 and R c14 in formula (c4a) are similar to R c7.
  • R c13 an alkyl group or a phenyl group is preferable.
  • R c13 is an alkyl group, the number of carbon atoms thereof is preferably 1 or less and 10 or more, more preferably 1 or more and 5 or less, particularly preferably 1 or more and 3 or less, and most preferably 1. That is, R c13 is most preferably a methyl group.
  • the ring may be an aromatic ring or an aliphatic ring.
  • n6 is an integer of 0 or more and 4 or less, preferably 0 or 1, and more preferably 0.
  • R c15 is an organic group.
  • the organic group include groups similar to the organic group described for R c7.
  • an alkyl group is preferable.
  • the alkyl group may be linear or branched.
  • the number of carbon atoms of the alkyl group is preferably 1 or more and 10 or less, more preferably 1 or more and 5 or less, and particularly preferably 1 or more and 3 or less.
  • R c15 a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group and the like are preferably exemplified, and among these, a methyl group is more preferable.
  • n8 is an integer of 1 or more and 5 or less, preferably an integer of 1 or more and 3 or less, and more preferably 1 or 2.
  • n9 is 0 or more (n8 + 3) or less, an integer of 0 or more and 3 or less is preferable, an integer of 0 or more and 2 or less is more preferable, and 0 is particularly preferable.
  • n7 is an integer of 1 or more and 8 or less, an integer of 1 or more and 5 or less is preferable, an integer of 1 or more and 3 or less is more preferable, and 1 or 2 is particularly preferable.
  • R c11 is a hydrogen atom, an alkyl group having 1 to 11 carbon atoms which may have a substituent, or an aryl group which may have a substituent.
  • R c11 is an alkyl group
  • a phenyl group, a naphthyl group and the like are preferably exemplified.
  • R c7 is an aryl group
  • an alkyl group having 1 or more and 5 or less carbon atoms an alkoxy group, a halogen atom and the like are preferably exemplified.
  • a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a phenyl group, a benzyl group, a methylphenyl group, a naphthyl group and the like are preferably exemplified. Of these, a methyl group or a phenyl group is more preferable.
  • R c11 are the same as R c11 in formula (c4).
  • the acylating agent to give the acyl group represented by -COR c11, (R c11 CO) or an acid anhydride represented by 2 O, R c11 COHal (Hal is a halogen atom) include acid halide represented by Be done.
  • Preferable specific examples of the compound represented by the formula (c4) include the following PI-43 to PI-83.
  • the content of the photopolymerization initiator is preferably 0.5 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the solid content of the energy-sensitive composition of the first aspect.
  • sufficient heat resistance and chemical resistance can be obtained, the coating film forming ability can be improved, and curing defects can be suppressed.
  • the energy-sensitive composition of the first aspect as the modified metal oxide fine particle dispersion liquid contains the metal oxide fine particles containing the above-mentioned modified metal oxide fine particles as described above. Therefore, the energy-sensitive composition of the first aspect can be used to form a pattern containing metal oxide fine particles.
  • the energy-sensitive composition of the first aspect may further contain a colorant.
  • the colorant is not particularly limited, but for example, a compound classified as Pigment in the Color Index (CI; The Society of Dyers and Colorists), specifically, the following. It is preferable to use a pigment having a color index (CI) number.
  • C. I. Pigment Yellow 1 (hereinafter, "CI Pigment Yellow” is the same and only the number is described), 3, 11, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53. , 55, 60, 61, 65, 71, 73, 74, 81, 83, 86, 93, 95, 97, 98, 99, 100, 101, 104, 106, 108, 109, 110, 113, 114, 116 , 117, 119, 120, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 166, 167, 168, 175, 180. 185; C. I.
  • Pigment Orange 1 (hereinafter, “CI Pigment Orange” is the same and only the number is described), 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46. , 49, 51, 55, 59, 61, 63, 64, 71, 73; C.
  • Pigment Violet 1 (hereinafter, “CI Pigment Violet” is the same and only the number is described), 19, 23, 29, 30, 32, 36, 37, 38, 39, 40, 50; C. I.
  • Pigment Red 1 (hereinafter, "CI Pigment Red” is the same and only the number is described) 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14 , 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 40, 41, 42, 48: 1, 48: 2, 48: 3, 48: 4, 49 1, 49: 2, 50: 1, 52: 1, 53: 1, 57, 57: 1, 57: 2, 58: 2, 58: 4, 60: 1, 63: 1, 63: 2, 64 1, 81: 1, 83, 88, 90: 1, 97, 101, 102, 104, 105, 106, 108, 112, 113, 114, 122, 123, 144, 146, 149, 150, 151, 155 , 166, 168, 170, 171, 172, 174, 175, 176, 177, 178, 179, 180, 185, 187, 188, 190, 192, 193, 194, 202, 206, 207, 208, 209, 215
  • I. Pigment Blue 1 (hereinafter, "CI Pigment Blue” is the same and only the number is described), 2, 15, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64 , 66; C. I. Pigment Green 7, C.I. I. Pigment Green 36, C.I. I. Pigment Green 37; C. I. Pigment Brown 23, C.I. I. Pigment Brown 25, C.I. I. Pigment Brown 26, C.I. I. Pigment Brown 28; C. I. Pigment Black 1, C.I. I. Pigment Black 7.
  • black pigments include metal oxides such as carbon black, titanium black, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium and silver, composite oxides, metal sulfides, metal sulfates and metal carbonates. , Various pigments regardless of organic or inorganic substances can be mentioned. Among these, it is preferable to use carbon black having a high light-shielding property.
  • carbon black known carbon blacks such as channel black, furnace black, thermal black, and lamp black can be used, but it is preferable to use channel black having excellent light-shielding properties. Further, resin-coated carbon black may be used. Resin-coated carbon black has lower conductivity than carbon black without resin coating.
  • the above organic pigment may be appropriately added as an auxiliary pigment.
  • a dispersant may be further used.
  • a dispersant it is preferable to use a polyethyleneimine-based, urethane resin-based, or acrylic resin-based polymer dispersant.
  • carbon black it is preferable to use an acrylic resin-based dispersant as the dispersant.
  • the inorganic pigment and the organic pigment may be used alone or in combination, but when they are used in combination, 10 parts by mass of the organic pigment is used with respect to 100 parts by mass of the total amount of the inorganic pigment and the organic pigment. It is preferably used in the range of 20 parts by mass or more and 80 parts by mass or less, and more preferably 20 parts by mass or more and 40 parts by mass or less.
  • the content of the colorant may be appropriately determined according to the use of the energy-sensitive composition of the first aspect, but as an example, with respect to 100 parts by mass of the solid content of the energy-sensitive composition of the first aspect. It is preferably 5 parts by mass or more and 70 parts by mass or less, and more preferably 25 parts by mass or more and 60 parts by mass or less.
  • the colorant is preferably added to the photosensitive composition after being prepared as a dispersion liquid dispersed at an appropriate concentration using a dispersant.
  • Examples of the organic solvent in the energy-sensitive composition of the first aspect include 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.
  • Other esters such as ethyl acetate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxobutano
  • propylene glycol monomethyl ether ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, 3-methoxybutyl acetate, N-methylpyrrolidone , N, N-dimethylformamide, N, N-dimethylacetamide, and amides such as the solvent represented by the above formula (S01) are used in the alkali-soluble resin, the photopolymerizable compound, and the photopolymerization initiator. On the other hand, it is preferable because it shows excellent solubility.
  • the content of the organic solvent is preferably such that the solid content concentration of the energy-sensitive composition of the first aspect is 1% by mass or more and 50% by mass or less, and more preferably 5% by mass or more and 30% by mass or less. ..
  • the energy sensitive composition of the second aspect is a negative photosensitive composition.
  • a negative photosensitive composition includes metal oxide fine particles containing modified metal oxide fine particles, an alkali-soluble resin having a phenolic hydroxyl group as a base material component (C), an acid crosslinkable substance, a photoacid generator, and a photoacid generator. Contains organic solvents.
  • a polyhydroxystyrene-based resin As the alkali-soluble resin having a phenolic hydroxyl group in the energy-sensitive composition of the second aspect, for example, a polyhydroxystyrene-based resin can be used.
  • the polyhydroxystyrene-based resin has at least a structural unit derived from hydroxystyrene.
  • hydroxystyrene refers to hydroxystyrene, a compound in which the hydrogen atom bonded to the ⁇ -position of hydroxystyrene is substituted with another substituent such as a halogen atom, an alkyl group, or an alkyl halide group, and derivatives thereof.
  • the concept includes the hydroxystyrene derivative (monomer) of.
  • hydroxystyrene derivative at least a benzene ring and a hydroxyl group bonded to the benzene ring are maintained.
  • the hydrogen atom bonded to the ⁇ -position of hydroxystyrene is a halogen atom or an alkyl group having 1 to 5 carbon atoms.
  • a compound substituted with another substituent such as an alkyl halide group, or a compound in which an alkyl group having 1 to 5 carbon atoms is further bonded to a benzene ring to which a hydroxyl group of hydroxystyrene is bonded, or a compound in which this hydroxyl group is bonded.
  • ⁇ -position of hydroxystyrene refers to a carbon atom to which a benzene ring is bonded, unless otherwise specified.
  • the structural unit derived from this hydroxystyrene is represented by, for example, the following formula (b-1).
  • R b1 represents a hydrogen atom, an alkyl group, a halogen atom, or an alkyl halide group
  • R b2 represents an alkyl group having 1 or more and 5 or less carbon atoms
  • p is 1 or more and 3 or more.
  • the following integers are indicated, and q indicates an integer of 0 or more and 2 or less.
  • the alkyl group of R b1 preferably has 1 or more carbon atoms and 5 or less carbon atoms. Further, a linear or branched alkyl group is preferable, and a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, a neopentyl group and the like are preferable. Can be mentioned. Among these, a methyl group is industrially preferable.
  • halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and a fluorine atom is preferable.
  • the alkyl halide group is a group in which a part or all of the hydrogen atoms of the above-mentioned alkyl group having 1 or more and 5 or less carbon atoms is substituted with a halogen atom. Among these, an alkyl group in which all hydrogen atoms are substituted with fluorine atoms is preferable.
  • a linear or branched alkyl fluorinated group is preferable, a trifluoromethyl group, a hexafluoroethyl group, a heptafluoropropyl group, a nonafluorobutyl group and the like are more preferable, and a trifluoromethyl group (-CF 3 ) is preferable. Is the most preferable.
  • R b1 a hydrogen atom or a methyl group is preferable, and a hydrogen atom is more preferable.
  • Examples of the alkyl group having 1 or more carbon atoms and 5 or less carbon atoms of R b2 include the same groups as in the case of R b1.
  • q is an integer of 0 or more and 2 or less. Among these, 0 or 1 is preferable, and industrially, it is particularly preferable to be 0.
  • the substitution position of R b2 may be any of the ortho position, the meta position, and the para position when q is 1, and any substitution position can be combined when q is 2.
  • p is an integer of 1 or more and 3 or less, and is preferably 1.
  • the hydroxyl group substitution position may be any of the ortho position, the meta position, and the para position, but the para position is preferable because it is easily available and inexpensive. Further, when p is 2 or 3, any substitution position can be combined.
  • the structural unit represented by the above formula (b-1) can be used alone or in combination of two or more.
  • the proportion of the constituent units derived from hydroxystyrene in the polyhydroxystyrene-based resin is preferably 60 mol% or more and 100 mol% or less, preferably 70 mol% or more, with respect to all the constituent units constituting the polyhydroxystyrene-based resin. It is more preferably 100 mol% or less, and further preferably 80 mol% or more and 100 mol% or less. By setting the content within the above range, appropriate alkali solubility can be obtained when the photosensitive composition is prepared.
  • the polyhydroxystyrene-based resin preferably further has a structural unit derived from styrene.
  • the "structural unit derived from styrene” is defined to include a structural unit formed by cleaving the ethylenic double bond of styrene and a styrene derivative (however, hydroxystyrene is not included).
  • the "styrene derivative” is a derivative in which the hydrogen atom bonded to the ⁇ -position of styrene is replaced with another substituent such as a halogen atom, an alkyl group or an alkyl halide group, and the hydrogen atom of the phenyl group of styrene is carbon.
  • styrene refers to a carbon atom to which a benzene ring is bonded, unless otherwise specified.
  • the structural unit derived from this styrene is represented by, for example, the following formula (b-2).
  • R b1 , R b2 , and q are synonymous with the above formula (b-1).
  • R b1 and R b2 include groups similar to R b1 and R b2 of the above formula (b-1), respectively.
  • q is an integer of 0 or more and 2 or less. Among these, 0 or 1 is preferable, and industrially, it is particularly preferable to be 0.
  • the substitution position of R b2 may be any of the ortho position, the meta position, and the para position when q is 1, and any substitution position can be combined when q is 2.
  • the structural unit represented by the above formula (b-2) can be used alone or in combination of two or more.
  • the ratio of the constituent units derived from styrene in the polyhydroxystyrene-based resin is preferably 40 mol% or less, more preferably 30 mol% or less, based on all the constituent units constituting the polyhydroxystyrene-based resin. It is preferably 20 mol% or less, and more preferably 20 mol% or less. Within the above range, an appropriate alkali solubility can be obtained when the photosensitive composition is prepared, and the balance with other constituent units is also improved.
  • the polyhydroxystyrene resin may have a structural unit derived from hydroxystyrene or a structural unit other than the structural unit derived from styrene. More preferably, the polyhydroxystyrene-based resin is a polymer composed of only a structural unit derived from hydroxystyrene, or a copolymer composed of a structural unit derived from hydroxystyrene and a structural unit derived from styrene.
  • the mass average molecular weight of the polyhydroxystyrene resin is not particularly limited, but is preferably 1500 or more and 40,000 or less, and more preferably 2000 or more and 8000 or less.
  • alkali-soluble resin having a phenolic hydroxyl group a phenol-xylylene glycol condensed resin, a cresol-xylylene glycol condensed resin, a phenol-dicyclopentadiene condensed resin or the like can also be used.
  • the content of the alkali-soluble resin having a phenolic hydroxyl group is preferably 20% by mass or more and 80% by mass or less, and 35% by mass or more and 65% by mass or less, based on the solid content of the photosensitive composition of the second aspect. Is more preferable. Within the above range, the developability tends to be easily balanced.
  • the acid-crosslinking substance in the energy-sensitive composition of the second aspect is not particularly limited, and a conventionally known acid-crosslinking substance can be used.
  • an amino resin having a hydroxy group or an alkoxyl group for example, melamine resin, urea resin, guanamine resin, acetoguanamine resin, benzoguanamine resin, glycoluryl-formaldehyde resin, succinylamide-formaldehyde resin, ethylene Urea-formaldehyde resin and the like can be mentioned.
  • These acid-crosslinking substances are melamine, urea, guanamine, acetoguanamine, benzoguanamine, glycoluryl, succinylamide, and ethyleneurea, which are reacted with formalin in boiling water to form methylol, or they are further reacted with a lower alcohol to form an alkoxyl. It can be easily obtained by converting to. Practically, it can be obtained as a melamine resin such as Nicarac MX-750, Nicarac MW-30, Nicarac MW100LM, and a urea resin such as Nicarac MX-290 (all manufactured by Sanwa Chemical Co., Ltd.). In addition, benzoguanamine resins such as Cymel 1123 and Cymel 1128 (manufactured by Mitsui Sianad Co., Ltd.) can also be obtained as commercially available products.
  • a benzene compound having an alkoxyl group such as 1,3,5-tris (methoxymethoxy) benzene, 1,2,4-tris (isopropoxymethoxy) benzene, and 1,4-bis (sec-butoxymethoxy) benzene
  • a phenol compound having a hydroxy group such as 2,6-dihydroxymethyl-p-tert-butylphenol or an alkoxyl group.
  • the content of the acid-crosslinkable substance is preferably 5 parts by mass or more and 50 parts by mass or less, and more preferably 10 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the alkali-soluble resin having a phenolic hydroxyl group. preferable. Within the above range, the curability and patterning characteristics of the photosensitive composition are improved.
  • the photoacid generator in the energy-sensitive composition of the second aspect is not particularly limited, and a conventionally known photoacid generator can be used.
  • the content of the photoacid generator is preferably 0.05 parts by mass or more and 30 parts by mass or less, and 0.1 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the alkali-soluble resin having a phenolic hydroxyl group. Is more preferable. Within the above range, the curability of the photosensitive composition becomes good.
  • the energy-sensitive composition of the second aspect contains the metal oxide fine particles containing the modified metal oxide fine particles described above. Therefore, the energy-sensitive composition of the second aspect can be used to form a patterned metal oxide fine particle-containing film.
  • the energy-sensitive composition of the second aspect may further contain a compound having 4 or more phenolic hydroxyl groups and a molecular weight of less than 2000.
  • such compounds include various benzophenone compounds such as tetrahydroxybenzophenone, pentahydroxybenzophenone, hexahydroxybenzophenone, and heptahydroxybenzophenone, as well as bis [2-hydroxy-3- (2'-hydroxy-5').
  • benzophenone-based compounds hydroxyaryl-based compounds, bis (hydroxyphenyl) alkane-based compounds, and polyhydroxystyrene-based compounds may have substituents other than hydroxyl groups. These compounds can be used alone or in combination of two or more.
  • the content of the compound having 4 or more phenolic hydroxyl groups and having a molecular weight of less than 2000 is preferably 0.5 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the alkali-soluble resin having phenolic hydroxyl groups. Within the above range, the tapering phenomenon when the photosensitive composition is patterned can be suppressed.
  • Examples of the organic solvent in the energy-sensitive composition of the second aspect include the organic solvent exemplified in the energy-sensitive composition of the first aspect.
  • the content of the organic solvent is preferably such that the solid content concentration of the energy-sensitive composition of the third aspect is 1% by mass or more and 50% by mass or less, and more preferably 5% by mass or more and 30% by mass or less. ..
  • the energy-sensitive composition of the second aspect may contain the above-mentioned various additives, if necessary, like the energy-sensitive composition of the first aspect.
  • the photosensitive composition of the third aspect includes the above-mentioned metal oxide fine particles containing the modified metal oxide fine particles, an epoxy group-containing polycarboxylic acid resin, and light. It is a negative type photosensitive composition containing an acid generator and an organic solvent.
  • the epoxy group-containing polycarboxylic acid resin in the photosensitive composition of the third aspect has, for example, an epoxy compound having two or more epoxy groups in one molecule and one or more alcoholic hydroxyl groups in one molecule.
  • a resin obtained by further reacting a polybasic acid anhydride with a reaction product obtained by reacting with a monocarboxylic acid can be used.
  • Examples of the epoxy compound having two or more epoxy groups in one molecule include the epoxy compound mentioned as the above-mentioned epoxy resin precursor and the same resin as the above-mentioned epoxy group-containing resin.
  • novolak type epoxy resin bisphenol type epoxy resin, trisphenol methane type epoxy resin, tris (2,3-epoxypropyl) isocyanurate, biphenyldiglycidyl ether, alicyclic epoxy resin, copolymerized epoxy resin and the like are mentioned. Be done.
  • the novolak type epoxy resin is obtained by reacting novolaks obtained by reacting phenols such as phenol, cresol, halogenated phenol, and alkylphenol with formaldehyde under an acidic catalyst with epichlorohydrin and methylepicrolhydrin.
  • Epoxy resin and the like can be mentioned.
  • Commercially available products include EOCN-102S, EOCN-103S, EOCN-104S, EOCN-1027, EPPN-201, BREN-S (all manufactured by Nippon Kayaku Co., Ltd.); DEN-431, DEN-439 (all Dow. (Manufactured by Chemical Corporation); N-730, N-770, N-865, N-665, N-673, VH-4150 (all manufactured by Dainippon Ink and Chemicals Co., Ltd.) and the like.
  • Examples of the bisphenol type epoxy resin include an epoxy resin obtained by reacting bisphenols such as bisphenol A, bisphenol F, bisphenol S, and tetrabrom bisphenol A with epichlorohydrin and methylepicrolhydrin, and diglycidyl of bisphenol A and bisphenol F.
  • Examples thereof include an epoxy resin obtained by reacting a condensate of ether and the above bisphenol with epichlorohydrin or methylepicrolhydrin.
  • Examples of commercially available products include Epicoat 1004, Epicoat 1002, Epicoat 4002, Epicoat 4004 (all manufactured by Oleochemical Shell Epoxy Co., Ltd.) and the like.
  • trisphenol methane type epoxy resin examples include an epoxy resin obtained by reacting trisphenol methane or triscresol methane with epichlorohydrin or methyl epichlorohydrin.
  • examples of commercially available products include EPPN-501 and EPPN-502 (both manufactured by Nippon Kayaku Co., Ltd.).
  • Examples of the alicyclic epoxy resin include compounds similar to the above-mentioned alicyclic epoxy compound.
  • Commercially available products include Serokiside 2021 manufactured by Daicel Chemicals, Epomic VG-3101 manufactured by Mitsui Chemicals, E-1031S manufactured by Oleochemical Shell Epoxy, EPB-13, EPB-27 manufactured by Nippon Soda, etc. Can be mentioned.
  • the copolymerized epoxy resin includes CP-50M and CP-50S manufactured by Nippon Oil & Fats Co., Ltd., which are copolymers of glycidyl methacrylate, styrene, and ⁇ -methylstyrene, or the common weight of glycidyl methacrylate and cyclohexylmaleimide. Coalescence and the like can be mentioned.
  • the epoxy resin having two or more epoxy groups in one of these molecules include, for example, cresol novolac type epoxy resin, phenol novolac type epoxy resin, bisphenol type epoxy resin, trisphenol methane type epoxy resin and the like. Be done.
  • a polycondensate of ⁇ -hydroxyphenyl- ⁇ -hydropoly (biphenyldimethylene-hydroxyphenylene) and 1-chloro-2,3-epoxypropane, and ⁇ -2,3-epoxypropoxyphenyl- ⁇ -hydropoly ⁇ 2- (2,3-epoxypropoxy) -benzylidene-2,3-epoxypropoxyphenylene ⁇ is preferable.
  • Examples of monocarboxylic acids having one or more alcoholic hydroxyl groups in one molecule include hydroxymonocarboxylic acids such as dimethylol propionic acid, dimethylol acetic acid, dimethylol butyric acid, dimethylol valerate, dimethylol caproic acid, and hydroxypivalic acid. Can be mentioned. Among these, a monocarboxylic acid having 1 to 5 alcoholic hydroxyl groups in one molecule is preferable.
  • polybasic acid anhydride examples include succinic anhydride, maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride and the like. Can be mentioned.
  • the reaction between the epoxy compound and the monocarboxylic acid is preferably 0.1 mol or more and 0.7 mol or less, and 0.2 mol or more and 0.5 mol or less, based on 1 equivalent of the epoxy group of the epoxy compound. Is more preferable.
  • catalysts eg, triphenylphosphine, benzyldimethylamine, trialkylammonium chloride, triphenylstibine, etc.
  • triphenylphosphine eg, benzyldimethylamine, trialkylammonium chloride, triphenylstibine, etc.
  • the reaction product obtained by inactivating the catalyst with an organic peroxide or the like after the reaction is completed is preferable because it is stable and has good storage stability.
  • the amount of the reaction catalyst used is preferably 0.1% by mass or more and 10% by mass or less with respect to the reaction mixture, and the reaction temperature is preferably 60 ° C. or more and 150 ° C. or less. Thereby, a reaction product of the epoxy compound and the monocarboxylic acid can be obtained.
  • an amount of the polybasic acid anhydride having an acid value of 50 mgKOH / g or more and 150 mgKOH / g or less of the finally obtained epoxy group-containing polycarboxylic acid resin is reacted.
  • the reaction temperature is preferably 60 ° C. or higher and 150 ° C. or lower. In this way, an epoxy group-containing polycarboxylic acid resin can be obtained.
  • epoxy group-containing polycarboxylic acid resins can be used alone or in combination of two or more.
  • the content of the epoxy group-containing polycarboxylic acid resin is preferably 30% by mass or more and 80% by mass or less, and 40% by mass or more and 70% by mass or less, based on the solid content of the energy-sensitive composition of the third aspect. Is more preferable. Within the above range, the coating film forming ability can be improved.
  • the photoacid generator in the energy-sensitive composition of the third aspect is not particularly limited, and conventionally known photoacid generators can be used.
  • the content of the photoacid generator is preferably 0.5% by mass or more and 30% by mass or less, preferably 1% by mass or more and 20% by mass or less, based on the solid content of the energy-sensitive composition of the third aspect. More preferably. Within the above range, the curability of the photosensitive composition becomes good.
  • the energy-sensitive composition of the third aspect may further contain a modifying component for adjusting moisture resistance, heat resistance, adhesion and the like.
  • the modified component itself may be cured by heat, ultraviolet rays, or the like, or may react with the residual hydroxyl group, carboxy group, or the like of the epoxy group-containing polycarboxylic acid resin by heat, ultraviolet rays, or the like.
  • an epoxy compound having one or more epoxy groups in one molecule, a melamine derivative for example, hexamethoxymelamine, hexabutoxydated melamine, condensed hexamethoxymelamine, etc.
  • a bisphenol A-based compound for example, tetramethylol.
  • Bisphenol A etc. oxazoline compounds and the like can be mentioned.
  • Epoxy compounds having one or more epoxy groups in one molecule include Epicoat 1009 and 1031 (all manufactured by Yuka Shell Co., Ltd.), Epicron N-3050, and N-7050 (all manufactured by Dainippon Ink and Chemicals Co., Ltd.).
  • Novolak type epoxy resin of bisphenol A such as Epicron N-880 manufactured by Dainippon Ink and Chemicals Co., Ltd .
  • Rubber-modified epoxy resin such as Epicron TSR-601 manufactured by Dainippon Ink and Chemicals Co., Ltd. and R-14151 manufactured by ACR Co., Ltd .
  • Bisphenol S type epoxy resin such as EBPS-200 manufactured by Nippon Kayaku Co., Ltd.
  • the content of the modified component is preferably 50% by mass or less, more preferably 30% by mass or less, based on the solid content of the energy-sensitive composition of the third aspect.
  • the energy-sensitive composition of the third aspect may further contain a colorant like the energy-sensitive composition of the first aspect.
  • Examples of the organic solvent in the energy-sensitive composition of the third aspect include the organic solvent exemplified in the photosensitive composition of the first aspect.
  • the content of the organic solvent is preferably such that the solid content concentration of the energy-sensitive composition of the third aspect is 1% by mass or more and 50% by mass or less, and more preferably 5% by mass or more and 30% by mass or less. ..
  • the energy-sensitive composition of the fourth aspect is the above-mentioned metal oxide fine particles containing the above-mentioned modified metal oxide fine particles and the above-mentioned base material component (C). It is a curable composition containing a curable compound represented by the formula (b-01) and a curable agent.
  • the curable compound is a compound represented by the formula (b-01), has a condensed polycyclic skeleton containing an aromatic ring as a main skeleton, and has a polymerizable group.
  • the energy-sensitive composition contains a compound containing an aromatic ring such as the compound represented by the formula (b-01), it may be difficult for the metal oxide fine particles to disperse well in the energy-sensitive composition.
  • the curable compound may contain a cationically polymerizable compound other than the compound represented by the above formula (b-01).
  • the amount of the compound represented by the above formula (b-01) in the curable compound is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, and 90% by mass or more. Is particularly preferable, and 100% by mass is most preferable.
  • the curable compound may contain a cationically polymerizable compound other than the compound represented by the formula (b-01), and includes, for example, a vinyl ether compound containing a vinyloxy group, an epoxy compound containing an epoxy group, and an episulfide group. Examples thereof include episulfide compounds and radically polymerizable compounds having unsaturated double bonds capable of radically polymerizable. Further, for the purpose of adjusting the refractive index of the cured product or the like, a compound in which both W 01 and W 02 of the compound represented by the above formula (b-01) have a hydrogen atom as R 03 may be combined.
  • rings Z 01 , X 01 , R 01 , R 02 , and M are the same as the compound represented by the formula (b-01).
  • vinyl ether compounds, epoxy compounds, episulfide compounds, and radically polymerizable compounds will be described.
  • the vinyl ether compound that can be used together with the compound represented by the formula (b-01) 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 (b-01) may or may not contain an aromatic group.
  • the vinyl ether compound used in combination with the compound represented by the formula (b-01) is preferably an aliphatic vinyl ether compound containing no aromatic group.
  • the vinyl ether compound used in combination with the compound represented by the formula (b-01) is preferably a compound having a vinyloxy group bonded to an aromatic group.
  • vinyl ether compound that can be used together with the compound represented by the formula (b-01) include ethyl vinyl ether, isobutyl vinyl ether, hydroxybutyl vinyl ether, butanediol divinyl ether, cyclohexyl vinyl ether, N-butyl vinyl ether and tert.
  • -Olipid vinyl ether compounds such as butyl vinyl ether, triethylene glycol divinyl ether octadecyl vinyl ether, cyclohexanedimethanol divinyl ether, diethylene glycol divinyl ether, and cyclohexanedimethanol monovinyl ether vinylphenyl ether, 4-vinyloxytoluene, 3-vinyloxytoluene, 2-vinyloxytoluene, 1-vinyloxy-4-chlorobenzene, 1-vinyloxy-3-chlorobenzene, 1-vinyloxy-2-chlorobenzene, 1-vinyloxy-2,3-dimethylbenzene, 1-vinyloxy-2,4-dimethyl Benzene, 1-vinyloxy-2,5-dimethylbenzene, 1-vinyloxy-2,6-dimethylbenzene, 1-vinyloxy-3,4-dimethylbenzene, 1-vinyloxy-3,5-
  • epoxy compound examples of the epoxy compound that can be used together with the compound represented by the formula (b-01) include the epoxy compounds similar to the epoxy resin precursor as the thermosetting material described above for the base material component (C). Be done.
  • episulfide compound The type of episulfide compound is not particularly limited as long as the object of the present invention is not impaired.
  • Preferred episulfide compounds include compounds in which the oxygen atom in the epoxy group is replaced with a sulfur atom in the above-mentioned epoxy compound.
  • radically polymerizable compound As the radically polymerizable compound, a compound having an ethylenically unsaturated group can be used.
  • the compound having an ethylenically unsaturated group includes a monofunctional compound and a polyfunctional compound.
  • Examples of the monofunctional compound include (meth) acrylamide, methylol (meth) acrylamide, methoxymethyl (meth) acrylamide, ethoxymethyl (meth) acrylamide, propoxymethyl (meth) acrylamide, butoxymethoxymethyl (meth) acrylamide, and N-methylol ( Meta) acrylamide, N-hydroxymethyl (meth) acrylamide, (meth) acrylic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, crotonic acid, 2-acrylamide- 2-Methylpropanesulfonic acid, tert-butylacrylamide sulfonic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate
  • polyfunctional compounds such as (meth) acrylamide methylene ether, a condensate of polyhydric alcohol and N-methylol (meth) acrylamide, and triacrylic formal. These polyfunctional compounds can be used alone or in combination of two or more.
  • a trifunctional or higher functional compound is preferable because it tends to increase the adhesion of the cured product to the substrate and the strength of the curable composition after curing.
  • a polyfunctional compound having four or more functionalities is more preferable, and a polyfunctional compound having five or more functionalities is further preferable.
  • the content of the curable compound in the energy-sensitive composition of the fourth aspect is not particularly limited as long as it does not impair the object of the present invention.
  • the content of the curable compound in the energy-sensitive composition of the fourth aspect is preferably 3% by mass or more and 95% by mass or less, and 5% by mass or more and 90% by mass, based on the total mass of the other components excluding the solvent.
  • the following is more preferable, 10% by mass or more and 85% by mass or less is further preferable, and 20% by mass or more and 80% by mass or less is particularly preferable.
  • the content of the metal oxide fine particles in the energy-sensitive composition of the fourth aspect is not particularly limited as long as the object of the present invention is not impaired.
  • the mass ratio of the curable compound to the metal oxide fine particles is typically 1: 99 to 95: 5 because it is easy to achieve both a high refractive index and good flexibility of the cured product. It is preferably 5:95 to 90:10, even more preferably 10:90 to 85:15, and particularly preferably 30:70 to 80:20.
  • the mass of the curable composition excluding the solvent for example, 5% by mass or more and 95% by mass or less is preferable, 10% by mass or more and 93% by mass or less is more preferable, and 15% by mass or more and 90% by mass or less is further preferable. It is preferable, and 20% by mass or more and 80% by mass or less is particularly preferable.
  • the curable composition contains a curing agent from the viewpoint of promoting curing.
  • the curing agent may be used alone or in combination of two or more.
  • the curing agent is preferably a cationic polymerization initiator or an anionic polymerization initiator, and more preferably a cationic polymerization initiator, from the viewpoint that the curable composition is a cationic curing type or an anionic curing type.
  • Onium salt (B01) Preferred cationic polymerization initiators include gallium-containing onium salts having an anion moiety represented by the following formula (bi) and boron-containing onium salts having an anionic moiety represented by the following formula (bi).
  • the gallium-containing onium salt having an anion portion represented by the following formula (bi) and the boron-containing onium salt having an anion portion represented by the following formula (bi) are also collectively referred to as "onium salt (B01)". ..
  • the cationic polymerization initiator includes both a gallium-containing onium salt having an anionic moiety represented by the following formula (ai) and a boron-containing onium salt having an anionic moiety represented by the following formula (aii). It is also preferable to include it.
  • R b01 , R b02 , R b03 and R b04 are each independently a hydrocarbon group which may have a substituent or a heterocyclic group which may have a substituent. And at least one of R b01 , R b02 , R b03 , and R b04 is an aromatic hydrocarbon group which may have a substituent.)
  • R b05 , R b06 , R b07 , and R b08 each independently have a hydrocarbon group which may have a substituent or a heterocycle which may have a substituent. It is a group, and at least one of R b05 , R b06 , R b07 , and R b08 is an aromatic hydrocarbon group which may have a substituent.
  • a gallium-containing onium salt having an anion portion represented by the formula (bi) and a boron-containing onium salt having an anion portion represented by the formula (bi) are represented by the formula (bi) or the formula (bii).
  • the counter cation (cation portion) with respect to the anion is not particularly limited as long as the curable composition is well cured.
  • the cation part has the following formula (viv): (R b09 ) T + 1- R b010 + ... (biv) (In the formula (viv), R b09 is a monovalent organic group.
  • R b010 is an element having a valence T in groups 15 to 17 of the Periodic Table of the Elements (IUPAC notation). T is 1. It is an integer of 3 or more.
  • a plurality of R b09s may be the same or different, and a plurality of R b09s may be combined to form a ring together with R b010.)
  • the number of carbon atoms of the hydrocarbon group or heterocyclic group as R b01 to R b04 in the formula (bi) is not particularly limited, but is preferably 1 or more and 50 or less, more preferably 1 or more and 30 or less, and 1 or more and 20 or less. Especially preferred.
  • Specific examples of the hydrocarbon groups as R b01 to R b04 include linear or branched alkyl groups, linear or branched alkenyl groups, linear or branched alkynyl groups, and aromatics. Examples thereof include group hydrocarbon groups, alicyclic hydrocarbon groups, and aralkyl groups.
  • At least one aromatic group which may have a substituent of R b01 ⁇ R b04, R b01 ⁇ aromatic also have three or more substituents of R b04 It is more preferably a group, and it is particularly preferable that all of R b01 to R b04 are aromatic groups which may have a substituent.
  • the hydrocarbon group as R b01 to R b04 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 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 b01 to R b04 are alkyl groups include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group and n-octyl group.
  • 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-nonadesyl 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 include a group and a branched alkyl group such as a 1,1,3,3-tetramethylbutyl group.
  • R b01 to R b04 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 b01 to R b04 are aromatic hydrocarbon groups are phenyl group, ⁇ -naphthyl group, ⁇ -naphthyl group, biphenyl-4-yl group, biphenyl-3-yl group, biphenyl-2. -Il group, anthryl group, phenyl group and the like can be mentioned.
  • R b01 to R b04 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 b01 to R b04 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 b01 to R b04 are heterocyclic groups include thienyl group, furanyl group, selenophenyl group, pyranyl group, pyrrolyl group, oxazolyl group, thiazolyl group, pyridyl group, pyrimidyl group and 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, a dibenzofuranyl group and the like.
  • the substituents that the hydrocarbon group as R b01 to R b04 or the heterocyclic group may have is an alkyl halide group
  • preferred examples of the alkyl halide group are a trifluoromethyl group and a trichloromethyl group.
  • the substituents that the hydrocarbon group as R b01 to R b04 or the heterocyclic group may have is a halogenated aliphatic cyclic group
  • a preferred example of the halogenated aliphatic cyclic group is penta. Examples thereof include a fluorocyclopropyl group, a nonafluorocyclobutyl group, a perfluorocyclopentyl group, a perfluorocyclohexyl group, a perfluoroadamantyl group and the like.
  • the hydrocarbon group as R b01 to R b04 or the substituent that the heterocyclic group may have is an alkoxy group
  • preferred examples of the alkoxy group are a methoxy group, an ethoxy group, and an n-propyloxy group.
  • the substituents that the hydrocarbon group as R b01 to R b04 or the heterocyclic group may have is an aryloxy group
  • preferred examples of the aryloxy group include a phenoxy group and an ⁇ -naphthyloxy group. Examples thereof include ⁇ -naphthyloxy group, biphenyl-4-yloxy group, biphenyl-3-yloxy group, biphenyl-2-yloxy group, anthryloxy group, phenanthryloxy group and the like.
  • the substituents that the hydrocarbon group as R b01 to R b04 or the heterocyclic group may have is an aliphatic acyl group
  • preferred examples of the aliphatic acyl group are an acetyl group, a propanoyl group and a butanoyl group. Examples thereof include a group, a pentanoyl group, a hexanoyl group, a heptanoyle group, an octanoyl group and the like.
  • the aromatic acyl group When the substituents that the hydrocarbon group as R b01 to R b04 or the heterocyclic group may have is an aromatic acyl group, preferred examples of the aromatic acyl group are a benzoyl group and an ⁇ -naphthoyl group. , ⁇ -naphthoyl group, biphenyl-4-ylcarbonyl group, biphenyl-3-ylcarbonyl group, biphenyl-2-ylcarbonyl group, anthrylcarbonyl group, phenanthrylcarbonyl group and the like.
  • the hydrocarbon group as R b01 to R b04 or the substituent that the heterocyclic group may have is an aliphatic acyloxy group
  • preferred examples of the aliphatic acyloxy group are an acetyloxy group and a propanoyloxy. Examples thereof include a group, a butanoyloxy group, a pentanoyloxy group, a hexanoyloxy group, a heptanoiloxy group, an octanoyloxy group and the like.
  • the substituents that the hydrocarbon group as R b01 to R b04 or the heterocyclic group may have is an aromatic acyloxy group
  • preferred examples of the aromatic acyloxy group are a benzoyloxy group and an ⁇ -naphtho.
  • the group etc. can be mentioned.
  • the substituents that the hydrocarbon group as R b01 to R b04 or the heterocyclic group may have is an alkylthio group or an arylthio group
  • a preferable example of the alkylthio group or the arylthio group is the above-mentioned alkoxy. Examples thereof include a group in which an oxygen atom in a group suitable as an aryloxy group is replaced with a sulfur atom.
  • the hydrocarbon group as R b01 to R b04 , or the substituent which the heterocyclic group may have is an amino group which may be substituted with an amine group, even if it is substituted with a hydrocarbon group.
  • Suitable examples of good amino groups are amino groups, methylamino groups, ethylamino groups, n-propylamino groups, dimethylamino groups, diethylamino groups, methylethylamino groups, di-n-propylamino groups, and piperidino groups. And so on.
  • halogen atom When the hydrocarbon group as R b01 to R b04 or the substituent that the heterocyclic group may have is a halogen atom, suitable examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and Examples include iodine atoms.
  • the hydrocarbon group as R b01 to R b04 or the heterocyclic group may have as described above, the cation of the gallium-containing onium salt having an anion portion represented by the formula (bi).
  • an alkyl halide group having 1 to 8 carbon atoms, a halogen atom, a nitro group, and a cyano group are preferable, and an alkyl fluorinated group having 1 to 8 carbon atoms is more preferable. preferable.
  • R b05 to R b08 in the formula (bi) include the same groups as those described above for R b01 to R b04 in the formula (bi).
  • R b09 in the formula (viv) which is a cation part is an organic group bonded to R b010.
  • a plurality of R b09 when R b09 are existing in plural numbers may be the same or different.
  • R b09 has an aromatic hydrocarbon group having 6 to 14 carbon atoms which may have a substituent, an alkyl group having 1 to 18 carbon atoms which may have a substituent, and a substituent. Examples thereof include an alkenyl group having 2 to 18 carbon atoms and an alkynyl group having 2 to 18 carbon atoms which may have a substituent.
  • R b09 is an aromatic hydrocarbon group having 6 to 14 carbon atoms and an alkyl having 1 to 18 carbon atoms.
  • a group, 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 aromatic hydrocarbon group, aralkyl group, alkyl group, alkenyl group, and alkynyl group as R b09 may have include an alkyl group having 1 to 18 carbon atoms and 2 or more carbon atoms.
  • Examples include an amino group which may be substituted with 18 or less hydrocarbon groups, and a halogen atom.
  • substituents are the same as the preferred examples of the hydrocarbon groups as R b01 to R b04 in the formula (bi), or the substituents that the heterocyclic group may have.
  • R b09 there are a plurality, the plurality of R b09 may form a ring together with R b010.
  • a plurality of R b09, ring and R b010 is formed, during which structure, -O -, - S -, - SO -, - SO 2 -, - NH -, - CO -, - COO-, and It may contain one or more bonds selected from the group consisting of -CONH-.
  • R b010 in the formula (viv) is an element having a valence T in groups 15 to 17 of the Periodic Table of the Elements (IUPAC notation). T is an integer of 1 or more and 3 or less.
  • the elements of Groups 15 to 17 in the Periodic Table of the Elements (IUPAC notation) as R b010 are under the conditions for producing the curable composition, the storage conditions, and the formation conditions for the metal oxide fine particle-containing film. Is an element that can exist stably.
  • R b010 combines with the organic group R b09 to form an onium ion [R b010 + ].
  • Periodic Table of 15 to Group 17 Group elements (IUPAC notation), preferred elements as R a10 is, O (oxygen), N (nitrogen), P (phosphorus), S (sulfur), or I ( Iodine).
  • Corresponding onium ions are oxonium ion, ammonium ion, phosphonium ion, sulfonium ion, and iodonium ion.
  • ammonium ion, phosphonium ion, sulfonium ion, and iodonium ion which are stable and easy to handle, are preferable, and sulfonium ion and iodonium ion are more preferable in that they are excellent in cationic polymerization performance and cross-linking reaction performance.
  • oxonium ion examples include oxoniums such as trimethyloxonium, diethylmethyloxonium, triethyloxonium, and tetramethylenemethyloxonium; 4-methylpyrrilinium, 2,4,6-trimethylpyrrilinium, 2,6. Examples thereof include pyririniums such as -di-tert-butylpyrrilinium and 2,6-diphenylpyrilinium; chromeniums such as 2,4-dimethylchromenium and 1,3-dimethylisochromenium, and isochromeniums.
  • ammonium ions include tetraalkylammonium such as tetramethylammonium, ethyltrimethylammonium, diethyldimethylammonium, triethylmethylammonium, and tetraethylammonium; N, N-dimethylpyrrolidinium, N-ethyl-N-methylpyrrolidi.
  • Nium, and pyrrolidiniums such as N, N-diethylpyrrolidinium; N, N'-dimethylimidazolinium, N, N'-diethylimidazolinium, N-ethyl-N'-methylimidazolinium, 1,3 , 4-trimethylimidazolinium, and imidazolinium such as 1,2,3,4-tetramethylimidazolinium; N, N'-tetrahydropyrimidinium such as dimethyltetrahydropyrimidinium; N, N'- Morphorinium such as dimethylmorpholinium; piperidinium such as N, N'-diethylpiperidinium; pyridinium such as N-methylpyridinium, N-benzylpyridinium, and N-phenacylpyridium; N, N'-dimethylimidazolium Imidazolium such as; quinolium such as N-methylquinolium, N-benzylquinolium, and N
  • the phosphonium ion include tetraaryl such as tetraphenylphosphonium, tetra-p-tolylphosphonium, tetrakis (2-methoxyphenyl) phosphonium, tetrakis (3-methoxyphenyl) phosphonium, and tetrakis (4-methoxyphenyl) phosphonium.
  • tetraaryl such as tetraphenylphosphonium, tetra-p-tolylphosphonium, tetrakis (2-methoxyphenyl) phosphonium, tetrakis (3-methoxyphenyl) phosphonium, and tetrakis (4-methoxyphenyl) phosphonium.
  • sulfonium ion examples include triphenylsulfonium, tri-p-tolylsulfonium, tri-o-tolylsulfonium, tris (4-methoxyphenyl) sulfonium, 1-naphthyldiphenylsulfonium, 2-naphthyldiphenylsulfonium, and tris (4).
  • Monoaryl sulfonium such as sulfonium; trialkyl sulfonium such as dimethylphenacil sulfonium, phenacil tetrahydrothiophenium, dimethylbenzyl sulfonium, benzyltetrahydrothiophenium, octadecylmethylphenacil sulfonium and the like can be mentioned.
  • the onium salt (B01) is a sulfonium composed of an anion portion, which is an anion represented by the above formula (bi) or formula (bi), and a cation portion, which is a sulfonium ion represented by the formula (c1) described later. It is also preferable to include salt.
  • 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.
  • Tetrakis (4-nonafluorobiphenyl) gallium anion Tetrakis (1-heptafluoronaphthyl) gallium anion, Tetrakis (pentafluorophenyl) gallium anion, Tetrakis (3,4,5-trifluorophenyl) gallium 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) phenyl) gallium anion, Tetrakis (3,5-bis (trifluoromethyl)
  • 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 (trimethoxy) octafluorobiphenyl) boron anion, Te
  • the cation portion has a cation portion represented by the following formula (biii).
  • the onium salt as the cationic polymerization initiator has a cationic portion represented by the formula (biii)
  • the onium salt can function as a heat-sensitive curing agent.
  • R B01 is a monovalent organic group
  • D B is 15 to Group 17 Group valence of the Periodic Table of the Elements (IUPAC notation) is an element of u
  • R B02 Is an alkyl group which may have a substituent or an aralkyl group which may have a substituent.
  • R B01 At least one is an alkyl group which may have a substituent.
  • U is an integer of 1 or more and 3 or less, and a plurality of RB01s may be the same or different, and a plurality of RB01s are bonded to each other. with D B may form a ring.
  • D B in formula (biii) is a Group 15 to 17 of the Periodic Table (IUPAC notation) is an element of valence u.
  • D B is the same as R b010 in formula (biv).
  • D binds to an organic group RB01 and a benzyl group optionally substituted with RB02 to form an onium ion.
  • S sulfur
  • N nitrogen
  • I iodine
  • P phosphorus
  • 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 because they are excellent in cationic polymerization performance and cross-linking reaction performance.
  • R B01 represents an organic group bonded to D B, a plurality of R B01 when R B01 are existing in plural numbers may be the same or different.
  • RB01 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. Examples include the alkynyl group.
  • Examples of the aromatic hydrocarbon group, alkyl group, alkenyl group, and alkynyl group as R B01 include the same groups as those described above for R b09 in the formula (viv).
  • RB01 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.
  • R B01 there are a plurality the plurality of R B01 may form a ring together with D B.
  • a plurality of R B01, the ring formed is a D B is in between structure, -O -, - S -, - SO -, - SO 2 -, - NH -, - CO -, - COO-, and It may contain more bonds selected from the group consisting of -CONH-.
  • alkyl group as RB02 examples include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-octyl group, an n-decyl group and 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, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group and a 4-decyl group.
  • Examples thereof include a cycloalkyl group having 3 or more and 18 or less carbon atoms such as a cyclohexyl group.
  • RB02 is an alkyl group which may have a substituent
  • at least one of the RB01 is an alkyl group which may have a substituent.
  • aralkyl group as R B02 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 an alkyl group having 1 or more and 4 or less carbon atoms.
  • aralkyl group having a substituent as RB02 include an aryl group having 6 to 10 carbon atoms which may have a substituent, such as a 2-methylbenzyl group. Examples thereof include an alkyl group having 1 or more and 4 or less carbon atoms substituted.
  • R B02 is preferably an aralkyl group which may have a substituent, more preferably a cation moiety represented by the following formula (biii-1).
  • R B01 is a monovalent organic radical
  • v is 0 to 5 integer
  • Multiple RB03s may be the same or different.
  • D' is an S atom or a Se atom, preferably an S atom.
  • Examples of the counter anion of the cation portion represented by the formula (bii) or the formula (bii-1) include an anion similar to the counter anion of the cation portion represented by the formula (c01) described later, but preferably.
  • the anion portion represented by the formula (bi) or the anion portion represented by the formula (bi), and the anion portion represented by the formula (bi) is more preferable.
  • the onium salt (B01) As the onium salt (B01), the above-mentioned anion shown as a suitable specific example of the anion represented by the formula (bi) or the formula (bII) and the preferred concrete of the counter cation represented by the formula (biv) are used.
  • a salt composed of the above-mentioned cations shown as an example is preferable.
  • Two or more suitable specific examples of the counter cation represented by the formula (b0iv) may be combined.
  • the content of the onium salt (B01) is preferably 10% by mass or more, more preferably 50% by mass or more, and 70% by mass, based on the total amount of the onium salt (B01) and the other cationic polymerization initiator (B02) described later. % Or more is even more preferable, 90% by mass or more is particularly preferable, and 100% by mass is most preferable.
  • an amount of the cationic polymerization initiator within such a range, a metal oxide fine particle-containing film having excellent refractive index and yellowing resistance, heat resistance (heat decomposition resistance), and adhesion to a substrate is formed. Cheap.
  • the cationic polymerization initiator includes another cationic polymerization initiator (B02) different from the onium salt (B01) (hereinafter, also simply referred to as “another cationic polymerization initiator (B02)”) together with the onium salt (B01). , Or may or may not be included alone.
  • the curable composition contains an onium salt (B01) and another cationic polymerization initiator (B02), so that it has excellent refractive index and yellowing resistance, and also has heat resistance (heat decomposition resistance) and adhesion to a substrate. It is easy to form a good metal oxide fine particle-containing film.
  • the other cationic polymerization initiator (B02) may be a thermal cationic polymerization initiator (B02-1) or a photocationic polymerization initiator (B02-2), and may be a photocationic polymerization initiator (B02-). 2) is preferable.
  • the thermal cationic polymerization initiator (B02-1) and the photocationic polymerization initiator (B02-2) will be described.
  • thermal cationic polymerization initiator examples include diphenyliodonium hexafluoroarsenate, diphenyliodonium hexafluorophosphate, diphenyliodonium trifluoromethanesulfonium, triphenylsulfonium tetrafluoroborate, and tri-p-tolylsulfonium.
  • thermal cationic polymerization initiators examples include diazonium salt-type initiators such as AMERICURE series (manufactured by American Can), ULTRASET series (manufactured by Adeca), and WPAG series (manufactured by Wako Pure Chemical Industries, Ltd .); UVE series.
  • Iodonium salt-type initiators such as (General Electric), FC series (3M), UV9310C (GE Toshiba Silicone), and WPI series (Wako Pure Chemical Industries); CYRACURE series (Union Carbide) (Made), UVI series (manufactured by General Electric), FC series (manufactured by 3M), CD series (manufactured by Sartmer), Optomer SP series (manufactured by Adeca), Optomer CP series (manufactured by Adeca), Sun Aid SI series Examples thereof include sulfonium salt-type initiators such as (manufactured by Sanshin Kagaku Kogyo Co., Ltd.), CI series (manufactured by Nippon Soda Co., Ltd.), WPAG series (manufactured by Wako Pure Chemical Industries, Ltd.), and CPI series (manufactured by San Apro Co., Ltd.).
  • the thermal cation polymerization initiator (B02-1) is preferably composed of a cation portion and an anion portion, and preferably contains a compound in which the cation portion is a cation represented by the following formula (c0-I).
  • a thermal cationic polymerization initiator (B02-1) By using such a thermal cationic polymerization initiator (B02-1), the above-mentioned curable compound (A) can be cured well to form a cured product having excellent refractive index and yellowing resistance, and heat resistance (heat-resistant decomposition). It is easy to obtain a curable composition having good properties) and adhesion to a substrate.
  • R c01 , R c02 , and R c03 are alkyl groups having 1 or more and 6 or less carbon atoms independently.
  • suitable examples of the alkyl group as R c01 , R c02 , and R c03 are methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, and the like. Examples thereof include a sec-butyl group, a tert-butyl group, an n-pentyl group, and an n-hexyl group.
  • As the alkyl group a methyl group or an ethyl group is preferable, and a methyl group is more preferable. It is particularly preferable that R c01 , R c02 , and R c03 are all methyl groups.
  • a commercially available compound As a compound composed of a cation portion and an anion portion represented by the above formula (c0-I), a commercially available compound can be used. Examples of commercially available products include CXC-1821 (manufactured by King Industries) and the like.
  • a quaternary ammonium salt composed of a cation represented by the formula (c0-II) and ((C 6 F 5 ) 4 B) ⁇ is more preferable.
  • the compound composed of the cation portion consisting of the cation represented by the formula (c0-I) and the anion portion one type may be used alone, or two or more types may be used in combination.
  • the amount of the compound composed of the cation portion and the anion portion represented by the above formula (c0-I) in the thermal cationic polymerization initiator (B02-1) is preferably 50% by mass or more, more preferably 70% by mass or more. , 80% by mass or more is even more preferable, 90% by mass or more is particularly preferable, and 100% by mass is most preferable.
  • the content of the thermal cationic polymerization initiator in the curable composition as the energy-sensitive composition of the fifth aspect is not particularly limited as long as it does not impair the object of the present invention.
  • the content of the thermocationic polymerization initiator in the curable composition is preferably 0.01 parts by mass or more and 30 parts by mass or less, more preferably 0.1 parts by mass or more and 10 parts by mass or less, with the curable compound as 100 parts by mass. Particularly preferably, it is 0.3 parts by mass or more and 5 parts by mass or less.
  • thermo cationic polymerization initiator By using an amount of the thermal cationic polymerization initiator within such a range, a metal oxide fine particle-containing film having good heat resistance (heat-decomposability) and good adhesion to a substrate or the like can be formed, and the curability is good. It is easy to obtain a curable composition.
  • -Photocationic polymerization initiator (B02-2)
  • a polymerization initiator other than the onium salt (B01) used for photocuring the cationically polymerizable curable composition can be used without particular limitation.
  • the photocationic polymerization initiator (B02-2) include an iodonium salt and a sulfonium salt.
  • iodonium salt examples include diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, di (4-nonylphenyl) iodonium hexafluorophosphate and the like.
  • a sulfonium salt is preferable.
  • a sulfonium salt composed of a cation portion represented by the following formula (c01) and an anion portion hereinafter, also referred to as “sulfonium salt (Q)”.
  • an onium salt (B01) is used.
  • the sulfonium salt is preferably classified as an onium salt (B01)).
  • R c11 and R c12 independently represent an alkyl group which may be substituted with a halogen atom or a group represented by the following formula (c02), and R c11 and R c12 are bonded to each other. and may form a ring with the sulfur atom in the formula, R c13 represents a group represented by the group or the following formula represented by the following formula (c03) (c04), a c1 is S, O, Or Se, but R c11 and R c12 are not alkyl groups that may be substituted with halogen atoms at the same time.
  • ring Z c1 represents an aromatic hydrocarbon ring
  • R c14 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 c15 is a hydroxy group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an arylthiocarbonyl group, an asyloxy group, an arylthio group, an alkylthio group, an aryl group, Heterocyclic group, aryloxy group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, hydroxy (poly) alkyleneoxy group, optionally substituted amino group, cyano group, nitro group, or halogen atom.
  • R c16 is a hydroxy group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, or an allyl group.
  • ruthiocarbonyl group asyloxy group, arylthio group, alkylthio group, aryl group, heterocyclic group, aryloxy group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, hydroxy (poly) alkyleneoxy group.
  • a c2 represents a single bond
  • S, O, sulfinyl Indicates a group or a carbonyl group
  • m2 indicates 0 or 1).
  • R c17 and R c18 are independently hydroxy group, alkoxy group, alkylcarbonyl group, arylcarbonyl group, alkoxycarbonyl group, aryloxycarbonyl group, arylthiocarbonyl group, asyloxy group, arylthio group, Alkoxythio group, aryl group, heterocyclic group, aryloxy group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, hydroxy (poly) alkyleneoxy group, optionally substituted amino group, cyano group, nitro group, or a group represented by an alkylene group or the following formula may be substituted with a halogen atom (c05), R c19 and R c 20 are independently an alkyl group which may be substituted with a halogen atom or a group represented by the formula (c02), R c19
  • the ring Z c2 represents an aromatic hydrocarbon ring
  • R c21 is an alkyl group, a hydroxy group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl which may be substituted with a halogen atom.
  • the ring Z c3 represents an aromatic hydrocarbon ring
  • R c22 is an alkyl group, a hydroxy group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl which may be substituted with a halogen atom.
  • both R c11 and R c12 are groups represented by the above formula (c02).
  • R c11 and R c12 may be the same or different from each other.
  • the number of ring-constituting atoms of the formed ring is 3 or more and 10 or less including the sulfur atom. Is preferable, and 5 or more and 7 or less are more preferable.
  • the ring formed may be a polycycle, and is preferably a condensed ring in which a 5- to 7-membered ring is condensed.
  • R c11 and R c12 are phenyl groups.
  • R c13 is preferably a group represented by the above formula (c03).
  • a c1 is preferably S or O, more preferably S.
  • R c14 may be substituted with an alkyl group, a hydroxy group, an alkylcarbonyl group, a thienylcarbonyl group, a furanylcarbonyl group, a selenophylcarbonyl group, which may be substituted with a halogen atom. It is preferably an amino 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 can be selected according to the type of ring Z c1 , 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 c15 is 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 (c05). Is preferable, and it is more preferable that the group is represented by the above formula (c05).
  • R c16 is 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 (c06). Is preferable, and it is more preferable that the group is represented by the above formula (c06).
  • a c2 is preferably a S or O, more preferably S.
  • m2 is preferably 0.
  • R c17 and R c18 are independently represented by an alkylene group; a hydroxy group, an optionally substituted amino group, or an alkylene group substituted with a nitro group; or the above formula (c05). It is preferably a group represented by the above formula (c05), and more preferably a group represented by the above formula (c05). R c17 and R c18 may be the same or different from each other. In the above formula (c04), it is preferred none of R c19 and R c 20 is a group represented by the formula (c02). R c19 and R c 20 may be the same or different from each other.
  • the ring constituting atoms of the ring to be formed is 3 to 10, including the sulfur atom Is preferable, and 5 or more and 7 or less are more preferable.
  • the ring formed may be a polycycle, and is preferably a condensed ring in which a 5- to 7-membered ring is condensed.
  • a c3 is preferably S or O, more preferably S.
  • m3 is preferably 0.
  • R c21 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. More preferably, it is an alkyl group which may be used.
  • m4 can be selected according to the type of ring Z c2 , 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 c22 may be substituted with an alkyl group, a hydroxy group, an alkylcarbonyl group, a thienylcarbonyl group, a furanylcarbonyl group, a selenophylcarbonyl group, which may be substituted with a halogen atom. It is preferably an amino 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.
  • m5 can be selected according to the type of ring Z c3 , 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.
  • Cation represented by the formula (c01) is usually a monovalent anion X - to form together with salt.
  • X - is a monovalent anion corresponding to the acid (HX) generated by irradiating the sulfonium salt (Q) with active energy (heat, visible light, ultraviolet rays, electron beams, X-rays, etc.).
  • X - is the monovalent polyatomic anion is suitably cited, M 1 Y a0 -, ( Rf) b0 PF (6-b0) -, R x1 SO 3 -, (R x1 SO 2) 3 C - , Or an anion represented by (R x 1 SO 2 ) 2 N ⁇ is more preferred.
  • X ⁇ may be a halogen anion, and examples thereof include fluoride ion, chloride ion, bromide ion, and iodide ion.
  • M 1 represents a phosphorus atom, a boron atom, or an antimony atom.
  • Y represents a halogen atom.
  • a fluorine atom is preferable.
  • Rf represents an alkyl group in which 80 mol% or more of hydrogen atoms are substituted with fluorine atoms.
  • the number of carbon atoms of the alkyl group substituted with a fluorine atom is preferably 1 or more and 8 or less.
  • Examples of the alkyl group to be Rf by fluorine substitution include a linear alkyl group, a branched chain alkyl group and a cycloalkyl group. Specific examples of the linear alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, an octyl group and the like.
  • branched chain alkyl group examples include an isopropyl group, an isobutyl group, a sec-butyl group and a tert-butyl group.
  • cycloalkyl group examples include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group and the like.
  • 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. It is mol% or more, particularly preferably 100 mol%.
  • the photosensitivity of the sulfonium salt (Q) is further improved.
  • the b Rfs are independent of each other and therefore may be the same or different from each other.
  • P represents a phosphorus atom and F represents a fluorine atom.
  • R x1 represents an alkyl group having 1 or more and 20 or less carbon atoms, a fluoroalkyl group having 1 or more and 20 or less carbon atoms, or an aryl group having 6 or more and 20 or less carbon atoms, and the alkyl group and
  • the fluoroalkyl group may be linear, branched or cyclic, and the alkyl group, fluoroalkyl group, or aryl group may be unsubstituted or having a substituent.
  • the substituent include a hydroxy group, an optionally substituted amino group, a nitro group and the like.
  • Examples of the amino group that may be substituted include groups exemplified in the following description of the above formulas (c02) to (c06).
  • the carbon chain in the alkyl group, fluoroalkyl group or aryl group represented by R x1 may have a hetero atom such as an oxygen atom, a nitrogen atom or a sulfur atom.
  • the carbon chain in the alkyl group represented by R x2 or the fluoroalkyl group may have a divalent functional group.
  • the divalent functional group include ether bond, carbonyl bond, ester bond, amino bond, amide bond, imide bond, sulfonyl bond, sulfonylamide bond, sulfonylimide bond, urethane bond and the like.
  • the alkyl group, fluoroalkyl group or aryl group represented by R x1 has the above-mentioned substituent, heteroatom or functional group
  • the number of the above-mentioned substituents, heteroatom 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
  • a0 represents an integer of 4 or more and 6 or less.
  • b0 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.
  • (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 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, benzene sulfonic acid anion, camphor sulfonic acid anion, methane sulfonic acid anion, ethane sulfonic acid anion, propane sulfonic acid anion and butane sulfonic acid anion.
  • trifluoromethanesulfonate anion nonafluorobutane sulfonic acid anion, methane sulfonic acid anion, butane sulfonic acid anion, camphor sulfonic acid anion, benzene sulfonic acid anion or p-toluene sulfonic acid anion are preferable.
  • the carboxylic acid ion, CH 3 COO -, CF 3 COO -, C 6 H 5 COO -, CH 3 C 6 H 4 COO -, C 6 F 5 COO -, and CF 3 C 6 H 4 COO - etc. Can be mentioned.
  • X - of, in terms of cationic polymerization performance, MY a -, (Rf) b PF 6-b -, and (R x1 SO 2) 3 C - anion is preferably represented by, SbF 6 -, More preferably, PF 6 ⁇ , (CF 3 CF 2 ) 3 PF 3 ⁇ , and (CF 3 SO 2 ) 3 C ⁇ .
  • examples of the aromatic hydrocarbon ring include a benzene ring, a condensed polycyclic 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 fused polycyclic aromatic hydrocarbon ring include a condensed 2- to 4-cyclic aromatic hydrocarbon ring such as a condensed bicyclic hydrocarbon ring and a condensed tricyclic aromatic hydrocarbon ring.
  • condensed bicyclic hydrocarbon ring for example, a C8-20 condensed bicyclic hydrocarbon ring such as a naphthalene ring is preferable, and a C10-16 condensed bicyclic hydrocarbon ring is more preferable.
  • fused tricyclic aromatic hydrocarbon ring include anthracene ring and phenanthrene ring.
  • examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • the alkyl group includes a 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, and a number of carbon atoms. Examples thereof include cycloalkyl groups having a value of 3 or more and 18 or less.
  • the alkyl group optionally substituted with a halogen atom means an alkyl group and an alkyl group substituted with a halogen atom. ..
  • alkyl group substituted with a halogen atom examples include the above-mentioned linear alkyl group, branched chain alkyl group, group in which at least one hydrogen atom in the cycloalkyl group is substituted with a halogen atom, and the like.
  • R c11, R c12, R c19, or the R c 20 is particularly preferably a trifluoromethyl group, R c14, R c16, R c21, or for R c22 Is particularly preferably a methyl group.
  • linear alkyl group examples include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-octyl group, an n-decyl group, an n-dodecyl group and an n-tetradecyl group. , N-Hexadecyl group, n-octadecyl group and the like.
  • branched alkyl group examples include an isopropyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an isopentyl group, a neopentyl group, a tert-pentyl group, an isohexyl group, and an isooctadecyl group.
  • cycloalkyl group examples include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a 4-decylcyclohexyl group and the like.
  • alkyl group substituted with the halogen atom examples include a monofluoromethyl group, a difluoromethyl group, a trifluoromethyl group and the like.
  • examples of the alkoxy group include a linear or branched-chain alkoxy group having 1 or more and 18 or less carbon atoms.
  • specific examples of the linear or branched alkoxy group include methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, hexyloxy group, decyloxy group and dodecyl. Examples thereof include an oxy group and an octadecyloxy group.
  • the alkyl group in the alkylcarbonyl group includes the above-mentioned linear alkyl group having 1 or more and 18 or less carbon atoms and the branched alkyl chain having 3 or more and 18 or less carbon atoms. Examples thereof include a group or a cycloalkyl group having 3 or more and 18 or less carbon atoms, and examples of the alkylcarbonyl group include a linear, branched or cyclic alkylcarbonyl group having 2 or more and 18 or less carbon atoms. Can be mentioned.
  • alkylcarbonyl group examples include an acetyl group, a propionyl group, a butanoyl group, a 2-methylpropionyl group, a heptanoil group, a 2-methylbutanoyl group, a 3-methylbutanoyl group, an octanoyl group, a decanoyyl group and a dodecanoyl group.
  • examples thereof include an octadecanoyl group, a cyclopentanoyl group, and a cyclohexanoyl group.
  • examples of the arylcarbonyl group include an arylcarbonyl group having 7 or more and 11 or less carbon atoms.
  • Specific examples of the arylcarbonyl group include a benzoyl group and a naphthoyl group.
  • examples of the alkoxycarbonyl group include a linear or branched-chain alkoxycarbonyl group having 2 or more and 19 or less carbon atoms.
  • Specific examples of the alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, an isopropoxycarbonyl group, a butoxycarbonyl group, an isobutoxycarbonyl group, a sec-butoxycarbonyl group, a tert-butoxycarbonyl group, and an octyloxycarbonyl group. Examples thereof include a group, a tetradecyloxycarbonyl group, and an octadecyloxycarbonyl group.
  • examples of the aryloxycarbonyl group include an aryloxycarbonyl group having 7 or more and 11 or less carbon atoms.
  • Specific examples of the aryloxycarbonyl group include a phenoxycarbonyl group and a naphthoxycarbonyl group.
  • examples of the arylthiocarbonyl group include an arylthiocarbonyl group having 7 or more and 11 or less carbon atoms.
  • Specific examples of the arylthiocarbonyl group include a phenylthiocarbonyl group and a naphthoxythiocarbonyl group.
  • examples of the asyloxy group include a linear or branched chain asyloxy group having 2 or more and 19 or less carbon atoms.
  • Specific examples of the acyloxy group include an acetoxy group, an ethylcarbonyloxy group, a propylcarbonyloxy group, an isopropylcarbonyloxy group, a butylcarbonyloxy group, an isobutylcarbonyloxy group, a sec-butylcarbonyloxy group, a tert-butylcarbonyloxy group, and the like.
  • examples thereof include an octylcarbonyloxy group, a tetradecylcarbonyloxy group, an octadecylcarbonyloxy group and the like.
  • examples of the arylthio group include an arylthio group having 6 or more and 20 or less carbon atoms.
  • Specific examples of the arylthio group include a phenylthio group, a 2-methylphenylthio group, a 3-methylphenylthio group, a 4-methylphenylthio group, a 2-chlorophenylthio group, a 3-chlorophenylthio group and a 4-chlorophenylthio group.
  • examples of the alkylthio group include a linear or branched-chain alkylthio group having 1 or more and 18 or less carbon atoms.
  • Specific examples of the alkylthio group include methylthio group, ethylthio group, propylthio group, isopropylthio group, butylthio group, isobutylthio group, sec-butylthio group, tert-butylthio group, pentylthio group, isopentylthio group and neopentylthio group.
  • examples of the aryl group include an aryl group having 6 or more and 10 or less carbon atoms.
  • Specific examples of the aryl group include a phenyl group, a tolyl group, a dimethylphenyl group, a naphthyl group and the like.
  • an aliphatic heterocyclic group having 2 or more and 20 or less carbon atoms is preferable, and an aliphatic heterocyclic group having 4 or more and 20 or less carbon atoms is more preferable.
  • Specific examples of the aliphatic cyclic group include pyrrolidinyl group, tetrahydrofuranyl group, tetrahydrothienyl group, piperidinyl group, tetrahydropyranyl group, tetrahydrothiopyranyl group, morpholinyl group and the like).
  • examples of the heterocyclic group include a heterocyclic group having 4 or more and 20 or less carbon atoms.
  • the heterocyclic group are thienyl group, furanyl group, selenophyl group, pyranyl group, pyrrolyl group, oxazolyl group, thiazolyl group, pyridyl group, pyrimidyl group, pyrazinyl group, indolyl group, benzofuranyl group and benzothienyl group.
  • examples of the aryloxy group include an aryloxy group having 6 or more and 10 or less carbon atoms.
  • Specific examples of the aryloxy group include a phenoxy group and a naphthyloxy group.
  • examples of the alkylsulfinyl group include a linear or branched-chain sulfinyl group having 1 or more and 18 or less carbon atoms.
  • Specific examples of the sulfinyl group include methylsulfinyl group, ethylsulfinyl group, propylsulfinyl group, isopropylsulfinyl group, butylsulfinyl group, isobutylsulfinyl group, sec-butylsulfinyl group, tert-butylsulfinyl group, pentylsulfinyl group and isopentyl.
  • Examples thereof include a sulfinyl group, a neopentylsulfinyl group, a tert-pentylsulfinyl group, an octylsulfinyl group, and an isooctadecylsulfinyl group.
  • examples of the arylsulfinyl group include an arylsulfinyl group having 6 or more and 10 or less carbon atoms.
  • Specific examples of the arylsulfinyl group include a phenylsulfinyl group, a tolylsulfinyl group, a naphthylsulfinyl group and the like.
  • examples of the alkylsulfonyl group include a linear or branched-chain alkylsulfonyl group having 1 or more and 18 or less carbon atoms.
  • Specific examples of the alkylsulfonyl group include methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group, isopropylsulfonyl group, butylsulfonyl group, isobutylsulfonyl group, sec-butylsulfonyl group, tert-butylsulfonyl group, pentylsulfonyl group, and iso.
  • Examples thereof include a pentylsulfonyl group, a neopentylsulfonyl group, a tert-pentylsulfonyl group, an octylsulfonyl group, and an octadecylsulfonyl group.
  • examples of the arylsulfonyl group include an arylsulfonyl group having 6 or more and 10 or less carbon atoms.
  • Specific examples of the arylsulfonyl group include a phenylsulfonyl group, a tolylsulfonyl group (tosyl group), a naphthylsulfonyl group and the like.
  • examples of the hydroxy (poly) alkyleneoxy group include a hydroxy (poly) alkyleneoxy group represented by HO (AO) q0 ⁇ .
  • AO independently represents an ethyleneoxy group and / or a propyleneoxy group.
  • q0 represents an integer of 1 or more and 5 or less.
  • examples of the amino group which may be substituted include an amino group ( ⁇ NH 2 ) and a substituted amino group having 1 or more and 15 or less carbon atoms.
  • the substituted amino group are methylamino group, dimethylamino group, ethylamino group, methylethylamino group, diethylamino group, n-propylamino group, methyl-n-propylamino group, ethyl-n-propylamino group.
  • di-n-propylamino group isopropylamino group, isopropylmethylamino group, isopropylethylamino group, diisopropylamino group, phenylamino group, diphenylamino group, methylphenylamino group, ethylphenylamino group, n-propylphenyl
  • examples thereof include an amino group and an isopropylphenylamino group.
  • examples of the alkylene group include a linear or branched alkylene group having 1 or more and 18 or less carbon atoms.
  • Specific examples of the alkylene group include a methylene group, a 1,2-ethylene group, a 1,1-ethylene group, a propane-1,3-diyl group, a propane-1,2-diyl group, and a propane-1,1-diyl group.
  • the sulfonium salt (Q) can be synthesized, for example, according to the following scheme. Specifically, 1-fluoro-2-methyl-4-nitrobenzene represented by the following formula (c1-1) is represented by the following formula (c1-2) in the presence of a base such as potassium hydroxide. The compound is reacted to obtain a nitro compound represented by the following formula (c1-3), and then reduction is carried out in the presence of reducing iron to obtain an amine compound represented by the following formula (c1-4). obtain. This amine compound is reacted with a nitrite such as sodium nitrite represented by MaNO 2 to obtain a diazo compound.
  • a base such as potassium hydroxide
  • Ma represents a metal atom, for example, an alkali metal atom such as a sodium atom.
  • this diazo compound is mixed with cuprous halide represented by CuX'and hydrogen halide represented by HX', and the reaction is allowed to proceed to proceed with the halogen represented by the following formula (c1-5).
  • X' represents a halogen atom such as a bromine atom.
  • X' indicates a halogen atom.
  • 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 (c1-6) in the presence of chlorotrimethylsilane to obtain the following formula (c1-).
  • the sulfonium salt represented by 7) can be obtained.
  • a salt represented by Mb + X " - and performing salt exchange a sulfonium salt represented by the following formula (c1-8) can be obtained.
  • Mb + is a metal cation, for example, .
  • X that represents an alkali metal cation such as potassium ion - is X - is represented by a monovalent anion other than a halide anion.
  • R c11 to R c13 and A c1 are the same as those in the above formula (c01).
  • Specific examples of the cation represented by the formula (c01), which is the cation portion of the sulfonium salt (Q), include the following cations.
  • Specific examples of the anion moiety of the sulfonium salt (Q), the X - can be exemplified anions such as mentioned in the description, conventionally known anionic.
  • the sulfonium salt (Q) containing the cation moiety represented by the above formula (c01) can be synthesized according to the above scheme, and the cation moiety can be combined with the desired anion moiety by further salt exchange if necessary. ..
  • the cation portion represented by the following formula is more preferable.
  • the other cationic polymerization initiator (B02) may contain other photocationic polymerization initiators other than the sulfonium salt (Q) in addition to the above-mentioned sulfonium salt (Q).
  • the content of the sulfonium salt (Q) in the other cationic polymerization initiator (B02) is not particularly limited, but is typically 70% by mass or more, more preferably 80% by mass or more, and particularly 90% by mass or more. It is preferably 100% by mass, most preferably 100% by mass.
  • the photocationic polymerization initiator (B02-2) may further contain a photocationic polymerization initiator other than the above-mentioned onium salt (B01) and sulfonium salt (Q) in addition to the above-mentioned sulfonium salt (Q).
  • a photocationic polymerization initiator other than the above-mentioned onium salt (B01) and sulfonium salt (Q) various cationic polymerization initiators conventionally used for cationic polymerization can be used without particular limitation.
  • onium salts such as iodonium salt and sulfonium salt are preferable, and other sulfonium salts other than sulfonium salt (Q) are preferable. Is more preferable.
  • the total content of the photocationic polymerization initiator in the curable composition is not particularly limited as long as the curing of the curable composition proceeds well. From the viewpoint that the curable composition can be easily cured, typically 0.001 part by mass or more and 30 parts by mass or less, preferably 0.01 part by mass or more and 10 parts by mass or less, with the curable compound as 100 parts by mass. Is more preferable, and 0.1 part by mass or more and 5 parts by mass or less is particularly preferable.
  • the radical polymerization initiator is not particularly limited and is unsaturated.
  • a conventionally known photopolymerization initiator can be used.
  • the photopolymerization initiator described for the energy-sensitive composition of the first aspect can be preferably used.
  • the content of the radical polymerization initiator is preferably 0.01 part by mass or more and 50 parts by mass or less, more preferably 0.1 part by mass or more and 30 parts by mass or less, and 0.3 parts by mass with respect to 100 parts by mass of the curable compound. More than 10 parts by mass or less is particularly preferable.
  • photoinitiator may be combined with the radical polymerization initiator.
  • Photoinitiator aids include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminobenzoate 2- Ethylhexyl, 2-dimethylaminoethyl benzoate, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone, 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9, 10-Diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-5
  • the curable composition as the energy-sensitive composition of the fourth aspect may contain a curing accelerator.
  • the curable composition contains a curing accelerator, the curability and the properties after curing of the curable composition are good.
  • Examples of the curing accelerator include urea compounds, tertiary amines and salts thereof, imidazoles and salts thereof, phosphine compounds and derivatives thereof, metal carboxylates and Lewis acids, blended acids and salts thereof, and tetraphenylboron. Examples include salt.
  • Preferred specific examples of the curing accelerator include 1,8-diazabicyclo (5,4,0) undecene-7, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol and the like.
  • Tertiary amines Tertiary amines; imidazoles such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, and 2-heptadecylimidazole; tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine, And phosphine compounds such as phenylphosphine; tetraphenylphosphonium tetraphenylborate, triphenylphosphine tetraphenylborate, 2-ethyl-4-methylimidazole tetraphenylborate, and tetraphenylborone salt of N-methylmorpholine tetraphenylborate. Can be mentioned.
  • phosphine compounds and derivatives thereof, and tetraphenylboron salts are preferable.
  • triphenylphosphine and triphenylphosphine triphenylborane are preferable.
  • the amount of the curing accelerator used is not particularly limited as long as it does not impair the object of the present invention.
  • the amount of the curing accelerator used is preferably 0.5 parts by mass or more and 8 parts by mass or less, more preferably 1.5 parts by mass or more and 6 parts by mass or less, and 3 parts by mass or more and 4 parts by mass, with the mass of the curing agent as 1 part by mass. 5.5 parts by mass or less is particularly preferable.
  • the curable composition as the energy-sensitive composition of the fourth aspect may contain a sensitizer.
  • a sensitizer a known sensitizer that has been conventionally used in combination with various cationic polymerization initiators can be used without particular limitation.
  • sensitizer examples 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; phenothiazine compounds such as phenothracene, N-methylphenothracene, N-ethylphenothracene, and N-phenylphenothracene; xanthone; 1-naphthol, 2-naphthol, 1-methoxynaphthalene, 2-methoxynaphthalene, 1, Naphthalene compounds such as 4-dihydroxynaphthalene and 4-methoxy-1-naphthol; dimethoxy
  • the amount of the sensitizer used is not particularly limited, but is preferably 1% by mass or more and 300% by mass or less, and more preferably 5% by mass or more and 200% by mass or less, based on the mass of the photocationic polymerization initiator. By using an amount of the sensitizer within such a range, it is easy to obtain a desired sensitizing effect.
  • the curable composition as the energy-sensitive composition of the fourth aspect includes, if necessary, a surfactant, a thermoplastic inhibitor, an antifoaming agent, a silane coupling agent, a colorant (pigment, dye), and the like.
  • Additives such as resins (thermoplastic resins, alkali-soluble resins, etc.), inorganic fillers other than metal oxide fine particles, and organic fillers can be contained.
  • Conventionally known additives can be used for any type of additive.
  • the surfactant include anionic, cationic and nonionic compounds
  • examples of the thermal polymerization inhibitor include hydroquinone and hydroquinone monoethyl ether
  • examples of the antifoaming agent include silicone and fluorine. Examples include compounds.
  • the curable composition as the energy-sensitive composition of the fourth aspect preferably contains a solvent 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 organic solvent is not particularly limited as long as the components contained in the curable composition can be uniformly dissolved or dispersed.
  • a suitable example of the organic solvent that can be used as the solvent is the same as the preferable example of the organic solvent in the energy-sensitive composition of the first aspect.
  • the amount of the solvent used in the curable composition as the energy-sensitive composition of the fourth aspect is not particularly limited. From the viewpoint of coatability of the curable composition, the amount of the solvent used is, for example, 30% by mass or more and 99.9% by mass or less, preferably 50% by mass or more and 98% by mass, based on the entire curable composition. It is as follows. Further, it is preferable to adjust the viscosity of the curable composition in the range of 300 mPa ⁇ s or less. The viscosity of the curable composition is more preferably 60 mPa ⁇ s or less, and particularly preferably 30 mPa ⁇ s or less. There is no particular lower limit, but it is 0.1 mPa ⁇ s or more. The above viscosity is a viscosity measured at 25 ° C. using an E-type viscometer.
  • the curable composition is a high-refractive-index material which has been conventionally used for various purposes. It can be preferably used for forming a high refractive index film.
  • the refractive index is 1.70 or more, preferably 1.72 or more, still more preferably 1.75 or more, even more preferably 1.80 or more, and most preferably 1.80 or more.
  • the curable composition is particularly preferably used for forming a transparent film for covering a metal wiring or the like in a display element such as a touch panel. When a transparent film is formed using the above curable composition, the metal wiring can be made difficult to see due to the high refractive index of the transparent film.
  • the cured film formed by using the above curable composition has excellent bending resistance and is hard to break even when bent, it is preferably used in a flexible display panel.
  • a film having a thickness of 50 nm made of a cured product of the above curable composition is wound around a cylindrical stainless steel rod having a radius of 6 mm, preferably a radius of 2 mm, cracks are unlikely to occur.
  • Energy-sensitive composition of the fifth aspect has a melting point of 140 ° C. together with the metal oxide fine particles containing the modified metal oxide fine particles and the base material component (C) described above.
  • a cationic or anionic curable composition containing the following ionic liquids.
  • the curing reaction can be uniformly promoted in the curable composition with little dependence on whether it is cationic polymerization or anionic polymerization, and as a result, the curing reaction can be promoted uniformly. It is possible to form a metal oxide fine particle-containing film which is excellent in refractive index and yellowing resistance (particularly yellowing resistance), and also has good heat resistance and adhesion to a substrate.
  • essential or arbitrary components contained in the curable composition will be described.
  • the curable composition contains at least one element selected from the group consisting of N, O, S and Si from the viewpoint of refractive index and yellowing resistance, heat resistance and adhesion to a substrate. It preferably contains a curable compound having a functional group.
  • Curable compounds having a functional group containing at least one element selected from the group consisting of N, O, S and Si tend to have a relatively high refractive index.
  • the curable compound preferably has a functional group containing at least one element selected from the group consisting of N, S and O, and at least selected from the group consisting of N and S. It is more preferable to have a functional group containing one element.
  • Examples of the functional group containing N include a triazine ring structure, an isocyanul ring structure, a carbazole group, an imide group, a nitrile group and the like.
  • Examples of the curable compound (A) having a functional group containing N include a polymer having a triazine ring, a compound represented by the above formula (a1-I) as an epoxy resin precursor, polyvinylcarbazole (PVK), polyimide and the like. Can be mentioned.
  • a polymer having a triazine ring is particularly preferable because it has a relatively high refractive index (1.70 or more) due to its structure.
  • Examples of the functional group containing O include an epoxy group, an isocyanul ring structure, a carboxy group, an ester group, a ketone group, a hydroxy group and the like.
  • Examples of the curable compound having a functional group containing O include the compound represented by the above-mentioned formula (b-01), and the above-mentioned epoxy compound as an epoxy resin precursor.
  • the functional group containing S thiirane group, a sulfonyl group (-SO 2 -), a thiol group, thioester group, and the like.
  • the curable compound having a functional group containing S include a compound represented by the above formula (b-01), polyethersulfone (PES), polysulfone, polyphenylsulfone and the like.
  • the curable compound having a functional group containing Si include a siloxane compound having a siloxane skeleton composed of a siloxane bond (Si—O—Si).
  • Examples of the siloxane skeleton in the siloxane compound include a cyclic siloxane skeleton and a cage-type or ladder-type polysilsesquioxane skeleton.
  • the curable compound has an aromatic group, a triazine ring structure, an isocyanul ring structure and a cyclic siloxane structure from the viewpoint of the refractive index and yellowing resistance of the metal oxide fine particle-containing film, and from the viewpoint of heat resistance and adhesion to the substrate. It is preferable to include at least one selected from the group consisting of.
  • the aromatic group is preferably an aromatic group that forms a cardo structure from the viewpoint of refractive index and yellowing resistance, heat resistance, and adhesion to a substrate.
  • the curable compound can be used as a polymer having a triazine ring structure or an epoxy resin precursor according to the above formula (b-01) from the viewpoint of refractive index and yellowing resistance, heat resistance and adhesion to a substrate. It may contain at least one selected from the group consisting of the compound represented by the above formula (a1-I) and the siloxane epoxy compound represented by the above formula ((a1-III)) as the epoxy resin precursor. preferable.
  • the amount of the compound represented by the above formula (b-01) in the curable compound is preferably 50% by mass or more. , 70% by mass or more is more preferable, 80% by mass or more is even more preferable, 90% by mass or more is particularly preferable, and 100% by mass is most preferable.
  • the above-mentioned epoxy compound can be used as the epoxy resin precursor.
  • episulfide compound The type of episulfide compound is not particularly limited as long as the object of the present invention is not impaired.
  • Preferred episulfide compounds include compounds in which the oxygen atom in the epoxy group is replaced with a sulfur atom in the above-mentioned epoxy compound.
  • the curable compound may or may not contain a vinyl ether compound containing a vinyloxy group.
  • the vinyl ether compound is not particularly limited as long as it has a vinyloxy group and is cationically polymerizable.
  • the vinyl ether compound may or may not contain an aromatic group. From the viewpoint of good thermal decomposition resistance of the cured product, the vinyl ether compound is preferably a compound having a vinyloxy group bonded to an aromatic group.
  • vinyl ether compound examples include vinylphenyl ether, 4-vinyloxytoluene, 3-vinyloxytoluene, 2-vinyloxytoluene, 1-vinyloxy-4-chlorobenzene, 1-vinyloxy-3-chlorobenzene, 1-.
  • Vinyloxy-2-chlorobenzene 1-vinyloxy-2,3-dimethylbenzene, 1-vinyloxy-2,4-dimethylbenzene, 1-vinyloxy-2,5-dimethylbenzene, 1-vinyloxy-2,6-dimethylbenzene, 1-vinyloxy-3,4-dimethylbenzene, 1-vinyloxy-3,5-dimethylbenzene, 1-vinyloxynaphthalene, 2-vinyloxynaphthalene, 2-vinyloxyfluorene, 3-vinyloxyfluorene, 4-vinyloxy- Aromatic monovinyl ether compounds such as 1,1'-biphenyl, 3-vinyloxy-1,1'-biphenyl, 2-vinyloxy-1,1'-biphenyl, 6-vinyloxytetraline, and 5-vinyloxytetraline; 1 , 4-Diviniroxybenzene, 1,3-Dibiniroxybenzene,
  • a polymer having a triazine ring structure is preferably used by being mixed with other curable compounds described above.
  • examples of the above-mentioned polymer having a triazine ring structure include polymers composed of structural units represented by the following formulas (t1) to (t16).
  • R t0 and R t1 independently represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group or an aralkyl group, and both are preferably hydrogen atoms from the viewpoint of further increasing the refractive index. ..
  • R t2 to R t4 and R t6 to R t9 independently have a hydrogen atom, a halogen atom, a carboxy group, a sulfo group, and an alkyl group having 1 or more and 10 or less carbon atoms.
  • an alkoxy group which may have a branched structure having 1 or more and 10 or less carbon atoms
  • R 102 and R 103 represent an alkyl group having 1 or more and 5 or less carbon atoms independently of each other.
  • R t0 to R t4 , R t6 to R t9 , R 102 and R 103 have the same meanings as described above.
  • R t0 to R t4 and R t6 to R t9 have the same meanings as described above.
  • R t0 to R t4 and R t6 to R t9 have the same meanings as above, and R t5 has a hydrogen atom, a halogen atom, a carboxy group, a sulfo group, and a branched structure having 1 or more and 10 or less carbon atoms.
  • R t5 has a hydrogen atom, a halogen atom, a carboxy group, a sulfo group, and a branched structure having 1 or more and 10 or less carbon atoms.
  • R 102 and R 103 are independent of each other and have 1 or more and 5 or less carbon atoms.
  • R t0 to R t9 , R 102 and R 103 have the same meanings as above.
  • R t0 to R t9 have the same meanings as above.
  • R t0 to R t4 and R t6 to R t9 have the same meanings as described above, and R 102 and R 103 independently represent alkyl groups having 1 or more and 5 or less carbon atoms.
  • R t0 to R t4 , R t6 to R t9 , R 102 and R 103 have the same meanings as described above.
  • R t0 to R t4 and R t6 to R t9 have the same meanings as described above.
  • R t0 to R t9 have the same meanings as described above, and R 102 and R 103 represent alkyl groups having 1 or more and 5 or less carbon atoms independently of each other.
  • R t0 to R t9 , R 102 and R 103 have the same meanings as above.
  • R t0 to R t9 have the same meanings as above.
  • the weight average molecular weight (Mw) of the triazine ring-containing polymer is not particularly limited.
  • the weight average molecular weight (Mw) of the triazine ring-containing polymer is preferably 500 or more and 500,000 or less, and more preferably 500 or more and 100,000 or less. From the viewpoint that the effect of the present invention can be easily achieved, 2,000 or more is preferable, and from the viewpoint of further increasing the solubility and lowering the viscosity of the obtained solution, 50,000 or less is preferable, and 30,000 or less is preferable. Is more preferable, and 10,000 or less is further preferable.
  • the weight average molecular weight (Mw) is an average molecular weight obtained in terms of standard polystyrene by gel permeation chromatography (hereinafter referred to as GPC) analysis.
  • the triazine ring-containing polymer can be produced, for example, by the method disclosed in International Publication No. 2010/128661.
  • the triazine ring-containing polymer has at least one diamine terminal, and at least one of the diamine ends is sealed with a carbonyl-containing group such as an acyl group, an alkoxycarbonyl group, an aralkyloxycarbonyl group or an aryloxycarbonyl group. It is preferable to have. By sealing the ends with carbonyl-containing groups in this way, coloring of the triazine ring-containing polymer can be suppressed.
  • a carbonyl-containing group such as an acyl group, an alkoxycarbonyl group, an aralkyloxycarbonyl group or an aryloxycarbonyl group. It is preferable to have.
  • acyl group examples include an acetyl group, an ethylcarbonyl group, an acryloyl group, a methacryloyl group, a benzoyl group and the like.
  • alkoxycarbonyl group examples include a methoxycarbonyl group, an ethoxycarbonyl group, a tert-butoxycarbonyl group and the like.
  • aralkyloxycarbonyl group include a benzyloxycarbonyl group and the like.
  • aryloxycarbonyl group include a phenoxycarbonyl group and the like.
  • an acyl group is preferable as the terminal-sealing group, and an acryloyl group, a methacryloyl group, and an acetyl group are more preferable in consideration of availability of reagents and the like.
  • the terminal sealing method a known method may be adopted, and for example, it may be treated with an acid halide, an acid anhydride or the like.
  • the amount of the end-capping agent used is preferably about 0.05 equivalents or more and 10 equivalents or less, and 0.1 equivalents or more and 5 equivalents, relative to 1 equivalent of the surplus diamino compound-derived amino group that was not used in the polymerization reaction. Equivalent or less is more preferable, and 0.5 equivalent or more and 2 equivalent or less is even more preferable.
  • the above curable compound may be used alone or in combination of two or more.
  • the content of the curable compound in the curable composition is not particularly limited as long as it does not impair the object of the present invention.
  • the content of the curable compound in the curable composition is preferably 60 parts by mass or more and 99.9 parts by mass or less, and 75 parts by mass or more and 99.5 parts by mass, when the total solid content of the curable composition is 100 parts by mass. More preferably, it is 90 parts by mass or less, and particularly preferably 90 parts by mass or more and 99 parts by mass or less.
  • the curable composition preferably contains a curing agent.
  • the same curing agent as the curing agent described for the energy-sensitive composition of the fifth aspect can be used.
  • the content of the cationic polymerization initiator as a curing agent in the curable composition is not particularly limited as long as it does not impair the object of the present invention.
  • the content of the cationic polymerization initiator in the curable composition is 0. as the total amount of the above-mentioned onium salt (B01) and the above-mentioned other cationic polymerization initiator (B02) with respect to 100 parts by mass of the curable compound. It is preferably 01 parts by mass or more and 5 parts by mass or less, more preferably 0.05 parts by mass or more and 3 parts by mass or less, and particularly preferably 0.1 parts by mass or more and 2 parts by mass or less.
  • the content of the onium salt (B01) is preferably 10% by mass or more, more preferably 50% by mass or more, based on the total amount of the sulfonium salt (B01) and the other cationic polymerization initiator (B02) described later. 70% by mass or more is even more preferable, 90% by mass or more is particularly preferable, and 100% by mass is most preferable.
  • an amount of the cationic polymerization initiator within such a range, a metal oxide fine particle-containing film having excellent refractive index and yellowing resistance, heat resistance (heat decomposition resistance), and adhesion to a substrate is formed. Cheap.
  • an anionic polymerization initiator can also be used as the curing agent.
  • the anionic polymerization initiator may be an anionic polymerization initiator by light or an anionic polymerization initiator by heat.
  • an anionic curable composition can be obtained.
  • the anion polymerization initiator by light is not particularly limited, and is, for example, photoactive carbamate such as triphenylmethanol, benzyl carbamate and benzoin carbamate; O-carbamoyl hydroxyamide, O-carbamoyl oxime, aromatic sulfonamide, alpha lactam. And amides such as N- (2-allylethynyl) amides and other amides; oxime ester compounds, ⁇ -aminoacetophenone, cobalt complexes and the like.
  • photoactive carbamate such as triphenylmethanol, benzyl carbamate and benzoin carbamate
  • O-carbamoyl hydroxyamide O-carbamoyl oxime
  • aromatic sulfonamide alpha lactam.
  • amides such as N- (2-allylethynyl) amides and other amides
  • oxime ester compounds ⁇ -aminoace
  • 2-nitrobenzylcyclohexylcarbamate triphenylmethanol, O-carbamoylhydroxyamide, O-carbamoyloxime, [[(2,6-dinitrobenzyl) oxy] carbonyl] cyclohexylamine, bis [[(2-nitrobenzyl) ) Oxy] carbonyl] hexane 1,6-diamine, 4- (methylthiobenzoyl) -1-methyl-1-morpholinoetan, (4-morpholinobenzoyl) -1-benzyl-1-dimethylaminopropane, N- (2-)
  • Preferable anion polymerization initiators include nitrobenzyloxycarbonyl) pyrrolidine, hexaammine cobalt (III) tris (triphenylmethylborate), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone and the like.
  • Preferable examples other than the above include compounds represented by the formula (d2) or (d3), which are decomposed by the action of light (and / or heat) to generate an imidazole compound.
  • the thermal anionic polymerization initiator a conventionally used compound can be used without particular limitation.
  • amine-epoxyadduct-based thermal anionic polymerization initiators thermal base generators composed of amine-isocyanate compounds, anionic polymerization-type curing agents such as dicyandiamides, hydrazines, or aromatic diamines, or different types of curing agents.
  • Examples thereof include a composite anionic polymerization type curing agent composed of a curing agent.
  • Examples of the amine-epoxyadduct-based thermal anionic polymerization initiator include "Amicure PN-23", “Amicure PN-40", Amicure PN-50 ", and” Amicure PN-H "(all of which are products of Ajinomoto Fine Techno Co., Ltd.). Name), “Hardener X-3661S” (product name of ACR), “Hardner X-3670S” (product name of ACR), “Novacure HX-3742” (product of Asahi Kasei) Name), “Novacure HX-3721” (trade name of Asahi Kasei Co., Ltd.), etc.
  • thermobase generator composed of an amine-isocyanate compound
  • a thermobase generator composed of an amine-isocyanate compound
  • 2-Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane-1-one can also function as an anionic polymerization initiator by the action of light.
  • the content of the anionic polymerization initiator in the curable composition is not particularly limited as long as it does not impair the object of the present invention.
  • the content of the anionic polymerization initiator in the curable composition is preferably 0.01 part by mass or more and 5 parts by mass or less, and more preferably 0.05 part by mass or more and 3 parts by mass or less with respect to 100 parts by mass of the curable compound. , 0.1 part by mass or more and 2 parts by mass or less is particularly preferable.
  • the ionic liquid is a salt that can be melted in a temperature range of 140 ° C. or lower, and is preferably a stable salt that becomes liquid at 140 ° C. or lower.
  • the melting point of the ionic liquid is preferably 120 ° C. or lower, more preferably 100 ° C. or lower, and 80 ° C. or lower, from the viewpoint of more reliably achieving the effect of the present invention and the coatability. It is more preferable to have.
  • the curable composition contains a solvent
  • it is contained in the curable composition at room temperature (25 ° C.) from the viewpoint of more reliably achieving the effect of the present invention, coatability and suppression of foreign substances.
  • the solubility of the ionic liquid in the solvent is preferably 70% by mass or more, more preferably 80% by mass or more, and particularly preferably 90% by mass or more.
  • the above-mentioned solubility means that 70 parts by mass, 80 parts by mass, 90 parts by mass, etc. of the ionic liquid is mixed with 100 parts by mass of the solvent contained in the curable composition, and the shaker is used for 5 minutes. The mass at which no precipitation is observed by visually confirming the presence or absence of precipitation during processing. Since the ionic liquid is a salt, it has good ionic conductivity, and when it is a liquid at a melting point of 140 ° C. or lower, it can be uniformly diffused in the curable composition. The thermal decomposition temperature is also relatively high.
  • the curable composition the dependence on whether it is cationic polymerization or anionic polymerization is low, and the curing reaction can be uniformly promoted, and as a result, the refractive index and yellowing resistance (particularly yellowing resistance) can be promoted. It is possible to form a metal oxide fine particle-containing film which is excellent in heat resistance and has good adhesion to a substrate.
  • the ionic liquid is preferably composed of an organic cation and an anion.
  • the ionic liquid is preferably composed of a nitrogen-containing organic cation, a phosphorus-containing organic cation, or a sulfur-containing organic cation and a counter anion, and more preferably a nitrogen-containing organic cation or a phosphorus-containing organic cation and a counter anion. preferable.
  • the alkyl chain quaternary ammonium cation, the piperidinium cation, the pyrimidinium cation, the pyrrolidinium cation, and the imidazolium cation have good affinity with the solvent described later.
  • Pyridinium cation, pyrazolium cation, guanidinium cation, morpholinium cation, phosphonium cation and sulfonium cation preferably at least one selected from the group consisting of alkyl chain quaternary ammonium cation, piperidinium.
  • a cation, a pyrrolidinium cation, an imidazolium cation, a morpholinium cation, or a phosphonium cation it is more preferably a cation, a pyrrolidinium cation, an imidazolium cation, a morpholinium cation, or a phosphonium cation, and in terms of the effects of the present invention, it may be a pyrrolidinium cation, an imidazolium cation, or a phosphonium cation. More preferred.
  • alkyl chain quaternary ammonium cation examples include a quaternary ammonium cation represented by the following formula (L1). Specific examples thereof include tetramethylammonium cations, ethyltrimethylammonium cations, diethyldimethylammonium cations, triethylmethylammonium cations, tetraethylammonium cations, octyltrimethylammonium cations, hexyltrimethylammonium cations, and methyltrioctylammonium cations. .. Specific examples of the piperidinium cation include a piperidinium cation represented by the following formula (L2).
  • pyrimidinium cation examples include 1,3-dimethyl-1,4,5,6-tetrahydropyrimidinium cation, 1,2,3-trimethyl-1,4,5,6-tetrahydro.
  • pyrrolidinium cation examples include pyrrolidinium cations represented by the following formula (L3), and more specifically, for example, 1,1-dimethylpyrrolidinium cation and 1-ethyl-1.
  • L3 pyrrolidinium cations represented by the following formula (L3), and more specifically, for example, 1,1-dimethylpyrrolidinium cation and 1-ethyl-1.
  • imidazolium cation examples include the imidazolium cation represented by the following formula (L5), and more specifically, for example, 1,3-dimethylimidazolium cation and 1,3-diethyl imidazolium cation.
  • pyridinium cation examples include a pyridinium cation represented by the following formula (L6). More specifically, for example, 1-ethylpyridinium cation, 1-butylpyridinium cation, 1-hexylpyridinium cation, 1 Examples thereof include -butyl-3-methylpyridinium cation, 1-butyl-4-methylpyridinium cation, 1-hexyl-3-methylpyridinium cation, 1-butyl-3,4-dimethylpyridinium cation and the like.
  • L6 pyridinium cation represented by the following formula (L6). More specifically, for example, 1-ethylpyridinium cation, 1-butylpyridinium cation, 1-hexylpyridinium cation, 1 Examples thereof include -butyl-3-methylpyridinium cation, 1-butyl-4-methylpyridinium cation, 1-hexyl-3-methyl
  • pyrazolium cation examples include 1-methylpyrazolium cation, 3-methylpyrazolium cation, 1-ethyl-2-methylpyrazolinium cation, 1-ethyl-2,3,5.
  • Examples thereof include -trimethylpyrazolium cation, 1-propyl-2,3,5-trimethylpyrazolium cation, 1-butyl-2,3,5-trimethylpyrazolium cation and the like. ..
  • the phosphonium cation include a phosphonium cation represented by the following formula (L4).
  • Specific examples thereof include tetraalkylphosphonium cations such as tetrabutylphosphonium cation, tributylmethylphosphonium cation and tributylhexylphosphonium cation, and triethyl (methoxymethyl) phosphonium cation.
  • sulfonium cation examples include triethyl sulfonium cation, dimethyl ethyl sulfonium cation, triethyl sulfonium cation, ethyl methyl propyl sulfonium cation, butyl dimethyl sulfonium cation, 1-methyl tetrahydrothiophenium cation, and 1-ethyl tetrahydrothiophenium cation. , 1-propyltetrahydrothiophenium cation, 1-butyltetrahydrothiophenium cation, 1-methyl- [1,4] -thioxonium cation and the like.
  • a sulfonium cation having a cyclic structure such as a tetrahydrothiophenium-based or hexahydrothiopyrilium-based 5-membered ring or 6-membered ring is preferable, and an oxygen atom or the like is contained in the cyclic structure. It may have a hetero atom.
  • R L1 ⁇ R L4 are each independently an alkyl group having 1 to 20 carbon atoms, or R L7 -O- (CH 2) Ln - alkoxyalkyl represented by Is the basis.
  • RL7 represents a methyl group or an ethyl group.
  • Ln represents an integer of 1 or more and 4 or less.
  • R L5 R L1 ⁇ R L4 are each independently an alkyl group having 1 to 20 carbon atoms, R L7 -O- (CH 2) Ln - alkoxyalkyl group represented by, or a hydrogen atom Is.
  • RL7 represents a methyl group or an ethyl group.
  • Ln represents an integer of 1 or more and 4 or less.
  • R L6 R L1 ⁇ R L6 are each independently an alkyl group having 1 to 20 carbon atoms, R L7 -O- (CH 2) Ln - alkoxyalkyl group represented by a hydrogen atom be.
  • RL7 represents a methyl group or an ethyl group.
  • Ln represents an integer of 1 or more and 4 or less.
  • the anion constituting the ionic liquid may be an organic anion or an inorganic anion.
  • An organic anion is preferable because the ionic liquid has a good affinity with the solvent (S) described later.
  • the organic anion is at least one selected from the group consisting of a carboxylic acid anion, an N-acyl amino acid ion, an acidic amino acid anion, a neutral amino acid anion, an alkyl sulfate anion, a fluorine-containing compound anion, and a phenol anion. It is preferably a carboxylic acid anion or an N-acylamino acid ion.
  • carboxylic acid-based anion examples include acetate ion, decanoate ion, 2-pyrrolidone-5-carboxylic acid ion, formate ion, ⁇ -lipoate ion, lactate ion, tartrate ion, horse urate ion, and N-methyl.
  • Horse urate ion and the like can be mentioned, and among them, acetate ion, 2-pyrrolidone-5-carboxylic acid ion, formate ion, lactic acid ion, tartrate ion, horse urate ion and N-methyl horse urate ion are preferable, and acetate ion and N- Methyl horseurate ion and formate ion are more preferable.
  • Specific examples of the N-acylamino acid ion include N-benzoylalanine ion, N-acetylphenylalanine ion, aspartate ion, glycine ion, N-acetylglycine ion and the like.
  • N-benzoylalanine ion and N. -Acetylphenylalanine ion and N-acetylglycine ion are preferable, and N-acetylglycine ion is more preferable.
  • the acidic amino acid anion include aspartate ion, glutamic acid ion and the like
  • specific examples of the neutral amino acid anion include glycine ion, alanine ion, phenylalanine ion and the like.
  • Specific examples of the alkyl sulfate anion include methanesulfonic acid ion
  • specific examples of the fluorine-containing compound anion include trifluoromethanesulfonic acid ion, hexafluorophosphonate ion, and trifluorotris (pentafluoro).
  • Examples thereof include ethyl) phosphonate ion, bis (fluoroalkylsulfonyl) imide ion (for example, bis (trifluoromethanesulfonyl) imide ion), trifluoroacetate ion, tetrafluoroborate ion, and the like, and specific examples of the above phenolic anion include bis (trifluoromethanesulfonyl) imide ion. Examples thereof include phenol ion, 2-methoxyphenol ion, 2,6-di-tert-butylphenol ion and the like.
  • F -, Cl -, Br -, I -, BF 4 -, PF 6 - from the group consisting of - and N (SO 2 F) 2 is preferably at least one selected, BF 4 -, PF 6 - or N (SO 2 F) 2 - more preferably, BF 4 - and still more preferably a - or PF 6.
  • the ionic liquid can be produced, for example, by the method disclosed in paragraph 0045 of International Publication No. 2014/178254.
  • the ionic liquid may be used alone or in combination of two or more.
  • the content of the ionic liquid is not particularly limited as long as the effects of the present invention can be achieved, but is preferably 0.0001 parts by mass or more and 1 part by mass or less with respect to 100 parts by mass of the curable compound, and is 0. .001 parts by mass or more and 1 part by mass or less, more preferably 0.002 parts by mass or more and 0.1 parts by mass or less, and 0.003 parts by mass or more and 0.07 parts by mass or less. Is particularly preferable.
  • the curable composition may contain a curing accelerator.
  • both the refractive index and the yellowing resistance are compatible, and the curability of the curable composition is improved.
  • a good metal oxide fine particle-containing film can be formed.
  • Examples of the curing accelerator include urea compounds, tertiary amines and salts thereof, imidazoles and salts thereof, phosphine compounds and derivatives thereof, metal carboxylates and Lewis acids, blended acids and salts thereof, and tetraphenylboron. Examples include salt.
  • Preferred specific examples of the curing accelerator include 1,8-diazabicyclo (5,4,0) undecene-7, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol and the like.
  • Tertiary amines Tertiary amines; imidazoles such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, and 2-heptadecylimidazole; tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine, And phosphine compounds such as phenylphosphine; tetraphenylphosphonium tetraphenylborate, triphenylphosphine tetraphenylborate, 2-ethyl-4-methylimidazole tetraphenylborate, and tetraphenylborone salt of N-methylmorpholine tetraphenylborate. Can be mentioned.
  • phosphine compounds and derivatives thereof, and tetraphenylboron salts are preferable.
  • triphenylphosphine and triphenylphosphine triphenylborane are preferable.
  • the amount of the curing accelerator used is not particularly limited as long as it does not impair the object of the present invention.
  • the amount of the curing accelerator used is preferably 0.01 part by mass or more and 5 parts by mass or less, more preferably 0.05 part by mass or more and 3 parts by mass or less, and 0.1 part by mass with respect to 100 parts by mass of the curable compound. More than 2 parts by mass or less is particularly preferable.
  • the curable composition may contain a sensitizer.
  • the curable composition comprises a cationic polymerization initiator and the cationic polymerization initiator comprises a sulfonium cation and / or an iodonium cation
  • the curable composition preferably comprises a sensitizer.
  • the sensitizer a known sensitizer that has been conventionally used in combination with various cationic polymerization initiators can be used without particular limitation.
  • Preferable examples of the sensitizer are similar to the sensitizer described for the energy sensitive composition of the fourth aspect.
  • the sensitizer may be used in combination of two or more.
  • the amount of the sensitizer used is not particularly limited, but is preferably 1% by mass or more and 300% by mass or less, and more preferably 5% by mass or more and 200% by mass or less with respect to the mass of the cationic polymerization initiator. By using an amount of the sensitizer within such a range, it is easy to obtain a desired sensitizing effect.
  • the curable composition may or may not contain an antioxidant, but from the viewpoint of yellowing resistance, it preferably contains an antioxidant.
  • the antioxidant include a phenol compound, a phosphite ester compound, a thioether compound and the like, and a phenol compound having a molecular weight of 500 or more, a phosphite ester compound having a molecular weight of 500 or more, or a thioether compound having a molecular weight of 500 or more is more preferable.
  • the antioxidant a phenol compound is preferable, and a phenol compound having a molecular weight of 500 or more is more preferable.
  • any phenol compound known as a phenol-based colorant can be used.
  • Preferred phenolic compounds include hindered phenolic compounds.
  • a compound having a substituent at a site (ortho position) adjacent to the phenolic hydroxyl group is preferable.
  • a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferable, and a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group and an isopentyl group are preferable.
  • groups More preferred are groups, tert-pentyl groups, hexyl groups, octyl groups, isooctyl groups and 2-ethylhexyl groups. Further, a compound having a phenol group and a phosphite ester group in the same molecule is also preferable.
  • tris [2-[[2,4,8,10-tetrakis (1,1-dimethylethyl) dibenzo [d, f] [1,3,2] dioxaphosfepine-6 -Il] Oxy] Ethyl] amine, Tris [2-[(4,6,9,11-tetra-tert-butyldibenzo [d, f] [1,3,2] dioxaphosfepin-2-yl] ) Oxy] ethyl] amine and ethylbis phosphite (2,4-ditert-butyl-6-methylphenyl) include at least one compound selected from the group.
  • Antioxidants are readily available as commercial products: ADEKA STAB AO-20, ADEKA STAB AO-30, ADEKA STAB AO-40, ADEKA STAB AO-50, ADEKA STAB AO-50F, ADEKA STAB AO-60, ADEKA STAB AO-60G, ADEKA STAB AO-80, ADEKA STAB AO-330, ADEKA STAB PEP-36A, ADEKA STAB AO-412S (ADEKA Corporation) and the like can be mentioned.
  • the content of the antioxidant is preferably 0.01% by mass or more and 20% by mass or less, and more preferably 0.3% by mass or more and 15% by mass or less among the components of the curable composition excluding the solvent.
  • the anti-coloring agent may be only one type or two or more types. In the case of two or more types, the total amount is preferably in the above range.
  • Curable compositions include surfactants, thermal polymerization inhibitors, defoamers, silane coupling agents, colorants (pigments, dyes), resins (thermoplastic resins, alkali-soluble resins, etc.), as required. Additives such as organic fillers can be included. Conventionally known additives can be used for any type of additive.
  • the curable composition preferably contains a solvent 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 organic solvent is not particularly limited as long as the components contained in the curable composition can be uniformly dissolved or dispersed.
  • a suitable example of an organic solvent that can be used as a solvent is the same as a suitable example of an organic solvent in the energy-sensitive composition of the first aspect.
  • the amount of solvent used in the curable composition is not particularly limited. From the viewpoint of coatability of the curable composition, the amount of the solvent used is, for example, 30% by mass or more and 99.9% by mass or less, preferably 50% by mass or more and 98% by mass, based on the entire curable composition. It is as follows.
  • the metal oxide fine particle-containing film obtained by curing the curable composition as the energy-sensitive composition of the fifth aspect described above is excellent in refractive index and yellowing resistance, and also has heat resistance and adhesion to a substrate.
  • the sex is also good.
  • the thickness of the cured film is not particularly limited, but is preferably 10 nm or more and 50 ⁇ m or less, more preferably 50 nm or more and 30 ⁇ m or less, further preferably 100 nm or more and 10 ⁇ m or less, and 300 nm or more and 5 ⁇ m or less. Is particularly preferable.
  • the cured film is, for example, an encapsulant for an OLED display element, an OLED lighting, a hard coat, an insulating film, an antireflection film, an interlayer insulating film, a carbon hard mask, a display panel material (flattening film, color filter pixels, organic). It is suitable for various applications such as EL bulkheads (spacers), optical members (lenses, microlenses, wafer-level lenses, optical fibers, optical waveguides, prism sheets, holograms, high-refractive-index films, retroreflective films). Further, since the cured film has excellent flexibility and is hard to break, it is suitably used in flexible display panels and flexible lighting. Further, the cured film is particularly preferably used as a transparent film for covering metal wiring or the like in a display element such as a touch panel.
  • a resin that forms a cured film by firing is also preferable as the precursor resin as the base material component (C).
  • the resin that forms a cured film by firing include a silicon-containing resin.
  • Preferred examples of the silicon-containing resin include one or more selected from a siloxane resin and polysilane.
  • siloxane resin The siloxane resin is not particularly limited as long as it is a resin that is soluble in a solvent described later.
  • a siloxane resin obtained by hydrolyzing and condensing at least one selected from the silane compounds represented by the following formula (CA) is preferably used. RY0 (4-n0) Si (OR') n0 ... (CA)
  • RY0 represents a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group
  • R' represents an alkyl group or a phenyl group
  • n0 represents an integer of 2 or more and 4 or less.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)

Abstract

L'invention fournit : un procédé de fabrication de microparticules d'oxyde métallique modifiées qui permet de fabriquer des microparticules d'oxyde métallique modifiées d'une excellente stabilité de dispersion dans des dispersions liquides présentant diverses compositions ; un procédé de fabrication d'une dispersion liquide de microparticules d'oxyde métallique modifiées contenant lesdites microparticules d'oxyde métallique modifiées ; et un procédé de fabrication d'un article solide formé à l'aide de ladite dispersion liquide de microparticules d'oxyde métallique modifiées.　Selon un procédé qui inclut une étape au cours de laquelle des microparticules d'oxyde métallique (B) sont préparées en présence d'un solvant (S-I) ou ces microparticules d'oxyde métallique (B) sont dispersées en présence d'un milieu de dispersion (S-II), et une étape au cours de laquelle les microparticules d'oxyde métallique (B) et un composé acide carboxylique à teneur en groupe aromatique (A) et/ou un carboxylate dérivé du composé acide carboxylique à teneur en groupe aromatique (A), sont mis en contact en présence du solvant (S-I) ou du milieu de dispersion (S-II), un solvant organique azoté est mis en œuvre en tant que solvant (S-I) ou milieu de dispersion (S-II).
PCT/JP2021/016227 2020-05-01 2021-04-21 Procédé de fabrication de microparticules d'oxyde métallique modifiées, procédé de fabrication de dispersion liquide de microparticules d'oxyde métallique modifiées, et procédé de fabrication d'article solide WO2021220919A1 (fr)

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Cited By (1)

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CN116444298A (zh) * 2023-04-10 2023-07-18 广东兴辉陶瓷集团有限公司 一种金属质感岩板

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JP2005109316A (ja) * 2003-10-01 2005-04-21 Rikogaku Shinkokai 高誘電率無機材料及びそれを用いた高誘電率コンポジット材料
JP2006179925A (ja) * 2004-12-21 2006-07-06 E I Du Pont De Nemours & Co 容量デバイス、有機誘電ラミネート、およびそのようなデバイスを組み込んだプリント配線板、ならびにそれらの製造方法
JP2009217119A (ja) * 2008-03-12 2009-09-24 Fujifilm Corp 金属酸化物微粒子分散液及び成形体
JP2010052985A (ja) * 2008-08-28 2010-03-11 Fujifilm Corp 金属酸化物微粒子分散液及び成形体
JP2010195636A (ja) * 2009-02-25 2010-09-09 Fujifilm Corp 金属酸化物微粒子、金属酸化物微粒子分散液、及び成形体
JP2015059244A (ja) * 2013-09-19 2015-03-30 学校法人関東学院 金属パターン付樹脂材の製造方法及び金属パターン付樹脂材

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Publication number Priority date Publication date Assignee Title
JP2005109316A (ja) * 2003-10-01 2005-04-21 Rikogaku Shinkokai 高誘電率無機材料及びそれを用いた高誘電率コンポジット材料
JP2006179925A (ja) * 2004-12-21 2006-07-06 E I Du Pont De Nemours & Co 容量デバイス、有機誘電ラミネート、およびそのようなデバイスを組み込んだプリント配線板、ならびにそれらの製造方法
JP2009217119A (ja) * 2008-03-12 2009-09-24 Fujifilm Corp 金属酸化物微粒子分散液及び成形体
JP2010052985A (ja) * 2008-08-28 2010-03-11 Fujifilm Corp 金属酸化物微粒子分散液及び成形体
JP2010195636A (ja) * 2009-02-25 2010-09-09 Fujifilm Corp 金属酸化物微粒子、金属酸化物微粒子分散液、及び成形体
JP2015059244A (ja) * 2013-09-19 2015-03-30 学校法人関東学院 金属パターン付樹脂材の製造方法及び金属パターン付樹脂材

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116444298A (zh) * 2023-04-10 2023-07-18 广东兴辉陶瓷集团有限公司 一种金属质感岩板
CN116444298B (zh) * 2023-04-10 2024-01-05 广东兴辉陶瓷集团有限公司 一种金属质感岩板

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