Method for producing modified metal oxide fine particles, method for producing modified metal oxide fine particle dispersion, and method for producing solid article

Abstract

Provided are: a method for producing surface-modified metal oxide microparticles that is for producing surface-modified metal oxide microparticles that have excellent dispersion stability in dispersion solutions having a variety of compositions; a method for producing a surface-modified metal oxide microparticle dispersion comprising said surface-modified metal oxide microparticles; and a method for producing a solid product formed using said surface-modified metal oxide microparticle dispersion.　A method comprising preparing metal oxide microparticles (B) in the presence of a solvent (S-I) or dispersing metal oxide microparticles (B) in the presence of a solvent (S-II), and bringing the metal oxide microparticles (B) into contact with an aromatic group-containing carboxylic acid compound (A) and / or a carboxylate derived from an aromatic group-containing carboxylic acid compound (A) in the presence of the solvent (S-I) or the solvent (S-II), wherein a nitrogen-containing organic solvent is used as the solvent (S-I) or the solvent (S-II).

Description

Technical Field

[0001] The present invention relates to a method for producing modified metal oxide fine particles capable of producing modified metal oxide fine particles excellent in dispersion stability in dispersion liquids of various compositions, a method for producing a modified metal oxide fine particle dispersion liquid containing the modified metal oxide fine particles, and a method for producing a solid article formed using the modified metal oxide fine particle dispersion liquid.

Background Art

[0002] Metal oxide fine particles are widely used as materials for optical materials, electronic component materials, and various articles such as abrasives. Such metal oxide fine particles are often used as a dispersion liquid because they are easy to transport, measure, handle, etc. However, when untreated metal oxide fine particles are dispersed in a dispersion medium such as an organic solvent, there is a problem that the metal oxide fine particles easily aggregate. When the metal oxide fine particles aggregate in the dispersion medium, it is difficult to exhibit the functions of the metal oxide fine particles. For this reason, a surface treatment method for metal oxide fine particles has been proposed in order to impart good dispersion stability to the dispersion medium such as an organic solvent.

[0003] As such a surface treatment method, a method of coating at least a part of the surface of metal oxide fine particles with a carboxylic acid compound having an aromatic structure has been proposed (Patent Document 1).

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] However, there was still room for further improvement in the dispersion stability of the metal oxide fine particles surface-treated by the method described in Patent Document 1. In addition, the metal oxide fine particles surface-treated by the method described in Patent Document 1 were likely to aggregate depending on the types of components contained in the dispersion liquid.

[0006] The present invention has been made in view of the above problems, and an object thereof is to provide a method for producing modified metal oxide fine particles capable of producing modified metal oxide fine particles excellent in dispersion stability in dispersion liquids of various compositions, a method for producing a modified metal oxide fine particle dispersion liquid containing the modified metal oxide fine particles, and a method for producing a solid article formed using the modified metal oxide fine particle dispersion liquid.

Means for Solving the Problems

[0007] The present inventors prepared metal oxide fine particles (B) in the presence of a solvent (S-I), or dispersed metal oxide fine particles (B) in the presence of a dispersion medium (S-II), and in a method including contacting metal oxide fine particles (B) with an aromatic group-containing carboxylic acid compound (A) and / or a carboxylate derived from the aromatic group-containing carboxylic acid compound (A) in the presence of the solvent (S-I) or the dispersion medium (S-II), found that the above problems can be solved by using a nitrogen-containing organic solvent as the solvent (S-I) or the dispersion medium (S-II), and thus completed the present invention. Specifically, the present invention provides the following.

[0008] A first aspect of the present invention includes preparing metal oxide fine particles (B) in the presence of a solvent (S-I), or dispersing metal oxide fine particles (B) in the presence of a dispersion medium (S-II), and contacting metal oxide fine particles (B) with an aromatic group-containing carboxylic acid compound (A) and / or a carboxylate derived from the aromatic group-containing carboxylic acid compound (A) in the presence of the solvent (S-I) or the dispersion medium (S-II), wherein the solvent (S-I) or the dispersion medium (S-II) contains a nitrogen-containing organic solvent, and is a method for producing modified metal oxide fine particles.

[0009] A second aspect of the present invention is to produce modified metal oxide fine particles by the method according to the first aspect, mixing the modified metal oxide fine particles and the base material component (C) in a solvent (S) to obtain a modified metal oxide fine particle dispersion, which is a method for producing a modified metal oxide fine particle dispersion.

[0010] 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 according to the shape of the solid article to be formed, and solidifying the molded modified metal oxide fine particle dispersion by one or more methods selected from the group consisting of drying, curing by moisture, heating, and exposure, which is a method for producing a solid article.

Advantages of the Invention

[0011] According to the present invention, it is possible to provide a method for producing modified metal oxide fine particles capable of producing modified metal oxide fine particles excellent in dispersion stability in dispersions of various compositions, 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 using the modified metal oxide fine particle dispersion.

Embodiments for Carrying Out the Invention

[0012] ≪Method for Producing Modified Metal Oxide Fine Particles≫ The method for producing modified metal oxide fine particles is to prepare metal oxide fine particles (B) in the presence of a solvent (S-I) or disperse metal oxide fine particles (B) in the presence of a dispersion medium (S-II), and contacting the metal oxide fine particles (B) with an aromatic group-containing carboxylic acid compound (A) and / or a carboxylate derived from the aromatic group-containing carboxylic acid compound (A) in the presence of the solvent (S-I) or the dispersion medium (S-II). Further, the solvent (S-I) or the dispersion medium (S-II) contains a nitrogen-containing organic solvent. Regarding the preparation, it includes mixing or stirring the metal oxide fine particles (B) or its raw materials. Regarding the dispersion, it includes bringing the metal oxide fine particles (B) into a dispersed state where they are scattered.

[0013] By performing such a treatment, an aromatic group-containing carboxylic acid compound (A) and / or a carboxylate derived from the aromatic group-containing carboxylic acid compound (A) bind or adhere to the surface of the metal oxide fine particles (B). Such binding or adhesion is considered to occur due to the interaction with -COOH or -COO - possessed by the aromatic group-containing carboxylic acid compound (A) and / or the carboxylate derived from the aromatic group-containing carboxylic acid compound (A).

[0014] When an aromatic group-containing carboxylic acid compound (A) and / or a carboxylate derived from the aromatic group-containing carboxylic acid compound (A) bind or adhere to the surface of the metal oxide fine particles (B), an aromatic group is exposed on the surface of the metal oxide fine particles (B). As a result, the aromatic group exposed on the surface of the metal oxide fine particles is considered to stabilize the dispersion of the modified metal oxide fine particles in the dispersion liquid.

[0015] The carboxylate is a carboxylic acid anion derived from the aromatic group-containing carboxylic acid compound (A) or a salt of the aromatic group-containing carboxylic acid compound (A) that can bind or adhere to the surface of the metal oxide fine particles (B). Regarding the binding or adhesion of the aromatic group-containing carboxylic acid compound (A) and / or the carboxylate derived from the aromatic group-containing carboxylic acid compound (A) to the surface of the metal oxide fine particles (B), it can be confirmed, for example, by an X-ray photoelectron spectrometer (XPS) or the like. In the salt of the aromatic group-containing carboxylic acid compound (A), the counter cation for the carboxylic acid anion may be an inorganic cation or an organic cation, and an inorganic cation is preferred. The counter cation may be a monovalent cation or a polyvalent cation with a valence of 2 or more. In the salt of the aromatic group-containing carboxylic acid compound (A), the counter cation to the carboxylate anion may be an inorganic cation or an organic cation, and an inorganic cation is preferred. The counter cation may be a monovalent cation or a polyvalent cation with a valence of 2 or more. The inorganic cation is not particularly limited, but alkali metal cations such as sodium ions and potassium ions, and cations derived from the metal elements contained in the metal oxide fine particles (B) are preferred. Preferred metal elements that can be contained in the metal oxide fine particles (B) will be described later.

[0016] The conditions for contacting the metal oxide fine particles (B) with the aromatic group-containing carboxylic acid compound (A) and / or the carboxylate derived from the aromatic group-containing carboxylic acid compound (A), and the solvent (S-I) or dispersion medium (S-II) used during the contact are not particularly limited as long as they contain a nitrogen-containing organic solvent.

[0017] When a hydrogen bond is formed between the hydroxyl groups on the surface of the metal oxide fine particles (B) and the aromatic group-containing carboxylic acid compound (A) and / or the carboxylate derived from the aromatic group-containing carboxylic acid compound (A), the nitrogen-containing organic solvent is thought to act buffer-like and promote the formation of the hydrogen bond. As a result, when the metal oxide fine particles (B) are contacted with the aromatic group-containing carboxylic acid compound (A) and / or the carboxylate derived from the aromatic group-containing carboxylic acid compound (A) in a nitrogen-containing organic solvent, the aromatic group-containing carboxylic acid compound (A) and / or the carboxylate derived from the aromatic group-containing carboxylic acid compound (A) can be well bonded or easily adhered to the surface of the metal oxide fine particles (B) (hereinafter, may also be referred to as coating).

[0018] 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, morpholine, aniline, etc., nitrogen-containing aromatic heterocyclic compounds such as pyridine, pyrimidine, etc., or compounds having an amide structure such as N,N-dimethylformamide, N,N-dimethylacetamide, etc. Among these, a compound having an amide structure is preferable because it easily promotes the bonding or attachment of the aromatic group-containing carboxylic acid compound (A) and / or the carboxylate derived from the aromatic group-containing carboxylic acid compound (A) to the metal oxide fine particles (B).

[0019] The amide structure in the compound having an amide structure is a structure represented by -(C=O)-N<. Preferable examples of the compound having an amide structure include a compound represented by the following formula (S1).

Chemical formula

Chemical formula

[0020] Among the compounds represented by the formula (S1), specific examples when R S3 is a group represented by the formula (S1-1) include N,N,2-trimethylpropionamide, N-ethyl,N,2-dimethylpropionamide, N,N-diethyl-2-methylpropionamide, N,N,2-trimethyl-2-hydroxypropionamide, N-ethyl-N,2-dimethyl-2-hydroxypropionamide, and N,N-diethyl-2-hydroxy-2-methylpropionamide, etc.

[0021] Among the compounds represented by formula (S1), R S3 Specific examples of the case where is a group represented by formula (S1-2) include N,N,N’,N’-tetramethylurea, N,N,N’,N’-tetraethylurea, and the like.

[0022] Among the compounds represented by formula (S1), N,N,2-trimethylpropionamide and N,N,N’,N’-tetramethylurea are particularly preferred.

[0023] Regarding compounds having an amide structure, preferred examples other than the compounds represented by formula (S1) include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, and 1,3-dimethyl-2-imidazolidinone, and the like. Compounds having an amide structure may be used alone or in combination of two or more.

[0024] The solvent (S-I) 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 inhibited. Solvents other than nitrogen-containing organic solvents that may contain a solvent (S-I) or a dispersion medium (S-II) include (poly)alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol - n - propyl ether, 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 - n - butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether; (poly)alkylene glycol monoalkyl ether acetates 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, propylene glycol monoethyl ether acetate; other ethers 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; alkyl lactates such as methyl 2 - hydroxypropionate, ethyl 2 - hydroxypropionate;Ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2-hydroxy-3-methylbutyl methyl, 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 propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxobutanoate and other esters; aromatic hydrocarbons such as toluene and xylene, etc. are included.;

[0025] 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. Typically, it is preferably 10 parts by mass or more and 5000 parts by mass or less, more preferably 20 parts by mass or more and 1000 parts by mass or less, and even more preferably 50 parts by mass or more and 500 parts by mass or less 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.

[0026] The amount of the solvent (S-I) or the dispersion medium (S-II) used for the coating treatment with the aromatic group-containing carboxylic acid compound (A) and / or the carboxylate derived from the aromatic group-containing carboxylic acid compound (A) is not particularly limited. Typically, it is preferably 10 parts by mass or more and 5000 parts by mass or less, more preferably 50 parts by mass or more and 1000 parts by mass or less, and even more preferably 100 parts 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).

[0027] When contacting the aromatic group-containing carboxylic acid compound (A) and / or the carboxylate derived from the aromatic group-containing carboxylic acid compound (A) with the metal oxide fine particles (B), the temperature is not particularly limited as long as it is a temperature at which the metal oxide fine particles (B), the aromatic group-containing carboxylic acid compound (A) and / or the carboxylate derived from the aromatic group-containing carboxylic acid compound (A) do not deteriorate or decompose by heating. When contacting the aromatic group-containing carboxylic acid compound (A) and / or the carboxylate derived from the aromatic group-containing carboxylic acid compound (A) with the metal oxide fine particles (B), the temperature 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.

[0028] When contacting the aromatic group-containing carboxylic acid compound (A) and / or the carboxylate derived from the aromatic group-containing carboxylic acid compound (A) with the metal oxide fine particles (B), the pressure is preferably under reduced pressure or high pressure, and more preferably under reduced pressure in terms of simplicity.

[0029] The time for contacting the aromatic group-containing carboxylic acid compound (A) and / or the carboxylate derived from the aromatic group-containing carboxylic acid compound (A) with the metal oxide fine particles (B) is not particularly limited. The time for contacting the aromatic group-containing carboxylic acid compound (A) and / or the carboxylate derived from the aromatic group-containing carboxylic acid compound (A) with the metal oxide fine particles (B) 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. When contacting the aromatic group-containing carboxylic acid compound (A) and / or the carboxylate derived from the aromatic group-containing carboxylic acid compound (A) with the metal oxide fine particles (B), the pH is preferably, for example, 3 or more and 6 or less. The pH can be confirmed with pH test paper or the like.

[0030] Hereinafter, in the method for producing the modified metal oxide fine particles, the main materials used, namely, the aromatic group-containing carboxylic acid compound (A) and the metal oxide fine particles (B), will be described.

[0031] <Aromatic group-containing carboxylic acid compound (A)> As described above, 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 preferred. Examples of the aromatic hydrocarbon group include monovalent or polyvalent groups obtained by removing one or more hydrogen atoms from a benzene ring, naphthalene ring, biphenyl ring, anthracene ring, fluorene ring, dibenzothiophene ring, stilbene ring, bisphenol ring, or phenanthrene ring. Specifically, a carboxylic acid compound having an aromatic structure having at least one structure selected from the group consisting of a benzene structure, fluorene structure, anthracene structure, dibenzothiophene structure, carbazole structure, stilbene ring, biphenyl ring, bisphenol structure, and naphthalene structure can be preferably used as the aromatic group-containing carboxylic acid compound (A). Further, a carboxylic acid compound having the above aromatic structure having a (meth)acryloyl structure can also be preferably used as the aromatic group-containing carboxylic acid compound (A). In the specification of the present application, for example, with respect to the aromatic group-containing carboxylic acid compound (A) having a condensed ring structure in which an aromatic hydrocarbon ring and a heterocyclic ring are condensed, such as a benzimidazole ring, carbazole ring, or quinoline ring, it is understood to have an aromatic hydrocarbon group.

[0032] As the aromatic group-containing carboxylic acid compound (A), one or more selected from the 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 are preferred. [Chemical formula] (In formula (1), R 1 and R 2 are each independently a hydrogen atom or a monovalent organic group, and R1 and R 2 may be bonded to each other to form a ring, and the ring may contain one or more elements selected from the group consisting of N, S, and O as ring-constituting elements, and R 3 is an aromatic group which may have a substituent, and R 4 is a methylene group or a single bond.) A method comprising coating with a carboxylic acid compound represented by the formula and / or a carboxylate derived from the carboxylic acid compound represented by the formula (1).

[0033] Hereinafter, for the sake of 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) can also be used for coating in the same manner as the carboxylic acid compound represented by the formula (1).

[0034] In the formula (1), R 1 and R 2 are each independently a hydrogen atom or a monovalent organic group. The monovalent organic group is not particularly limited. Examples of the monovalent organic group include an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an aralkyl group which may have a substituent, an aliphatic heterocyclic group which may have a substituent, and an aromatic group which may have a substituent, etc. R 1 and R 2 When is a monovalent organic group, 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, still more preferably 1 or more and 20 or less, and particularly preferably 1 or more and 10 or less. Also, R 1 and R 2 may be bonded to each other to form a ring.

[0035] R 1 and R 2 As, R 1 and R 2 are each independently a hydrogen atom, an alkyl group which may have a substituent, or an aromatic group which may have a substituent, or R 1 and R 2It is preferably combined to form a ring.

[0036] R 1 and R 2 When it is an alkyl group, the alkyl group may have an ether bond, an ester bond, an amide bond, a sulfide bond, a disulfide bond, etc. in the chain. R 1 and R 2 The number of carbon atoms of the alkyl group as R and R is preferably 1 or more and 40 or less, more preferably 1 or more and 30 or less, even more preferably 1 or more and 20 or less, particularly preferably 1 or more and 10 or less, and most preferably 1 or more and 5 or less.

[0037] R 1 and R 2 The substituents that the alkyl group as R and R may have are not particularly limited as long as they do not inhibit the object of the present invention. Specific examples of the substituents that the alkyl group may have include a hydroxyl group, an alkoxy group, an amino group, a cyano group, and a halogen atom. The alkylene group may be a linear alkyl group or a branched alkyl group, and a linear alkyl group is preferred.

[0038] R 1 and R 2 Specific examples of the alkyl group as R and R 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, an n-pentyl group, an isopentyl group, a tert-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, a 2-ethyl-n-hexyl group, an n-nonyl group, an n-decyl group, an n-undecyl group, an n-dodecyl group, an n-tridecyl group, an n-tetradecyl group, an n-pentadecyl group, an n-hexadecyl group, an n-heptadecyl group, an n-octadecyl group, an n-nonadecyl group, and an n-icosyl group.

[0039] R 1 and R 2 The aromatic group that may have a substituent as R and R may be an aromatic hydrocarbon group that may have a substituent or an aromatic heterocyclic group that may have a substituent.

[0040] The type of the aromatic hydrocarbon group is not particularly limited as long as it does not inhibit the object of the present invention. The aromatic hydrocarbon group may be a monocyclic aromatic group, a group formed by condensation of two or more aromatic hydrocarbon groups, or a group formed by bonding of two or more aromatic hydrocarbon groups via a single bond. As the aromatic hydrocarbon group, a phenyl group, a naphthyl group, a biphenylyl group, an anthryl group, and a phenanthrenyl group are preferable.

[0041] The type of the aromatic heterocyclic group is not particularly limited as long as it does not inhibit the object of the present invention. The aromatic heterocyclic group may be a monocyclic group or a polycyclic group. As the aromatic heterocyclic group, a pyridyl group, a furyl group, a thienyl group, an imidazolyl group, a pyrazolyl group, an oxazolyl group, a thiazolyl group, an isoxazolyl group, an isothiazolyl group, a benzoxazolyl group, a benzothiazolyl group, and a benzimidazolyl group are preferable.

[0042] Examples of the substituent 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, a nitroso group, a sulfino group, a sulfo group, a sulfonato group, a phosphino group, a phosphinyl group, a phosphono group, a phosphonato group, an amino group, an ammonio group, and an organic group. When the phenyl group, polycyclic aromatic hydrocarbon group, or aromatic heterocyclic group has a plurality of substituents, the plurality of substituents may be the same or different.

[0043] When the substituent that the aromatic group has 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, and an aralkyl group. This organic group may contain a bond or a substituent other than a hydrocarbon group such as a hetero atom in the organic group. Further, this organic group may be linear, branched, cyclic, or any 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.

[0044] When the aromatic group has a substituent on an adjacent carbon atom, the two substituents bonded to the adjacent carbon atoms may combine to form a cyclic structure. Examples of the cyclic structure include an aliphatic hydrocarbon ring and an aliphatic ring containing a heteroatom.

[0045] When the substituent of the aromatic group is an organic group, the bond contained in the organic group is not particularly limited as long as the effects of the present invention are not impaired, and the organic group may contain a bond containing a heteroatom such as an oxygen atom, a nitrogen atom, or a silicon atom. Specific examples of the bond containing a heteroatom include an ether bond, a thioether bond, a carbonyl bond, a thiocarbonyl bond, an ester bond, an amide bond, a urethane bond, an imino bond (-N = C (-R)-, -C (= NR)-: R represents a hydrogen atom or an organic group), a carbonate bond, a sulfonyl bond, a sulfinyl bond, an azo bond, and the like.

[0046] From the viewpoint of the heat resistance of the carboxylic acid compound represented by the formula (1), the bond containing a heteroatom that the organic group may have is preferably an ether bond, a thioether bond, a carbonyl bond, a thiocarbonyl bond, an ester bond, an amide bond, an amino bond (-NR-: R represents a hydrogen atom or a monovalent organic group), a urethane bond, an imino bond (-N = C (-R)-, -C (= NR)-: R represents a hydrogen atom or a monovalent organic group), a carbonate bond, a sulfonyl bond, or a sulfinyl bond.

[0047] When the organic group is a substituent other than a hydrocarbon group, the type of the substituent other than the hydrocarbon group is not particularly limited as long as it does not inhibit the object of the present invention. Specific examples of the substituent other than the hydrocarbon group include a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a cyano group, an isocyano group, a cyanato group, an isocyanato group, a thiocyanato group, an isothiocyanato group, a silyl group, a silanol group, an alkoxy group, an alkoxycarbonyl group, an amino group, a monoalkylamino group, a dialkylamino group, a monoarylamino group, a diarylamino group, a carbamoyl group, a thiocarbamoyl group, a nitro group, a nitroso group, a carboxylate group, an acyl group, an acyloxy group, a sulfino group, a sulfonato group, a phosphino group, a phosphinyl group, a phosphonato group, an alkyl ether group, an alkenyl ether group, an alkyl thioether group, an alkenyl thioether group, an aryl ether group, an aryl thioether group, etc. The hydrogen atom contained in the above substituent may be substituted by a hydrocarbon group. Further, the hydrocarbon group contained in the above substituent may be linear, branched, or cyclic.

[0048] As the substituent that a phenyl group, a polycyclic aromatic hydrocarbon group, or an aromatic heterocyclic group has, an alkyl group having 1 or more and 12 or less carbon atoms, an aryl group having 1 or more and 12 or less carbon atoms, an alkoxy group having 1 or more and 12 or less carbon atoms, an aryloxy group having 1 or more and 12 or less carbon atoms, an arylamino group having 1 or more and 12 or less carbon atoms, and a halogen atom are preferable.

[0049] R 1 and R 2 may be bonded to each other to form a ring. R 1 and R 2 The ring formed by the bonding of and is a nitrogen-containing heterocyclic ring. The nitrogen-containing ring contains one or more elements selected from the group consisting of N, S, and O as ring-constituting elements. The nitrogen-containing ring may be a monocyclic ring or a polycyclic ring, and a monocyclic ring is preferable. Further, the nitrogen-containing heterocyclic ring may be an aliphatic ring, an aromatic ring, or a condensed polycyclic ring in which one or more aliphatic monocyclic rings and one or more aromatic monocyclic rings are condensed.

[0050] R1 and R 2 Preferable examples of the nitrogen-containing heterocyclic ring formed by the combination of and are piperidine, piperazine, morpholine, pyrrolidine, pyrrole, imidazole, pyrazole, indole, benzimidazole, purine, phenoxazine, and phenothiazine. Among these, pyrrolidine, pyrrole, imidazole, and pyrazole are preferable, and imidazole is more preferable. That is, in formula (1), R 1 and R 2 It is preferable that and are combined to form an imidazole ring. R 1 and R 2 The carboxylic acid compound having an imidazole ring formed by the combination of and has excellent coating effects when coating the metal oxide fine particles (B).

[0051] R 1 and R 2 The nitrogen-containing heterocyclic ring formed by the combination of and may have a substituent. Examples of the substituent 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 sulfonate group, a phosphino group, a phosphinyl group, a phosphonate group, and an organic group. The number of substituents on the nitrogen-containing heterocyclic ring is not particularly limited. When a plurality of substituents are present on the nitrogen-containing heterocyclic ring, the plurality of substituents may be the same or different from each other.

[0052] When the substituent of the nitrogen-containing heterocyclic ring is an organic group, the organic group is the same as the organic group as a substituent in the case where and are aromatic groups which may have a substituent. 1 and R 2

[0053] ​When the substituent of the nitrogen-containing heterocyclic ring is an organic group, the organic group is preferably an alkyl group, an aromatic hydrocarbon group, or an aromatic heterocyclic group. As 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. As the 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. As the aromatic heterocyclic group, a pyridyl group, a furyl group, a thienyl group, an imidazolyl group, a pyrazolyl group, an oxazolyl group, a thiazolyl group, an isoxazolyl group, an isothiazolyl group, a benzoxazolyl group, a benzothiazolyl group, and a benzimidazolyl group are preferable, and a furyl group and a thienyl group are more preferable.

[0054] In formula (1), R 3 is an aromatic group which may have a substituent. As the monovalent organic group as R 3 , 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 .

[0055] R 4 is a single bond or a methylene group. When R 4 is a methylene group, as the compound represented by formula (1), a carboxylic acid compound represented by the following formula (1-1) is preferable in terms of easily obtaining a desired effect by coating.

Chemical formula

[0056] In the above formula (1-1), R 3 is as described above for formula (1). Also, when R in formula (1-1) 5 is an organic group, 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 substituents. When n is 2 or 3, a plurality of R 5 may be the same or different.

[0057] Among the carboxylic acid compounds represented by the above formula (1-1), the compound represented by the following formula (1-2) is preferable in that it is inexpensive and can be easily synthesized.

[0058]

Chemical formula

[0059] In formula (1-2), R 6 , R7 , R 8 , R 9 , and R 10 is an organic group, the organic group is the same as the organic group that R 1 and R 2 has as substituents. R 6 , R 7 , R 8 , and R 9 are preferably hydrogen atoms from the viewpoint of the solubility of the carboxylic acid compound in the solvent.

[0060] Among them, at least one of R 6 , R 7 , R 8 , R 9 , and R 10 is preferably the following substituent, and it is particularly preferable that R 10 is the following substituent. When R 10 is the following substituent, R 6 , R 7 , R 8 , and R 9 are preferably hydrogen atoms. -O-R 11 (R 11 is a hydrogen atom or an organic group.)

[0061] R 11 is an organic group, the organic group is the same as the organic group that R 1 and R 2 has as substituents. R 11 is preferably an alkyl group, more preferably an alkyl group having 1 to 8 carbon atoms, particularly preferably an alkyl group having 1 to 3 carbon atoms, and most preferably a methyl group.

[0062] Specific preferred examples of the carboxylic acid compound represented by formula (1) in which R 4 in formula (1) is a methylene group include the following compounds.

Chemical formula

[0063] Examples of the substituents in benzoic acid which may have a substituent and naphthoic acid which may have a substituent include alkyl groups such as methyl group, ethyl group, n-propyl group, isopropyl group, and n-butyl group; alkoxy groups such as methoxy group, ethoxy group, n-propyloxy group, isopropyloxy group, and n-butyloxy group; aryl groups 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 acetoxy group, propanoyloxy group, (meth)acryloyloxy group, benzoyl group, 1-naphthoyl group, and 2-naphthoyl group; halogen atoms such as fluorine atom, chlorine atom, bromine atom, and iodine atom; amino group; nitro group; alkoxycarbonyl groups such as methoxycarbonyl group and ethoxycarbonyl group; alkoxyalkoxycarbonyl groups such as 2-methoxyethoxycarbonyl group and 2-ethoxyethoxycarbonyl group; acyloxyalkoxycarbonyl groups such as 2-acetoxyethoxycarbonyl group and 2-(meth)acryloyloxyethoxycarbonyl group, and the like.

[0064] Among these substituents, alkoxycarbonyl groups such as methoxycarbonyl group and ethoxycarbonyl group; alkoxyalkoxycarbonyl groups such as 2-methoxyethoxycarbonyl group and 2-ethoxyethoxycarbonyl group; acyloxyalkoxycarbonyl groups such as 2-acetoxyethoxycarbonyl group and 2-(meth)acryloyloxyethoxycarbonyl group are preferred. Since these groups are hydrophilic when compared with the aromatic structure, they are preferred in that the balance between the hydrophobicity and hydrophilicity of the modified metal oxide fine particles after treatment is improved. Further, since they can be copolymerized with other compounding components, acyloxyalkoxycarbonyl groups such as 2-(meth)acryloyloxyethoxycarbonyl group are more preferred in that the properties of the cured product are good without causing problems such as aggregation and bleed-out during curing.

[0065] Examples of the benzoic acid which may have a substituent include benzoic acid; alkyl-substituted benzoic acids such as o-methylbenzoic acid, m-methylbenzoic acid, p-methylbenzoic acid, o-ethylbenzoic acid, m-ethylbenzoic acid, and p-ethylbenzoic acid; phenyl-substituted benzoic acids such as o-phenylbenzoic acid, m-phenylbenzoic acid, and p-phenylbenzoic acid; alkoxy-substituted benzoic acids such as o-methoxybenzoic acid, m-methoxybenzoic acid, p-methoxybenzoic acid, o-ethoxybenzoic acid, m-ethoxybenzoic acid, and p-ethoxybenzoic acid; phenoxy-substituted benzoic acids such as o-phenoxybenzoic acid, m-phenoxybenzoic acid, and p-phenoxybenzoic acid; acyloxy-substituted benzoic acids such as o-acetoxybenzoic acid, m-acetoxybenzoic acid, p-acetoxybenzoic acid, o-benzoyloxybenzoic acid, m-benzoyloxybenzoic acid, and p-benzoyloxybenzoic acid; halogenated benzoic acids such as 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-fluorobenzoic acid; amino-substituted benzoic acids such as o-aminobenzoic acid, m-aminobenzoic acid, and p-aminobenzoic acid; nitro-substituted benzoic acids such as o-nitrobenzoic acid, m-nitrobenzoic acid, and p-nitrobenzoic acid; and benzenedicarboxylic acid monoesters such as monomethyl terephthalate, monomethyl isophthalate, monomethyl phthalate, monoethyl terephthalate, monoethyl isophthalate, monomethyl phthalate, mono-2-methoxyethyl terephthalate, mono-2-methoxyethyl isophthalate, mono-2-methoxyethyl phthalate, mono-2-acryloyloxyethyl terephthalate, mono-2-acryloyloxyethyl isophthalate, and mono-2-acryloyloxyethyl phthalate (2-acryloyloxyethyl phthalate).

[0066] Examples of naphthoic acids which may have substituents include naphthoic acids such as 1-naphthoic acid and 2-naphthoic acid; alkylnaphthoic acids such as 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-2-naphthoic acid; alkoxynaphthoic acids such as 2-methoxy-1-naphthoic acid, 3-methoxy-1-naphthoic acid, 4-methoxy-1-naphthoic acid, 5-methoxy-1-naphthoic acid, 6-methoxy-1-naphthoic acid, 7-methoxy-1-naphthoic acid, 8-methoxy-1-naphthoic acid, 1-methoxy-2-naphthoic acid, 3-methoxy-2-naphthoic acid, 4-methoxy-2-naphthoic acid, 5-methoxy-2-naphthoic acid, 6-methoxy-2-naphthoic acid, 7-methoxy-2-naphthoic acid, and 8-methoxy-2-naphthoic acid; acyloxynaphthoic acids such as 2-acetoxy-1-naphthoic acid, 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, 7-acetoxy-2-naphthoic acid, and 8-acetoxy-2-naphthoic acid;Examples of the naphthalenedicarboxylic acid monoesters include 2,6-naphthalenedicarboxylic acid monomethyl ester, 2,7-naphthalenedicarboxylic acid monomethyl ester, 1,4-naphthalenedicarboxylic acid monomethyl ester, 2,6-naphthalenedicarboxylic acid monoethyl ester, 2,7-naphthalenedicarboxylic acid monoethyl ester, 1,4-naphthalenedicarboxylic acid monoethyl ester, 2,6-naphthalenedicarboxylic acid mono-2-methoxyethyl ester, 2,7-naphthalenedicarboxylic acid mono-2-methoxyethyl ester, 1,4-naphthalenedicarboxylic acid mono-2-methoxyethyl ester, 2,6-naphthalenedicarboxylic acid mono-2-acryloyloxyethyl ester, 2,7-naphthalenedicarboxylic acid mono-2-acryloyloxyethyl ester, and 1,4-naphthalenedicarboxylic acid mono-2-acryloyloxyethyl ester.;

[0067] Among the benzoic acids which may have the above substituents and the naphthoic acids which may have the substituents, benzenedicarboxylic acid monoesters are preferred, and phthalic acid monoesters are more preferred because of their high effect of dispersion stabilization. It is more preferable that the benzoic acids which may have these substituents and the naphthoic acids which may have the substituents have a substituent containing a polymerizable unsaturated double bond and an ester bond (-CO-O-) in terms of good properties of the cured product of the modified metal oxide fine particle dispersion containing the polymerizable base material component (C).

[0068] In addition, 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 inhibited. Specific examples of the aliphatic carboxylic acid compound include hydrocarbons having a carboxylic acid group of a linear carboxylic acid having 4 to 20 carbon atoms (linear aliphatic carboxylic acid, preferably linear saturated aliphatic carboxylic acid, etc.), a branched carboxylic acid having 4 to 20 carbon atoms (branched aliphatic carboxylic acid), and a cyclic carboxylic acid having 4 to 20 carbon atoms (alicyclic carboxylic acid, preferably alicyclic carboxylic acid having no unsaturated double bond, etc.). Specific examples of the aliphatic carboxylic acid include linear carboxylic acids such as butyric acid, valeric acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, dodecanoic acid, tetradecanoic acid, and stearic acid; branched-chain carboxylic acids such as pivalic acid, 2,2-dimethylbutyric acid, 3,3-dimethylbutyric acid, 2,2-dimethylvaleric acid, 2,2-diethylbutyric acid, 3,3-diethylbutyric acid, 2-ethylhexanoic acid, 2-methylheptanoic acid, 4-methyloctanoic acid, and neodecanoic acid; and cyclic carboxylic acids such as naphthenic acid and cyclohexanedicarboxylic acid. The ratio of the mass of the aromatic group-containing carboxylic acid compound (A) and / or the carboxylate derived from the aromatic group-containing carboxylic acid compound (A) to the total mass of the aromatic group-containing carboxylic acid compound (A) and / or the carboxylate derived from the aromatic group-containing carboxylic acid compound (A) and the mass of the aliphatic carboxylic acid compound is preferably 70% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more, and particularly preferably 100% by mass.

[0069] The amount of the aromatic group-containing carboxylic acid compound (A) and / or the carboxylate derived from the aromatic group-containing carboxylic acid compound (A) used for the surface treatment of the metal oxide fine particles (B) is preferably 0.1 part by mass or more and 300 parts by mass or less, more preferably 0.5 part by mass or more and 200 parts by mass or less, and still more preferably 1 part by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the metal oxide fine particles (B).

[0070] <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. For example, a metal oxide such as ZrO2 fine particles is used as a filler for achieving a high refractive index in a high refractive index material.

[0071] The shape of the metal oxide fine particles (B) is not particularly limited. Examples of the shape of the metal oxide fine particles (B) include spherical, granular, ellipsoidal, cubic, rectangular parallelepiped, pyramidal, needle-like, columnar, rod-like, tubular, flaky, plate-like, and sheet-like, etc. Spherical, granular, columnar, etc. are preferred.

[0072] The type of the metal oxide constituting the metal oxide fine particles (B) is not particularly limited as long as it does not inhibit the object of the present invention. The metal oxide fine particles may be fine particles composed of a single metal oxide, or may be fine particles composed of two or more metal oxides. In the production method according to the present invention, one type of metal oxide fine particles (B) may be used alone, or two or more types of metal oxide fine particles (B) may be used in combination.

[0073] As the metal contained in the metal oxide constituting the metal oxide fine particles (B), for example, at least one selected from the group consisting of Ag, Cu, In, Sn, Ti, Hf, Al, Zr, Zn, Sn, Ru, and Ce is preferable. From the viewpoint of being able to provide a metal oxide with a high refractive index, among the above metal elements, at least one selected from the group consisting of Ti, Al, Zr, Zn, Sn, and Ce is preferable, and Zr is particularly preferable. Preferable examples of the metal oxide constituting the metal oxide fine particles (B) include single metal oxides such as aluminum oxide (Al2O3), titanium oxide (TiO2), hafnium oxide (HfO2), zirconium oxide (ZrO2), indium oxide (In2O3), zinc oxide (ZnO), tin oxide (SnO2), lanthanum oxide (La2O3), yttrium oxide (Y2O3), cerium oxide (CeO2), ruthenium oxide (RuO2), and magnesium oxide (MgO); solid solutions of metal oxides such as ITO and ATO; and composite metal oxides such as barium titanate (BaTiO3), perovskite (CaTiO3), and spinel (MgAl2O4).

[0074] The average particle diameter of the metal oxide fine particles (B) is not particularly limited as long as it does not inhibit the object of the present invention. The average particle diameter of the metal oxide fine particles (B) is preferably, for example, 50 nm or less, more preferably 20 nm or less, still more preferably 15 nm or less, and particularly preferably 12 nm or less. The lower limit of the average particle diameter of the metal oxide fine particles (B) is, for example, 1 nm or more, and may be 2 nm or more. The average particle diameter of the metal oxide fine particles (B) is the Z-average diameter (Z-Average size) measured using a particle size distribution analyzer. The particle diameter at a cumulative value of 99.99% in the cumulative particle size volume distribution of the metal oxide fine particles (B) measured using the dynamic light scattering method is preferably, for example, 50 nm or less, more preferably 30 nm or less, and still more preferably 20 nm or less from the viewpoint of increasing the refractive index. There is no particular lower limit value, but it is, for example, 5 nm or more.

[0075] By performing the coating treatment on the metal oxide fine particles (B) as described above, modified metal oxide fine particles in which at least a part of the surface is coated with the aromatic group-containing carboxylic acid compound (A) and / or the carboxylate derived from the aromatic group-containing carboxylic acid compound (A) can be obtained.

[0076] The modified metal oxide fine particles may be coated with other coating agents together with the aromatic group-containing carboxylic acid compound (A) and / or the carboxylate derived from the aromatic group-containing carboxylic acid compound (A). The ratio of the total mass of the aromatic group-containing carboxylic acid compound (A) and the mass of the carboxylate derived from the aromatic group-containing carboxylic acid compound (A) to the total mass of the aromatic group-containing carboxylic acid compound (A), the mass of the carboxylate derived from the aromatic group-containing carboxylic acid compound (A), and the mass of other coating agents is not particularly limited and can be appropriately adjusted within the range of 1% by mass to 100% by mass.

[0077] After the metal oxide fine particles (B) are coated with the above aromatic group-containing carboxylic acid compound (A) and / or a carboxylate derived from the aromatic group-containing carboxylic acid compound (A), the surface of the obtained modified metal oxide fine particles may be further coated with another coating material, or the surface of the metal oxide fine particles may be coated with another coating material before being coated with the aromatic group-containing carboxylic acid compound (A) and / or a carboxylate derived from the aromatic group-containing carboxylic acid compound (A). Examples of other coating agents include · Various epoxy compounds described below · Compounds exemplified by the following silane compounds (i) to (iii); monovinyltrialkoxysilanes such as vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane; (meth)acryloxyalkylmonoalkyldialkoxysilanes such as 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane; (meth)acryloxyalkyltrialkoxysilanes such as 3-acryloxypropyltrimethoxysilane; non-alicyclic epoxyfluororenylidene group-containing alkyltri(or di)alkoxysilanes such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane; non-alicyclic epoxy group-containing alkylmonoalkyldialkoxysilanes such as 3-glycidoxypropylmethyldiethoxysilane; alicyclic epoxy group-containing alkyltri(or di)alkoxysilanes such as 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, 2-(3,4-epoxycyclohexyl)methyldimethoxysilane, 2-(3,4-epoxycyclohexyl)methyldiethoxysilane; alicyclic epoxy group-containing alkylmonoalkyldialkoxysilanes such as 2-(3,4-epoxycyclohexyl)ethylmethyldiethoxysilane; oxetanyl group-containing alkyltrialkoxysilanes such as [(3-ethyl-3-oxetanyl)methoxy]propyltrimethoxysilane, [(3-ethyl-3-oxetanyl)methoxy]propyltriethoxysilane; mercaptoalkyltrialkoxysilanes such as 3-mercaptopropyltrimethoxysilane; mercaptoalkylmonoalkyldialkoxysilanes such as 3-mercaptopropylmethyldimethoxysilane;n-octyltriethoxysilane, n-dodecyltrimethoxysilane, n-dodecyltriethoxysilane, n-hexadecyltrimethoxysilane, octadecyltrimethoxysilane, 2-[methoxy(polyethyleneoxy)propyl]-trimethoxysilane, methoxytris(ethyleneoxy)propyltrimethoxysilane, 3-{2-methoxy[poly(ethyleneoxy)]}propyltrimethoxysilane, 3-{2-methoxy[poly(ethyleneoxy)]}propyltriethoxysilane, 3-{2-methoxy[tris(ethyleneoxy)]}propyltrimethoxysilane, 3-{2-methoxy[tris(ethyleneoxy)]}propyltriethoxysilane, 1-hexenyltrimethoxysilane, 1-octenyltrimethoxysilane and other chain trialkoxysilanes; hydrolyzable and condensable silicon compounds such as; etc. may be mentioned, and they may be used alone or in combination of two or more.;

[0078] As the coating agent used when further coating is carried out after coating with the aromatic group-containing carboxylic acid compound (A) and / or the carboxylate derived from the aromatic group-containing carboxylic acid compound (A), the compound represented by the following formula (a-I) is preferable. The compound represented by the following formula (a-I) adheres or binds well to the surface of the modified metal oxide fine particles coated with the aromatic group-containing carboxylic acid compound (A) and / or the carboxylate derived from the aromatic group-containing carboxylic acid compound (A). The modified metal oxide fine particles having at least a part of the outermost surface thereof coated with the compound represented by the following formula (a-I) are particularly stably dispersed in dispersions of various compositions as a result of the coating.;

[0079] As described above, the aromatic group-containing carboxylic acid compound (A) and / or the carboxylate derived from the aromatic group-containing carboxylic acid compound (A) binds or adheres to the surface of the metal oxide fine particles (B).;

[0080] The compound represented by the following formula (a-I) is W 1 and W 2On the other hand, the metal oxide fine particles (B) usually have hydroxyl groups and hydrophilic moieties derived from carboxylates derived from the aromatic group-containing carboxylic acid compound (A) and / or the aromatic group-containing carboxylic acid compound (A) on their surfaces. Therefore, when the compound represented by the formula (a-I) is brought into contact with the modified metal oxide fine particles, the hydroxyl groups and the like present on the surface of the modified metal oxide fine particles interact with the hydroxyl groups or the glycidyl groups having lone pairs of electrons of the compound represented by the following formula (a-I), and thus the compound represented by the following formula (a-I) is considered to adhere well to the surface of the modified metal oxide fine particles.

[0081] In addition, the compound represented by the formula (a-I) has a polycyclic group containing an aromatic ring. Such a polycyclic group is hydrophobic and bulky. Therefore, it is considered that micelle-like coated metal oxide fine particles are formed by the adhesion of the compound represented by the formula (a-I) to the surface of the modified metal oxide fine particles. As a result, the modified metal oxide fine particles with the compound represented by the formula (a-I) attached to the surface are considered to disperse well in dispersions of various compositions.

[0082]

Chemical formula

Chemical formula

[0083] In the above formula (a-II), as the ring Z, for example, a benzene ring, a condensed polycyclic aromatic hydrocarbon ring [for example, a condensed bicyclic hydrocarbon ring (for example, a C 8-20 condensed bicyclic hydrocarbon ring, preferably a C 10-16Condensed bicyclic hydrocarbon rings), condensed tricyclic aromatic hydrocarbon rings (e.g., anthracene ring, phenanthrene ring, etc.), and other condensed 2- to 4-ring aromatic hydrocarbon rings] and the like can be mentioned. Ring Z is preferably a benzene ring or a naphthalene ring, and more preferably a naphthalene ring. In the formula (a-I), W 1 and W 2 are each independently a group represented by the above formula (a-II). Therefore, W 1 and W 2 each contain ring Z. The ring Z contained in W 1 and the ring Z contained in W 2 may be the same or different. For example, one ring may be a benzene ring and the other ring may be a naphthalene ring, etc., but it is particularly preferable that both rings are naphthalene rings from the viewpoints of hydrophobization or high refractive index of the coating agent.

[0084] Also, the substitution position of ring Z to which both W 1 and W 2 are directly bonded through X is not particularly limited. For example, when ring Z is a naphthalene ring, the group corresponding to ring Z bonded to the above carbon atom may be a 1-naphthyl group, a 2-naphthyl group, etc.

[0085] In the above formula (a-II), X independently represents a single bond or a group represented by -S-, and is typically a single bond.

[0086] In the above formula (a-II), as R A1 , for example, a single bond; an alkylene group having 1 or more and 4 or less carbon atoms such as a methylene group, an ethylene group, a trimethylene group, a propylene group, a butane-1,2-diyl group; an alkyleneoxy group having 1 or more and 4 or less carbon atoms such as a methyleneoxy group, an ethyleneoxy group, a propyleneoxy group, etc. can be mentioned. A single bond; a C 2-4 alkylene group (particularly, a C 2-3 alkylene group such as an ethylene group, a propylene group, etc.); a C 2-4 alkyleneoxy group (particularly, a C 2-3 alkylene group such as an ethyleneoxy group, a propyleneoxy group, etc.) are preferable, and a single bond is more preferable. In addition, R A1When it is an alkyleneoxy group, the oxygen atom in the alkyleneoxy group binds to ring Z. Also, W in formula (a-I) 1 and W 2 are each independently a group represented by the above formula (a-II). Therefore, W 1 and W 2 are each a divalent group containing R A1 . R contained in W 1 and R contained in W A1 and R contained in W 2 and R contained in W A1 may be the same or different.

[0087] In the above formula (a-II), examples of R A2 include an alkyl group (for example, a C 1-12 alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, etc., preferably a C 1-8 alkyl group, more preferably a C 1-6 alkyl group, etc.), a cycloalkyl group (a C 5-10 cycloalkyl group such as a cyclohexyl group, etc., preferably a C 5-8 cycloalkyl group, more preferably a C 5-6 cycloalkyl group, etc.), an aryl group (for example, a C 6-14 aryl group such as a phenyl group, a tolyl group, a xylyl group, a naphthyl group, etc., preferably a C 6-10 aryl group, more preferably a C 6-8 aryl group, etc.), an aralkyl group (a C 6-10 aryl-C 1-4 alkyl group such as a benzyl group, a phenethyl group, etc.) and other monovalent hydrocarbon groups; a hydroxyl group; an alkoxy group (a C 1-12 alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, a butoxy group, etc., preferably a C 1-8 alkoxy group, more preferably a C 1-6 alkoxy group, etc.), a cycloalkoxy group (a C 5-10 cycloalkoxy group such as a cyclohexyloxy group, etc.), an aryloxy group (a C 6-10 aryloxy group such as a phenoxy group), an aralkyloxy group (for example, a C 6-10 aryl-C 1-4-OR such as an alkyloxy group 4a a group represented by [wherein, R 4a represents a monovalent hydrocarbon group (such as the monovalent hydrocarbon groups exemplified above).]; an alkylthio group (a C 1-12 alkylthio group, preferably a C 1-8 alkylthio group, more preferably a C 1-6 alkylthio group, etc.), a cycloalkylthio group (a C 5-10 cycloalkylthio group, etc.), an arylthio group (a C 6-10 arylthio group), an aralkylthio group (for example, a C 6-10 aryl-C 1-4 alkylthio group, etc.) of -SR 4b a group represented by [wherein, R 4b represents a monovalent hydrocarbon group (such as the monovalent hydrocarbon groups exemplified above).]; an acyl group (a C 1-6 acyl group, etc.); an alkoxycarbonyl group (a C 1-4 alkoxy-carbonyl group, etc.); a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.); a nitro group; a cyano group; a mercapto group; a carboxy group; an amino group; a carbamoyl group; an alkylamino group (a C 1-12 alkylamino group, preferably a C 1-8 alkylamino group, more preferably a C 1-6 alkylamino group, etc.), a cycloalkylamino group (a C 5-10 cycloalkylamino group, etc.), an arylamino group (a C 6-10 arylamino group), an aralkylamino group (for example, a C 6-10 aryl-C 1-4 alkylamino group, etc.) of -NHR 4c a group represented by [wherein, R 4c represents a monovalent hydrocarbon group (such as the monovalent hydrocarbon groups exemplified above).]; a dialkylamino group (di(C 1-12(alkyl)amino group, preferably di(C 1-8 (alkyl)amino group, more preferably di(C 1-6 (alkyl)amino group, etc.), dicycloalkylamino group (di(C such as dicyclohexylamino group 5-10 (cycloalkyl)amino group, etc.), diarylamino group (di(C such as diphenylamino group 6-10 (aryl)amino group), dialkylamino group (e.g., di(C such as dibenzylamino group 6-10 (aryl-C 1-4 (alkyl)amino group), etc.) of -N(R 4d )2 [In the formula, R 4d (s) independently represent a monovalent hydrocarbon group (such as the monovalent hydrocarbon groups exemplified above).]; (meth)acryloyloxy group; sulfo group; the above monovalent hydrocarbon group, -OR 4a (s) represented by the group, -SR 4b (s) represented by the group, acyl group, alkoxycarbonyl group, -NHR 4c (s) represented by the group, or at least a part of the hydrogen atoms bonded to the carbon atoms contained in the group represented by -N(R 4d )2 is the above monovalent hydrocarbon group, hydroxyl group, -OR 4a (s) represented by the group, -SR 4b (s) represented by the group, acyl group, alkoxycarbonyl group, halogen atom, nitro group, cyano group, mercapto group, carboxy group, amino group, carbamoyl group, -NHR 4c (s) represented by the group, -N(R 4d )2, (meth)acryloyloxy group, mesyloxy group, or a group substituted with a sulfo group [e.g., alkoxyaryl group (e.g., C such as methoxyphenyl group 1-4 alkoxyC 6-10 aryl group), alkoxycarbonylaryl group (e.g., C such as methoxycarbonylphenyl group, ethoxycarbonylphenyl group 1-4 alkoxy-carbonylC 6-10 aryl group, etc.)].

[0088] Among these, typically, R A2 is a monovalent hydrocarbon group, -OR 4a (s) represented by the group, -SR4b a group represented by, an acyl group, an alkoxycarbonyl group, a halogen atom, a nitro group, a cyano group, -NHR 4c a group represented by, -N(R 4d )2 and the like may be used.

[0089] Preferred R A2 is, for example, a monovalent hydrocarbon group [e.g., an alkyl group (e.g., C 1-6 alkyl group), a cycloalkyl group (e.g., C 5-8 cycloalkyl group), an aryl group (e.g., C 6-10 aryl group), an aralkyl group (e.g., C 6-8 aryl-C 1-2 alkyl group), etc.], an alkoxy group (C 1-4 alkoxy group), etc. In particular, R 2a and R 2b are preferably a monovalent hydrocarbon group [e.g., C 1-4 alkyl group (especially methyl group), etc.], an aryl group [e.g., C 6-10 aryl group (especially phenyl group), etc.], etc., especially a monovalent hydrocarbon group (especially an alkyl group).

[0090] When m is an integer of 2 or more, the plurality of R A2 may be different from each other or the same. Also, R 1 contained in W A2 and R 2 contained in W A2 may be the same or different.

[0091] In the above formula (a-II), the number m of R A2 can be selected according to the type of ring Z. For example, it may be 0 or more and 4 or less, preferably 0 or more and 3 or less, more preferably 0 or more and 2 or less. Note that m in W 1 and m in W 2 may be the same or different.

[0092] In the above formula (a3), R A3 is a hydrogen atom or a glycidyl group.

[0093] W 1 The R contained in A3 and W 2 The R contained in A3 and W may be the same or different. W 1 The R contained in A3 and W 2 The R contained in A3 and W are preferably the same group.

[0094] In the above formula (a-I), ring Y 1 and ring Y 2 Examples of these include a benzene ring, a condensed polycyclic aromatic hydrocarbon ring [e.g., a condensed bicyclic hydrocarbon ring (e.g., a C 8-20 condensed bicyclic hydrocarbon ring, preferably a C 10-16 condensed bicyclic hydrocarbon ring), a condensed tricyclic aromatic hydrocarbon ring (e.g., an anthracene ring, a phenanthrene ring, etc.), etc., a condensed 2- to 4-ring aromatic hydrocarbon ring]. Ring Y 1 and ring Y 2 are preferably a benzene ring or a naphthalene ring, more preferably a benzene ring. Note that ring Y 1 and ring Y 2 may be the same or different. For example, one ring may be a benzene ring and the other ring may be a naphthalene ring, etc.

[0095] In the above formula (a-I), R represents a single bond, a methylene group which may have a substituent, an ethylene group which may have a substituent and may contain a heteroatom between two carbon atoms, a group represented by -O-, a group represented by -NH-, or a group represented by -S-, and is typically a single bond. Here, examples of the substituent include a cyano group, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, etc.), a monovalent hydrocarbon group [e.g., an alkyl group (a C 1-6 alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a t-butyl group, etc.), an aryl group (a C 6-10 aryl group such as a phenyl group, etc.)], etc. Examples of the heteroatom include an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, etc.

[0096] In the above formula (a-I), 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.), a monovalent hydrocarbon group [e.g., an alkyl group, an aryl group (C such as a phenyl group 6-10 aryl group) etc.], etc., and it is preferably a cyano group or an alkyl group, and particularly preferably an alkyl group. Examples of the alkyl group include C 1-6 alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, t-butyl group, etc. (e.g., C 1-4 alkyl group, particularly methyl group) etc. can be exemplified. When n1 is an integer of 2 or more, R 3a may be different from each other or the same. Also, when n2 is an integer of 2 or more, R 3b may be different from each other or the same. Further, R 3a and R 3b may be the same or different. Also, the bonding positions (substitution positions) of R 1 and R 2 with respect to ring Y 3a and R 3b are not particularly limited. Preferred substitution numbers n1 and n2 are 0 or 1, particularly 0. Note that n1 and n2 may be the same as or different from each other.

[0097] The compound represented by the above formula (a-I) retains excellent optical and thermal properties. In particular, when ring Y 1 and ring 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 is further excellent in optical and thermal properties.

[0098] Among the compounds represented by the above formula (a-I), particularly preferred specific examples include epoxy group-containing fluorene compounds such as 9,9-bis[4-[2-(glycidyloxy)ethoxy]phenyl]-9H-fluorene, 9,9-bis[4-[2-(glycidyloxy)ethyl]phenyl]-9H-fluorene, 9,9-bis[4-(glycidyloxy)-3-methylphenyl]-9H-fluorene, 9,9-bis[4-(glycidyloxy)-3,5-dimethylphenyl]-9H-fluorene, 9,9-bis(6-glycidyloxynaphthalen-1-yl)-9H-fluorene, and 9,9-bis(5-glycidyloxynaphthalen-2-yl)-9H-fluorene; hydroxy group-containing fluorene compounds such as 9,9-bis[4-(2-hydroxyethoxy)phenyl)]-9H-fluorene, 9,9-bis[4-(2-hydroxyethyl)phenyl]-9H-fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)-9H-fluorene, 9,9-bis(4-hydroxy-3,5-dimethylphenyl)-9H-fluorene, 9,9-bis(6-hydroxynaphthalen-1-yl)-9H-fluorene, and 9,9-bis(5-hydroxynaphthalen-2-yl)-9H-fluorene; and compounds represented by the following formula.

[0099]

Chemical formula

[0100]

Chemical formula

[0101]

Chemical formula

[0102]

Chemical formula

[0103]

Chemical formula

[0104]

Chem.

[0105]

Chem.

[0106]

Chem.

[0107] Among the compounds represented by the formula (a-I) described above, the following compounds are particularly preferred.

Chem.

[0108] 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 (a-I) into contact with the modified metal oxide fine particles in the presence of an organic solvent. The organic solvent used during coating is not particularly limited as long as it can disperse the modified metal oxide fine particles and the coating agent is soluble therein. From the viewpoint of facilitating good coating with the coating agent, the organic solvent preferably has no hydroxyl group and no carboxyl group.

[0109] Specific examples of the organic solvent include (poly)alkylene glycol monoalkyl ether acetates 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; other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, and tetrahydrofuran; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone; other esters such as 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 propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, and ethyl 2-oxobutanoate; and aromatic hydrocarbons such as toluene and xylene.

[0110] The amount of the organic solvent used for the coating treatment with a coating agent such as the compound represented by the formula (a-I) is not particularly limited. Typically, it is preferably 0.1 part by mass or more and 5000 parts by mass or less, more preferably 50 parts by mass or more and 1000 parts by mass or less, and even more preferably 100 parts by mass or more and 500 parts by mass or less with respect to 100 parts by mass of the modified metal oxide fine particles.

[0111] When bringing a coating agent such as the compound represented by formula (a-I) into contact with the modified metal oxide fine particles, the temperature is not particularly limited as long as it is a temperature at which the modified metal oxide fine particles and the coating agent do not deteriorate or decompose due to heating. The temperature when bringing the coating agent into contact with the modified metal oxide fine particles 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 when bringing a coating agent such as the compound represented by formula (a-I) 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 simplicity, atmospheric pressure or reduced pressure is preferred.

[0112] The time for bringing a coating agent such as the compound represented by formula (a-I) into contact with the modified metal oxide fine particles is also not particularly limited. The time when bringing the coating agent into contact with the modified metal oxide fine particles is, for example, 5 minutes or longer and 24 hours or shorter, preferably 10 minutes or longer and 12 hours or shorter, and more preferably 30 minutes or longer and 6 hours or shorter.

[0113] The pH when bringing a coating agent such as the compound represented by formula (a-I) into contact with the metal oxide fine particles (B) is preferably, for example, 3 or higher and 6 or lower. The pH can be confirmed with a pH test paper or the like.

[0114] Among other coating agents, the usage amount of the compound represented by formula (a-I) is, for example, 0.1 part by mass or more and 500 parts by mass or less, preferably 0.5 part by mass or more and 300 parts by mass or less, more preferably 1 part by mass or more and 100 parts by mass or less, and even more preferably 2 parts by mass or more and 20 parts by mass or less, based on 100 parts by mass of the metal oxide fine particles (B). Further, based on 100 parts by mass in total of the mass of the aromatic group-containing carboxylic acid compound (A) and / or the carboxylate derived from the aromatic group-containing carboxylic acid compound (A) and the mass of the metal oxide fine particles (B), the usage amount of the compound represented by formula (a-I) 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 more preferably 5 parts by mass or more and 100 parts by mass or less. Further, the amount of the compound represented by the formula (a-I) per 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) is preferably 0.5 part by mass or more and 70 parts by mass or less, more preferably 0.7 part by mass or more and 50 parts by mass or less, and particularly preferably 0.8 part by mass or more and 45 parts by mass or less. In terms of the balance between the hydrophobicity and hydrophilicity of the modified metal oxide fine particles after coating, it is preferable that the amount of the compound represented by the formula (a-I) is equal to or more than the amount of the aromatic group-containing carboxylic acid compound (A) and / or the carboxylate derived from the aromatic group-containing carboxylic acid compound (A).

[0115] The modified metal oxide fine particles obtained by the above method are used in various applications in a state dispersed in a dispersion medium, in a state dried, or in a state separated from the dispersion medium by a method such as centrifugation.

[0116] ≪Modified metal oxide fine particle dispersion≫ The modified metal oxide fine particle dispersion contains the above-described 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-described modified metal oxide fine particles in the total mass of the metal oxide fine particles in the modified metal oxide fine particle dispersion is not particularly limited as long as it does not inhibit the object of the present invention. 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.

[0117] The modified metal oxide fine particle dispersion may be a dispersion in which the modified metal oxide fine particles are dispersed in a molten resin or the like, may be a dispersion in which the modified metal oxide fine particles are dispersed in a solvent, or may be a dispersion in which the modified metal oxide fine particles are dispersed in a liquid in which various additive components are dissolved in a solvent. When such a modified metal oxide fine particle dispersion contains the aforementioned 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 suitably used in various applications.

[0118] The use of the modified metal oxide fine particle dispersion is not particularly limited. Examples of the use of the modified metal oxide fine particle dispersion include polishing liquids, sealing compositions, and compositions for forming high refractive index films. When the modified metal oxide fine particle dispersion is used for sealing applications, film forming applications, etc., it is preferable that the metal oxide fine particle dispersion contains a base material component (C).

[0119] When the modified metal oxide fine particle dispersion contains a base material component (C) and metal oxide fine particles, the amount of the metal oxide fine particles in the modified metal oxide fine particle dispersion is appropriately determined in consideration of the use of the modified metal oxide fine particle dispersion. When the modified metal oxide fine particle dispersion contains a base material component (C), the amount of the metal oxide fine particles 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 with respect to 100 parts by mass of the base material component (C) in the modified metal oxide fine particle dispersion. 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).

[0120] <Base material component (C)> The base material component (C) is a component that imparts to the modified metal oxide fine particle dispersion the formability capable of manufacturing an article of a desired shape by a well-known method such as a melt processing method as it is, or the formability capable of manufacturing an article of a desired shape by treatment such as exposure, heating, and reaction with water. The base material component (C) is not particularly limited as long as it can impart the desired formability to the modified metal oxide fine particle dispersion liquid. Typical examples of the base material component (C) include resin materials composed of polymer compounds, thermosetting materials that cure by crosslinking upon heating to form polymer compounds or by undergoing chemical modifications such as intramolecular cyclization upon heating, photopolymerizable compounds that can cure upon exposure, and hydrolyzable and condensable silane compounds that undergo hydrolytic condensation with moisture in the composition or in the atmosphere. Examples of the hydrolyzable and condensable silane compounds include alkoxysilane compounds such as tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, diethyldimethoxysilane, dimethyldiethoxysilane, diethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, etc. The hydrolyzable and condensable silane compound may be a partial hydrolyzate and condensate of these silane compounds.

[0121] In addition, in terms of easily forming articles with a high refractive index, particularly high refractive index films, the modified metal oxide fine particle dispersion liquid uses, as the base material component (C), the following formula (b-01):

Chemical formula

Chemical formula

[0122] In the above formula (b-02), ring Z 01 Examples of the ring Z 8-20 include, for example, a benzene ring, a condensed polycyclic aromatic hydrocarbon ring [e.g., a condensed bicyclic hydrocarbon ring (e.g., a naphthalene ring, etc., a C 10-16 condensed bicyclic hydrocarbon ring, preferably a C 01 condensed bicyclic hydrocarbon ring), a condensed tricyclic aromatic hydrocarbon ring (e.g., an anthracene ring, a phenanthrene ring, etc.), etc., a condensed 2- to 4-ring aromatic hydrocarbon ring]. Ring Z 01 and W 02 are each independently a group represented by the above formula (b-02). Therefore, W 01 and W 02 each contain ring Z 01 . Ring Z 01 contained in W 01 and ring Z 02 contained in W 01 may be the same or different. For example, one ring may be a benzene ring and the other ring may be a naphthalene ring, etc., but it is particularly preferable that both rings are naphthalene rings.

[0123] Also, the substitution position of ring Z 01 bonded to the carbon atom to which both W 02 and W 01 are directly bonded through X 01 is not particularly limited. For example, when ring Z 01 is a naphthalene ring, the group corresponding to ring Z 01 bonded to the above carbon atom may be a 1-naphthyl group, a 2-naphthyl group, etc.

[0124] In the above formula (b-02), X 01 independently represents a group represented by a single bond or -S-, and is typically a single bond.

[0125] In the above formula (b-02), R 01 includes, for example, a single bond; an alkylene group having 1 to 4 carbon atoms such as a methylene group, an ethylene group, a trimethylene group, a propylene group, a butane-1,2-diyl group; an alkyleneoxy group having 1 to 4 carbon atoms such as a methyleneoxy group, an ethyleneoxy group, a propyleneoxy group, etc., a single bond; C 2-4 alkylene group (especially, C 2-3 alkylene group such as an ethylene group, a propylene group, etc.); C 2-4 alkyleneoxy group (especially, C 2-3 alkylene group such as an ethyleneoxy group, a propyleneoxy group, etc.) is preferred, and a single bond is more preferred. When R 01 is an alkyleneoxy group, the oxygen atom in the alkyleneoxy group binds to the ring Z 01 . Also, since W 01 and W 02 in the formula (b-01) are each independently a group represented by the above formula (b-02), W 01 and W 02 each contain a divalent group R 01 . R 01 contained in W 01 and R 02 contained in W 01 may be the same or different.

[0126] In the above formula (b-02), R 02 includes, for example, an alkyl group (e.g., a C 1-12 alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, etc., preferably a C 1-8 alkyl group, more preferably a C 1-6 alkyl group, etc.), a cycloalkyl group (a C 5-10 cycloalkyl group such as a cyclohexyl group, etc., preferably a C 5-8 cycloalkyl group, more preferably a C 5-6a monovalent hydrocarbon group such as a cycloalkyl group, an aryl group (e.g., a C 6-14 aryl group, preferably a C 6-10 aryl group, more preferably a C 6-8 aryl group, etc.), an aralkyl group (a C such as a benzyl group or a phenethyl group 6-10 aryl-C 1-4 alkyl group, etc.); a hydroxyl group; an alkoxy group (a C such as a methoxy group, an ethoxy group, a propoxy group, or a butoxy group 1-12 alkoxy group, preferably a C 1-8 alkoxy group, more preferably a C 1-6 alkoxy group, etc.), a cycloalkoxy group (a C such as a cyclohexyloxy group 5-10 cycloalkoxy group, etc.), an aryloxy group (a C such as a phenoxy group 6-10 aryloxy group), an aralkyloxy group (e.g., a C such as a benzyloxy group 6-10 aryl-C 1-4 alkyloxy group), etc. -OR 4A group [wherein, R 4A represents a monovalent hydrocarbon group (such as the monovalent hydrocarbon groups exemplified above).]; an alkylthio group (a C such as a methylthio group, an ethylthio group, a propylthio group, or a butylthio group 1-12 alkylthio group, preferably a C 1-8 alkylthio group, more preferably a C 1-6 alkylthio group, etc.), a cycloalkylthio group (a C such as a cyclohexylthio group 5-10 cycloalkylthio group, etc.), an arylthio group (a C such as a phenylthio group 6-10 arylthio group), an aralkylthio group (e.g., a C such as a benzylthio group 6-10 aryl-C 1-4 alkylthio group), etc. -SR 4B group [wherein, R 4B represents a monovalent hydrocarbon group (such as the monovalent hydrocarbon groups exemplified above).]; an acyl group (a C such as an acetyl group 1-6 acyl group, etc.); an alkoxycarbonyl group (a C such as a methoxycarbonyl group 1-4an alkoxy-carbonyl group, etc.); a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.); a nitro group; a cyano group; a mercapto group; a carboxy group; an amino group; a carbamoyl group; an alkylamino group (a C 1-12 alkylamino group, preferably a C 1-8 alkylamino group, more preferably a C 1-6 alkylamino group, etc.), a cycloalkylamino group (a C 5-10 cycloalkylamino group, etc.), an arylamino group (a C 6-10 arylamino group), an aralkylamino group (e.g., a C 6-10 aryl-C 1-4 alkylamino group), etc., of -NHR 4C group represented by [wherein, R 4C represents a monovalent hydrocarbon group (such as the monovalent hydrocarbon groups exemplified above).]; a dialkylamino group (a di(C 1-12 alkyl)amino group such as a dimethylamino group, a diethylamino group, a dipropylamino group, a dibutylamino group, preferably a di(C 1-8 alkyl)amino group, more preferably a di(C 1-6 alkyl)amino group, etc.), a dicycloalkylamino group (a di(C 5-10 cycloalkyl)amino group such as a dicyclohexylamino group, etc.), a diarylamino group (a di(C 6-10 aryl)amino group such as a diphenylamino group), a diarylamino group (e.g., a di(C 6-10 aryl-C 1-4 alkyl)amino group), etc., of -N(R 4D )2 group represented by [wherein, R 4D independently represents a monovalent hydrocarbon group (such as the monovalent hydrocarbon groups exemplified above).]; a (meth)acryloyloxy group; a sulfo group; the above monovalent hydrocarbon group, a group represented by -OR 4A , a group represented by -SR 4B , an acyl group, an alkoxycarbonyl group, a group represented by -NHR 4C , or -N(R 4D)At least a part of the hydrogen atoms bonded to the carbon atoms contained in the group represented by 2 is the above monovalent hydrocarbon group, hydroxyl group, -OR 4A group represented by, -SR 4B group represented by, acyl group, alkoxycarbonyl group, halogen atom, nitro group, cyano group, mercapto group, carboxy group, amino group, carbamoyl group, -NHR 4C group represented by, -N(R 4D )2 group represented by, (meth)acryloyloxy group, mesyloxy group, or a group substituted with a sulfo group [for example, an alkoxyaryl group (for example, a C such as a methoxyphenyl group 1-4 alkoxy C 6-10 aryl group), alkoxycarbonylaryl group (for example, a C such as a methoxycarbonylphenyl group, an ethoxycarbonylphenyl group, etc. 1-4 alkoxy-carbonyl C 6-10 aryl group, etc.)].

[0127] Among these, typically, R 02 is a monovalent hydrocarbon group, -OR 4A group represented by, -SR 4B group represented by, acyl group, alkoxycarbonyl group, halogen atom, nitro group, cyano group, -NHR 4C group represented by, -N(R 4D )2 group represented by, etc. may also be used.

[0128] Preferred R 02 is a monovalent hydrocarbon group [for example, an alkyl group (for example, a C 1-6 alkyl group), a cycloalkyl group (for example, a C 5-8 cycloalkyl group), an aryl group (for example, a C 6-10 aryl group), an aralkyl group (for example, a C 6-8 aryl-C 1-2 alkyl group), etc.], an alkoxy group (C 1-4 alkoxy group, etc.). In particular, R 02 is an alkyl group [C 1-4 alkyl group (especially a methyl group, etc.), an aryl group [for example, a C 6-10It is preferably a monovalent hydrocarbon group (particularly, an alkyl group) such as an aryl group (particularly a phenyl group) or the like.

[0129] When M is an integer of 2 or more, a plurality of Rs 02 may be different from each other or may be the same. Further, the R 01 contained in W 02 and the R 2 contained in W 02 may be the same or different from each other.

[0130] In the above formula (b-02), the number M of Rs 02 can be selected according to the type of ring Z 01 and may be, for example, 0 or more and 4 or less, preferably 0 or more and 3 or less, more preferably 0 or more and 2 or less. The M in W 01 and the M in W 02 may be the same or different.

[0131] In the above formula (b-02), R 03 is a hydrogen atom, a vinyl group, a thietan-2-ylmethyl group, a glycidyl group, or a (meth)acryloyl group. Note that both W 01 and W 02 do not have a hydrogen atom as R 03 . A vinyloxy group, a thietan-2-ylmethyl group, and a glycidyl group are all cation-polymerizable functional groups. Therefore, a compound represented by the formula (b-01) and having a vinyl group, a thietan-2-ylmethyl group, or a glycidyl group as R 03 is a cation-polymerizable compound. On the other hand, a compound represented by the formula (b-01) and having a (meth)acryloyl group as R 03 is a radical-polymerizable compound.

[0132] W 01 The R 03 contained in 02 and the R 03That is, as long as both are not hydrogen atoms, they may be the same or different. W 01 The R contained in 03 and W 02 The R contained in 03 That is, it is preferable that both are a vinyl group, a thietan-2-ylmethyl group, or a glycidyl group, and it is more preferable that both are the same group selected from the group consisting of a vinyl group, a thietan-2-ylmethyl group, and a glycidyl group. Also, W 01 The R contained in 03 and W 02 The R contained in 03 That is, it is also preferable that both are a (meth)acryloyl group.

[0133] R 03 As R, since the synthesis and availability of the compound represented by the formula (b-01) are easy, a vinyl group, a glycidyl group, or a (meth)acryloyl group is preferable. In addition, 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) preferably has only a group selected from a vinyl group, a thietan-2-ylmethyl group, and a glycidyl group as a reactive group, or has only a (meth)acryloyl group as a reactive group.

[0134] In the above formula (b-01), ring Y 01 and ring Y 02 Examples of these include a benzene ring, a condensed polycyclic aromatic hydrocarbon ring [for example, a condensed bicyclic hydrocarbon ring (for example, a C of a naphthalene ring, etc.) 8-20 Condensed bicyclic hydrocarbon ring, preferably C 10-16 Condensed bicyclic hydrocarbon ring), a condensed tricyclic aromatic hydrocarbon ring (for example, an anthracene ring, a phenanthrene ring, etc.) and other condensed 2- to 4-ring aromatic hydrocarbon rings]. Ring Y 01 and ring Y 02 are preferably a benzene ring or a naphthalene ring, and more preferably a benzene ring. In addition, ring Y 01 and ring Y 02They may be the same or different. For example, one ring may be a benzene ring and the other ring may be a naphthalene ring or the like.

[0135] In the above formula (b-01), R 00 represents a single bond, a methylene group which may have a substituent, an ethylene group which may have a substituent and may contain a heteroatom between two carbon atoms, a group represented by -O-, a group represented by -NH-, or a group represented by -S-. Typically, it is a single bond. Here, examples of the substituent include a cyano group, a halogen atom (such as a fluorine atom, a chlorine atom, a bromine atom), a monovalent hydrocarbon group [for example, an alkyl group (such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a tert-butyl group, etc., a C 1-6 alkyl group), an aryl group (such as a phenyl group, a C 6-10 aryl group), etc.]. Examples of the heteroatom include an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, etc.

[0136] In the above formula (b-01), R 3A and R 3B are usually non-reactive substituents, such as a cyano group, a halogen atom (such as a fluorine atom, a chlorine atom, a bromine atom), a monovalent hydrocarbon group [for example, an alkyl group, an aryl group (such as a phenyl group, a C 6-10 aryl group), etc.]. It is preferably a cyano group or an alkyl group, and particularly preferably an alkyl group. Examples of the alkyl group include a C 1-6 alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a tert-butyl group, etc. (for example, a C 1-4 alkyl group, particularly a methyl group), etc. When N1 is an integer of 2 or more, R 3A may be different from each other or the same. When N2 is an integer of 2 or more, R 3B may be different from each other or the same. Further, R 3A and R 3B may be the same or different. Also, for ring Y 01 and ring Y 02 , R 3A and R3B The bonding position (substitution position) of is not particularly limited. Preferred substitution numbers N1 and N2 are 0 or 1, particularly 0. Note that N1 and N2 may be the same as or different from each other.

[0137] The compound represented by the above formula (b-01) has excellent optical and thermal properties and has a cationic polymerizable functional group, so it has high reactivity. In particular, ring Y 01 and ring Y 02 are benzene rings, and R 00 is a single bond, the compound represented by the above formula (b-01) has a fluorene skeleton and is further excellent in optical and thermal properties. Furthermore, 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.

[0138] Among the compounds represented by the above formula (b-01), particularly preferred specific examples include epoxy group-containing fluorene compounds such as 9,9-bis[4-[2-(glycidyloxy)ethoxy]phenyl]-9H-fluorene, 9,9-bis[4-[2-(glycidyloxy)ethyl]phenyl]-9H-fluorene, 9,9-bis[4-(glycidyloxy)-3-methylphenyl]-9H-fluorene, 9,9-bis[4-(glycidyloxy)-3,5-dimethylphenyl]-9H-fluorene, 9,9-bis(6-glycidyloxynaphthalen-1-yl)-9H-fluorene, and 9,9-bis(5-glycidyloxynaphthalen-2-yl)-9H-fluorene; and compounds represented by the following formula.

[0139]

Chemical formula

[0140]

Chemical formula

[0141]

Chemical formula

[0142]

Chem.

[0143]

Chem.

[0144]

Chem.

[0145]

Chem.

[0146]

Chem.

[0147]

Chem.

[0148]

Chem.

[0149]

Chem.

[0150]

Chem.

[0151] Among the compounds represented by the formula (b-01) described above, the following compounds are particularly preferred.

Chem.

[0152] [[Resin material]] Among the base material components (C), examples of 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, AS resin, ABS resin, polyphenylene oxide resin, polyphenylene sulfide resin, polysulfone resin, polyethersulfone resin, polyetheretherketone resin, fluorine-based resin, polyimide resin, polyamideimide resin, polyamidebismaleimide resin, polyetherimide resin, polybenzoxazole resin, polybenzothiazole resin, polybenzimidazole resin, silicone resin, BT resin, polymethylpentene, ultra-high molecular weight polyethylene, FR-polypropylene, (meth)acrylic resin (for example, polymethyl methacrylate, etc.), and polystyrene, etc.

[0153] When using the resin material as the base material component (C), by molding a modified metal oxide particle dispersion liquid in which a predetermined amount of metal oxide particles containing the aforementioned modified metal oxide fine particles is blended into a film or the like by a conventionally known method with respect to the resin material, various articles in the form of a film or the like are manufactured. As the form of the article manufactured using the modified metal oxide particle dispersion liquid, a film is preferable. Note that the modified metal oxide particle dispersion liquid may be a melt or a solution.

[0154] Examples of the film-forming method include melt processing methods such as the T-die method (casting method), inflation method, and press method, and casting methods using a solution, inkjet method, spin coating method, etc. In the casting method, inkjet method, and spin coating method, after applying or casting a liquid containing a resin material and metal oxide particles onto a substrate to form a film, if necessary, a solvent is removed from the film by a method such as heating to form a metal oxide particle-containing film. The metal oxide fine particle-containing film obtained using the modified metal oxide fine particle dispersion may be subjected to stretching treatments such as uniaxial stretching or biaxial stretching, if necessary.

[0155] When using the above resin material as the base material component (C), the modified metal oxide fine particle dispersion may contain additives such as antioxidants, ultraviolet absorbers, flame retardants, mold release agents, plasticizers, fillers other than metal oxide fine particles, and reinforcing materials, if necessary. Further, when 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 the solvent is appropriately selected according to the type of the resin material.

[0156] [Thermosetting material] Examples of the thermosetting material include precursor materials of various conventionally widely used thermosetting resins. 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, polybenzoxazole resin, polybenzimidazole resin, and the like.

[0157] In addition, resins that cause an aromatic ring formation reaction within the molecule and / or a crosslinking reaction between molecules by heating are also preferably used as the thermosetting material. Hereinafter, a resin that causes an aromatic ring formation reaction within the molecule and / or a crosslinking reaction between molecules by heating is also referred to as a precursor resin.

[0158] Among these, an epoxy resin precursor and a precursor resin are particularly preferable because it is particularly easy to form a metal oxide fine particle-containing film having excellent heat resistance, chemical resistance, mechanical properties, and the like. Hereinafter, the thermosetting material will be described with respect to precursor materials that are particularly suitable as the base material component (C).

[0159] (Epoxy resin precursor) As the epoxy resin precursor, various epoxy compounds that have been widely known conventionally can be used. In the modified metal oxide fine particle dispersion, if necessary, by using a curing agent or a curing accelerator in combination with the epoxy resin precursor, the modified metal oxide fine particle dispersion can be made into a thermosetting composition. In addition, in the modified metal oxide fine particle dispersion, by using a photosensitive curing agent in combination with the epoxy resin precursor, the modified metal oxide fine particle dispersion can also be made into a photosensitive composition that can be photocured. The molecular weight of the epoxy compound as the epoxy resin precursor is not particularly limited. Among epoxy compounds, polyfunctional epoxy compounds having two or more epoxy groups in the molecule are preferable because they easily form a metal oxide fine particle-containing film excellent in heat resistance, chemical resistance, mechanical properties, etc. The epoxy resin precursor can be used alone or in combination of two or more.

[0160] The polyfunctional epoxy compound is not particularly limited as long as it is an epoxy compound having two or more functional groups. Examples of the polyfunctional epoxy compound include bifunctional epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD type epoxy resin, naphthalene type epoxy resin, tetrabromobisphenol A type epoxy resin, and biphenyl type epoxy resin; glycidyl ester type epoxy resins such as dimer acid glycidyl ester and triglycidyl ester; glycidyl amine type epoxy resins such as tetraglycidyl aminodiphenylmethane, triglycidyl-p-aminophenol, tetraglycidyl metaxylylenediamine, and tetraglycidyl bisaminomethylcyclohexane; hydantoin type epoxy resins such as 1,3-diglycidyl-5-methyl-5-ethylhydantoin; hydroquinone type epoxy resins; fluorene type epoxy resins; heterocyclic epoxy resins such as triglycidyl isocyanurate; trifunctional type epoxy resins such as phloroglucinol 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)phenyl]-1-methylethyl]phenyl]ethyl]phenoxy]-2-propanol; and tetrafunctional type epoxy resins such as tetrahydroxyphenylethane tetraglycidyl ether, tetraglycidyl benzophenone, bisresorcinol tetraglycidyl ether, and tetraglycidoxy biphenyl. These epoxy compounds may be halogenated or hydrogenated.

[0161] Examples of commercially available polyfunctional epoxy compounds include, but are not limited to, JER Coat 828, 1001, 801N, 806, 807, 152, 604, 630, 871, YX8000, YX8034, YX4000 manufactured by Japan Epoxy Resins Co., Ltd., Epiclon 830, EXA835LV, HP4032D, HP820 manufactured by DIC Corporation, EP4100 series, EP4000 series, EPU series manufactured by ADEKA Corporation, the Celoxide series (2021, 2021P, 2083, 2085, 3000, etc.), the Epolide series, the EHPE series manufactured by Daicel Corporation, the YD series, the YDF series, the YDCN series, the YDB series manufactured by Nippon Steel Chemical Co., Ltd., phenoxy resins (polyhydroxy polyethers synthesized from bisphenols and epichlorohydrin and having epoxy groups at both ends; YP series, etc.), the Denacol series manufactured by Nagase ChemteX Corporation, the Epolite series manufactured by Kyoeisha Chemical Co., Ltd., and the like.

[0162] In addition, alicyclic epoxy compounds are also preferable as polyfunctional epoxy compounds in that they give cured products with high hardness. Specific examples of alicyclic epoxy compounds include 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-metha-dioxane, bis(3,4-epoxycyclohexylmethyl) adipate, bis(3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl-3’,4’-epoxy-6’-methylcyclohexanecarboxylate, ε-caprolactone-modified 3,4-epoxycyclohexylmethyl-3’,4’-epoxycyclohexanecarboxylate, trimethylcaprolactone-modified 3,4-epoxycyclohexylmethyl-3’,4’-epoxycyclohexanecarboxylate, β-methyl-δ-valerolactone-modified 3,4-epoxycyclohexylmethyl-3’,4’-epoxycyclohexanecarboxylate, methylenebis(3,4-epoxycyclohexane), di(3,4-epoxycyclohexylmethyl) ether of ethylene glycol, ethylenebis(3,4-epoxycyclohexanecarboxylate), dioctyl epoxycyclohexahydrophthalate, and di-2-ethylhexyl epoxycyclohexahydrophthalate, epoxy resins having tricyclodecene oxide groups, and compounds represented by the following formulas (a01-1) to (a01-5).

[0163] Among these specific examples of alicyclic epoxy compounds, alicyclic epoxy compounds represented by the following formulas (a01-1) to (a01-5) are preferable because they give cured products with high hardness.

Chemical formula

[0164] Linking group Z 01Examples thereof include a divalent hydrocarbon group, -O-, -O-CO-, -S-, -SO-, -SO2-, -CBr2-, -C(CBr3)2-, -C(CF3)2-, and -R a019 Examples thereof include a divalent group selected from the group consisting of -O-CO- and a group formed by bonding a plurality of these groups.

[0165] Examples of the divalent hydrocarbon group as the linking group Z include a linear or branched alkylene group having 1 to 18 carbon atoms, a divalent alicyclic hydrocarbon group, and the like. Examples of the linear or branched alkylene group having 1 to 18 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 cycloalkylene groups (including cycloalkylidene groups) such as a 1,2-cyclopentylene group, a 1,3-cyclopentylene group, a cyclopentylidene group, a 1,2-cyclohexylene group, a 1,3-cyclohexylene group, a 1,4-cyclohexylene group, and a cyclohexylidene group.

[0166] R a019 is an alkylene group having 1 to 8 carbon atoms, preferably a methylene group or an ethylene group.

[0167]

Chemical formula

[0168] Examples of the alicyclic epoxy compound represented by the above formula (a01-2) include m in the above formula (a01-2) a1The compound represented by the following formula (a01-2-1), which corresponds to the compound where [a certain condition] is 0, is preferable.

Chemical formula

[0169]

Chemical formula

[0170]

Chemical formula

[0171]

Chemical formula

[0172] In formulas (a01-1) to (a01-5), R a01 ~R a018When the organic group is an organic group, the organic group is not particularly limited as long as it does not inhibit the object of the present invention, and it may be a hydrocarbon group, a group consisting of a carbon atom and a halogen atom, or a group containing a hetero atom such as a halogen atom, an oxygen atom, a sulfur atom, a nitrogen atom, or a silicon atom together with a carbon atom and a hydrogen atom. Examples of the halogen atom include a chlorine atom, a bromine atom, an iodine atom, and a fluorine atom.

[0173] As the organic group, 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 group consisting of a carbon atom, a hydrogen atom, an oxygen atom, and a halogen atom are preferable. When the organic group is a hydrocarbon group, the hydrocarbon group may be an aromatic hydrocarbon group, an aliphatic hydrocarbon group, or a group containing an aromatic skeleton and an aliphatic skeleton. The number of carbon atoms of the organic group is preferably 1 or more and 20 or less, more preferably 1 or more and 10 or less, and particularly preferably 1 or more and 5 or less.

[0174] Specific examples of the hydrocarbon group include chain alkyl groups such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group, n-undecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, and n-icosyl group; chain alkenyl groups such as vinyl group, 1-propenyl group, 2-n-propenyl group (allyl group), 1-n-butenyl group, 2-n-butenyl group, and 3-n-butenyl group; cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, and cycloheptyl group; aryl groups such as phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, α-naphthyl group, β-naphthyl group, biphenyl-4-yl group, biphenyl-3-yl group, biphenyl-2-yl group, anthryl group, and phenanthryl group; and aralkyl groups such as benzyl group, phenethyl group, α-naphthylmethyl group, β-naphthylmethyl group, α-naphthylethyl group, and β-naphthylethyl group.

[0175] Specific examples of the halogenated hydrocarbon group include halogenated chain alkyl groups such as 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, perfluoropentyl group, perfluorohexyl group, perfluoroheptyl group, perfluorooctyl group, perfluorononyl group, and perfluorodecyl group; halogenated cycloalkyl groups such as 2-chlorocyclohexyl group, 3-chlorocyclohexyl group, 4-chlorocyclohexyl group, 2,4-dichlorocyclohexyl group, 2-bromocyclohexyl group, 3-bromocyclohexyl group, and 4-bromocyclohexyl group; halogenated aryl groups such as 2-chlorophenyl group, 3-chlorophenyl group, 4-chlorophenyl group, 2,3-dichlorophenyl group, 2,4-dichlorophenyl group, 2,5-dichlorophenyl group, 2,6-dichlorophenyl group, 3,4-dichlorophenyl group, 3,5-dichlorophenyl group, 2-bromophenyl group, 3-bromophenyl group, 4-bromophenyl group, 2-fluorophenyl group, 3-fluorophenyl group, and 4-fluorophenyl group; and halogenated aralkyl groups such as 2-chlorophenylmethyl group, 3-chlorophenylmethyl group, 4-chlorophenylmethyl group, 2-bromophenylmethyl group, 3-bromophenylmethyl group, 4-bromophenylmethyl group, 2-fluorophenylmethyl group, 3-fluorophenylmethyl group, and 4-fluorophenylmethyl group.

[0176] Specific examples of the group consisting of a carbon atom, a hydrogen atom, and an oxygen atom include hydroxy chain alkyl groups such as hydroxymethyl group, 2-hydroxyethyl group, 3-hydroxy-n-propyl group, and 4-hydroxy-n-butyl group; halogenated cycloalkyl groups such as 2-hydroxycyclohexyl group, 3-hydroxycyclohexyl group, and 4-hydroxycyclohexyl group; hydroxyaryl groups such as 2-hydroxyphenyl group, 3-hydroxyphenyl group, 4-hydroxyphenyl group, 2,3-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; chain alkoxy groups such as 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, n-nonadecyloxy group, and n-icosyloxy group; chain alkenyloxy groups such as vinyloxy group, 1-propenyloxy group, 2-n-propenyloxy group (allyloxy group), 1-n-butenyloxy group, 2-n-butenyloxy group, and 3-n-butenyloxy group; aryloxy groups such as phenoxy group, o-tolyloxy group, m-tolyloxy group, p-tolyloxy group, α-naphthyloxy group, β-naphthyloxy group, biphenyl-4-yloxy group, biphenyl-3-yloxy group, biphenyl-2-yloxy group, anthryloxy group, and phenanthryloxy group; aralkyloxy groups such as benzyloxy group, phenethyloxy group, α-naphthylmethyloxy group, β-naphthylmethyloxy group, α-naphthylethyloxy group, and β-naphthylethyloxy group;Alkoxyalkyl groups such as methoxymethyl group, ethoxymethyl group, n-propoxymethyl group, 2-methoxyethyl group, 2-ethoxyethyl group, 2-n-propoxyethyl group, 3-methoxy-n-propyl group, 3-ethoxy-n-propyl group, 3-n-propoxy-n-propyl group, 4-methoxy-n-butyl group, 4-ethoxy-n-butyl group, and 4-n-propoxy-n-butyl group; alkoxyalkoxy groups such as methoxymethoxy group, ethoxymethoxy group, n-propoxymethoxy group, 2-methoxyethoxy group, 2-ethoxyethoxy group, 2-n-propoxyethoxy group, 3-methoxy-n-propoxy group, 3-ethoxy-n-propoxy group, 3-n-propoxy-n-propoxy group, 4-methoxy-n-butyloxy group, 4-ethoxy-n-butyloxy group, and 4-n-propoxy-n-butyloxy group; alkoxyaryl groups such as 2-methoxyphenyl group, 3-methoxyphenyl group, and 4-methoxyphenyl group; alkoxyaryloxy groups such as 2-methoxyphenoxy group, 3-methoxyphenoxy group, and 4-methoxyphenoxy group; aliphatic acyl groups such as formyl group, acetyl group, propionyl group, butanoyl group, pentanoyl group, hexanoyl group, heptanoyl group, octanoyl group, nonanoyl group, and decanoyl group; aromatic acyl groups such as benzoyl group, α-naphthoyl group, and β-naphthoyl group; chain alkyl oxycarbonyl groups such as methoxycarbonyl group, 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-decyloxycarbonyl group; aryloxycarbonyl groups such as phenoxycarbonyl group, α-naphthoxycarbonyl group, and β-naphthoxycarbonyl group; aliphatic acyloxy groups such as formyloxy group, acetyloxy group, propionyloxy group, butanoyloxy group, pentanoyloxy group, hexanoyloxy group, heptanoyloxy group, octanoyloxy group, nonanoyloxy group, and decanoyloxy group; aromatic acyloxy groups such as benzoyloxy group, α-naphthoyloxy group, and β-naphthoyloxy group.;

[0177] R a01 ~R a018 is independently preferably a group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, and an alkoxy group having 1 to 5 carbon atoms. In particular, since it is easy to form a cured film having excellent mechanical properties, R a01 ~R a018 is more preferably all hydrogen atoms.

[0178] In formulas (a01-2) to (a01-5), R a01 ~R a018 is the same as R a01 ~R a018 in formula (a01-1). In formulas (a01-2) and (a01-4), when R a02 and R a010 are bonded to each other, in formula (a01-2), when R a013 and R a016 are bonded to each other, and in formula (a01-3), when R a02 and R a08 are bonded to each other, examples of the divalent group formed include -CH2- and -C(CH3)2-.

[0179] Among the alicyclic epoxy compounds represented by formula (a01-1), specific examples of suitable compounds include alicyclic epoxy compounds represented by the following formulas (a01-1a), (a01-1b), and (a01-1c), and 2,2-bis(3,4-epoxycyclohexan-1-yl)propane [=2,2-bis(3,4-epoxycyclohexyl)propane] and the like. [Chemical formula]

[0180] Among the alicyclic epoxy compounds represented by formula (a01-2), specific examples of suitable compounds include alicyclic epoxy compounds represented by the following formulas (a01-2a) and (a01-2b). [Chemical formula]

[0181] Among the alicyclic epoxy compounds represented by formula (a01-3), specific examples of suitable compounds include S-spiro[3-oxatricyclo[3.2.1.0 2,4 octane-6,2'-oxirane] and the like.

[0182] Among the alicyclic epoxy compounds represented by formula (a01-4), specific examples of suitable compounds include 4-vinylcyclohexene dioxide, dipentene dioxide, limonene dioxide, 1-methyl-4-(3-methyloxiran-2-yl)-7-oxabicyclo[4.1.0]heptane and the like.

[0183] Among the alicyclic epoxy compounds represented by formula (a01-5), specific examples of suitable compounds include 1,2,5,6-diepoxycyclooctane and the like.

[0184] Furthermore, the compound represented by the following formula (a1-I) can be suitably used as an epoxy resin precursor.

Chemical formula

[0185] As the compound represented by the above formula (a1-I), the compound represented by the following formula (a1-II) is preferable.

Chemical formula

[0186] In formula (a1-II), R a20 and E 1 , R a21 and E 2 , and R a22 and E 3 The groups represented by are preferably such that at least two of them are each a group represented by the following formula (a1-IIa), and more preferably all of them are each a group represented by the following formula (a1-IIa). The groups represented by a plurality of formula (a1-IIa) bonded to one compound are preferably the same group. -L-C a (a1-IIa) (In formula (a1-IIa), L is a group composed of a linear, branched or cyclic alkylene group, an arylene group, -O-, -C(=O)-, -NH- and combinations thereof, and C a is an epoxy group. In formula (a1-IIa), L and C a may combine to form a cyclic structure. )

[0187] In formula (a1-IIa), the linear, branched or cyclic alkylene group as L is preferably an alkylene group having 1 to 10 carbon atoms, and the arylene group as L is preferably an arylene group having 5 to 10 carbon atoms. In formula (a1-IIa), L is preferably a group composed of an alkylene group having a linear carbon atom number of 1 to 3, a phenylene group, -O-, -C(=O)-, -NH- and combinations thereof, and at least one of an alkylene group having a linear carbon atom number of 1 to 3 such as a methylene group and a phenylene group, or a group composed of a combination of these and at least one of -O-, -C(=O)- and NH- is preferred.

[0188] In formula (a1-IIa), when L and C a are bonded to form a cyclic structure, for example, when a branched alkylene group and an epoxy group are bonded to form a cyclic structure (a structure having an epoxy group of an alicyclic structure), the organic groups represented by the following formulas (a1-IIb) to (a1-IId) can be mentioned.

Chemical formula

[0189] Hereinafter, examples of the compound represented by formula (a1-II) are shown as examples of an epoxy compound having an oxiranyl group or an alicyclic epoxy group, but are not limited thereto.

Chemical formula

[0190]

Chemical formula

[0191] In addition, a siloxane compound having two or more glycidyl groups or alicyclic epoxy groups in the molecule (hereinafter, also simply referred to as "siloxane compound") can be preferably used as an epoxy resin precursor.

[0192] The siloxane compound is a compound having a siloxane skeleton composed of siloxane bonds (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, a cage-type or ladder-type polysilsesquioxane skeleton.

[0193] Among the siloxane compounds, a compound having a cyclic siloxane skeleton represented by the following formula (a1-III) (hereinafter sometimes referred to as "cyclic siloxane") is preferable.

Chemical formula

[0194] In formula (a1-III), R a24 , and R a25 represent a monovalent group containing an epoxy group or an alkyl group. However, among the x1 R a24 and x1 R a25 in the compound represented by formula (a1-III), at least two are monovalent groups containing an epoxy group. Also, x1 in formula (a1-III) represents an integer of 3 or more. In addition, R a24 , R a25 may be the same or different. Also, a plurality of R a24 may be the same or different. A plurality of R a25 may also be the same or different. Examples of the above alkyl group include linear or branched alkyl groups having 1 to 18 carbon atoms such as a methyl group, an ethyl group, a propyl group, and an isopropyl group. The number of carbon atoms of the above alkyl group is preferably 1 or more and 6 or less, and particularly preferably 1 or more and 3 or less.

[0195] In formula (a1-III), x1 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 crosslinking reactivity when forming a cured film.

[0196] The number of epoxy groups contained in the siloxane compound in the molecule is 2 or more, and from the viewpoint of excellent crosslinking reactivity when forming a cured film, 2 or more and 6 or less are preferable, and particularly preferably 2 or more and 4 or less.

[0197] Examples of the monovalent group containing the epoxy group include an alicyclic epoxy group and a glycidyl ether group represented by -D-O-R a26 [where D represents an alkylene group and R a26 represents a glycidyl group] are preferable, an alicyclic epoxy group is more preferable, and an alicyclic epoxy group represented by the following formula (a1-IIIa) or the following formula (a1-IIIb) is even more preferable. Examples of the above D (alkylene group) include linear or branched alkylene groups having 1 to 18 carbon atoms such as a methylene group, a methylmethylene group, a dimethylmethylene group, a dimethylene group, and a trimethylene group.

Chemical formula

[0198] In addition to the siloxane compound represented by formula (a1-III) as an epoxy resin precursor, the modified metal oxide fine particle dispersion may contain a siloxane skeleton-containing compound such as an alicyclic epoxy group-containing cyclic siloxane, an alicyclic epoxy group-containing silicone resin described in JP-A-2008-248169, and an organopolysilsesquioxane resin having at least two epoxy functional groups in one molecule described in JP-A-2008-19422.

[0199] As the siloxane compound, more specifically, cyclic siloxanes having two or more glycidyl groups or alicyclic epoxy groups in the molecule, represented by the following formula, etc. can be mentioned. Further, as the siloxane compound, for example, commercially available products such as trade names "X-40-2670", "X-40-2701", "X-40-2728", "X-40-2738", "X-40-2740" (manufactured by Shin-Etsu Chemical Co., Ltd.) etc. can be used.

[0200] [Chemical formula]

[0201] [Chemical formula]

[0202] [Precursor resin] As the base material component (C), a precursor resin which is a resin that causes an aromatic ring formation reaction in the molecule and / or a crosslinking reaction between molecules by heating is preferable. Further, a precursor resin that gives a cured product by firing is also preferable as the base material component (CD).

[0203] According to the aromatic ring formation reaction in the molecule, the structure of the molecular chain constituting the resin is rigidified, and a metal oxide fine particle-containing film excellent in heat resistance and mechanical properties can be formed. As preferable reactions among the aromatic ring formation reactions in the molecule, for example, the reactions represented by the following formulas (I) to (VI) can be mentioned. Note that the reactions in the following formulas are merely examples of the aromatic ring formation reaction, and the structure of the resin that causes an aromatic ring formation reaction in the molecule and is used as the base material component (C) by heating is not limited to the structure of the precursor polymer shown in the following formulas.

[0204] [Chemical formula]

[0205] (Resin having a group selected from a hydroxyl group, a carboxylic anhydride group, a carboxy group, and an epoxy group in the molecule) According to the crosslinking reaction between molecules, the molecular chains constituting the resin are crosslinked with each other to form a three-dimensional crosslinked structure. Therefore, when a resin having a group selected from a hydroxyl group, a carboxylic anhydride group, a carboxy group, and an epoxy group in the molecule, which causes a crosslinking reaction by heating, is used as the base material component (C), a metal oxide fine particle-containing film excellent in heat resistance and mechanical properties can be obtained.

[0206] When a resin having a hydroxyl group is used, crosslinking by dehydration condensation between hydroxyl groups occurs between the molecules contained in the resin due to the action of a dehydration condensing agent. Further, since the hydroxyl group contains an active hydrogen atom and is rich in reactivity, it reacts with various crosslinking agents to give a cured product containing a crosslinked resin.

[0207] When a resin having a carboxylic anhydride group is used, carboxy groups generated by hydrolysis of the acid anhydride group are dehydrated and condensed by the action of a dehydration condensing agent to crosslink. Further, since the acid anhydride group itself is also rich in reactivity, for example, by using a crosslinking agent such as a polyol having two or more hydroxyl groups or a polyamine having two or more amino groups, a cured product containing a crosslinked resin is given.

[0208] When a resin having a carboxy group is used, crosslinking by dehydration condensation between carboxy groups occurs between the molecules contained in the resin due to the action of a dehydration condensing agent. It is also possible to crosslink using a crosslinking agent having a functional group capable of reacting with a carboxy group such as an isocyanate group.

[0209] When a resin having an epoxy group is used, crosslinking by polyaddition reaction between epoxy groups occurs between the molecules contained in the resin by using a well-known curing accelerator or the like as necessary.

[0210] As the resin having a carboxylic anhydride group in the molecule, a copolymer obtained by polymerizing a mixture of monomers having an unsaturated double bond, which contains one or more monomers selected from maleic anhydride, citraconic anhydride, and itaconic anhydride, is preferable. As such a polymer, a styrene-maleic acid copolymer is preferable.

[0211] Examples of the resin having a carboxy group in the molecule include a resin obtained by hydrolyzing the acid anhydride group in the resin having a carboxylic anhydride group in the molecule described above, and a copolymer obtained by polymerizing a mixture of monomers having an unsaturated double bond containing at least one monomer selected from (meth)acrylic acid, crotonic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, and itaconic acid.

[0212] The epoxy group-containing resin having an epoxy group in the molecule will be described in detail later.

[0213] Among the compounds that cause an aromatic ring formation reaction in the molecule and a crosslinking reaction between molecules by such heating, polyamic acid, polybenzoxazole precursor, polybenzothiazole precursor, polybenzimidazole precursor, styrene-maleic acid copolymer, and epoxy group-containing resin are preferable because they easily form a metal oxide fine particle-containing film having excellent heat resistance.

[0214] [Polyimide resin precursor] Examples of the polyimide resin precursor include polyamic acid. When a modified metal oxide fine particle dispersion liquid containing polyamic acid is formed into a film as the base material component (C) and then the formed film is heated in the presence of an imidizing agent as necessary, a metal oxide fine particle-containing film having excellent heat resistance and containing a polyimide resin is formed.

[0215] The molecular weight of the polyamic acid is preferably 5,000 or more and 30,000 or less, more preferably 10,000 or more and 20,000 or less, as the mass average molecular weight. When polyamic acid having a mass average molecular weight within such a range is used, it is easy to form a metal oxide fine particle-containing film having excellent heat resistance. Preferable polyamic acids include, for example, polyamic acids composed of structural units represented by the following formula (A1).

[0216] [Chemical formula] (In formula (A1), Ra020 is a tetravalent organic group, and R a021 is a divalent organic group, and n a is the number of repeating units of the structural unit represented by the formula (A1).)

[0217] In the formula (A1), R a020 and R a021 preferably have 2 or more and 50 or less carbon atoms, more preferably 2 or more and 30 or less carbon atoms. R a020 and R a021 may each be an aliphatic group, an aromatic group, or a group combining these structures. The tetravalent aromatic group is the same as R a022 described later. R a020 and R a021 may contain a halogen atom, an oxygen atom, and a sulfur atom in addition to a carbon atom and a hydrogen atom. R a020 and R a021 When containing an oxygen atom, a nitrogen atom, or a sulfur atom, the oxygen atom, the nitrogen atom, or the sulfur atom is selected as a group from a nitrogen-containing heterocyclic group, -CONH-, -NH-, -N=N-, -CH=N-, -COO-, -O-, -CO-, -SO-, -SO2-, -S-, and -S-S-, and may be contained in R a020 and R a021 and is more preferably contained in R a020 and R a021 as a group selected from -O-, -CO-, -SO-, -SO2-, -S-, and -S-S-.

[0218] The polyamic acid is usually prepared by reacting a tetracarboxylic dianhydride component with a diamine component. Hereinafter, the tetracarboxylic dianhydride component, the diamine component, and the production method of the polyamic acid used for the preparation of the polyamic acid will be described.

[0219] (Tetracarboxylic dianhydride component) The tetracarboxylic dianhydride component serving as a synthetic raw material for the polyamic acid is not particularly limited as long as it can form a polyamic acid by reacting with the diamine component. The tetracarboxylic dianhydride component can be appropriately selected from the tetracarboxylic dianhydrides that have been conventionally used as synthetic raw materials for polyamic acids. The tetracarboxylic dianhydride component may be an aromatic tetracarboxylic dianhydride or an aliphatic tetracarboxylic dianhydride. For example, the tetracarboxylic dianhydride represented by the following formula (a1-01) can be mentioned, and an aromatic tetracarboxylic dianhydride is preferred. Two or more kinds of the tetracarboxylic dianhydride components may be used in combination.

Chemical formula

[0220] Preferable specific examples of the aromatic tetracarboxylic dianhydride include pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 4,4'-oxydiphthalic anhydride, and 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride. Among these, 3,3',4,4'-biphenyltetracarboxylic dianhydride and pyromellitic dianhydride are preferred in terms of price, availability, etc.

[0221] (Diamine component) The diamine component serving as a synthetic raw material for the polyamic acid is not particularly limited as long as it can form a polyamic acid by reacting with the tetracarboxylic dianhydride component. The diamine component can be appropriately selected from the diamines that have been conventionally used as synthetic raw materials for polyamic acids. For example, the diamine component represented by the following formula (a1-02) and Y described later dExamples of diamines that provide the following are given. The diamine component may be an aromatic diamine or an aliphatic diamine, but an aromatic diamine is preferred. Two or more kinds of diamine components may be used in combination.

Chemical formula

[0222] Suitable specific examples of aromatic diamines include p-phenylenediamine, m-phenylenediamine, 2,4-diaminotoluene, 4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl methane, 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-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 9,9-bis(4-aminophenyl)-9H-fluorene, 9,9-bis(4-amino-3-methylphenyl)-9H-fluorene, 4,4'-[1,4-phenylenebis(1-methylethane-1,1-diyl)]dianiline, and the like. Among these, p-phenylenediamine, m-phenylenediamine, 2,4-diaminotoluene, and 4,4'-diaminodiphenyl ether are preferred in terms of price, availability, etc.

[0223] (Method for producing polyamic acid) The 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 amounts of the tetracarboxylic dianhydride component and the diamine component used in synthesizing the polyamic acid are not particularly limited. Preferably, 0.50 mol or more and 1.50 mol or less of the diamine component are used per 1 mol of the tetracarboxylic dianhydride component, more preferably 0.60 mol or more and 1.30 mol or less, and particularly preferably 0.70 mol or more and 1.20 mol or less.

[0224] Examples of the solvent that can be used for synthesizing the polyamic acid include aprotic polar organic solvents such as N,N,N’,N’-tetramethylurea, N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, hexamethylphosphoramide, 1,3-dimethyl-2-imidazolidinone, and γ-butyrolactone, and glycol ethers such as diethylene glycol dialkyl ether, ethylene glycol monoalkyl ether acetate, diethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether acetate, and propylene glycol monoalkyl ether propionate. These solvents can be used in combination of two or more. Among these, it is preferable to use N,N,N’,N’-tetramethylurea.

[0225] The amount of the solvent used in synthesizing the polyamic acid is not particularly limited as long as a polyamic acid having a desired molecular weight can be synthesized. Typically, the amount of the solvent used is preferably 100 parts by mass or more and 4000 parts by mass or less, more preferably 150 parts by mass or more and 2000 parts by mass or less, based on 100 parts by mass in total of the amount of the tetracarboxylic dianhydride component and the amount of the diamine component.

[0226] When reacting the tetracarboxylic dianhydride component with the diamine component, the temperature is not particularly limited as long as the reaction proceeds well. Typically, 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. Also, the reaction time for reacting the tetracarboxylic dianhydride component with the diamine component varies depending on the reaction temperature, but typically, it is preferably 1 hour or longer and 50 hours or shorter, more preferably 2 hours or longer and 40 hours or shorter, and particularly preferably 5 hours or longer and 30 hours or shorter.

[0227] According to the above method, a solution or paste of polyamic acid can be obtained. Such a solution or paste may be used as it is for the preparation of the modified metal oxide fine particle dispersion. Also, the solid polyamic acid obtained by removing the solvent from the solution or paste of polyamic acid may be used for the preparation of the modified metal oxide fine particle dispersion.

[0228] [Polybenzoxazole precursor] The polybenzoxazole precursor is typically produced by reacting an aromatic diamine diol with a dicarbonyl compound having a specific structure. Hereinafter, the aromatic diamine diol, the dicarbonyl compound, the solvent used in the synthesis of the polybenzoxazole precursor, and the production method of the polybenzoxazole precursor will be described.

[0229] (Aromatic diamine diol) As the aromatic diamine diol, the aromatic diamine diols conventionally used in 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. [Chemical formula] (In formula (a02), R a022is a tetravalent organic group containing one or more aromatic rings. Regarding the combinations of two sets of amino groups and hydroxyl groups contained in the aromatic diamine diol represented by the formula (a02), in each combination, the amino group and the hydroxyl group are R a022 bonded to two adjacent carbon atoms on the aromatic ring contained in ).)

[0230] In the formula (a02), R a022 is a tetravalent organic group containing one or more aromatic rings, preferably having 6 to 50 carbon atoms, more preferably 6 to 30 carbon atoms. R a022 may be an aromatic group, or a group in which two or more aromatic groups are bonded via a bond containing an aliphatic hydrocarbon group, a halogenated aliphatic hydrocarbon group, or a heteroatom such as an oxygen atom, a sulfur atom, and a nitrogen atom. a022 Examples of the bond containing a heteroatom such as an oxygen atom, a sulfur atom, and a nitrogen atom contained in include -CONH-, -NH-, -N=N-, -CH=N-, -COO-, -O-, -CO-, -SO-, -SO2-, -S-, and -S-S-, etc., and -O-, -CO-, -SO-, -SO2-, -S-, and -S-S- are preferred.

[0231] R a022 The aromatic ring contained in may be an aromatic heterocyclic ring. a022 The aromatic ring bonded to the amino group and the hydroxyl group in is preferably a benzene ring. a022 When the ring bonded to the amino group and the hydroxyl group in is a condensed 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.

[0232] R a022 Preferable examples of include groups represented by the following formulas (a02-1) to (a02-9).

Chemical formula

[0233] The groups represented by the above formulas (a02-1) to (a02-9) may have one or more substituents on the aromatic ring. Preferred examples of the substituent include 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 fluorinated alkoxy group having 1 to 6 carbon atoms. When the substituent is a fluorinated alkyl group or a fluorinated alkoxy group, a perfluoroalkyl group or a perfluoroalkoxy group is preferred.

[0234] Specific examples of the compound represented by the above formula (a02) include 2,4-diamino-1,5-benzenediol, 2,5-diamino-1,4-benzenediol, 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, 3,4'-diamino-4,3'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxy-6,6'-ditrifluoromethylbiphenyl, 3,3'-diamino-4,4'-dihydroxy-6,6'-ditrifluoromethylbiphenyl, 2,3'-diamino-3,2'-dihydroxy-6,6'-ditrifluoromethylbiphenyl, 3,4'-diamino-4,3'-dihydroxy-6,6'-ditrifluoromethylbiphenyl, 4,4'-diamino-3,3'-dihydroxy-5,5'-ditrifluoromethylbiphenyl, 3,3'-diamino-4,4'-dihydroxy-5,5'-ditrifluoromethylbiphenyl, 2,3'-diamino-3,2'-dihydroxy-5,5'-ditrifluoromethylbiphenyl, 3,4'-diamino-4,3'-dihydroxy-5,5'-ditrifluoromethylbiphenyl, bis(4-amino-3-hydroxyphenyl)methane, bis(3-amino-4-hydroxyphenyl)methane, 3,4'-diamino-4,3'-dihydroxydiphenylmethane, bis(4-amino-3-hydroxy-6-trifluoromethyl)methane, bis(3-amino-4-hydroxy-6-trifluoromethyl)methane, 3,4'-diamino-4,3'-dihydroxy-6,6'-ditrifluoromethyldiphenylmethane, bis(4-amino-3-hydroxyphenyl)difluoromethane, bis(3-amino-4-hydroxyphenyl)difluoromethane, 3,4'-diamino-4,3'-dihydroxydiphenyldifluoromethane, bis(4-amino-3-hydroxy-6-trifluoromethylphenyl)difluoromethane, bis(3-amino-4-hydroxy-6-trifluoromethylphenyl)difluoromethane, 3,4'-diamino-4,3'-dihydroxy-6,6'-ditrifluoromethyldiphenyldifluoromethane, bis(4-amino-3-hydroxyphenyl)ether, bis(3-amino-4-hydroxyphenyl)ether, 3,4'-diamino-4,3'-dihydroxydiphenyl ether, bis(4-amino-3-hydroxy-6-trifluoromethylphenyl)ether, bis(3-amino-4-hydroxy-6-trifluoromethylphenyl)ether, 3,4'-diamino-4,3'-dihydroxy-6,6'-ditrifluoromethyldiphenyl ether, bis(4-amino-3-hydroxyphenyl)ketone, bis(3-amino-4-hydroxyphenyl)ketone, 3,4'-diamino-4,3'-dihydroxydiphenyl ketone, bis(4-amino-3-hydroxy-6-trifluoromethyl)ketone, bis(3-amino-4-hydroxy-6-trifluoromethyl)ketone, 3,4'-diamino-4,3'-dihydroxy-6,6'-ditrifluoromethyldiphenyl ketone, 2,2-bis(4-amino-3-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2-(3-amino-4-hydroxyphenyl)-2-(4'-amino-3'-hydroxyphenyl)propane, 2,2-bis(4-amino-3-hydroxy-6-trifluoromethylphenyl)propane, 2,2-bis(3-amino-4-hydroxy-6-trifluoromethylphenyl)propane, 2-(3-amino-4-hydroxy-6-trifluoromethylphenyl)-2-(4'-amino-3'-hydroxy-6'-trifluoromethylphenyl)propane, 2,2-bis(3-amino-4-hydroxy-5-trifluoromethylphenyl)propane, 2,2-bis(4-amino-3-hydroxyphenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 2-(3-amino-4-hydroxyphenyl)-2-(4'-amino-3'-hydroxyphenyl)hexafluoropropane, 2,2-Bis(4-amino-3-hydroxy-6-trifluoromethylphenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxy-6-trifluoromethylphenyl)hexafluoropropane, 2-(3-amino-4-hydroxy-6-trifluoromethylphenyl)-2-(4'-amino-3'-hydroxy-6'-trifluoromethylphenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxy-5-trifluoromethylphenyl)hexafluoropropane, bis(4-amino-3-hydroxyphenyl)sulfone, bis(3-amino-4-hydroxyphenyl)sulfone, 3,4'-diamino-4,3'-dihydroxydiphenyl sulfone, bis(4-amino-3-hydroxy-6-trifluoromethyl)sulfone, bis(3-amino-4-hydroxy-6-trifluoromethyl)sulfone, 3,4'-diamino-4,3'-dihydroxy-6,6'-ditrifluoromethyldiphenyl sulfone, bis(4-amino-3-hydroxyphenyl)sulfide, bis(3-amino-4-hydroxyphenyl)sulfide, 3,4'-diamino-4,3'-dihydroxydiphenyl sulfide, bis(4-amino-3-hydroxy-6-trifluoromethyl)sulfide, bis(3-amino-4-hydroxy-6-trifluoromethyl)sulfide, 3,4'-diamino-4,3'-dihydroxy-6,6'-ditrifluoromethyldiphenyl sulfide, (4-amino-3-hydroxyphenyl) 4-amino-3-hydroxyphenyl benzoate, (3-amino-4-hydroxyphenyl) 3-amino 4-hydroxyphenyl benzoate, (3-amino-4-hydroxyphenyl) 4-amino-3-hydroxyphenyl benzoate, (4-amino-3-hydroxyphenyl) 3-amino-4-hydroxyphenyl benzoate, N-(4-amino-3-hydroxyphenyl) 4-amino-3-hydroxybenzamide, N-(3-amino-4-hydroxyphenyl) 3-amino 4-hydroxyphenyl benzamide, N-(3-amino-4-hydroxyphenyl) 4-amino-3-hydroxyphenyl benzamide, N-(4-amino-3-hydroxyphenyl) 3-amino-4-hydroxyphenyl benzamide, 2,4'-bis(4-amino-3-hydroxyphenoxy)biphenyl, 2,4'-bis(3-amino-4-hydroxyphenoxy)biphenyl, 4,4'-bis(4-amino-3-hydroxyphenoxy)biphenyl, 4,4'-bis(3-amino-4-hydroxyphenoxy)biphenyl, di[4-(4-amino-3-hydroxyphenoxy)phenyl]ether, di[4-(3-amino-4-hydroxyphenoxy)phenyl]ether, 2,4'-bis(4-amino-3-hydroxyphenoxy)benzophenone, 2,4'-bis(3-amino-4-hydroxyphenoxy)benzophenone, 4,4'-bis(4-amino-3-hydroxyphenoxy)benzophenone, 4,4'-bis(3-amino-4-hydroxyphenoxy)benzophenone, 2,4'-bis(4-amino-3-hydroxyphenoxy)octafluorobiphenyl, 2,4'-bis(3-amino-4-hydroxyphenoxy)octafluorobiphenyl, 4,4'-bis(4-amino-3-hydroxyphenoxy)octafluorobiphenyl, 4,4'-bis(3-amino-4-hydroxyphenoxy)octafluorobiphenyl, 2,4'-bis(4-amino-3-hydroxyphenoxy)octafluorobenzophenone, 2,4'-bis(3-amino-4-hydroxyphenoxy)octafluorobenzophenone, 4,4'-bis(4-amino-3-hydroxyphenoxy)octafluorobenzophenone, 4,4'-bis(3-amino-4-hydroxyphenoxy)octafluorobenzophenone, 2,2-bis[4-(4-amino-3-hydroxyphenoxy)phenyl]propane, 2,2-bis[4-(3-amino-4-hydroxyphenoxy)phenyl]propane, 2,2-bis[4-(4-amino-3-hydroxyphenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(3-amino-4-hydroxyphenoxy)phenyl]hexafluoropropane, 2,8-diamino-3,7-dihydroxydibenzofuran, 2,8-diamino-3,7-dihydroxyfluorene, 2,6-diamino-3,7-dihydroxyxanthene, 9,9-bis-(4-amino-3-hydroxyphenyl)fluorene, and 9,9-bis-(3-amino-4-hydroxyphenyl)fluorene are included.,

[0235] Among these, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane is preferable.

[0236] (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. By condensing the aforementioned aromatic diamine diol and the dicarbonyl compound represented by the following formula (a03), a polybenzoxazole precursor can be obtained.

[0237] [Chemical formula] (In formula (a03), R a023 is a divalent organic group, and A 0 represents a hydrogen atom or a halogen atom.)

[0238] R in formula (a03) a023 may be an aromatic group, an aliphatic group, or a group combining an aromatic group and an aliphatic group. From the viewpoint that the resulting polybenzoxazole resin has good heat resistance, mechanical properties, chemical resistance, etc., R a023 is preferably a group containing an aromatic group and / or an alicyclic group. The aromatic group contained in R a023 may be an aromatic hydrocarbon group or an aromatic heterocyclic group.

[0239] R a023 may contain, in addition to carbon atoms and hydrogen atoms, halogen atoms, oxygen atoms, and sulfur atoms. When R a023 contains an oxygen atom, a nitrogen atom, or a sulfur atom, the oxygen atom, nitrogen atom, or sulfur atom may be contained in R a023 as a group selected from a nitrogen-containing heterocyclic group, -CONH-, -NH-, -N=N-, -CH=N-, -COO-, -O-, -CO-, -SO-, -SO2-, -S-, and -S-S-, and may be contained in Ra023 It is more preferably contained in

[0240] In formula (a03), two A's 0 One of them may be a hydrogen atom and the other may be a halogen atom, but it is preferable that both A's are hydrogen atoms or both A's 0 are both halogen atoms. When A 0 is a halogen atom, chlorine, bromine, and iodine are preferable as A 0 , and chlorine is more preferable.

[0241] As the dicarbonyl compound represented by formula (a03), when a dialdehyde compound in which both A's 0 are hydrogen atoms is used, a polybenzoxazole precursor represented by the following formula (A2) is produced.

Chemical formula

[0242] As the dicarbonyl compound represented by formula (a03), when a dicarboxylic acid dihalide in which both A's 0 are halogen atoms is used, a polybenzoxazole precursor represented by the following formula (A3) is produced.

Chemical formula

[0243] Hereinafter, a dialdehyde compound and a dicarboxylic acid dihalide, which are compounds suitable as the dicarbonyl compound, will be described.

[0244] (Dialdehyde compound) The dialdehyde compound used as a raw material for the polybenzoxazole precursor is a compound represented by the following formula (a02-I). The dialdehyde compound may be used alone or in combination of two or more kinds.

Chemical formula

[0245] As a preferable aromatic group or aromatic ring-containing group for R in formula (a2-I), the following groups can be mentioned. a203

Chemical formula

[0246] As a preferable alicyclic group or alicyclic ring-containing group for R in formula (a2-I), the following groups can be mentioned. a023

Chemical formula

[0247] The above R a023 The aromatic ring or alicyclic ring included in the group suitable as may have one or more substituents on the ring. Preferred examples of the substituent include 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 fluorinated alkoxy group having 1 to 6 carbon atoms. When the substituent is a fluorinated alkyl group or a fluorinated alkoxy group, a perfluoroalkyl group or a perfluoroalkoxy group is preferred.

[0248] When the dialdehyde compound represented by the formula (a2-I) is an aromatic dialdehyde, preferred examples thereof include benzenedialdehydes, pyridinedialdehydes, pyrazinedialdehydes, pyrimidinedialdehydes, naphthalenedialdehydes, biphenyldialdehydes, diphenyl ether dialdehydes, diphenyl sulfone dialdehydes, diphenyl sulfide dialdehydes, bis(formylphenoxy)benzenes, [1,4-phenylenebis(1-methylethylidene)]bisbenzaldehyde, 2,2-bis[4-(formylphenoxy)phenyl]propane, bis[4-(formylphenoxy)phenyl]sulfide, bis[4-(formylphenoxy)phenyl]sulfone, and fluorene-containing dialdehyde.

[0249] Specific examples of 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-trifluoromethylterephthalaldehyde, 3,4,5,6-tetrafluorophthalaldehyde, 2,4,5,6-tetrafluoroisophthalaldehyde, and 2,3,5,6-tetrafluoroterephthalaldehyde, etc.

[0250] Specific examples of pyridinedialdehydes include pyridine-2,3-dialdehyde, pyridine-3,4-dialdehyde, and pyridine-3,5-dialdehyde, etc. Specific examples of pyrazinedialdehydes include pyrazine-2,3-dialdehyde, pyrazine-2,5-dialdehyde, and pyrazine-2,6-dialdehyde, etc. Specific examples of pyrimidinedialdehydes include pyrimidine-2,4-dialdehyde, pyrimidine-4,5-dialdehyde, and pyrimidine-4,6-dialdehyde, etc.

[0251] Specific examples of naphthalenedialdehydes include naphthalene-1,5-dialdehyde, naphthalene-1,6-dialdehyde, naphthalene-2,6-dialdehyde, naphthalene-3,7-dialdehyde, 2,3,4,6,7,8-hexafluoronaphthalene-1,5-dialdehyde, 2,3,4,5,6,8-hexafluoronaphthalene-1,6-dialdehyde, 1,3,4,5,7,8-hexafluoronaphthalene-2,6-dialdehyde, 1-trifluoromethylnaphthalene-2,6-dialdehyde, 1,5-bis(trifluoromethyl)naphthalene-2,6-dialdehyde, 1-trifluoromethylnaphthalene-3,7-dialdehyde, 1,5-bis(trifluoromethyl)naphthalene-3,7-dialdehyde, 1-trifluoromethyl-2,4,5,6,8-pentafluoronaphthalene-3,7-dialdehyde, 1-bis(trifluoromethyl)methoxy-2,4,5,6,8-pentafluoronaphthalene-3,7-dialdehyde, 1,5-bis(trifluoromethyl)-2,4,6,8-tetrafluoronaphthalene-3,7-dialdehyde, and 1,5-bis[bis(trifluoromethyl)methoxy]-2,4,6,8-tetrafluoronaphthalene-3,7-dialdehyde, etc.

[0252] Specific examples of 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'-difluorobiphenyl-3,4'-dialdehyde, 6,6'-difluorobiphenyl-4,4'-dialdehyde, 6,6'-ditrifluoromethylbiphenyl-2,2'-dialdehyde, 6,6'-ditrifluoromethylbiphenyl-2,4'-dialdehyde, 6,6'-ditrifluoromethylbiphenyl-3,3'-dialdehyde, 6,6'-ditrifluoromethylbiphenyl-3,4'-dialdehyde, and 6,6'-ditrifluoromethylbiphenyl-4,4'-dialdehyde, etc.

[0253] Specific examples of 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, etc.

[0254] Specific examples of diphenyl sulfone dialdehydes include diphenyl sulfone-3,3'-dialdehyde, diphenyl sulfone-3,4'-dialdehyde, and diphenyl sulfone-4,4'-dialdehyde, etc.

[0255] Specific examples of diphenyl sulfide dialdehydes include diphenyl sulfide-3,3'-dialdehyde, diphenyl sulfide-3,4'-dialdehyde, and diphenyl sulfide-4,4'-dialdehyde, etc.

[0256] Specific examples of diphenyl ketone dialdehydes include diphenyl ketone-3,3'-dialdehyde, diphenyl ketone-3,4'-dialdehyde, and diphenyl ketone-4,4'-dialdehyde, etc.

[0257] Specific examples of bis(formylphenoxy)benzenes include 1,3-bis(3-formylphenoxy)benzene, 1,4-bis(3-formylphenoxy)benzene, and 1,4-bis(4-formylphenoxy)benzene, etc.

[0258] Specific examples of [1,4-phenylenebis(1-methylethylidene)]bisbenzaldehydes include 3,3'-[1,4-phenylenebis(1-methylethylidene)]bisbenzaldehyde, 3,4'-[1,4-phenylenebis(1-methylethylidene)]bisbenzaldehyde, and 4,4'-[1,4-phenylenebis(1-methylethylidene)]bisbenzaldehyde, etc.

[0259] Specific examples of 2,2-bis[4-(formylphenoxy)phenyl]propane compounds include 2,2-bis[4-(2-formylphenoxy)phenyl]propane, 2,2-bis[4-(3-formylphenoxy)phenyl]propane, 2,2-bis[4-(4-formylphenoxy)phenyl]propane, 2,2-bis[4-(3-formylphenoxy)phenyl]hexafluoropropane, and 2,2-bis[4-(4-formylphenoxy)phenyl]hexafluoropropane, etc.

[0260] Specific examples of bis[4-(formylphenoxy)phenyl]sulfide compounds include bis[4-(3-formylphenoxy)phenyl]sulfide, and bis[4-(4-formylphenoxy)phenyl]sulfide, etc.

[0261] Specific examples of bis[4-(formylphenoxy)phenyl]sulfone compounds include bis[4-(3-formylphenoxy)phenyl]sulfone, and bis[4-(4-formylphenoxy)phenyl]sulfone, etc.

[0262] Specific examples of fluorene-containing dialdehydes include fluorene-2,6-dialdehyde, fluorene-2,7-dialdehyde, dibenzofuran-3,7-dialdehyde, 9,9-bis(4-formylphenyl)fluorene, 9,9-bis(3-formylphenyl)fluorene, and 9-(3-formylphenyl)-9-(4'-formylphenyl)fluorene, etc.

[0263] In addition, diphenylalkanedialdehydes or diphenylfluoroalkanedialdehydes represented by the following formula can also be suitably used as aromatic dialdehyde compounds. [Chemical formula]

[0264] Furthermore, compounds having an imide bond represented by the following formula can also be suitably used as aromatic dialdehyde compounds. [Chem.]

[0265] When the dicarbonyl compound represented by the formula (a2-I) is an alicyclic dialdehyde containing an alicyclic group, suitable examples thereof include cyclohexane-1,4-dialdehyde, cyclohexane-1,3-dialdehyde, bicyclo[2.2.1]heptane-2,5-dialdehyde, bicyclo[2.2.2]octane-2,5-dialdehyde, bicyclo[2.2.2]oct-7-ene-2,5-dialdehyde, bicyclo[2.2.1]heptane-2,3-dialdehyde, bicyclo[2.2.1]hept-5-ene-2,3-dialdehyde, tricyclo[5.2.1.0 2,6 decane-3,4-dialdehyde, tricyclo[5.2.1.0 2,6Deca-4-en-8,9-dialdehyde, perhydro-2,3-naphthalenedialdehyde, perhydro-1,4-naphthalenedialdehyde, perhydro-1,6-naphthalenedialdehyde, perhydro-1,4-methanonaphthalene-2,3-dialdehyde, perhydro-1,4-methanonaphthalene-2,7-dialdehyde, perhydro-1,4-methanonaphthalene-7,8-dialdehyde, perhydro-1,4:5,8-dimethanonaphthalene-2,3-dialdehyde, perhydro-1,4:5,8-dimethanonaphthalene-2,7-dialdehyde, perhydro-1,4:5,8:9,10-trimethanoanthracene-2,3-dialdehyde, bicyclohexyl-4,4'-dialdehyde, dicyclohexyl ether-3,4'-dialdehyde, dicyclohexylmethane-3,3'-dialdehyde, dicyclohexylmethane-3,4'-dialdehyde, dicyclohexylmethane-4,4'-dialdehyde, dicyclohexyl difluoromethane-3,3'-dialdehyde, dicyclohexyl difluoromethane-3,4'-dialdehyde, dicyclohexyl difluoromethane-4,4'-dialdehyde, dicyclohexyl sulfone-3,3'-dialdehyde, dicyclohexyl sulfone-3,4'-dialdehyde, dicyclohexyl sulfone-4,4'-dialdehyde, dicyclohexyl sulfide-3,3'-dialdehyde, dicyclohexyl sulfide-3,4'-dialdehyde, dicyclohexyl sulfide-4,4'-dialdehyde, dicyclohexyl ketone-3,3'-dialdehyde, dicyclohexyl ketone-3,4'-dialdehyde, dicyclohexyl ketone-4,4'-dialdehyde, 2,2-bis(3-formylcyclohexyl)propane, 2,2-bis(4-formylcyclohexyl)propane, 2,2-bis(3-formylcyclohexyl)hexafluoropropane, 2,2-bis(4-formylcyclohexyl)hexafluoropropane, 1,3-bis(3-formylcyclohexyl)benzene, 1,4-bis(3-formylcyclohexyl)benzene, 1,4-bis(4-formylcyclohexyl)benzene, 3,3'-[1,4-cyclohexylenebis(1-methylethylidene)]biscyclohexanecarbaldehyde, 3,4'-[1,4-Cyclohexylenebis(1-methylethylidene)]bis-cyclohexanecarbaldehyde, 4,4'-[1,4-cyclohexylenebis(1-methylethylidene)]bis-cyclohexanecarbaldehyde, 2,2-bis[4-(3-formylcyclohexyl)cyclohexyl]propane, 2,2-bis[4-(4-formylcyclohexyl)cyclohexyl]propane, 2,2-bis[4-(3-formylcyclohexyl)cyclohexyl]hexafluoropropane, 2,2-bis[4-(4-formylphenoxy)cyclohexyl]hexafluoropropane, bis[4-(3-formylcyclohexyloxy)cyclohexyl]sulfide, bis[4-(4-formylcyclohexyloxy)cyclohexyl]sulfide, bis[4-(3-formylcyclohexyloxy)cyclohexyl]sulfone, bis[4-(4-formylcyclohexyloxy)cyclohexyl]sulfone, 2,2'-bicyclo[2.2.1]heptane-5,6'-dialdehyde, 2,2'-bicyclo[2.2.1]heptane-6,6'-dialdehyde, and 1,3-diformyladamantane, etc. may be mentioned.,

[0266] Among the dialdehyde compounds described above, isophthalaldehyde is preferred because it is easy to synthesize and obtain, and it is easy to obtain a polybenzoxazole precursor that gives a polybenzoxazole resin excellent in heat resistance and mechanical properties.,

[0267] (Dicarboxylic acid dichloride) The dicarboxylic acid dichloride used as a raw material for the polybenzoxazole precursor is a compound represented by the following formula (a2-II). The dicarboxylic acid dichloride may be used alone or in combination of two or more kinds.,

Chemical formula

[0268] In formula (a2-II), Hal is preferably chlorine, bromine, or iodine, more preferably chlorine.

[0269] Preferred compounds as the compound represented by formula (a2-II) include compounds in which the two aldehyde groups of the compounds described above as preferred examples of the dialdehyde compound are substituted with a halocarbonyl group, preferably a chlorocarbonyl group.

[0270] Among the dicarboxylic acid dihalides described above, terephthaloyl dichloride is preferred because it is easy to synthesize and obtain, and it is easy to obtain a polybenzoxazole precursor that gives a polybenzoxazole resin excellent in heat resistance and mechanical properties.

[0271] (Solvent) 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 aforementioned formula (S01).

[0272] When synthesizing a polybenzoxazole precursor using a solvent containing the compound represented by the aforementioned formula (S01), even when the polybenzoxazole precursor is heat-treated at a low temperature, it is possible to produce a polybenzoxazole resin excellent in mechanical properties such as tensile elongation and chemical resistance while suppressing a decrease in transparency due to coloring of the resin when heating the polybenzoxazole precursor.

[0273] In addition, when producing a polybenzoxazole resin by heating a polybenzoxazole precursor synthesized using a solvent containing the compound represented by the aforementioned formula (S01), the occurrence of defects such as swelling, cracking, and foaming on the surface of the polybenzoxazole resin can be suppressed. Therefore, when producing a film of a polybenzoxazole resin by heating a film containing a polybenzoxazole precursor synthesized using a solvent containing the compound represented by the formula (S01), it is easy to produce a film with excellent appearance without defects such as cracks, blisters, and pinholes.

[0274] Suitable examples of the compound represented by the formula (S01) are as described above.

[0275] Among the compounds represented by the formula (S01), N,N,2-trimethylpropionamide and N,N,N',N'-tetramethylurea are particularly preferred. The boiling point of N,N,2-trimethylpropionamide under atmospheric pressure is 175 °C, and the boiling point of N,N,N',N'-tetramethylurea under atmospheric pressure is 177 °C. Thus, N,N,2-trimethylpropionamide and N,N,N',N'-tetramethylurea have relatively low boiling points among solvents capable of dissolving aromatic diamine diols, dicarbonyl compounds, and the resulting polybenzoxazole precursor. Therefore, when forming a polybenzoxazole resin using a polybenzoxazole precursor synthesized using a solvent containing at least one selected from N,N,2-trimethylpropionamide and N,N,N',N'-tetramethylurea, when heating the polybenzoxazole precursor, it is difficult for the solvent to remain in the resulting polybenzoxazole resin, and it is difficult to cause a decrease in the tensile elongation of the obtained polybenzoxazole resin.

[0276] Furthermore, N,N,2-trimethylpropionamide and N,N,N',N'-tetramethylurea are also useful in that they are substances with low toxicity so as not to be designated as SVHC (Substance of Very High Concern), substances of concern for toxicity, in the REACH regulation in the EU (European Union).

[0277] When the solvent used for the preparation of the polybenzoxazole precursor contains a compound represented by the formula (S01), the content of the compound represented by the formula (S01) in the solvent is preferably 70% by mass or more, more preferably 80% by mass or more, particularly preferably 90% by mass or more, and most preferably 100% by mass.

[0278] When the solvent contains a compound represented by the formula (S01), examples of the organic solvent that can be used together with the compound represented by the formula (S01) include nitrogen-containing polar solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, hexamethylphosphoramide, and 1,3-dimethyl-2-imidazolidinone; ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and isophorone; esters such as γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone, ε-caprolactone, α-methyl-γ-butyrolactone, ethyl lactate, methyl acetate, ethyl acetate, and n-butyl acetate; cyclic ethers such as dioxane and tetrahydrofuran; cyclic esters such as ethylene carbonate and propylene carbonate; aromatic hydrocarbons such as toluene and xylene; and sulfoxides such as dimethyl sulfoxide.

[0279] (Method for producing polybenzoxazole precursor) The polybenzoxazole precursor is produced by reacting the aforementioned aromatic diamine diol and the dicarbonyl compound in a solvent according to a well-known method. Hereinafter, as typical examples of the method for producing the polybenzoxazole precursor, the production method when the dicarbonyl compound is a dialdehyde compound and the production method when the dicarbonyl compound is a dicarboxylic acid halide will be described.

[0280] · Reaction of aromatic diamine diol and dialdehyde compound The reaction between the aromatic diamine diol and the 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 usually, it is 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.

[0281] The reaction between the aromatic diamine diol and the dialdehyde compound may be carried out while adding an entrainer to the solvent and refluxing to remove water. The entrainer is not particularly limited and is appropriately selected from organic solvents that form an azeotropic mixture with water and form a two-phase system with water at room temperature. Preferred examples of the entrainer include esters such as isobutyl acetate, allyl acetate, n-propyl propionate, isopropyl propionate, n-butyl propionate, and isobutyl propionate; ethers such as dichloromethyl ether and ethyl isoamyl ether; ketones such as ethyl propyl ketone; and aromatic hydrocarbons such as toluene.

[0282] The reaction time between the aromatic diamine diol and the dialdehyde compound is not particularly limited, but typically, it is preferably about 2 hours or more and 72 hours or less.

[0283] When producing the polybenzoxazole precursor, the amount of the dialdehyde compound used is preferably 0.5 mol or more and 1.5 mol or less, more preferably 0.7 mol or more and 1.3 mol or less, per 1 mol of the aromatic diamine diol.

[0284] The amount of the solvent used is not particularly limited as long as the reaction between the aromatic diamine diol and the dialdehyde compound proceeds well. Typically, a solvent with a mass 1 time or more and 40 times or less, preferably 1.5 times or more and 20 times or less, the total mass of the aromatic diamine diol and the dialdehyde compound is used.

[0285] The reaction between the aromatic diamine diol and the dialdehyde compound is carried out until the number average molecular weight of the resulting polybenzoxazole precursor is preferably 1000 or more and 20000 or less, more preferably 1200 or more and 5000 or less.

[0286] · Reaction between aromatic diamine diol and dicarboxylic acid dihalide The reaction temperature for reacting the aromatic diamine diol and the dicarboxylic acid dihalide is not particularly limited, but usually, -20°C or higher and 150°C or lower is preferable, -10°C or higher and 150°C or lower is more preferable, and -5°C or higher and 70°C or lower is particularly preferable. In the reaction between the aromatic diamine diol and the dicarboxylic acid dihalide, hydrogen halide is by-produced. In order to neutralize such hydrogen halide, 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 may be added in a small amount to the reaction solution.

[0287] The reaction time between the aromatic diamine diol and the dicarboxylic acid dihalide is not particularly limited, but typically about 2 hours or more and 72 hours or less is preferable.

[0288] When producing the polybenzoxazole precursor, the amount of the dicarboxylic acid dihalide used is preferably 0.5 mol or more and 1.5 mol or less, more preferably 0.7 mol or more and 1.3 mol or less, per 1 mol of the aromatic diamine diol.

[0289] The amount of the solvent used is not particularly limited as long as the reaction between the aromatic diamine diol and the dicarboxylic acid dihalide proceeds well. Typically, a solvent having a mass of 1 time or more and 40 times or less, preferably 1.5 times or more and 20 times or less, the total mass of the aromatic diamine diol and the dicarboxylic acid dihalide is used.

[0290] The reaction between the aromatic diamine diol and the dicarboxylic acid dihalide is carried out until the number average molecular weight of the resulting polybenzoxazole precursor is preferably 1000 or more and 20000 or less, more preferably 1200 or more and 5000 or less.

[0291] By the method described above, a solution of the polybenzoxazole precursor is obtained. When preparing a modified metal oxide fine particle dispersion containing the polybenzoxazole precursor as the base material component (C), the solution of the polybenzoxazole precursor may be used as it is. Also, at a low temperature such that the conversion of the polybenzoxazole precursor to the polybenzoxazole resin does not occur under reduced pressure, at least a part of the solvent is removed from the solution of the polybenzoxazole precursor, and the paste or solid of the polybenzoxazole precursor thus obtained can also be used for the preparation of the modified metal oxide fine particle dispersion.

[0292] [Polybenzothiazole Precursor] The polybenzothiazole precursor is typically produced by reacting an aromatic diamine dithiol with a dicarbonyl compound having a specific structure. As the aromatic diamine dithiol, a compound in which the hydroxyl group of the aromatic diamine diol used for the synthesis of the polybenzoxal precursor is substituted with a mercapto group can be used. As the dicarbonyl compound, a compound similar to the dicarbonyl compound used for the synthesis of the polybenzoxazole precursor can be used.

[0293] The reaction method, reaction conditions, etc. when synthesizing the polybenzothiazole precursor by reacting the aromatic diamine dithiol with the dicarbonyl compound are the same as those in the case of synthesizing the polybenzoxazole precursor by reacting the aromatic diamine diol with the dicarbonyl compound.

[0294] [Polybenzimidazole Precursor] The polybenzimidazole precursor is typically produced by reacting an aromatic tetraamine with a dicarboxylic acid dihalide. As the aromatic tetraamine, a compound in which the hydroxyl group of the aromatic diamine diol used for the synthesis of the polybenzoxazole precursor is substituted with an amino group can be used. As the dicarboxylic acid dihalide, a compound similar to the dicarboxylic acid dihalide used for the synthesis of the polybenzoxazole precursor can be used.

[0295] When synthesizing a polybenzimidazole precursor by reacting an aromatic tetraamine with a dicarboxylic acid dihalide, the reaction method, reaction conditions, etc. are the same as those in the case of synthesizing a polybenzoxazole precursor by reacting an aromatic diamine diol with a dicarboxylic acid dihalide.

[0296] [Styrene-maleic acid copolymer] The type of styrene-maleic acid copolymer is not particularly limited as long as it does not inhibit the object of the present invention. In the styrene-maleic acid copolymer, the copolymerization ratio (mass ratio) of styrene / maleic acid is preferably 1 / 9 or more and 9 / 1 or less, more preferably 2 / 8 or more and 8 / 1 or less, and particularly preferably 1 / 1 or more and 8 / 1 or less. The molecular weight of the styrene-maleic acid copolymer is not particularly limited, but is preferably 1000 or more and 100000 or less, more preferably 5000 or more and 12000 or less, as the mass average molecular weight in terms of polystyrene.

[0297] [Epoxy group-containing resin] When using an epoxy group-containing resin as the base material component (C), by heating the modified metal oxide fine particle dispersion formed into a desired shape in the presence of a curing agent and a curing accelerator as needed, the epoxy groups of the epoxy group-containing resin are crosslinked with each other. As a result, a cured product excellent in 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 epoxy groups.

[0298] 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 may also be a resin obtained by introducing an epoxy group into a polymer having a functional group with reactivity such as a hydroxyl group, a carboxyl group, or an amino group using a compound having an epoxy group such as epichlorohydrin. Since it is easy to obtain, prepare, and adjust the amount of epoxy groups in the polymer, as the polymer having an epoxy group, a polymer obtained by polymerizing a monomer having an epoxy group or a monomer mixture containing a monomer having an epoxy group is preferred.

[0299] Preferable examples of the epoxy group-containing resin include novolak epoxy resins such as phenol novolak type epoxy resin, brominated phenol novolak type epoxy resin, orthocresol novolak type epoxy resin, bisphenol A novolak type epoxy resin, and bisphenol AD novolak type epoxy resin; cycloaliphatic epoxy resins such as epoxidized products of dicyclopentadiene type phenol resins; and aromatic epoxy resins such as epoxidized products of naphthalene type phenol resins.

[0300] Among the epoxy group-containing resins, a homopolymer of a (meth)acrylate having an epoxy group or a copolymer of a (meth)acrylate having an epoxy group and another monomer is preferred because the preparation is easy and the physical properties of the metal oxide particle-containing film can be easily adjusted.

[0301] (Meth)acrylic acid esters having an epoxy group may be (meth)acrylic acid esters having an aliphatic epoxy group in a chain or (meth)acrylic acid esters having an alicyclic epoxy group as described below. Further, the (meth)acrylic acid esters having an epoxy group may contain an aromatic group. Among the (meth)acrylic acid esters having an epoxy group, aliphatic (meth)acrylic acid esters having an aliphatic epoxy group in a chain or aliphatic (meth)acrylic acid esters 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, aliphatic (meth)acrylic acid esters having an alicyclic epoxy group containing a polycyclic structure in the ring structure of the alicyclic epoxy group are even more preferable.

[0302] Examples of the (meth)acrylic acid esters containing an aromatic group and having an epoxy group include 4-glycidyloxyphenyl (meth)acrylate, 3-glycidyloxyphenyl (meth)acrylate, 2-glycidyloxyphenyl (meth)acrylate, 4-glycidyloxyphenylmethyl (meth)acrylate, 3-glycidyloxyphenylmethyl (meth)acrylate, and 2-glycidyloxyphenylmethyl (meth)acrylate.

[0303] Examples of the aliphatic (meth)acrylic acid esters having an aliphatic epoxy group in a chain include (meth)acrylic acid esters in which an aliphatic epoxy group in a chain is bonded to an oxygen group (-O-) in an ester group (-O-CO-), such as epoxyalkyl (meth)acrylate and epoxyalkyloxyalkyl (meth)acrylate. The aliphatic epoxy group in such a (meth)acrylic acid ester may contain one or more oxygen groups (-O-) in the chain. The number of carbon atoms of the aliphatic epoxy group in a chain 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.

[0304] Specific examples of the aliphatic (meth)acrylate having a chain-like aliphatic epoxy group include epoxyalkyl (meth)acrylates such as glycidyl (meth)acrylate, 2-methylglycidyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, 6,7-epoxyheptyl (meth)acrylate; and epoxyalkyloxyalkyl (meth)acrylates such as 2-glycidyloxyethyl (meth)acrylate, 3-glycidyloxy-n-propyl (meth)acrylate, 4-glycidyloxy-n-butyl (meth)acrylate, 5-glycidyloxy-n-hexyl (meth)acrylate, 6-glycidyloxy-n-hexyl (meth)acrylate.

[0305] Specific examples of the aliphatic (meth)acrylate having an alicyclic epoxy group include, for example, compounds represented by the following formulas (a05-1) to (a05-15). Among these, compounds represented by the following formulas (a05-1) to (a05-5) are preferable, and compounds represented by the following formulas (a05-1) to (a05-2) are more preferable. Also, regarding each of these compounds, the bonding site of the oxygen atom of the ester group to the alicyclic ring is not limited to the positions shown here, and may include some positional isomers.

[0306]

Chemical formula

[0307]

Chemical formula

[0308]

Chemical formula

[0309] In the above formula, 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 a034represents a divalent hydrocarbon group having 1 to 10 carbon atoms, and t 0 represents an integer of 0 to 10. R a033 is preferably a linear or branched alkylene group, such as a methylene group, an ethylene group, a propylene group, a tetramethylene group, an ethylethylene group, a pentamethylene group, a hexamethylene group. R a034 is preferably, 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, a cyclohexylene group.

[0310] As the polymer having an epoxy group, either a homopolymer of (meth)acrylate having an epoxy group or a copolymer of (meth)acrylate having an epoxy group and another monomer can be used. However, the content of the unit derived from (meth)acrylate 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, preferably 10% by mass or more and 90% by mass or less, more preferably 30% by mass or more and 80% by mass or less, and particularly preferably 50% by mass or more and 75% by mass or less.

[0311] When the polymer having an epoxy group is a copolymer of (meth)acrylate having an epoxy group and another monomer, examples of the other monomer include unsaturated carboxylic acids, (meth)acrylates having no epoxy group, (meth)acrylamides, allyl compounds, vinyl ethers, vinyl esters, styrenes, etc. These compounds can be used alone or in combination of two or more. From the viewpoint of the storage stability of the modified metal oxide fine particle dispersion liquid and the chemical resistance of articles such as films formed using the modified metal oxide fine particle dispersion liquid to alkalis, etc., the copolymer of (meth)acrylate having an epoxy group and another monomer preferably does not contain a unit derived from an unsaturated carboxylic acid.

[0312] Examples of unsaturated carboxylic acids include (meth)acrylic acid; (meth)acrylamide; crotonic acid; maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, and anhydrides of these dicarboxylic acids.

[0313] Examples of (meth)acrylate esters having no epoxy group include linear or branched alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, amyl (meth)acrylate, tert-octyl (meth)acrylate; chloroethyl (meth)acrylate, 2,2-dimethylhydroxypropyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, trimethylolpropane mono(meth)acrylate, benzyl (meth)acrylate, furfuryl (meth)acrylate; (meth)acrylate esters having a group with an alicyclic skeleton. Among the (meth)acrylate esters having no epoxy group, (meth)acrylate esters having a group with an alicyclic skeleton are preferred.

[0314] In the (meth)acrylate ester having a group with an alicyclic skeleton, the alicyclic group constituting the alicyclic skeleton may be a monocyclic or polycyclic group. Examples of the monocyclic alicyclic group include a cyclopentyl group and a cyclohexyl group. Examples of the polycyclic alicyclic group include a norbornyl group, an isobornyl group, a tricyclononyl group, a tricyclodecyl group, and a tetracyclododecyl group.

[0315] Examples of the (meth)acrylate ester having a group with an alicyclic skeleton include compounds represented by the following formulas (a06-1) to (a06-8). Among these, compounds represented by the following formulas (a06-3) to (a06-8) are preferred, and compounds represented by the following formula (a06-3) or (a06-4) are more preferred.

[0316]

Chemical formula

[0317] [Chemical]

[0318] In the above formula, R a035 represents a hydrogen atom or a methyl group, and R a036 represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, and R a037 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. As R a036 , a single bond, a linear or branched alkylene group, such as a methylene group, an ethylene group, a propylene group, a tetramethylene group, an ethylethylene group, a pentamethylene group, or a hexamethylene group, is preferable. As R a037 , a methyl group or an ethyl group is preferable.

[0319] 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.

[0320] Examples of allyl compounds include allyl esters such as allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, and allyl lactate; allyloxyethanol; and the like.

[0321] Examples of vinyl ethers include aliphatic vinyl ethers such as hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl ether, 2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether; vinyl aryl ethers such as vinyl phenyl ether, vinyl tolyl ether, vinyl chlorophenyl ether, vinyl-2,4-dichlorophenyl ether, vinyl naphthyl ether, vinyl anthranyl ether; etc.

[0322] Examples of vinyl esters include vinyl butyrate, vinyl isobutyrate, vinyl trimethylacetate, vinyl diethylacetate, vinyl valerate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxyacetate, vinyl butoxyacetate, vinyl phenylacetate, vinyl acetoacetate, vinyl lactate, vinyl-β-phenylbutyrate, vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, vinyl naphthoate, etc.

[0323] Examples of styrenes include styrene; alkylstyrenes such as methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, isopropylstyrene, butylstyrene, hexylstyrene, cyclohexylstyrene, decylstyrene, benzylstyrene, chloromethylstyrene, trifluoromethylstyrene, ethoxymethylstyrene, acetoxymethylstyrene; alkoxystyrenes such as methoxystyrene, 4-methoxy-3-methylstyrene, dimethoxystyrene; halostyrenes such as chlorostyrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethylstyrene, 4-fluoro-3-trifluoromethylstyrene; and the like.

[0324] The molecular weight of the epoxy group-containing resin is not particularly limited as long as it does not inhibit the object of the present invention, but is preferably 3,000 or more and 30,000 or less, more preferably 5,000 or more and 15,000 or less, in terms of the mass average molecular weight in terms of polystyrene.

[0325] [Resin that forms a cured film by firing] As described above, a resin that forms a cured film by firing is also preferable as a precursor resin as the base material component (C). Examples of the resin that forms a cured film by firing include, for example, silicon-containing resins. Preferable examples of the silicon-containing resin include one or more selected from siloxane resins and polysilanes. A metal oxide fine particle-containing film containing a silicon-containing resin can be obtained by applying a modified metal oxide fine particle dispersion liquid containing these silicon-containing resins. The modified metal oxide fine particle dispersion liquid, which is a silicon-containing resin composition, will be described in detail later.

[0326] When using the above-mentioned thermosetting material or a resin that forms a cured film by firing as the base material component (C), the modified metal oxide fine particle dispersion may contain additives such as a curing agent, a curing accelerator, a dehydration condensing agent, an antioxidant, an ultraviolet absorber, a flame retardant, a mold release agent, a plasticizer, a filler, and a reinforcing material, as necessary. Also, in order to facilitate film formation, the modified metal oxide fine particle dispersion preferably contains a solvent. The type of the solvent is appropriately selected according to the type of the thermosetting material.

[0327] As the modified metal oxide fine particle dispersion, in addition to the non-energizing composition containing a non-thermosetting resin as the base material component (C) and the heat-sensitive composition containing a thermosetting material as the base material component (C) described above, a photosensitive composition known as a so-called photoresist composition is also preferable. Since it contains well-dispersed metal oxide fine particles and is easy to form articles such as films containing metal oxide fine particles excellent in heat resistance and chemical resistance, the modified metal oxide fine particle dispersion is preferably an energy-sensitive composition having heat sensitivity and / or photosensitivity.

[0328] A modified metal oxide fine particle dispersion which is an energy-sensitive composition can be obtained by adding metal oxide fine particles containing a desired amount of modified metal oxide fine particles to various conventionally known energy-sensitive compositions. Conventionally known energy-sensitive compositions contain various thermosetting or photocurable compounds, an alkali-soluble resin, a resin whose solubility in alkali increases when exposed, etc. as the base material component (C). The photosensitive modified metal oxide fine particle dispersion may be a negative-type photosensitive composition that becomes insoluble in a developer upon exposure, or a positive-type photosensitive composition that becomes soluble in a developer upon exposure. Hereinafter, a suitable energy-sensitive composition and a silicon-containing resin composition which is a suitable example of a composition containing a resin that forms a cured film by firing will be described.

[0329] (1) The energy-sensitive composition of the first aspect The energy-sensitive composition of the first aspect is a negative photosensitive composition containing metal oxide fine particles including modified metal oxide fine particles, and an organic solvent, together with an alkali-soluble resin, a photopolymerizable compound, and a photoinitiator. In the energy-sensitive composition of the first aspect, the alkali-soluble resin and the photopolymerizable compound correspond to the base material component (C).

[0330] The energy-sensitive composition of the first aspect may contain, as the alkali-soluble resin as described later, a (meth)acrylic resin obtained by polymerizing (meth)acrylic acid, (meth)acrylic acid ester, etc. For example, when incorporating metal oxide fine particles subjected to a coating treatment as described in Patent Document 1 into a composition containing a (meth)acrylic resin, the metal oxide fine particles may not disperse 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.

[0331] 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 or may not have an ethylenically unsaturated group. In this specification, the alkali-soluble resin means a resin that, when a resin film with a thickness of 1 μm is formed on a substrate using a resin solution with a resin concentration of 20% by mass (solvent: propylene glycol monomethyl ether acetate) and immersed in a 2.38% by mass aqueous solution of tetramethylammonium hydroxide (TMAH) for 1 minute, dissolves with a film thickness of 0.01 μm or more.

[0332] As the alkali-soluble resin having an ethylenically unsaturated group, for example, a resin obtained by reacting a reaction product of an epoxy compound and an unsaturated carboxylic acid with a polybasic acid anhydride can be used.

[0333] Among them, 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 itself.

[0334]

Chemical formula

[0335] In the above formula (a-1), X a represents a group represented by the following formula (a-2).

[0336]

Chemical formula

[0337] In the above formula (a-2), R a1 each independently represents a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a halogen atom, and R a2 each independently represents a hydrogen atom or a methyl group, and W a represents a single bond or a group represented by the following formula (a-3).

[0338]

Chemical formula

[0339] In the above formula (a-1), Y a represents a residue obtained by removing the acid anhydride group (-CO-O-CO-) from a dicarboxylic anhydride. Examples of the dicarboxylic anhydride include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylendomethylene tetrahydrophthalic anhydride, chlorendic anhydride, methyltetrahydrophthalic anhydride, glutaric anhydride, and the like.

[0340] In the above formula (a-1), Z arepresents the residue obtained by removing two acid anhydride groups from a tetracarboxylic dianhydride. Examples of the tetracarboxylic dianhydride include pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, biphenyl ether tetracarboxylic dianhydride, and the like. In the above formula (a-1), m represents an integer of 0 or more and 20 or less.

[0341] Examples of the alkali-soluble resin having an ethylenically unsaturated group include polyester (meth)acrylate obtained by reacting a polyester prepolymer obtained by condensing polyhydric alcohols and a monobasic acid or polybasic acid with (meth)acrylic acid; polyurethane (meth)acrylate obtained by reacting a polyol and a compound having two isocyanate groups and then reacting with (meth)acrylic acid; epoxy (meth)acrylate resin obtained by reacting an epoxy resin such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol or cresol novolak 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, dihydroxybenzene type epoxy resin, etc. with (meth)acrylic acid, and the like can also be used. In this specification, “(meth)acrylic acid” means both acrylic acid and methacrylic acid. Similarly, “(meth)acrylate” means both acrylate and methacrylate.

[0342] On the other hand, as the alkali-soluble resin having no ethylenically unsaturated group, a resin obtained by copolymerizing an unsaturated carboxylic acid and another unsaturated compound can be used. As 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.

[0343] 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; anhydrides of these dicarboxylic acids; and the like. Among these, (meth)acrylic acid and maleic anhydride are preferred from the viewpoints of copolymerization reactivity, alkali solubility of the resulting resin, ease of availability, and the like. These unsaturated carboxylic acids can be used alone or in combination of two or more.

[0344] 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 the compounds represented by the aforementioned formulas (a05-1) to (a05-15). Examples of the epoxy group-containing unsaturated compound having no alicyclic group include epoxyalkyl (meth) acrylates such as glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, and 6,7-epoxyheptyl (meth) acrylate; epoxyalkyloxyalkyl (meth) acrylates such as 2-glycidyloxyethyl (meth) acrylate, 3-glycidyloxy-n-propyl (meth) acrylate, 4-glycidyloxy-n-butyl (meth) acrylate, 5-glycidyloxy-n-pentyl (meth) acrylate, and 6-glycidyloxy-n-hexyl (meth) acrylate; epoxyalkyl esters of α-alkylacrylic acids such as glycidyl α-ethylacrylate, glycidyl α-n-propylacrylate, glycidyl α-n-butylacrylate, and 6,7-epoxyheptyl α-ethylacrylate; glycidyl ethers such as o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, and p-vinylbenzyl glycidyl ether; and the like. Among these, glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, 6,7-epoxyheptyl (meth) acrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, and p-vinylbenzyl glycidyl ether are preferred from the viewpoints of copolymerization reactivity, strength of the resin after curing, and the like. These epoxy group-containing unsaturated compounds can be used alone or in combination of two or more.

[0345] 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, and a tetracyclododecyl group. Specifically, examples of the alicyclic group-containing unsaturated compound include the compounds represented by the aforementioned formulas (a06-1) to (a06-8).

[0346] It is also preferable to further polymerize other compounds with respect to the unsaturated carboxylic acid. Examples of such other compounds include (meth)acrylate 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.

[0347] Regarding other compounds, preferred examples of (meth)acrylamides, allyl compounds, vinyl ethers, vinyl esters, and styrenes are the same as the preferred examples of (meth)acrylamides, allyl compounds, vinyl ethers, vinyl esters, and styrenes described for the copolymer of a (meth)acrylate ester having an epoxy group and another monomer.

[0348] Examples of (meth)acrylate esters as other compounds include linear or branched alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, amyl (meth)acrylate, tert-octyl (meth)acrylate; chloroethyl (meth)acrylate, 2,2-dimethylhydroxypropyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, trimethylolpropane mono(meth)acrylate, benzyl (meth)acrylate, furfuryl (meth)acrylate; and the like.

[0349] Examples of maleimides as other compounds include maleimides N-substituted with an alkyl group having 1 to 10 carbon atoms such as N-methylmaleimide, N-ethylmaleimide, N-n-propylmaleimide, N-isopropylmaleimide, N-n-butylmaleimide, N-n-pentylmaleimide, and N-n-hexylmaleimide; maleimides N-substituted with an alicyclic group having 3 to 20 carbon atoms such as N-cyclopentylmaleimide, N-cyclohexylmaleimide, and N-cycloheptylmaleimide; N-arylmaleimides N-substituted with an aryl group having 6 to 20 carbon atoms such as N-phenylmaleimide, N-α-naphthylmaleimide, and N-β-naphthylmaleimide; and N-aralkylmaleimides N-substituted with an aralkyl group having 7 to 20 carbon atoms such as N-benzylmaleimide and N-phenethylmaleimide.

[0350] In addition, 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 copolymer having at least a structural unit derived from an unsaturated carboxylic acid, a structural unit derived from an epoxy group-containing unsaturated compound, and a structural unit having a polymerizable site with a photopolymerizable compound described later can also be suitably used as the alkali-soluble resin. When using these alkali-soluble resins, a metal oxide fine particle-containing film excellent in mechanical strength and adhesion to a substrate can be formed.

[0351] The copolymer having a structural unit having a polymerizable site with the above-mentioned photopolymerizable compound may further have one or more structural units derived from the above-mentioned (meth)acrylic esters, (meth)acrylamides, allyl compounds, vinyl ethers, vinyl esters, styrenes, maleimides, and the like.

[0352] The structural unit having a polymerizable site with a photopolymerizable compound preferably has an ethylenically unsaturated group as the polymerizable site with the photopolymerizable compound. A copolymer having such a structural unit can be prepared by reacting at least a part of the carboxy groups contained in the homopolymer of an unsaturated carboxylic acid with an epoxy group-containing unsaturated compound. Also, a copolymer having a structural unit derived from an unsaturated carboxylic acid and a structural unit derived from an epoxy group-containing unsaturated compound can be prepared by reacting at least a part of the epoxy groups in the copolymer with an unsaturated carboxylic acid to obtain a copolymer having a structural unit having a polymerizable site with a photopolymerizable compound.

[0353] 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, more preferably 5% by mass or more and 25% by mass or less. Also, 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, more preferably 50% by mass or more and 90% by mass or less. Further, 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, more preferably 3% by mass or more and 25% by mass or less, still more preferably 5% by mass or more and 20% by mass or less. By setting the above ranges, while making the alkali solubility of the resulting resin appropriate, the adhesion of the cured product of the energy-sensitive composition of the first aspect to the substrate and the strength after curing of the energy-sensitive composition of the first aspect can be enhanced.

[0354] The mass average molecular weight of the alkali-soluble resin is preferably 1000 or more and 40000 or less, more preferably 2000 or more and 30000 or less. By setting the above range, good developability can be obtained while obtaining sufficient heat resistance and film strength.

[0355] The content of the alkali-soluble resin is preferably 5% by mass or more and 80% by mass or less, 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. By setting it within the above range, the balance of developability tends to be easily achieved.

[0356] In the energy-sensitive composition of the first aspect, the photopolymerizable compound includes a monofunctional monomer and a polyfunctional monomer. Examples of the monofunctional monomer include (meth)acrylamide, methylol (meth)acrylamide, methoxymethyl (meth)acrylamide, ethoxymethyl (meth)acrylamide, propoxymethyl (meth)acrylamide, butoxymethoxymethyl (meth)acrylamide, N-methylol (meth)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-acrylamido-2-methylpropanesulfonic acid, tert-butylacrylamidosulfonic acid, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-phenoxy-2-hydroxypropyl (meth)acrylate, 2-(meth)acryloyloxy-2-hydroxypropyl phthalate, glycerin mono(meth)acrylate, tetrahydrofurfuryl (meth)acrylate, dimethylamino (meth)acrylate, glycidyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate, and half (meth)acrylate of phthalic acid derivatives. These monofunctional monomers can be used alone or in combination of two or more.

[0357] On the one hand, examples of polyfunctional monomers include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6 - hexanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, glycerin di(meth)acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 2,2 - bis(4-(meth)acryloxydiethoxyphenyl)propane, 2,2 - bis(4-(meth)acryloxypolyethoxyphenyl)propane, 2 - hydroxy - 3-(meth)acryloyloxypropyl (meth)acrylate, ethylene glycol diglycidyl ether di(meth)acrylate, diethylene glycol diglycidyl ether di(meth)acrylate, phthalic acid diglycidyl ester di(meth)acrylate, glycerin triacrylate, glycerin polyglycidyl ether poly(meth)acrylate, urethane (meth)acrylate (i.e., tolylene diisocyanate), the reaction product of trimethylhexamethylene diisocyanate, hexamethylene diisocyanate, and 2 - hydroxyethyl (meth)acrylate, methylene bis(meth)acrylamide, (meth)acrylamide methylene ether, condensates of polyhydric alcohols and N - methylol (meth)acrylamide, and other polyfunctional monomers such as triacryl formal. These polyfunctional monomers can be used alone or in combination of two or more kinds.

[0358] The content of the photopolymerizable compound is preferably 1% by mass or more and 30% by mass or less, more preferably 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. By setting it within the above range, the balance of sensitivity, developability, and resolution tends to be easily achieved.

[0359] The photoinitiator in the energy-sensitive composition of the first aspect is not particularly limited, and a conventionally known photoinitiator can be used.

[0360] Specific examples of the photoinitiator include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-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-diphenylethan-1-one, bis(4-dimethylaminophenyl) ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl], 1-(O-acetyl oxime), (9-ethyl-6-nitro-9H-carbazol-3-yl)[4-(2-methoxy-1-methylethoxy)-2-methylphenyl]methanone O-acetyl oxime, 2-(benzoyloxyimino)-1-[4-(phenylthio)phenyl]-1-octanone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 4-benzoyl-4'-methyldimethyl sulfide, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, butyl 4-dimethylaminobenzoate, 4-dimethylamino-2-ethylhexyl benzoate, 4-dimethylamino-2-isoamyl benzoic acid, benzyl-β-methoxyethyl acetal, benzyldimethyl ketal, 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl) oxime, methyl o-benzoylbenzoate, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 1-chloro-4-propoxythioxanthone, thioxanthene, 2-chlorothioxanthene, 2,4-diethylthioxanthene, 2-methylthioxanthene, 2-isopropylthioxanthene, 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-diphenylanthraquinone, azobisisobutyronitrile, benzoyl peroxide, cumene hydroperoxide, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2-(o-chlorophenyl)-4,5-di(m-methoxyphenyl)-imidazolyl dimer, benzophenone, 2-chlorobenzophenone, p,p'-bisdimethylaminobenzophenone, 4,4'-bisdiethylaminobenzophenone, 4,4'-dichlorobenzophenone, 3,3-dimethyl-4-methoxybenzophenone, benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, benzoin butyl ether, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p-tert-butylacetophenone, p-dimethylaminoacetophenone, p-tert-butyltrichloroacetophenone, p-tert-butyldichloroacetophenone, α,α-dichloro-4-phenoxyacetophenone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, dibenzosuberone, pentyl-4-dimethylaminobenzoate, 9-phenylacridine, 1,7-bis-(9-acridinyl)heptane, 1,5-bis-(9-acridinyl)pentane, 1,3-bis-(9-acridinyl)propane, p-methoxy triazine, 2,4,6-tris(trichloromethyl)-s-triazine, 2-methyl-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(5-methylfuran-2-yl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(furan-2-yl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(4-diethylamino-2-methylphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(3,4-dimethoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-n-butoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-bis-trichloromethyl-6-(3-bromo-4-methoxy)phenyl-s-triazine, 2,4-bis-trichloromethyl-6-(2-bromo-4-methoxy)phenyl-s-triazine, 2,4-bis-trichloromethyl-6-(3-bromo-4-methoxy)styrylphenyl-s-triazine, 2,4-bis-trichloromethyl-6-(2-bromo-4-methoxy)styrylphenyl-s-triazine, and the like. These photoinitiators can be used alone or in combination of two or more kinds.,

[0361] Among these, it is particularly preferable to use an oxime ester-based photoinitiator in terms of sensitivity. Among the oxime-based photoinitiators, particularly preferable compounds include O-acetyl-1-[6-(2-methylbenzoyl)-9-ethyl-9H-carbazol-3-yl]ethanone oxime, ethanone, 1-[9-ethyl-6-(pyrrole-2-carbonyl)-9H-carbazol-3-yl], 1-(O-acetoxyoxime), and 1,2-octanedione, 1-[4-(phenylthio)-, 2-(O-benzoyloxyoxime)].

[0362] As the photoinitiator, it is also preferable to use an oxime ester compound represented by the following formula (c1). [Chemical formula] (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 c3is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.)

[0363] In formula (c1), R c1 is not particularly limited as long as it does not inhibit the object of the present invention and is appropriately selected from various organic groups. Preferred examples of the case where 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, a phenyl group which may have a substituent, a phenoxy group which may have a substituent, a benzoyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, a benzoyloxy group which may have a substituent, a phenylalkyl group which may have a substituent, a naphthyl group which may have a substituent, a naphthoxy group which may have a substituent, a naphthoyl group which may have a substituent, a naphthoxycarbonyl group which may have a substituent, a naphthoyloxy group which may have a substituent, a naphthylalkyl group which may have a substituent, a heterocyclyl group which may have a substituent, an amino group, an amino group substituted with 1 or 2 organic groups, a morpholin-1-yl group, and a piperazin-1-yl group, a halogen, a nitro group, and a cyano group, etc. are mentioned. When n1 is an integer of 2 or more and 4 or less, R c1 may be the same or different. Also, the number of carbon atoms of the substituent does not include the number of carbon atoms of the substituent that the substituent further has.

[0364] R c1 When R is an alkyl group, the number of carbon atoms is preferably 1 or more and 20 or less, more preferably 1 or more and 6 or less. Also, when R c1 is an alkyl group, it may be linear or branched. R c1Specific examples of the case where R 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, an n-pentyl group, an isopentyl group, a sec-pentyl group, a tert-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an isooctyl group, a sec-octyl group, a tert-octyl group, an n-nonyl group, an isononyl group, an n-decyl group, and an isodecyl group, etc. Further, when R c1 is an alkyl group, the alkyl group may contain an ether bond (-O-) in the carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include a methoxyethyl group, an ethoxyethyl group, a methoxyethoxyethyl group, an ethoxyethoxyethyl group, a propyloxyethoxyethyl group, and a methoxypropyl group, etc.

[0365] R c1 When R is an alkoxy group, the number of carbon atoms is preferably 1 or more and 20 or less, more preferably 1 or more and 6 or less. Further, when R c1 is an alkoxy group, it may be linear or branched. When R c1 is an alkoxy group, specific examples 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, an n-pentyloxy group, an isopentyloxy group, a sec-pentyloxy group, a tert-pentyloxy group, an n-hexyloxy group, an n-heptyloxy group, an n-octyloxy group, an isooctyloxy group, a sec-octyloxy group, a tert-octyloxy group, an n-nonyloxy group, an isononyloxy group, an n-decyloxy group, and an isodecyloxy group, etc. Further, when R c1 is an alkoxy group, the alkoxy group may contain an ether bond (-O-) in the carbon chain. Examples of the alkoxy group having an ether bond in the carbon chain include a methoxyethoxy group, an ethoxyethoxy group, a methoxyethoxyethoxy group, an ethoxyethoxyethoxy group, a propyloxyethoxyethoxy group, and a methoxypropyloxy group, etc.

[0366] R c1 When R is a cycloalkyl group or a cycloalkoxy group, it preferably has 3 to 10 carbon atoms, more preferably 3 to 6 carbon atoms. R c1 Specific examples of the case where R is a cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group, etc. R c1 Specific examples of the case where R is a cycloalkoxy group include a cyclopropyloxy group, a cyclobutyloxy group, a cyclopentyloxy group, a cyclohexyloxy group, a cycloheptyloxy group, and a cyclooctyloxy group, etc.

[0367] R c1 When R is a saturated aliphatic acyl group or a saturated aliphatic acyloxy group, it preferably has 2 to 20 carbon atoms, more preferably 2 to 7 carbon atoms. R c1 Specific examples of the case where R 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, an n-hexanoyl group, an n-heptanoyl group, an n-octanoyl group, an n-nonanoyl group, an n-decanoyl group, an n-undecanoyl group, an n-dodecanoyl group, an n-tridecanoyl group, an n-tetradecanoyl group, an n-pentadecanoyl group, and an n-hexadecanoyl group, etc. R c1 Specific examples of the case where R is a saturated aliphatic acyloxy group include an acetyloxy group, a propanoyloxy group, an n-butanoyloxy group, a 2-methylpropanoyloxy group, an n-pentanoyloxy group, a 2,2-dimethylpropanoyloxy group, an n-hexanoyloxy group, an n-heptanoyloxy group, an n-octanoyloxy group, an n-nonanoyloxy group, an n-decanoyloxy group, an n-undecanoyloxy group, an n-dodecanoyloxy group, an n-tridecanoyloxy group, an n-tetradecanoyloxy group, an n-pentadecanoyloxy group, and an n-hexadecanoyloxy group, etc.

[0368] R c1When it is an alkoxycarbonyl group, the number of carbon atoms is preferably 2 or more and 20 or less, more preferably 2 or more and 7 or less. R c1 Specific examples of the case where R is an alkoxycarbonyl group include methoxycarbonyl group, ethoxycarbonyl group, n-propyloxycarbonyl group, isopropyloxycarbonyl group, n-butyloxycarbonyl group, isobutyloxycarbonyl group, sec-butyloxycarbonyl group, tert-butyloxycarbonyl group, n-pentyloxycarbonyl group, isopentyloxycarbonyl group, sec-pentyloxycarbonyl group, tert-pentyloxycarbonyl group, n-hexyloxycarbonyl group, n-heptyloxycarbonyl group, n-octyloxycarbonyl group, isooctyloxycarbonyl group, sec-octyloxylcarbonyl group, tert-octyloxycarbonyl group, n-nonyloxycarbonyl group, isononyloxycarbonyl group, n-decyloxycarbonyl group, and isodecyloxycarbonyl group, etc.

[0369] R c1 When R is a phenylalkyl group, the number of carbon atoms is preferably 7 or more and 20 or less, more preferably 7 or more and 10 or less. Also, R c1 When R is a naphthylalkyl group, the number of carbon atoms is preferably 11 or more and 20 or less, more preferably 11 or more and 14 or less. R c1 Specific examples of the case where R is a phenylalkyl group include benzyl group, 2-phenylethyl group, 3-phenylpropyl group, and 4-phenylbutyl group. R c1 Specific examples of the case where R is a naphthylalkyl group include α-naphthylmethyl group, β-naphthylmethyl group, 2-(α-naphthyl)ethyl group, and 2-(β-naphthyl)ethyl group. c1 When R is a phenylalkyl group or a naphthylalkyl group, R c1 may further have a substituent on the phenyl group or the naphthyl group.

[0370] R c1When it is a heterocyclic group, the heterocyclic group is a 5- or 6-membered monocyclic ring containing one or more N, S, O, or a heterocyclic group formed by condensation of such monocyclic rings with each other or such monocyclic rings and a benzene ring. When the heterocyclic group is a condensed ring, the number of monocyclic rings constituting the condensed ring is up to 3. Examples of the heterocyclic ring constituting such a heterocyclic group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, pyridazine, benzofuran, benzothiophene, indole, isoindole, indolizine, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalazine, cinnoline, and quinoxaline, etc. R c1 When it is a heterocyclic group, the heterocyclic group may further have a substituent.

[0371] R c1 When it is an amino group substituted with one or two organic groups, preferred examples of the organic group include 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, a phenyl group which may have a substituent, a benzoyl group which may have a substituent, a phenylalkyl group having 7 to 20 carbon atoms which may have a substituent, a naphthyl group which may have a substituent, a naphthoyl group which may have a substituent, a naphthylalkyl group having 11 to 20 carbon atoms which may have a substituent, and a heterocyclic group, etc. Specific examples of these preferred organic groups are R c1It is the same as above. Specific examples of the amino group substituted with an organic group of 1 or 2 include methylamino group, ethylamino group, diethylamino group, n-propylamino group, di-n-propylamino group, isopropylamino group, n-butylamino group, di-n-butylamino group, n-pentylamino group, n-hexylamino group, n-heptylamino group, n-octylamino group, n-nonylamino group, n-decylamino group, phenylamino group, naphthylamino group, acetylamino group, propanoylamino group, n-butanoylamino group, n-pentanoylamino group, n-hexanoylamino group, n-heptanoylamino group, n-octanoylamino group, n-decanoylamino group, benzoylamino group, α-naphthoylamino group, and β-naphthoylamino group, etc.

[0372] R c1 When the phenyl group, naphthyl group, and heterocyclyl group contained in R further have substituents, examples of the substituents include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a saturated aliphatic acyl group having 2 to 7 carbon atoms, an alkoxycarbonyl group having 2 to 7 carbon atoms, a saturated aliphatic acyloxy group having 2 to 7 carbon atoms, 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, morpholin-1-yl group, piperazin-1-yl group, halogen, nitro group, and cyano group, etc. R c1 When the phenyl group, naphthyl group, and heterocyclyl group contained in R further have substituents, the number of the substituents is not limited as long as it does not inhibit the object of the present invention, but 1 to 4 is preferable. R c1 When the phenyl group, naphthyl group, and heterocyclyl group contained in R have a plurality of substituents, the plurality of substituents may be the same or different.

[0373] R c1Among them, a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and a saturated aliphatic acyl group having 2 to 7 carbon atoms is preferable because it is chemically stable, has less steric hindrance, and is easy to synthesize an oxime ester compound. An alkyl group having 1 to 6 carbon atoms is more preferable, and a methyl group is particularly preferable.

[0374] R c1 The position where R c1 is bonded to the phenyl group is preferably the 4-position or the 5-position, more preferably the 5-position, when the position of the bond between the phenyl group to which R

[0375] R c2 is a phenyl group which may have a substituent or a carbazolyl group which may have a substituent. When 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 to 6 carbon atoms.

[0376] R c2In this case, the substituents of the phenyl group or the carbazolyl group are not particularly limited as long as they do not inhibit the object of the present invention. Examples of suitable substituents that the phenyl group or the carbazolyl group may have on a carbon atom include an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a cycloalkoxy group having 3 to 10 carbon atoms, a saturated aliphatic acyl group having 2 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, a saturated aliphatic acyloxy group having 2 to 20 carbon atoms, a phenyl group which may have a substituent, a phenoxy group which may have a substituent, a phenylthio group which may have a substituent, a benzoyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, a benzoyloxy group which may have a substituent, a phenylalkyl group having 7 to 20 carbon atoms which may have a substituent, a naphthyl group which may have a substituent, a naphthoxy group which may have a substituent, a naphthoyl group which may have a substituent, a naphthoxycarbonyl group which may have a substituent, a naphthoyloxy group which may have a substituent, a naphthylalkyl group having 11 to 20 carbon atoms which may have a substituent, a heterocyclyl group which may have a substituent, a heterocyclylcarbonyl group which may have a substituent, an amino group, an amino group substituted with 1 or 2 organic groups, a morpholin-1-yl group, and a piperazin-1-yl group, a halogen, a nitro group, and a cyano group, etc.

[0377] R c2When it is a carbazolyl group, examples of suitable substituents that the carbazolyl group may have on the nitrogen atom include 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, an alkoxycarbonyl group having 2 to 20 carbon atoms, a phenyl group which may have a substituent, a benzoyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, a phenylalkyl group having 7 to 20 carbon atoms which may have a substituent, a naphthyl group which may have a substituent, a naphthoyl group which may have a substituent, a naphthoxycarbonyl group which may have a substituent, a naphthylalkyl group having 11 to 20 carbon atoms which may have a substituent, a heterocyclyl group which may have a substituent, and a heterocyclylcarbonyl group which may have a substituent, and the like. Among these substituents, an alkyl group having 1 to 20 carbon atoms is preferred, an alkyl group having 1 to 6 carbon atoms is more preferred, and an ethyl group is particularly preferred.

[0378] Regarding the specific examples of the alkyl group, alkoxy group, cycloalkyl group, cycloalkoxy group, saturated aliphatic acyl group, alkoxycarbonyl group, saturated aliphatic acyloxy group, phenylalkyl group which may have a substituent, naphthylalkyl group which may have a substituent, heterocyclyl group which may have a substituent, and an amino group substituted with one or two organic groups with respect to the phenyl group or the substituents that the carbazolyl group may have, R c1 is the same as

[0379] R c2Among them, when the phenyl group, naphthyl group, and heterocyclyl group contained in the substituent of the phenyl group or carbazolyl group further have a substituent, examples of the substituent include an alkyl group having 1 to 6 carbon atoms; an alkoxy group having 1 to 6 carbon atoms; a saturated aliphatic acyl group having 2 to 7 carbon atoms; an alkoxycarbonyl group having 2 to 7 carbon atoms; a saturated aliphatic acyloxy group having 2 to 7 carbon atoms; a phenyl group; a naphthyl group; a benzoyl group; a naphthoyl group; a benzoyl group substituted by a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, and a phenyl 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; a piperazin-1-yl group; a halogen; a nitro group; a cyano group. When the phenyl group, naphthyl group, and heterocyclyl group contained in the substituent of the phenyl group or carbazolyl group further have a substituent, the number of the substituents is not limited as long as it does not inhibit the object of the present invention, but is preferably 1 to 4. When the phenyl group, naphthyl group, and heterocyclyl group have a plurality of substituents, the plurality of substituents may be the same or different.

[0380] R c2 Among them, from the viewpoint of easily obtaining a photopolymerization initiator having excellent sensitivity, a group represented by the following formula (c2) or (c3) is preferable, a group represented by the following formula (c2) is more preferable, and a group represented by the following formula (c2) in which A is S is particularly preferable.

[0381]

Chemical formula

[0382]

Chemical formula

[0383] When R c4 in formula (c2) is an organic group, it can be selected from various organic groups as long as it does not inhibit the object of the present invention. In formula (c2), when R c4 is an organic group, preferred examples include an alkyl group having 1 to 6 carbon atoms; an alkoxy group having 1 to 6 carbon atoms; a saturated aliphatic acyl group having 2 to 7 carbon atoms; an alkoxycarbonyl group having 2 to 7 carbon atoms; a saturated aliphatic acyloxy group having 2 to 7 carbon atoms; a phenyl group; a naphthyl group; a benzoyl group; a naphthoyl group; a benzoyl group substituted by a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, and a phenyl 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; a piperazin-1-yl group; a halogen; a nitro group; and a cyano group.

[0384] R c4 Among them, a benzoyl group; a naphthoyl group; a benzoyl group substituted by a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, and a phenyl group; a nitro group are preferred, and a benzoyl group; a naphthoyl group; a 2-methylphenylcarbonyl group; a 4-(piperazin-1-yl)phenylcarbonyl group; a 4-(phenyl)phenylcarbonyl group are more preferred.

[0385] Also, in formula (c2), 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. When n3 is 1, the bonding position of R c4 is preferably the para position with respect to the bond to which the phenyl group to which R c4 is bonded is bonded to an oxygen atom or a sulfur atom.

[0386] R in formula (c3)c5 can be selected from various organic groups as long as it does not inhibit the object of the present invention. R c5 Preferable examples of R include 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, an alkoxycarbonyl group having 2 to 20 carbon atoms, a phenyl group which may have a substituent, a benzoyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, a phenylalkyl group having 7 to 20 carbon atoms which may have a substituent, a naphthyl group which may have a substituent, a naphthoyl group which may have a substituent, a naphthoxycarbonyl group which may have a substituent, a naphthylalkyl group having 11 to 20 carbon atoms which may have a substituent, a heterocyclyl group which may have a substituent, and a heterocyclylcarbonyl group which may have a substituent, and the like.

[0387] R c5 Among them, 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.

[0388] R in formula (c3) c6 is not particularly limited as long as it does not inhibit the object of the present invention and can be selected from various organic groups. R c6 Specific examples of preferable groups as R 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 heterocyclyl group which may have a substituent. R c6 Among these groups, a phenyl group which may have a substituent is more preferable, and a 2-methylphenyl group is particularly preferable.

[0389] R c4 、R c5 、or R c6When the phenyl group, naphthyl group, and heterocyclyl group contained therein further have substituents, examples of the substituents include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a saturated aliphatic acyl group having 2 to 7 carbon atoms, an alkoxycarbonyl group having 2 to 7 carbon atoms, a saturated aliphatic acyloxy group having 2 to 7 carbon atoms, 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, a piperazin-1-yl group, a halogen, a nitro group, and a cyano group, etc. R c4 R c5 or R c6 When the phenyl group, naphthyl group, and heterocyclyl group contained therein further have substituents, the number of the substituents is not limited as long as it does not inhibit the object of the present invention, but is preferably 1 to 4. R c4 R c5 or R c6 When the phenyl group, naphthyl group, and heterocyclyl group contained therein have a plurality of substituents, the plurality of substituents may be the same or different.

[0390] R in formula (c1) c3 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. R c3 is preferably a methyl group or an ethyl group, and more preferably a methyl group.

[0391] Among the oxime ester compounds represented by formula (c1), particularly preferred compounds include the following PI-1 to PI-42.

Chemical formula

[0392]

Chemical formula

[0393]

Chemical formula

[0394] [Chemical formula]

[0395] [Chemical formula]

[0396] [Chemical formula]

[0397] In addition, an oxime ester compound represented by the following formula (c4) is also preferable as a photopolymerization initiator.

[0398] [Chemical formula] (R c7 is a hydrogen atom, a nitro group or a monovalent organic group, and R c8 and R c9 are each a chain alkyl group which may have a substituent, a cyclic organic group which may have a substituent, 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 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, n4 is an integer of 0 or more and 4 or less, and n5 is 0 or 1.)

[0399] Here, as the oxime compound for producing the oxime ester compound of the formula (c4), a compound represented by the following formula (c5) is preferable.

[0400] [Chemical formula] (R c7 , R c8 , R c9 , Rc10 n4 and n5 are the same as in formula (c4).)

[0401] In formulas (c4) and (c5), R c7 is a hydrogen atom, a nitro group or a monovalent organic group. R c7 on the fluorene ring in formula (c4) is bonded to a 6-membered aromatic ring different from the 6-membered aromatic ring bonded to the group represented by -(CO) n5 -. In formula (c4), the bonding position of R c7 to the fluorene ring is not particularly limited. When the compound represented by formula (c4) has one or more R c7 , since the synthesis of the compound represented by formula (c4) is easy, etc., it is preferable that one of the one or more R c7 is bonded to the 2-position in the fluorene ring. When there are a plurality of R c7 , the plurality of R c7 may be the same or different.

[0402] When R c7 is an organic group, R c7 is not particularly limited as long as it does not inhibit the object of the present invention, and is appropriately selected from various organic groups. Preferred examples when 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, a phenyl group which may have a substituent, a phenoxy group which may have a substituent, a benzoyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, a benzoyloxy group which may have a substituent, a phenylalkyl group which may have a substituent, a naphthyl group which may have a substituent, a naphthoxy group which may have a substituent, a naphthoyl group which may have a substituent, a naphthoxycarbonyl group which may have a substituent, a naphthoyloxy group which may have a substituent, a naphthylalkyl group which may have a substituent, a heterocyclyl group which may have a substituent, a heterocyclylcarbonyl group which may have a substituent, an amino group substituted with one or two organic groups, a morpholin-1-yl group, and a piperazin-1-yl group, etc.

[0403] R c7 When R is an alkyl group, the number of carbon atoms in the alkyl group is preferably from 1 to 20, more preferably from 1 to 6. Further, when R c7 is an alkyl group, it may be linear or branched. When R c7 is an alkyl group, specific examples thereof 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, an n-pentyl group, an isopentyl group, a sec-pentyl group, a tert-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an isooctyl group, a sec-octyl group, a tert-octyl group, an n-nonyl group, an isononyl group, an n-decyl group, and an isodecyl group. Further, when R c7 is an alkyl group, the alkyl group may contain an ether bond (-O-) in the carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include a methoxyethyl group, an ethoxyethyl group, a methoxyethoxyethyl group, an ethoxyethoxyethyl group, a propyloxyethoxyethyl group, and a methoxypropyl group.

[0404] R c7 When R is an alkoxy group, the number of carbon atoms in the alkoxy group is preferably from 1 to 20, more preferably from 1 to 6. Further, when R c7 is an alkoxy group, it may be linear or branched. When R c7 is an alkoxy group, specific examples thereof 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, an n-pentyloxy group, an isopentyloxy group, a sec-pentyloxy group, a tert-pentyloxy group, an n-hexyloxy group, an n-heptyloxy group, an n-octyloxy group, an isooctyloxy group, a sec-octyloxy group, a tert-octyloxy group, an n-nonyloxy group, an isononyloxy group, an n-decyloxy group, and an isodecyloxy group. Further, when R c7When it is an alkoxy group, the alkoxy group may contain an ether bond (-O-) in the carbon chain. Examples of the alkoxy group having an ether bond in the carbon chain include a methoxyethoxy group, an ethoxyethoxy group, a methoxyethoxyethoxy group, an ethoxyethoxyethoxy group, a propyloxyethoxyethoxy group, and a methoxypropyloxy group, etc.

[0405] R c7 When R is a cycloalkyl group or a cycloalkoxy group, the number of carbon atoms of the cycloalkyl group or the cycloalkoxy group is preferably 3 or more and 10 or less, more preferably 3 or more and 6 or less. R c7 Specific examples when R is a cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group, etc. R c7 Specific examples when R is a cycloalkoxy group include a cyclopropyloxy group, a cyclobutyloxy group, a cyclopentyloxy group, a cyclohexyloxy group, a cycloheptyloxy group, and a cyclooctyloxy group, etc.

[0406] R c7 When R 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, more preferably 2 or more and 7 or less. R c7 Specific examples when R 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, an n-hexanoyl group, an n-heptanoyl group, an n-octanoyl group, an n-nonanoyl group, an n-decanoyl group, an n-undecanoyl group, an n-dodecanoyl group, an n-tridecanoyl group, an n-tetradecanoyl group, an n-pentadecanoyl group, and an n-hexadecanoyl group, etc. R c7Specific examples where it is a saturated aliphatic acyloxy group include an acetyloxy group, a propanoyloxy group, an n-butanoyloxy group, a 2-methylpropanoyloxy group, an n-pentanoyloxy group, a 2,2-dimethylpropanoyloxy group, an n-hexanoyloxy group, an n-heptanoyloxy group, an n-octanoyloxy group, an n-nonanoyloxy group, an n-decanoyloxy group, an n-undecanoyloxy group, an n-dodecanoyloxy group, an n-tridecanoyloxy group, an n-tetradecanoyloxy group, an n-pentadecanoyloxy group, and an n-hexadecanoyloxy group, etc.

[0407] R c7 When R is an alkoxycarbonyl group, the number of carbon atoms in the alkoxycarbonyl group is preferably 2 or more and 20 or less, more preferably 2 or more and 7 or less. R c7 Specific examples where R 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, a sec-butyloxycarbonyl group, a tert-butyloxycarbonyl group, an n-pentyloxycarbonyl group, an isopentyloxycarbonyl group, a sec-pentyloxycarbonyl group, a tert-pentyloxycarbonyl group, an n-hexyloxycarbonyl group, an n-heptyloxycarbonyl group, an n-octyloxycarbonyl group, an isooctyloxycarbonyl group, a sec-octyloxycarbonyl group, a tert-octyloxycarbonyl group, an n-nonyloxycarbonyl group, an isononyloxycarbonyl group, an n-decyloxycarbonyl group, and an isodecyloxycarbonyl group, etc.

[0408] R c7 When R is a phenylalkyl group, the number of carbon atoms in the phenylalkyl group is preferably 7 or more and 20 or less, more preferably 7 or more and 10 or less. Also, R c7 When R is a naphthylalkyl group, the number of carbon atoms in the naphthylalkyl group is preferably 11 or more and 20 or less, more preferably 11 or more and 14 or less. R c7Specific examples where it is a phenylalkyl group include a benzyl group, a 2-phenylethyl group, a 3-phenylpropyl group, and a 4-phenylbutyl group. R c7 Specific examples where it is a naphthylalkyl group include an α-naphthylmethyl group, a β-naphthylmethyl group, a 2-(α-naphthyl)ethyl group, and a 2-(β-naphthyl)ethyl group. R c7 When R is a phenylalkyl group or a naphthylalkyl group, R c7 may further have a substituent on the phenyl group or the naphthyl group.

[0409] R c7 When R is a heterocyclyl group, the heterocyclyl group is a 5- or 6-membered monocyclic ring containing one or more N, S, O, or a heterocyclyl group formed by condensation of such monocyclic rings or such a monocyclic ring and a benzene ring. When the heterocyclyl group is a condensed ring, the number of monocyclic rings constituting the condensed ring is up to 3. The heterocyclyl group may be an aromatic group (heteroaryl group) or a non-aromatic group. Examples of the heterocyclic ring constituting such a heterocyclyl group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, pyridazine, benzofuran, benzothiophene, indole, isoindole, indolizine, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalazine, cinnoline, quinoxaline, piperidine, piperazine, morpholine, tetrahydropyran, and tetrahydrofuran, etc. R c7 When R is a heterocyclyl group, the heterocyclyl group may further have a substituent.

[0410] R c7 When R is a heterocyclylcarbonyl group, the heterocyclyl group contained in the heterocyclylcarbonyl group is the same as when R c7 is a heterocyclyl group.

[0411] R c7 When the amino group is substituted with one or two organic groups, preferred examples of the organic group include 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 21 carbon atoms, a phenyl group which may have a substituent, a benzoyl group which may have a substituent, a phenylalkyl group having 7 to 20 carbon atoms which may have a substituent, a naphthyl group which may have a substituent, a naphthoyl group which may have a substituent, a naphthylalkyl group having 11 to 20 carbon atoms which may have a substituent, and a heterocyclyl group and the like. Specific examples of these preferred organic groups are the same as those of R c7 Specific examples of the amino group substituted with one or two organic groups include methylamino group, ethylamino group, diethylamino group, n-propylamino group, di-n-propylamino group, isopropylamino group, n-butylamino group, di-n-butylamino group, n-pentylamino group, n-hexylamino group, n-heptylamino group, n-octylamino group, n-nonylamino group, n-decylamino group, phenylamino group, naphthylamino group, acetylamino group, propanoylamino group, n-butanoylamino group, n-pentanoylamino group, n-hexanoylamino group, n-heptanoylamino group, n-octanoylamino group, n-decanoylamino group, benzoylamino group, α-naphthoylamino group, and β-naphthoylamino group and the like.

[0412] R c7 When the phenyl group, naphthyl group, and heterocyclyl group contained in R further have a substituent, examples of the substituent include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a saturated aliphatic acyl group having 2 to 7 carbon atoms, an alkoxycarbonyl group having 2 to 7 carbon atoms, a saturated aliphatic acyloxy group having 2 to 7 carbon atoms, 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, morpholin-1-yl group, piperazin-1-yl group, halogen, nitro group, and cyano group and the like. R c7When the phenyl group, naphthyl group, and heterocyclyl group contained therein further have substituents, the number of the substituents is not limited as long as the object of the present invention is not inhibited, but is preferably 1 or more and 4 or less. R c7 When the phenyl group, naphthyl group, and heterocyclyl group contained therein have a plurality of substituents, the plurality of substituents may be the same or different.

[0413] Among the groups described above, R c7 is preferably a nitro group or a group represented by R c12 -CO- because the sensitivity tends to improve. R c12 is not particularly limited as long as the object of the present invention is not inhibited and can be selected from various organic groups. R c12 Examples of preferred groups for 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 heterocyclyl group which may have a substituent. R Further, R c7 is preferably a hydrogen atom because the transparency tends to be good. Incidentally, when R c7 is a hydrogen atom and R c10 is a group represented by the following formula (c4a) or (c4b), the transparency tends to be better.

[0414] In formula (c4), R c8 and R c9 are each a chain alkyl group which may have a substituent, a cyclic organic group which may have a substituent, or a hydrogen atom. R c8 and R c9 may be bonded to each other to form a ring. Among these groups, R c8 and R c9 are preferably a chain alkyl group which may have a substituent. R c8 and R c9 When they are a chain alkyl group which may have a substituent, the chain alkyl group may be a linear alkyl group or a branched alkyl group.

[0415] R c8 and R c9 When the chain alkyl group has 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. R c8 and R c9 Specific examples of the case where R c8 and R c9 are chain alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, 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 group, isononyl group, n-decyl group, and isodecyl group. Further, R

[0416] R c8 and R c9 When the chain alkyl group has 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. In this case, 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 inhibit the object of the present invention. Preferable examples of the substituent include a cyano group, a halogen atom, a cyclic organic group, and an alkoxycarbonyl group. Examples of 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. Examples of the cyclic organic group include a cycloalkyl group, an aromatic hydrocarbon group, and a heterocyclyl group. Specific examples of the cycloalkyl group include Rc7 This is the same as the preferred examples when it is a cycloalkyl group. Specific examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, a biphenylyl group, an anthryl group, and a phenanthryl group, etc. Specific examples of the heterocyclyl group include R c7 This is the same as the preferred examples when R is a heterocyclyl group. R c7 When R is an alkoxycarbonyl group, the alkoxy group contained in the alkoxycarbonyl group may be linear or branched, and a linear one is preferred. The number of carbon atoms of the alkoxy group contained in the alkoxycarbonyl group is preferably 1 or more and 10 or less, more preferably 1 or more and 6 or less.

[0417] When the chain alkyl group has a substituent, the number of substituents is not particularly limited. The preferred number of substituents varies according to the number of carbon atoms of 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, more preferably 1 or more and 6 or less.

[0418] R c8 and R c9 When they are cyclic organic groups, the cyclic organic group may be an alicyclic group or an aromatic group. Examples of the cyclic organic group include an aliphatic cyclic hydrocarbon group, an aromatic hydrocarbon group, and a heterocyclyl group. R c8 and R c9 When they are cyclic organic groups, the substituents that the cyclic organic group may have are the same as those when R c8 and R c9 are chain alkyl groups.

[0419] R c8 and R c9When it is an aromatic hydrocarbon group, the aromatic hydrocarbon group is preferably a phenyl group, a group formed by a plurality of benzene rings bonded through carbon-carbon bonds, or a group formed by a plurality of benzene rings condensed. When the aromatic hydrocarbon group is a phenyl group or a group formed by a plurality of benzene rings bonded or condensed, the number of benzene rings contained in the aromatic hydrocarbon group is not particularly limited, preferably 3 or less, more preferably 2 or less, and particularly preferably 1. Preferred specific examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, a biphenylyl group, an anthryl group, and a phenanthryl group.

[0420] R c8 and R c9 When it is an aliphatic cyclic hydrocarbon group, 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 preferably 3 or more and 20 or less, and more preferably 3 or more and 10 or less. Examples of the monocyclic cyclic hydrocarbon group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a norbornyl group, an isobornyl group, a tricyclononyl group, a tricyclodecyl group, a tetracyclododecyl group, and an adamantyl group.

[0421] R c8 and R c9When it is a heterocyclic group, the heterocyclic group is a 5- or 6-membered monocyclic ring containing one or more N, S, O, or a heterocyclic group formed by condensation of such monocyclic rings or such a monocyclic ring and a benzene ring. When the heterocyclic group is a condensed ring, the number of monocyclic rings constituting the condensed ring is up to 3. The heterocyclic group may be an aromatic group (heteroaryl group) or a non-aromatic group. Examples of the heterocyclic ring constituting such a heterocyclic group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, pyridazine, benzofuran, benzothiophene, indole, isoindole, indolizine, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalazine, cinnoline, quinoxaline, piperidine, piperazine, morpholine, tetrahydropyran, and tetrahydrofuran, etc.

[0422] R c8 and R c9 may be bonded to each other to form a ring. R c8 and R c9 The group formed by the ring formed by R c8 and R c9 is preferably a cycloalkylidene group. When R c8 and R c9 are bonded to form a cycloalkylidene group, the ring constituting the cycloalkylidene group is preferably a 5- or 6-membered ring, more preferably a 5-membered ring.

[0423] R c8 and R c9 When the group formed by the bond between R c8 and R c9 is a cycloalkylidene group, the cycloalkylidene group may be condensed with one or more other rings. Examples of the ring that may be condensed with the cycloalkylidene group include benzene ring, naphthalene ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, furan ring, thiophene ring, pyrrole ring, pyridine ring, pyrazine ring, and pyrimidine ring, etc.

[0424] Among the R described above c8 and R c9 Examples of preferred groups include the group represented by the formula -A 1 -A 2 In the formula, A 1 is a linear alkylene group, and A 2 is an alkoxy group, a cyano group, a halogen atom, a halogenated alkyl group, a cyclic organic group, or an alkoxycarbonyl group.

[0425] A 1 The number of carbon atoms of the linear alkylene group of A is preferably 1 or more and 10 or less, more preferably 1 or more and 6 or less. When A 2 is an alkoxy group, the alkoxy group may be linear or branched, and is preferably linear. The number of carbon atoms of the alkoxy group is preferably 1 or more and 10 or less, more preferably 1 or more and 6 or less. When A 2 is a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom is preferred, and a fluorine atom, a chlorine atom, or a bromine atom is more preferred. When A 2 is a halogenated alkyl group, the halogen atom contained in the halogenated alkyl group is preferably a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, and a fluorine atom, a chlorine atom, or a bromine atom is more preferred. The halogenated alkyl group may be linear or branched, and is preferably linear. When A 2 is a cyclic organic group, examples of the cyclic organic group are the same as the cyclic organic groups that R c8 and R c9 have as substituents. When A 2 is an alkoxycarbonyl group, examples of the alkoxycarbonyl group are the same as the alkoxycarbonyl groups that R c8 and R c9 have as substituents.

[0426] R c8 and R c9Preferable specific examples thereof include alkyl groups such as an ethyl group, an n-propyl group, an n-butyl group, an n-hexyl group, an n-heptyl group, and an n-octyl group; alkoxyalkyl groups such as a 2-methoxyethyl group, a 3-methoxy-n-propyl group, a 4-methoxy-n-butyl group, a 5-methoxy-n-pentyl group, a 6-methoxy-n-hexyl group, a 7-methoxy-n-heptyl group, an 8-methoxy-n-octyl group, a 2-ethoxyethyl group, a 3-ethoxy-n-propyl group, a 4-ethoxy-n-butyl group, a 5-ethoxy-n-pentyl group, a 6-ethoxy-n-hexyl group, a 7-ethoxy-n-heptyl group, and an 8-ethoxy-n-octyl group; cyanoalkyl groups such as a 2-cyanoethyl group, a 3-cyano-n-propyl group, a 4-cyano-n-butyl group, a 5-cyano-n-pentyl group, a 6-cyano-n-hexyl group, a 7-cyano-n-heptyl group, and an 8-cyano-n-octyl group; phenylalkyl groups such as a 2-phenylethyl group, a 3-phenyl-n-propyl group, a 4-phenyl-n-butyl group, a 5-phenyl-n-pentyl group, a 6-phenyl-n-hexyl group, a 7-phenyl-n-heptyl group, and an 8-phenyl-n-octyl group; cycloalkylalkyl groups such as a 2-cyclohexylethyl group, a 3-cyclohexyl-n-propyl group, a 4-cyclohexyl-n-butyl group, a 5-cyclohexyl-n-pentyl group, a 6-cyclohexyl-n-hexyl group, a 7-cyclohexyl-n-heptyl group, an 8-cyclohexyl-n-octyl group, a 2-cyclopentylethyl group, a 3-cyclopentyl-n-propyl group, a 4-cyclopentyl-n-butyl group, a 5-cyclopentyl-n-pentyl group, a 6-cyclopentyl-n-hexyl group, a 7-cyclopentyl-n-heptyl group, and an 8-cyclopentyl-n-octyl group;2-methoxycarbonylethyl group, 3-methoxycarbonyl-n-propyl group, 4-methoxycarbonyl-n-butyl group, 5-methoxycarbonyl-n-pentyl group, 6-methoxycarbonyl-n-hexyl group, 7-methoxycarbonyl-n-heptyl group, 8-methoxycarbonyl-n-octyl group, 2-ethoxycarbonylethyl group, 3-ethoxycarbonyl-n-propyl group, 4-ethoxycarbonyl-n-butyl group, 5-ethoxycarbonyl-n-pentyl group, 6-ethoxycarbonyl-n-hexyl group, 7-ethoxycarbonyl-n-heptyl group, and alkoxycarbonylalkyl groups such as 8-ethoxycarbonyl-n-octyl group; 2-chloroethyl group, 3-chloro-n-propyl group, 4-chloro-n-butyl group, 5-chloro-n-pentyl group, 6-chloro-n-hexyl group, 7-chloro-n-heptyl group, 8-chloro-n-octyl group, 2-bromoethyl group, 3-bromo-n-propyl group, 4-bromo-n-butyl group, 5-bromo-n-pentyl group, 6-bromo-n-hexyl group, 7-bromo-n-heptyl group, 8-bromo-n-octyl group, 3,3,3-trifluoropropyl group, and halogenated alkyl groups such as 3,3,4,4,5,5,5-heptafluoro-n-pentyl group are mentioned.

[0427] R c8 and R c9 As, among the above, preferred groups 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 3,3,4,4,5,5,5-heptafluoro-n-pentyl group.

[0428] R c10 Examples of preferred organic groups for R c7Similarly, 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, a phenyl group which may have a substituent, a phenoxy group which may have a substituent, a benzoyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, a benzoyloxy group which may have a substituent, a phenylalkyl group which may have a substituent, a naphthyl group which may have a substituent, a naphthoxy group which may have a substituent, a naphthoyl group which may have a substituent, a naphthoxycarbonyl group which may have a substituent, a naphthoyloxy group which may have a substituent, a naphthylalkyl group which may have a substituent, a heterocyclyl group which may have a substituent, a heterocyclylcarbonyl group which may have a substituent, an amino group substituted with 1 or 2 organic groups, a morpholin-1-yl group, a piperazin-1-yl group, etc. may be mentioned. Specific examples of these groups are the same as the groups described for R c7 and are the same as those described for R c10 In addition, as R c7 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 which the phenoxyalkyl group and the phenylthioalkyl group may have are the same as the substituents which the phenyl group contained in R

[0429] Among the organic groups, R c10Examples of the group represented by R include an alkyl group, a cycloalkyl group, a phenyl group which may have a substituent, or a cycloalkylalkyl group, and a phenylthioalkyl group which may have a substituent on the aromatic ring. As 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 most preferable. Among the phenyl groups which may have a substituent, 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 to 10, more preferably 5 to 8, and particularly preferably 5 or 6. The number of carbon atoms of the alkylene group contained in the cycloalkylalkyl group is preferably 1 to 8, more preferably 1 to 4, and particularly preferably 2. Among the cycloalkylalkyl groups, 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 to 8, more preferably 1 to 4, and particularly preferably 2. Among the phenylthioalkyl groups which may have a substituent on the aromatic ring, a 2-(4-chlorophenylthio)ethyl group is preferable.

[0430] Also, R c10 is preferably a group represented by -A 3 -CO-O-A 4 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.

[0431] When A 3 is an alkylene group, the alkylene group may be linear or branched, and a linear alkylene group is preferable. When A 3 is an alkylene group, the number of carbon atoms of the alkylene group is preferably 1 to 10, more preferably 1 to 6, and particularly preferably 1 to 4.

[0432] A 4Preferable examples include an alkyl group having 1 to 10 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, and an aromatic hydrocarbon group having 6 to 20 carbon atoms. A 4 Preferable specific examples 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, an n-pentyl group, an n-hexyl group, a phenyl group, a naphthyl group, a benzyl group, a phenethyl group, an α-naphthylmethyl group, and a β-naphthylmethyl group, etc.

[0433] -A 3 -CO-O-A 4 Preferable specific examples of the group represented by include a 2-methoxycarbonylethyl group, a 2-ethoxycarbonylethyl group, a 2-n-propyloxycarbonylethyl group, a 2-n-butyloxycarbonylethyl group, a 2-n-pentyloxycarbonylethyl group, a 2-n-hexyloxycarbonylethyl group, a 2-benzyloxycarbonylethyl group, a 2-phenoxycarbonylethyl group, a 3-methoxycarbonyl-n-propyl group, a 3-ethoxycarbonyl-n-propyl group, a 3-n-propyloxycarbonyl-n-propyl group, a 3-n-butyloxycarbonyl-n-propyl group, a 3-n-pentyloxycarbonyl-n-propyl group, a 3-n-hexyloxycarbonyl-n-propyl group, a 3-benzyloxycarbonyl-n-propyl group, and a 3-phenoxycarbonyl-n-propyl group, etc.

[0434] As described above, R c10 has been described, but as R c10 , a group represented by the following formula (c4a) or (c4b) is preferable.

Chemical formula

[0435] In formula (c4a), R c13 and R c14 Examples of the organic group for are the same as those for R c7 Similar. As R c13 an alkyl group or a phenyl group is preferred. When R c13 is an alkyl group, the number of carbon atoms thereof is preferably 1 or more and 10 or less, 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. When R c13 and R c14 are bonded to each other to form a ring, the ring may be an aromatic ring or an aliphatic ring. A group represented by formula (c4a) in which R c13 and R c14 form a ring, preferred examples of which include a naphthalene-1-yl group and a 1,2,3,4-tetrahydronaphthalene-5-yl group. In the above formula (c4a), n6 is an integer of 0 or more and 4 or less, preferably 0 or 1, and more preferably 0.

[0436] In the above formula (c4b), R c15 is an organic group. Examples of the organic group include the same groups as those described for R c7 Among the organic groups, an alkyl group is preferred. 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. As R c15 methyl group, ethyl group, propyl group, isopropyl group, butyl group, etc. are preferably exemplified, and among these, a methyl group is more preferable.

[0437] In the above formula (c4b), n8 is an integer of 1 or more and 5 or less, preferably an integer of 1 or more and 3 or less, more preferably 1 or 2. In the above formula (c4b), n9 is 0 or more and (n8 + 3) or less, preferably an integer of 0 or more and 3 or less, more preferably an integer of 0 or more and 2 or less, particularly preferably 0. In the above formula (c4b), n7 is an integer of 1 or more and 8 or less, preferably an integer of 1 or more and 5 or less, more preferably an integer of 1 or more and 3 or less, particularly preferably 1 or 2.

[0438] In formula (c4), 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. When R c11 is an alkyl group, preferred examples of the substituent which may be present include a phenyl group and a naphthyl group. Further, when R c7 is an aryl group, preferred examples of the substituent which may be present include an alkyl group having 1 to 5 carbon atoms, an alkoxy group, and a halogen atom.

[0439] In formula (c4), examples of R c11 preferably include 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, etc. Among these, a methyl group or a phenyl group is more preferred.

[0440] The compound represented by formula (c4) is produced by a method including a step of converting the oxime group (>C=N-OH) contained in the compound represented by the aforementioned formula (c5) into an oxime ester group represented by >C=N-O-COR c11 . R c11 is the same as R c11 in formula (c4).

[0441] The conversion of the oxime group (>C=N-OH) into an oxime ester group represented by >C=N-O-COR c11 is carried out by reacting the compound represented by the aforementioned formula (c5) with an acylating agent. -COR c11Examples of acylating agents that provide an acyl group represented by (R c11 CO)2O include acid anhydrides, and acid halides represented by R c11 COHal (Hal is a halogen atom).

[0442] Preferable specific examples of the compound represented by formula (c4) include the following PI-43 to PI-83. [Chemical formula]

[0443] [Chemical formula]

[0444] 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. By setting the content within the above range, sufficient heat resistance and chemical resistance can be obtained, the film-forming ability can be improved, and curing defects can be suppressed.

[0445] As described above, the energy-sensitive composition of the first aspect as a modified metal oxide fine particle dispersion contains metal oxide fine particles including the aforementioned modified metal oxide fine particles. Therefore, using the energy-sensitive composition of the first aspect, a pattern containing metal oxide fine particles can be formed.

[0446] The energy-sensitive composition of the first aspect may further contain a colorant. The colorant is not particularly limited. For example, compounds classified as Pigment in the Color Index (C.I.; published by The Society of Dyers and Colourists) can be used. Specifically, it is preferable to use pigments with the following Color Index (C.I.) numbers.

[0447] C.I. Pigment Yellow 1 (hereinafter, the same shall apply to "C.I. Pigment Yellow", and only the numbers will be listed.), 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, the same shall apply to "C.I. Pigment Orange", and only the numbers will be listed.), 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 55, 59, 61, 63, 64, 71, 73; C.I. Pigment Violet 1 (hereinafter, the same shall apply to "C.I. Pigment Violet", and only the numbers will be listed.), 19, 23, 29, 30, 32, 36, 37, 38, 39, 40, 50; C.I. Pigment Red 1 (hereinafter, the same shall apply to "C.I. Pigment Red", and only the numbers will be listed.), 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, 216, 217, 220, 223, 224, 226, 227, 228, 240, 242, 243, 245, 254, 255, 264, 265; C.I. Pigment Blue 1 (hereinafter, the same shall apply to "C.I. Pigment Blue", and only the numbers are described.), 2, 15, 15:3, 15:4, 15:6, 16, 22, 60, 64, 66; C.I. Pigment Green 7, C.I. Pigment Green 36, C.I. Pigment Green 37; C.I. Pigment Brown 23, C.I. Pigment Brown 25, C.I. Pigment Brown 26, C.I. Pigment Brown 28; C.I. Pigment Black 1, C.I. Pigment Black 7.

[0448] When using a colorant as a light-shielding agent, it is preferable to use a black pigment as the light-shielding agent. As the black pigment, various pigments can be mentioned regardless of whether they are organic or inorganic substances such as carbon black, titanium black, metal oxides such as copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, silver, composite oxides, metal sulfides, metal sulfates, metal carbonates, etc. Among these, it is preferable to use carbon black having high light-shielding properties.

[0449] As the 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. Also, resin-coated carbon black may be used. Resin-coated carbon black has lower conductivity than carbon black without resin coating.

[0450] In addition, in order to adjust the color tone of the carbon black, the above organic pigments may be appropriately added as auxiliary pigments.

[0451] In addition, in order to uniformly disperse the colorant in the photosensitive composition, a dispersant may be further used. As such a dispersant, it is preferable to use a polymer dispersant of a polyethyleneimine type, a urethane resin type, or an acrylic resin type. In particular, when using carbon black as the colorant, it is preferable to use a dispersant of an acrylic resin type as the dispersant.

[0452] In addition, the inorganic pigment and the organic pigment may each be used alone or in combination. When used in combination, the organic pigment is preferably used in the range of 10 parts by mass or more and 80 parts by mass or less, more preferably in the range of 20 parts by mass or more and 40 parts by mass or less, based on 100 parts by mass of the total amount of the inorganic pigment and the organic pigment.

[0453] The content of the colorant may be appropriately determined according to the use of the energy-sensitive composition of the first aspect. As an example, it is preferably 5 parts by mass or more and 70 parts by mass or less, more preferably 25 parts by mass or more and 60 parts by mass or less, based on 100 parts by mass of the solid content of the energy-sensitive composition of the first aspect.

[0454] It should be noted that the colorant is preferably added to the photosensitive composition after being made into a dispersion liquid dispersed at an appropriate concentration using a dispersant.

[0455] Examples of the organic solvent in the energy-sensitive composition of the first aspect include (poly)alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol - n - propyl ether, 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 - n - butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether; (poly)alkylene glycol monoalkyl ether acetates 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, propylene glycol monoethyl ether acetate; other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran, dioxane; ketones such as methyl ethyl ketone, cyclohexanone, 2 - heptanone, 3 - heptanone, methyl isoamyl ketone; polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol; alkyl lactates such as methyl 2 - hydroxypropionate, ethyl 2 - hydroxypropionate;Ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2-hydroxy-3-methylbutyl methyl, 3-methoxybutyl acetate, 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 propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxobutanoate, ethyl lactate and other esters; aromatic hydrocarbons such as toluene and xylene; amides such as N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, and the solvent represented by the aforementioned formula (S01). These organic solvents can be used alone or in combination of two or more.;

[0456] Among the above organic solvents, 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 aforementioned formula (S01) are preferable because they exhibit excellent solubility in the above alkali-soluble resin, the above photopolymerizable compound, and the above photoinitiator.

[0457] The content of the organic solvent is preferably an amount such that the solid content concentration of the energy-sensitive composition in 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.

[0458] (2) The energy-sensitive composition of the second aspect The photosensitive energy composition of the second aspect is a negative photosensitive composition. Such a negative photosensitive composition contains metal oxide fine particles including 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 an organic solvent.

[0459] As the alkali-soluble resin having a phenolic hydroxyl group in the photosensitive energy 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. Here, "hydroxystyrene" is a concept including hydroxystyrene, a compound in which a hydrogen atom bonded to the α-position of hydroxystyrene is substituted with another substituent such as a halogen atom, an alkyl group, or a halogenated alkyl group, and hydroxystyrene derivatives (monomers) of these derivatives. "Hydroxystyrene derivatives" maintain at least a benzene ring and a hydroxyl group bonded thereto. For example, a compound in which a hydrogen atom bonded to the α-position of hydroxystyrene is substituted with another substituent such as a halogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group, a compound in which an alkyl group having 1 to 5 carbon atoms is further bonded to the benzene ring to which the hydroxyl group of hydroxystyrene is bonded, or a compound in which 1 to 2 hydroxyl groups are further bonded to the benzene ring to which this hydroxyl group is bonded (in this case, the total number of hydroxyl groups is 2 or more and 3 or less), etc. are included. Examples of the halogen atom include a chlorine atom, a fluorine atom, a bromine atom, etc., and a fluorine atom is preferable. In addition, the "α-position of hydroxystyrene" refers to the carbon atom to which the benzene ring is bonded unless otherwise specified.

[0460] The structural unit derived from this hydroxystyrene is represented by, for example, the following formula (b-1).

[0461]

Chemical formula

[0462] In the above formula (b-1), R b1 represents a hydrogen atom, an alkyl group, a halogen atom, or a halogenated alkyl group, and R b2 represents an alkyl group having 1 to 5 carbon atoms, p represents an integer of 1 to 3, and q represents an integer of 0 to 2.

[0463] The alkyl group of R b1 preferably has 1 to 5 carbon atoms. Also, a linear or branched alkyl group is preferred, and examples include 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, etc. Among these, the methyl group is preferred industrially. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc., and the fluorine atom is preferred. The halogenated alkyl group is a group in which some or all of the hydrogen atoms of the above-mentioned alkyl group having 1 to 5 carbon atoms are substituted with halogen atoms. Among these, an alkyl group in which all of the hydrogen atoms are substituted with fluorine atoms is preferred. Also, a linear or branched fluorinated alkyl group is preferred, and a trifluoromethyl group, a hexafluoroethyl group, a heptafluoropropyl group, a nonafluorobutyl group, etc. are more preferred, and the trifluoromethyl group (-CF3) is most preferred. As R b1 , a hydrogen atom or a methyl group is preferred, and a hydrogen atom is more preferred.

[0464] As the alkyl group of R b2 having 1 to 5 carbon atoms, the same groups as in the case of R b1 can be mentioned. q is an integer of 0 to 2. Among these, 0 or 1 is preferred, and 0 is particularly preferred industrially. R b2The substitution position may be any of the ortho, meta, or para positions when q is 1, and furthermore, when q is 2, any combination of substitution positions can be combined. p is an integer of 1 or more and 3 or less, preferably 1. The substitution position of the hydroxyl group may be any of the ortho, meta, or para positions when p is 1, but the para position is preferred because it is easily available and inexpensive. Furthermore, when p is 2 or 3, any combination of substitution positions can be combined.

[0465] The structural unit represented by the above formula (b-1) can be used alone or in combination of two or more.

[0466] In the polyhydroxystyrene resin, the proportion of the structural unit derived from hydroxystyrene is preferably 60 mol% or more and 100 mol% or less, more preferably 70 mol% or more and 100 mol% or less, and even more preferably 80 mol% or more and 100 mol% or less with respect to all the structural units constituting the polyhydroxystyrene resin. By setting it within the above range, appropriate alkali solubility can be obtained when the photosensitive composition is prepared.

[0467] The polyhydroxystyrene resin preferably further has a structural unit derived from styrene. Here, the "structural unit derived from styrene" is defined to include the structural unit formed by the cleavage of the ethylenic double bond of styrene and styrene derivatives (however, hydroxystyrene is not included). The "styrene derivative" is defined to include derivatives in which the hydrogen atom bonded to the α-position of styrene is substituted with another substituent such as a halogen atom, an alkyl group, a halogenated alkyl group, etc., and derivatives in which the hydrogen atom of the phenyl group of styrene is substituted with a substituent such as an alkyl group having 1 or more and 5 or less carbon atoms. Examples of the halogen atom include a chlorine atom, a fluorine atom, a bromine atom, etc., and a fluorine atom is preferred. In addition, the "α-position of styrene" refers to the carbon atom to which the benzene ring is bonded unless otherwise specified.

[0468] The structural unit derived from this styrene is represented by, for example, the following formula (b-2). In the formula, R b1 , R b2 , and q have the same meanings as in the above formula (b-1).

[0469]

Chemical formula

[0470] R b1 and R b2 include the same groups as R b1 and R b2 in the above formula (b-1), respectively. q is an integer of 0 or more and 2 or less. Among these, it is preferably 0 or 1, and particularly preferably 0 in industry. R b2 When q is 1, the substitution position of R

[0471] may be any of the ortho, meta, and para positions, and when q is 2, any combination of substitution positions can be combined.

[0472] The proportion of the structural unit derived from styrene in the polyhydroxystyrene-based resin is preferably 40 mol% or less, more preferably 30 mol% or less, and even more preferably 20 mol% or less with respect to all the structural units constituting the polyhydroxystyrene-based resin. By setting it within the above range, appropriate alkali solubility can be obtained when forming a photosensitive composition, and the balance with other structural units also becomes good.

[0473] Incidentally, the polyhydroxystyrene-based resin may have structural units other than the structural units derived from hydroxystyrene and the structural units derived from styrene. More preferably, the polyhydroxystyrene-based resin is a polymer composed only of structural units derived from hydroxystyrene, or a copolymer composed of structural units derived from hydroxystyrene and structural units derived from styrene.

[0474] The mass average molecular weight of the polyhydroxystyrene-based resin is not particularly limited, but is preferably 1500 or more and 40000 or less, and more preferably 2000 or more and 8000 or less.

[0475] In addition, as the alkali-soluble resin having a phenolic hydroxyl group, a phenol-xylylene glycol condensate, a cresol-xylylene glycol condensate, a phenol-dicyclopentadiene condensate, or the like can also be used.

[0476] 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 more preferably 35% by mass or more and 65% by mass or less with respect to the solid content of the photosensitive composition of the second embodiment. By setting it within the above range, the balance of developability tends to be easily achieved.

[0477] The acid crosslinkable substance in the energy-sensitive composition of the second embodiment is not particularly limited, and a conventionally known acid crosslinkable substance can be used.

[0478] Specific examples of the acid-crosslinkable substance include amino resins having a hydroxy group or an alkoxyl group, such as melamine resins, urea resins, guanamine resins, acetoguanamine resins, benzoguanamine resins, glycoluril-formaldehyde resins, succinylamide-formaldehyde resins, ethyleneurea-formaldehyde resins, and the like. These acid-crosslinkable substances can be easily obtained by reacting melamine, urea, guanamine, acetoguanamine, benzoguanamine, glycoluril, succinylamide, or ethyleneurea with formalin in boiling water for methylolation, or further reacting with a lower alcohol for alkoxylation. Practically, they can be obtained as melamine resins such as Nikalac MX-750, Nikalac MW-30, and Nikalac MW100LM, and urea resins such as Nikalac MX-290 (all manufactured by Sanwa Chemical Co., Ltd.). Also, benzoguanamine resins such as Cymel 1123 and Cymel 1128 (manufactured by Mitsui Cyanaad Co., Ltd.) are commercially available.

[0479] In addition, benzene compounds 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, and phenolic compounds having a hydroxy group or an alkoxyl group, such as 2,6-dihydroxymethyl-p-tert-butylphenol, can also be used. These acid-crosslinkable substances can be used alone or in combination of two or more.

[0480] The content of the acid-crosslinkable substance is preferably 5 to 50 parts by mass, more preferably 10 to 30 parts by mass, based on 100 parts by mass of the alkali-soluble resin having a phenolic hydroxyl group. By setting the content within the above range, the curability and patterning properties of the photosensitive composition are improved.

[0481] The photoacid generator in the energy-sensitive composition of the second embodiment is not particularly limited, and conventionally known photoacid generators can be used.

[0482] The content of the photoacid generator is preferably 0.05 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, based on 100 parts by mass of the alkali-soluble resin having a phenolic hydroxyl group. By setting it within the above range, the curability of the photosensitive composition becomes good.

[0483] As described above, the energy-sensitive composition of the second aspect contains metal oxide fine particles including the modified metal oxide fine particles described above. Therefore, a patterned metal oxide fine particle-containing film can be formed using the energy-sensitive composition of the second aspect.

[0484] 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.

[0485] Specific examples of such compounds include, in addition to benzophenone compounds such as various tetrahydroxybenzophenones, pentahydroxybenzophenones, hexahydroxybenzophenones, heptahydroxybenzophenones, etc., bis[2-hydroxy-3-(2'-hydroxy-5'-methylbenzyl)-5-methylphenyl]methane, bis(4-hydroxy-3,5-dimethylphenyl)-3,4-dihydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-3,4-dihydroxyphenylmethane, bis(4-hydroxy-3,5-dimethylphenyl)-2,4-dihydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-2,4-dihydroxyphenylmethane, bis(3-cyclohexyl-4-hydroxy-6-methylphenyl)-3,4-dihydroxyphenylmethane, bis(3-cyclohexyl-6-hydroxy-4-methylphenyl)-3,4-dihydroxyphenylmethane, bis(4-hydroxy-2,3,5-trimethylphenyl)-3,4-dihydroxyphenylmethane and other hydroxyaryl compounds; bis(hydroxyphenyl)alkane compounds such as 2-(2,3,4-trihydroxyphenyl)-2-(2',3',4'-trihydroxyphenyl)propane, 2-(2,4-dihydroxyphenyl)-2-(2',4'-dihydroxyphenyl)propane; polyhydroxystyrene compounds such as poly(o-hydroxystyrene), poly(m-hydroxystyrene), poly(p-hydroxystyrene), poly(α-methyl-p-hydroxystyrene), poly(4-hydroxy-3-methylstyrene) with a molecular weight of less than 2000; etc. These benzophenone compounds, hydroxyaryl compounds, bis(hydroxyphenyl)alkane compounds, and polyhydroxystyrene compounds may have substituents other than hydroxyl groups. These compounds can be used alone or in combination of two or more.

[0486] The content of the compound having 4 or more phenolic hydroxyl groups and 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 a phenolic hydroxyl group. By setting it within the above range, the tapering phenomenon when the photosensitive composition is patterned can be suppressed.

[0487] Examples of the organic solvent in the energy-sensitive composition of the second aspect include the organic solvents exemplified in the energy-sensitive composition of the first aspect. The content of the organic solvent is preferably an amount 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 an amount of 5% by mass or more and 30% by mass or less. Similar to the energy-sensitive composition of the first aspect, the energy-sensitive composition of the second aspect may contain the above various additives as necessary.

[0488] (3) Energy-sensitive composition of the third aspect The photosensitive composition of the third aspect is a negative photosensitive composition containing an epoxy group-containing polycarboxylic acid resin, a photoacid generator, and an organic solvent, together with the metal oxide fine particles containing the modified metal oxide fine particles described above.

[0489] Examples of the epoxy group-containing polycarboxylic acid resin in the photosensitive composition of the third aspect include a resin obtained by reacting a reaction product obtained by reacting an epoxy compound having 2 or more epoxy groups in one molecule with a monocarboxylic acid having 1 or more alcoholic hydroxyl groups in one molecule, with a polybasic acid anhydride.

[0490] Examples of epoxy compounds having two or more epoxy groups in one molecule include, for example, the epoxy compounds listed as the above-mentioned epoxy resin precursors and resins similar to the above-mentioned epoxy group-containing resins. Among them, novolak-type epoxy resins, bisphenol-type epoxy resins, trisphenolmethane-type epoxy resins, tris(2,3-epoxypropyl)isocyanurate, biphenyldiglycidyl ether, alicyclic epoxy resins, copolymer-type epoxy resins, etc. can be mentioned.

[0491] Examples of novolak-type epoxy resins include, for example, novolaks obtained by reacting phenols such as phenol, cresol, halogenated phenol, alkylphenol, etc. with formaldehyde under an acidic catalyst, and epoxy resins obtained by reacting epichlorohydrin or methyl epichlorohydrin therewith. 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 (both manufactured by Dow Chemical Co.); N-730, N-770, N-865, N-665, N-673, VH-4150 (all manufactured by Dainippon Ink and Chemicals, Inc.), etc.

[0492] Examples of bisphenol-type epoxy resins include, for example, epoxy resins obtained by reacting bisphenols such as bisphenol A, bisphenol F, bisphenol S, tetrabromobisphenol A, etc. with epichlorohydrin or methyl epichlorohydrin, and epoxy resins obtained by reacting diglycidyl ethers of bisphenol A or bisphenol F, condensates of the above bisphenols, with epichlorohydrin or methyl epichlorohydrin. Commercially available products include Epicoat 1004, Epicoat 1002, Epicoat 4002, Epicoat 4004 (all manufactured by Yuka Shell Epoxy Co., Ltd.), etc.

[0493] Examples of the trisphenol methane type epoxy resin include epoxy resins obtained by reacting trisphenol methane or triscresol methane with epichlorohydrin or methyl epichlorohydrin. Commercially available products include EPPN-501 and EPPN-502 (both manufactured by Nippon Kayaku Co., Ltd.).

[0494] Examples of the alicyclic epoxy resin include compounds similar to the above-mentioned alicyclic epoxy compounds. Commercially available products include Celoxide 2021 manufactured by Daicel Chemical Industries, Ltd.; Epomic VG-3101 manufactured by Mitsui Petrochemical Industries, Ltd.; E-1031S manufactured by Yuka Shell Epoxy Co., Ltd.; EPB-13 and EPB-27 manufactured by Nippon Soda Co., Ltd. Examples of the copolymer type epoxy resin include CP-50M and CP-50S manufactured by NOF Corporation, which are copolymers of glycidyl methacrylate, styrene, and α-methylstyrene, or copolymers of glycidyl methacrylate and cyclohexyl maleimide, etc.

[0495] Particularly preferred examples of the epoxy resin having two or more epoxy groups in one molecule include, for example, cresol novolak type epoxy resin, phenol novolak type epoxy resin, bisphenol type epoxy resin, trisphenol methane type epoxy resin, etc. In particular, a polycondensate of α-hydroxyphenyl-ω-hydrotopoly(biphenyldimethylene-hydroxyphenylene) and 1-chloro-2,3-epoxypropane, and α-2,3-epoxypropoxyphenyl-ω-hydrotopoly{2-(2,3-epoxypropoxy)-benzylidene-2,3-epoxypropoxyphenylene} are preferred.

[0496] Examples of the monocarboxylic acid having one or more alcoholic hydroxyl groups in one molecule include hydroxymonocarboxylic acids such as dimethylolpropionic acid, dimethylolacetic acid, dimethylolbutyric acid, dimethylolvaleric acid, dimethylolcaproic acid, and hydroxypivalic acid. Among these, monocarboxylic acids having one or more and five or less alcoholic hydroxyl groups in one molecule are preferred.

[0497] Examples of the polybasic acid anhydride include succinic anhydride, maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylendomethylene tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and the like.

[0498] In the reaction between the epoxy compound and the monocarboxylic acid, 0.1 mol or more and 0.7 mol or less of the monocarboxylic acid is preferably used per 1 equivalent of the epoxy group of the epoxy compound, and more preferably 0.2 mol or more and 0.5 mol or less. In this reaction, it is prefera...

Claims

1. Preparing metal oxide fine particles (B) in the presence of a solvent (S-I) or dispersing the metal oxide fine particles (B) in the presence of a dispersion medium (S-II); contacting the metal oxide fine particles (B) with an aromatic group-containing carboxylic acid compound (A) and / or a carboxylate derived from the aromatic group-containing carboxylic acid compound (A) in the presence of the solvent (S-I) or the dispersion medium (S-II); wherein the solvent (S-I) or the dispersion medium (S-II) contains a nitrogen-containing organic solvent; wherein the aromatic group-containing carboxylic acid compound (A) contains at least one selected from the group consisting of a compound represented by the following formula (1), benzoic acid which may have a substituent, naphthoic acid which may have a substituent, and a phthalic acid monoester; a method for producing modified metal oxide fine particles, wherein the substituent in the benzoic acid which may have a substituent is a substituent selected from the group consisting of a methyl group, an ethyl group, an n-butyl group, a methoxy group, an ethoxy group, an n-propyloxy group, an isopropyloxy group, an n-butyloxy group, a phenyl group, a naphthalen-1-yl group, a naphthalen-2-yl group, a phenoxy group, a naphthalen-1-yloxy group, a naphthalen-2-yloxy group, an acetoxy group, a propanoyloxy group, a (meth)acryloyloxy group, a benzoyl group, a 1-naphthoyl group, a 2-naphthoyl group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an amino group, a nitro group, a methoxycarbonyl group, an ethoxycarbonyl group, a 2-methoxyethoxycarbonyl group, a 2-ethoxyethoxycarbonyl group, a 2-acetoxyethoxycarbonyl group, and a 2-(meth)acryloyloxyethoxycarbonyl group. 【Chemical 1】 (In formula (1), R1 and R2 are each independently a hydrogen atom or a monovalent organic group, R1 and R2 may be bonded to each other to form a ring, the ring may contain one or more elements selected from the group consisting of N, S, and O as ring-constituting elements, R3 is an aromatic group which may have a substituent, and R4 is a methylene group or a single bond.)

2. The method for producing modified metal oxide fine particles according to claim 1, wherein the aromatic group-containing carboxylic acid compound (A) is a phthalic acid monoester.

3. The method for producing modified metal oxide fine particles according to claim 1 or 2, wherein the nitrogen-containing organic solvent contains a nitrogen-containing compound represented by the following formula (S1): 【Chemical 2】 (In formula (S1), R Ｓ１ and R Ｓ２ are each independently an alkyl group having 1 to 3 carbon atoms, and R Ｓ３ is a hydrogen atom, or the following formula (S1-1) or the following formula (S1-2): 【Chemical 3】 is a group represented by, R Ｓ４ is a hydrogen atom or a hydroxyl group, R Ｓ５ and R Ｓ６ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R Ｓ７ and R Ｓ８ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R Ｓ３ When is a group represented by the formula (S1-1), R Ｓ２ and R Ｓ３ may be bonded to each other to form a ring.)

4. ​ Manufacturing modified metal oxide fine particles by the method according to any one of claims 1 to 3, and mixing the modified metal oxide fine particles and a base material component (C) in a solvent (S) to obtain a modified metal oxide fine particle dispersion liquid, the method for manufacturing a modified metal oxide fine particle dispersion liquid including this.

5. Manufacturing a modified metal oxide fine particle dispersion liquid by the method according to claim 4, and molding the modified metal oxide fine particle dispersion liquid according to the shape of the solid article to be formed, and solidifying the molded modified metal oxide fine particle dispersion liquid by one or more methods selected from the group consisting of drying, curing by moisture, heating, and exposure, the method for manufacturing a solid article including this.

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