CN104102091B - Composition for forming transparent insulating film - Google Patents

Abstract

The invention provides a composition for forming a transparent insulating film, which can form a transparent insulating film with excellent transparency and high dielectric constant, a transparent insulating film obtained by using the composition for forming the transparent insulating film, and a display device with the transparent insulating film. The composition for forming a transparent insulating film contains, as a filler, 1 or more selected from the group consisting of simple substances, oxides, chelate compounds, salts, and alloys of elements whose ground states accommodate electrons in the 4f orbital or the 5d orbital. As the composition for forming a transparent insulating film, preferred are: a composition comprising (A) a filler, (B1) a compound having an alicyclic epoxy group-containing group, and (C) an acid generator; or a composition containing (A) a filler and (B2) a resin, wherein the resin (B2) is at least 1 selected from the group consisting of silicone resins, polyamideimides, polyimides, polycarbonates, polyethers, polythioethers, and polymers of monomers having ethylenically unsaturated double bonds.

Description

Composition for forming transparent insulating film

Technical Field

The present invention relates to a composition for forming a transparent insulating film, a transparent insulating film obtained using the composition for forming a transparent insulating film, and a display device provided with the transparent insulating film.

Background

In a display device such as a liquid crystal display device, a material such as an insulating film needs to efficiently transmit light emitted from a light source such as a backlight. Therefore, a material having excellent transparency and a high dielectric constant is required for forming the insulating film.

As described above, as a material for forming an insulating film having excellent transparency and high dielectric constant, for example, a BaTiO having a perovskite (perovskite) crystal structure containing a resin such as a thermosetting resin has been proposed₃Such as inorganic particles and an organic solvent (patent document 1).

Documents of the prior art

Patent document

Patent document 1: japanese laid-open patent publication No. 2007-214107

Disclosure of Invention

Problems to be solved by the invention

However, there is still room for improvement in the transparency of the insulating film formed using the paste composition described in patent document 1. It is considered that the transparency of the insulating film can be improved by reducing the particle diameter of the inorganic particles having a specific crystal structure. However, in this case, there is a problem that the dielectric constant of the insulating film to be formed is lowered. Therefore, it is difficult to form a transparent insulating film having both high transparency and high dielectric constant.

The present invention has been made in view of the above problems, and an object thereof is to provide a composition for forming a transparent insulating film capable of forming a transparent insulating film having excellent transparency and a high dielectric constant, a transparent insulating film obtained using the composition for forming a transparent insulating film, and a display device provided with the transparent insulating film

Means for solving the problems

The present inventors have found that the above-mentioned problems can be solved by adding 1 or more selected from the group consisting of simple substances, oxides, chelate compounds, salts, and alloys of elements whose ground states accommodate electrons in the 4f orbital or 5d orbital as a filler to a composition for forming a transparent insulating film, and have completed the present invention.

The first aspect of the present invention is a composition for forming a transparent insulating film, which contains 1 or more kinds selected from a simple substance, an oxide, a chelate compound, a salt and an alloy of an element that holds electrons in a 4f orbit or a 5d orbit in a ground state as (a) a filler, and which can form a film having a transmittance of light having a wavelength of 400nm of 90% or more when measured using a sample having a thickness of 2 μm.

The second aspect of the present invention is a transparent insulating film obtained by using the composition for forming a transparent insulating film of the first aspect.

A third aspect of the present invention is a display device including the transparent insulating film according to the second aspect.

Effects of the invention

According to the present invention, it is possible to provide a composition for forming a transparent insulating film capable of forming a transparent insulating film having excellent transparency and a high dielectric constant, a transparent insulating film obtained using the composition for forming a transparent insulating film, and a display device provided with the transparent insulating film.

Detailed Description

Composition for forming transparent insulating film

The composition for forming a transparent insulating film (hereinafter, also referred to as a composition for forming a film) of the present invention contains 1 or more kinds selected from a simple substance, an oxide, a chelate compound, a salt, and an alloy of an element that holds electrons in a 4f orbital or a 5d orbital in a ground state as (a) a filler. The composition for forming a transparent insulating film of the present invention can form a film having a transmittance of 90% or more for light having a wavelength of 400nm when measured using a sample having a thickness of 2 μm.

In the transparent film containing the filler (a), absorption tends to increase as the wavelength of light decreases. Therefore, if the transparent insulating film formed using the composition for forming a transparent insulating film has a transmittance of 90% or more at a wavelength of 400nm, the transparent insulating film has sufficiently high transparency in the wavelength range of visible light. For this reason, the transmittance of light having a wavelength of 400nm is used as an index of the transparency of the transparent insulating film.

The filler (a) contained in the composition for forming a transparent insulating film will be described below.

[ (A) Filler Material ]

(A) The filler is selected from a simple substance, an oxide, a chelate compound, a salt, and an alloy of an element whose ground state accommodates electrons in the 4f orbital or the 5d orbital. The elements in which electrons are held in the 4f orbital or 5d orbital in the ground state are the elements having atomic numbers of 57 to 86. Specifically, these elements are La (57), Ce (58), Pr (59), Nd (60), Pm (61), Sm (62), Eu (63), Gd (64), Tb (65), Dy (66), Ho (67), Er (68), Tm (69), Yb (70), Lu (71), Hf (72), Ta (73), W (74), Re (75), Os (76), Ir (77), Pt (78), Au (79), Hg (80), T1(81), Pb (82), Bi (83), Po (84), At (85) and Rn (86). The numerical values in parentheses represent the atomic numbers of the respective elements. These elements have high electron density. Therefore, the simple substance, oxide, chelate compound, salt and alloy of these elements have a high dielectric constant. In addition, in the film formed using the film-forming composition, the simple substance, oxide, chelate compound, salt, and alloy of such an element are dispersed in the matrix constituting the film, and the transmission of visible light is not hindered. Therefore, the transparent insulating film formed using the film-forming composition containing the filler (a) has a high dielectric constant and excellent transparency.

As an element contained in a simple substance, an oxide, a chelate compound, a salt, or an alloy, which contains electrons in the 4f orbital or the 5d orbital in the ground state, from the viewpoint of increasing the dielectric constant of the filler (a), an element containing electrons in the 5d orbital in the number of electrons equal to or less than the number of electrons when the 5d orbital becomes a half-filled shell, or an element containing electrons in the 4f orbital in the number of electrons equal to or less than the number of electrons when the 4f orbital becomes a half-filled shell is preferable. Specific examples of such preferable elements are La (57), Ce (58), Pr (59), Nd (60), Pm (61), Sm (62), Eu (63), Gd (64), Lu (71), Hf (72), Ta (73), W (74) and Re (75). Among these elements, La (57), Ce (58), Gd (64), Lu (71) and Hf (72) are more preferable.

When the filler (a) is an oxide, the atomic valence of an element which contains electrons in the 4f orbital or the 5d orbital in the ground state contained in the oxide is not particularly limited.

When the filler (a) is a chelate compound, examples of the ligand that forms a chelate with an element that holds electrons in the 4f orbital or 5d orbital in the ground state include pyridine, triphenylphosphine, carbon monoxide, ethylenediamine, bipyridine, catechol, ethylenediaminetetraacetic acid (EDTA), and the like.

When the filler (a) is a salt of an element that holds electrons in the 4f orbital or 5d orbital in the ground state, the salt may be a salt of an inorganic acid or a salt of an organic acid. Preferred salts include halides, sulfates, nitrates, phosphates, acetates, formates, propionates, benzoates and the like. The valency of the element constituting the salt which holds an electron in the 4f orbital or 5d orbital in the ground state is not particularly limited.

When the filler (a) is an alloy, the combination of the metals (elements) contained in the alloy is not particularly limited. The mixing ratio of the plurality of metals (elements) contained in the alloy is also not particularly limited.

Among simple substances, oxides, chelate compounds, salts and alloys of elements whose ground states accommodate electrons in the 4f orbital or 5d orbital, oxides are preferable in terms of being stable in the composition and easily forming a film excellent in transparency by using the film-forming composition.

As a preferable specific example of the oxide of an element whose ground state contains electrons in the 4f orbital or 5d orbital, La can be mentioned₂O₃、CeO₂、Nd₂O₃、Gd₂O₃、Ho₂O₃、Lu₂O₃、HfO₂And Ta₂O₅。

(A) The shape of the filler is not particularly limited. (A) The particle size of the filler is preferably 1 to 200 μm, more preferably 1 to 50 μm, in terms of primary particle size. (A) The particle size of the filler is preferably 10 to 1000 μm, more preferably 10 to 200 μm in terms of secondary particle size.

The content of the filler (a) in the film-forming composition is not particularly limited as long as the object of the present invention is not impaired. Typically, the content of the filler (a) in the film-forming composition is preferably 1 to 80 mass%, more preferably 1 to 70 mass%, and particularly preferably 3 to 60 mass% with respect to the mass of the solid components in the film-forming composition. When the filler (a) is added to the film-forming composition in an amount within such a range, a transparent insulating film having a high dielectric constant can be easily formed, and a film-forming composition having excellent film-forming properties can be easily obtained.

The film-forming composition is a composition containing the filler (a) and is capable of forming a film. Therefore, the film-forming composition contains a matrix material for forming a film in addition to the filler (a). The material for forming the matrix is not particularly limited as long as it is a material capable of forming a film having a predetermined transparency by using the film-forming composition. Examples of such a material include a curable material, a thermoplastic resin, and a resin soluble in a solvent. The curable material is usually used together with a curing agent and a polymerization initiator. When the curable substance can be self-cured by heat or light, a curing agent or a polymerization initiator is not necessarily required.

Various additives may be added to the film-forming composition as needed. Specifically, examples thereof include a solvent, a sensitizer, a crosslinking agent, an antioxidant, an ultraviolet absorber, an antifoaming agent, an adhesion enhancer, a surfactant, and the like. The amount of these additives to be used is not particularly limited, and may be appropriately determined depending on the kind of the additives, within a range not to impair the object of the present invention.

Preferred specific examples of the film-forming composition containing (a) a filler and a material for forming a matrix of a film described above include: a film-forming composition containing (A) a filler, (B1) a compound having an alicyclic epoxy group, and (C) an acid generator; and a film-forming composition containing (A) a filler and (B2) a resin. (B2) The resin needs to be transparent. Therefore, as the (B2) resin, 1 or more selected from silicone resins, polyamideimides, polyimides, polycarbonates, polyethers, polythioethers, and polymers of monomers having an ethylenically unsaturated double bond are preferably used.

< composition for forming transparent insulating film containing alicyclic epoxy Compound >

The components contained in the film-forming composition containing (a) a filler, (B1) a compound having an alicyclic epoxy group, and (C) an acid generator will be described below. Note that the description of the filler (a) is omitted.

[ (B1) Compound having an alicyclic epoxy group ]

When (B1) the compound having an alicyclic epoxy group is cured by the action of the acid generated from (C) the acid generator, a cured product having high transparency can be obtained. When the specific filler (a) is dispersed in the cured product of the compound having an alicyclic epoxy group (B1), the dielectric constant of the cured product can be improved without impairing the transparency. Therefore, when a film-forming composition containing (a) a filler, (B1) a compound having an alicyclic epoxy group, and (C) an acid generator is used, a transparent insulating film having excellent transparency and a high dielectric constant can be formed. (B1) The molecular weight of the alicyclic epoxy compound is preferably 100 to 800, and more preferably 500 or less. The total content of the compound having an alicyclic epoxy group (B1) and the acid generator (C) in the solid content of the film-forming composition is preferably 20 to 99% by mass, more preferably 30 to 80% by mass, and still more preferably 40 to 70% by mass.

Specific examples of the alicyclic epoxy compound include 2- (3, 4-epoxycyclohexyl-5, 5-spiro-3, 4-epoxy) cyclohexane-meta-dioxane, bis (3, 4-epoxycyclohexylmethyl) adipate, bis (3, 4-epoxy-6-methylcyclohexylmethyl) adipate, 3, 4-epoxy-6-methylcyclohexyl-3 ', 4 ' -epoxy-6 ' -methylcyclohexaneformate, epsilon-caprolactone-modified 3, 4-epoxycyclohexylmethyl-3 ', 4 ' -epoxycyclohexanecarboxylate, trimethylcaprolactone-modified 3, 4-epoxycyclohexylmethyl-3 ', 4 ' -epoxycyclohexanecarboxylate, β -methyl-delta-valerolactone-modified 3, 4-epoxycyclohexylmethyl-3 ', 4 ' -epoxycyclohexanecarboxylate, methylenebis (3, 4-epoxycyclohexane), bis (3, 4-epoxycyclohexylmethyl) ether of ethylene glycol, ethylenebis (3, 4-epoxycyclohexane formate), dioctylphthalate and di-2-epoxyethylhexyl phthalate, and those compounds represented by the following specific examples are preferable in terms of the hardness of these alicyclic epoxy compounds, and those compounds are given by excellent transparency and high hardness.

[ CHEM 1 ]

(in the formula (1), X is selected from the group consisting of a single bond, -O-CO-, -S-, -SO-, -SO₂－、－CH₂－、－C(CH₃)₂－、－CBr₂－、－C(CBr₃)₂－、－C(CF₃)₂-and-R¹⁹The 2-valent radical in-O-CO-, R¹⁹Is C1-C8 alkylene, R¹～R¹⁸Each independently is a group selected from a hydrogen atom, a halogen atom and an organic group. )

Formula (A), (B) and1) in, R¹⁹Is an alkylene group having 1 to 8 carbon atoms, preferably a methylene group or an ethylene group.

At R¹～R¹⁸In the case of an organic group, the organic group is not particularly limited insofar as it does not inhibit the object of the present invention, and may be a hydrocarbon group, a group containing a carbon atom and a halogen atom, or a group containing a carbon atom, a hydrogen atom, and a heteroatom such as a halogen atom, an oxygen atom, a sulfur atom, a nitrogen atom, or a silicon atom. Examples of the halogen atom include a chlorine atom, a bromine atom, an iodine atom, a fluorine atom and the like.

As the organic group, preferred are: a hydrocarbyl group; a group containing a carbon atom, a hydrogen atom and an oxygen atom; a halogenated hydrocarbon group; a group containing a carbon atom, an oxygen atom and a halogen atom; a group containing a carbon atom, a hydrogen atom, an oxygen atom and a halogen atom. 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 carbon number of the organic group is preferably 1 to 20, more preferably 1 to 10, and particularly preferably 1 to 5.

Specific examples of the hydrocarbon group include chain alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl and n-eicosyl, chain alkenyl groups such as vinyl, 1-propenyl, 2-n-propenyl (allyl), 1-n-butenyl, 2-n-butenyl and 3-n-butenyl, cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cycloheptyl, aryl groups such as phenyl, o-tolyl, m-tolyl, p-tolyl, α -naphthyl, β -naphthyl, 4-biphenyl, 3-biphenyl, 2-biphenyl, anthryl and phenanthryl, and aralkyl groups such as benzyl, phenethyl, α -naphthylmethyl, β -naphthylmethyl, 36 α -naphthylethyl and β -naphthylethyl.

Specific examples of the halogenated hydrocarbon groups are: halogenated chain alkyl groups such as chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, fluoromethyl, difluoromethyl, trifluoromethyl, 2, 2, 2-trifluoroethyl, pentafluoroethyl, heptafluoropropyl, perfluorobutyl, perfluoropentyl, perfluorohexyl, perfluoroheptyl, perfluorooctyl, perfluorononyl, and perfluorodecyl; halocycloalkyl groups such as 2-chlorocyclohexyl, 3-chlorocyclohexyl, 4-chlorocyclohexyl, 2, 4-dichlorocyclohexyl, 2-bromocyclohexyl, 3-bromocyclohexyl and 4-bromocyclohexyl; halogenated aryl groups such as 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, 2, 3-dichlorophenyl, 2, 4-dichlorophenyl, 2, 5-dichlorophenyl, 2, 6-dichlorophenyl, 3, 4-dichlorophenyl, 3, 5-dichlorophenyl, 2-bromophenyl, 3-bromophenyl, 4-bromophenyl, 2-fluorophenyl, 3-fluorophenyl, and 4-fluorophenyl; and halogenated aralkyl groups such as 2-chlorophenylmethyl, 3-chlorophenylmethyl, 4-chlorophenylmethyl, 2-bromophenylmethyl, 3-bromophenylmethyl, 4-bromophenylmethyl, 2-fluorophenylmethyl, 3-fluorophenylmethyl, and 4-fluorophenylmethyl.

Examples of the group containing a carbon atom, a hydrogen atom and an oxygen atom include a hydroxyalkyl group such as a hydroxymethyl group, a 2-hydroxyethyl group, a 3-hydroxy-n-propyl group and a 4-hydroxy-n-butyl group, a halocycloalkyl group such as a 2-hydroxycyclohexyl group, a 3-hydroxycyclohexyl group and a 4-hydroxycyclohexyl group, a hydroxyaryl group such as a 2-hydroxyphenyl group, a 3-hydroxyphenyl group, a 4-hydroxyphenyl group, a 2, 3-dihydroxyphenyl group, a 2, 4-dihydroxyphenyl group, a 2, 5-dihydroxyphenyl group, a 2, 6-dihydroxyphenyl group, a 3, 4-dihydroxyphenyl group and a 3, 5-dihydroxyphenyl group, a hydroxyaryl group such as a 2-hydroxyphenylmethyl group, a 3-hydroxyphenylmethyl group and a 4-hydroxyphenylmethyl group, a hydroxyarylphenoxy group such as a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, an iso-butoxy group, an sec-butoxy group, a tert-butoxy group, an n-pentyloxy group, an n-hexyloxy group, an n-heptyloxy group, an n-octyloxy group, a 2-ethylhexyloxy group, an n-nonyloxy group, an aliphatic decyloxy group, an n-undecyloxy group, an n-tridecyloxy group, an n-tetradecyloxy group, a n-decyloxy group, a 2-decyloxy group, a 3-decyloxy group, a 2-decyloxy group, a 3-octyloxy group, a 2-octyloxy group, a 3-octylpropoxy group, a 2-octylpropoxy group, a benzoyloxy group, a 2-octylpropoxy group, a 2-.

R¹～R¹⁸Each independently preferably being 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, and more preferably R is used from the viewpoint of the hardness of a transparent insulating film obtained using the film-forming composition¹～R¹⁸All are hydrogen atoms.

Among the alicyclic epoxy compounds represented by formula (1), preferable specific examples of the compounds include the following compounds 1 and 2.

[ CHEM 2 ]

The film-forming composition may contain (B1) the compound having an alicyclic epoxy group and an epoxy compound other than (B1) the compound having an alicyclic epoxy group, within a range not to impair the object of the present invention. Examples of the epoxy compound that can be used together with (B1) the compound having an alicyclic epoxy group are: epoxy alkyl (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-hexyl (meth) acrylate, and 6-glycidyloxy-n-hexyl (meth) acrylate; 2-functional 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, and biphenyl type epoxy resin; novolac epoxy resins such as phenol novolac epoxy resin, brominated phenol novolac epoxy resin, o-cresol novolac epoxy resin, bisphenol a novolac epoxy resin, and bisphenol AD novolac epoxy resin; an epoxy resin having an oxytetracyclodecene group; cyclic aliphatic epoxy resins such as epoxides of dicyclopentadiene type phenol resins; aromatic epoxy resins such as epoxides of naphthalene-based phenol resins; 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 m-xylylenediamine, and tetraglycidyl diaminomethylcyclohexane; heterocyclic epoxy resins such as triglycidyl isocyanurate; 3-functional epoxy resins such as phloroglucinol triglycidyl ether, trihydroxybiphenyl triglycidyl ether, trihydroxyphenylmethane triglycidyl ether, glycerol 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-methylethyl ] phenyl ] ethyl ] phenoxy ] -2-propanol; 4-functional epoxy resins such as tetrahydroxyphenylethane tetraglycidyl ether, tetraglycidyl benzophenone, bisresorcinol tetraglycidyl ether and tetracyclooxypropoxybiphenyl.

When the film-forming composition contains an epoxy compound other than the (B1) compound having an alicyclic epoxy group, the amount of the epoxy compound represented by formula (1) is preferably 70% by mass or more, more preferably 80% by mass or more, and particularly preferably 90% by mass or more, relative to the total mass of the epoxy compounds in the film-forming composition.

[ (C) acid generators ]

As the acid generator, a photoacid generator which generates an acid by irradiation of active light or radiation, or a thermal acid generator which generates an acid by heating is suitably used.

The photoacid generator is preferably the acid generator according to any of the first to fifth embodiments described below. The photoacid generators of the preferred embodiments of the photoacid generators will be described below.

The photoacid generator of the first embodiment includes a compound represented by the following formula (c 1).

[ CHEM 3]

In the above formula (c1), X^1cRepresents a sulfur atom or an iodine atom having a valence of g, and g is 1 or 2. h represents the number of repeating units of the structure in parentheses. R^1cIs equal to X^1cA bonded organic group which represents an aryl group having 6 to 30 carbon atoms, a heterocyclic group having 4 to 30 carbon atoms, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms or an alkynyl group having 2 to 30 carbon atoms, R^1cMay be substituted with at least 1 kind of group selected from alkyl, hydroxy, alkoxy, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, arylthiocarbonyl, acyloxy, arylthio, alkylthio, aryl, heterocycle, aryloxy, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, alkyleneoxy, amino, cyano, nitro and halogen. R^1cThe number of (b) is g + h (g-1) +1, R^1cEach may be the same or different. In addition, 2 or more R^1cCan be directly bonded to each other or via-O-, -S-, -SO₂－、－NH－、－NR^2c-, -CO-, -COO-, -CONH-, an alkylene group having 1 to 3 carbon atoms, or a phenylene group are bonded to form a group containing X^1cThe ring structure of (a). R^2cIs an alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 10 carbon atoms.

X^2cThe structure is represented by the following formula (c 2).

[ CHEM 4 ]

In the above formula (c2), X^4cX represents a 2-valent group of an alkylene group having 1 to 8 carbon atoms, an arylene group having 6 to 20 carbon atoms or a heterocyclic compound having 8 to 20 carbon atoms^4cCan be substituted with at least 1 kind selected from alkyl with 1-8 carbon atoms, alkoxy with 1-8 carbon atoms, aryl with 6-10 carbon atoms, hydroxyl, cyano, nitro and halogen. X^5crepresents-O-, -S-, -SO-, -SO₂－、－NH－、－NR^2c-, -CO-, -COO-, -CONH-, an alkylene group having 1 to 3 carbon atoms, or a phenylene group. h represents the number of repeating units of the structure in parentheses. h + 1X^4cAnd h of X^5cMay be the same or different, respectively. R^2cAs defined above.

X^3c-Examples of the onium counter ion include an alkylfluorophosphate anion represented by the following formula (c17) and a borate anion represented by the following formula (c 18).

[ CHEM 5 ]

In the above formula (c17), R^3cRepresents an alkyl group which may be substituted by a fluorine atom. At R^3cIn the case of an alkyl group substituted with a fluorine atom, it is preferable that 80% or more of hydrogen atoms in the alkyl group be substituted with a fluorine atom. j represents R^3cThe number of (a) is an integer of 1 to 5. j R^3cMay be the same or different, respectively.

[ CHEM 6]

In the above formula (c18), R^4c～R^7cEach independently represents a fluorine atom or a phenyl group, and a part or all of hydrogen atoms of the phenyl group may be substituted by at least 1 selected from a fluorine atom and a trifluoromethyl group.

Examples of the onium ion in the compound represented by the formula (c1) include: triphenylsulfonium, tri-p-tolylsulfonium, 4- (phenylthio) phenyldiphenylsulfonium, bis [ 4- (diphenylsulfonium) phenyl ] sulfide, bis [ 4- { bis [ 4- (2-hydroxyethoxy) phenyl ] sulfonium } phenyl ] sulfide, bis { 4- [ bis (4-fluorophenyl) sulfonium ] phenyl } sulfide, 4- (4-benzoyl-2-chlorophenylthio) phenylbis (4-fluorophenyl) sulfonium, 7-isopropyl-9-oxo-10-thia-9, 10-dihydro-2-anthracenyl-di-p-tolylsulfonium, 7-isopropyl-9-oxo-10-thia-9, 10-dihydro-2-anthracenyl diphenylsulfonium, 2- [ (diphenyl) sulfonium ] thioxanthone, 4- [ 4- (4-tert-butylbenzoyl) phenylthio ] phenyl-di-p-tolylsulfonium, 4- (4-benzoylphenylthio) phenyldiphenylsulfonium, diphenylphenylacetylsulfonium, diphenylbenzenesulfonium, 4-hydroxyphenylmethylbenzylsulfonium, 2-naphthylmethyl (1-ethoxycarbonyl) ethylsulfonium, 4-hydroxyphenylmethylbenzoylacetylsulfonium, phenyl [ 4- (4-biphenylthio) phenyl ] 4-biphenylsulfonium, phenyl [ 4- (4-biphenylthio) phenyl ] 3-biphenylsulfonium, [ 4- (4-acetylphenylsulfanyl) phenyl ] diphenylsulfonium, octadecylmethylbenzoylsulfonium, diphenyliodonium, di-p-tolyliodonium, bis (4-dodecylphenyl) iodonium, bis (4-methoxyphenyl) iodonium, (4-octyloxyphenyl) phenyliodonium, bis (4-decyloxy) phenyliodonium, 4- (2-hydroxytetradecyloxy) phenyliodonium, 4-isopropylphenyl (p-tolyl) iodonium, or 4-isobutylphenyl (p-tolyl) iodonium, and the like.

Among the onium ions in the compound represented by the above formula (c1), a preferable onium ion is a sulfonium ion represented by the following formula (c 19).

[ CHEM 7 ]

In the above formula (c19), R^8cEach independently represents a group selected from a hydrogen atom, an alkyl group, a hydroxyl group, an alkoxy group, an alkylcarbonyl group, an alkylcarbonyloxy group, an alkoxycarbonyl group, a halogen atom, an aryl group which may have a substituent, and an arylcarbonyl group. X^2cX in the above formula (c1)^2cThe same meaning is used.

Specific examples of the sulfonium ion represented by the above formula (c19) include 4- (phenylthio) phenyldiphenylsulfonium, 4- (4-benzoyl-2-chlorophenylthio) phenylbis (4-fluorophenyl) sulfonium, 4- (4-benzoylphenylthio) phenyldiphenylsulfonium, phenyl [ 4- (4-biphenylthio) phenyl ] 4-biphenylsulfonium, phenyl [ 4- (4-biphenylthio) phenyl ] 3-biphenylsulfonium, [ 4- (4-acetylphenylthio) phenyl ] diphenylsulfonium, and diphenyl [ 4- (p-terphenylthio) phenyl ] diphenylsulfonium.

In the alkylfluorophosphate anion represented by the above formula (c17), R^3cRepresents an alkyl group substituted with a fluorine atom, and preferably has 1 to 8 carbon atoms, and more preferably has 1 to 4 carbon atoms. Specific examples of the alkyl group include straight-chain alkyl groups such as methyl, ethyl, propyl, butyl, pentyl and octyl; branched alkyl groups such as isopropyl, isobutyl, sec-butyl, and tert-butyl; and cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl, and the proportion of hydrogen atoms in the alkyl groups substituted by fluorine atoms is usually 80% or more, preferably 90% or more, and more preferably 100%. When the substitution rate of fluorine atoms is less than 80%, the acid strength of the onium alkyl fluorophosphate represented by the above formula (c1) decreases.

Particularly preferred R^3cIs a linear or branched perfluoroalkyl group having 1 to 4 carbon atoms and a fluorine atom substitution rate of 100%, and specific examples thereof include CF₃、CF₃CF₂、(CF₃)₂CF、CF₃CF₂CF₂、CF₃CF₂CF₂CF₂、(CF₃)₂CFCF₂、CF₃CF₂(CF₃)CF、(CF₃)₃C。R^3cThe number j of (a) is an integer of 1 to 5, preferably 2 to 4, and particularly preferably 2 or 3.

Specific examples of preferred alkylfluorophosphate anions include: [ (CH)₃CH₂)₂PF₄]^-、[(CH₃CH₂)₃PF₃]^-、[((CH₃)₂CH)₂PF₄]^-、[((CH₃)₂CH)₃PF₃]^-、[(CH₃CH₂CH₂)₂PF₄]^-、[(CH₃CH₂CH₂)₃PF₃]^-、[((CH₃)₂CHCH₂)₂PF₄]^-、[((CH₃)₂CHCH₂)₃PF₃]^-、[(CH₃CH₂CH₂CH₂)₂PF₄]^-(ii) a Or [ (CH)₃CH₂CH₂)₃PF₃]^-、[(CF₃CF₂)₂PF₄]^-、[(CF₃CF₂)₃PF₃]^-、[((CF₃)₂CF)₂PF₄]^-、[((CF₃)₂CF)₃PF₃]^-、[(CF₃CF₂CF₂)₂PF₄]^-、[(CF₃CF₂CF₂)₃PF₃]^-、[((CF₃)₂CFCF₂)₂PF₄]^-、[((CF₃)₂CFCF₂)₃PF₃]^-、[(CF₃CF₂CF₂CF₂)₂PF₄]^-(ii) a Or [ (CF)₃CF₂CF₂)₃PF₃]^-. Among them, particularly preferred are: [ (CH)₃CH₂)₃PF₃]^-、[(CH₃CH₂CH₂)₃PF₃]^-、[((CH₃)₂CH)₃PF₃]^-、[((CH₃)₂CH)₂PF₄]^-、[((CH₃)₂CHCH₂)₃PF₃]^-(ii) a Or [ ((CH)₃)₂CHCH₂)₂PF₄]^-、[(CF₃CF₂)₃PF₃]^-、[(CF₃CF₂CF₂)₃PF₃]^-、[((CF₃)₂CF)₃PF₃]^-、[((CF₃)₂CF)₂PF₄]^-、[((CF₃)₂CFCF₂)₃PF₃]^-(ii) a Or [ ((CF)₃)₂CFCF₂)₂PF₄]^-。

As the boric acid represented by the above formula (c18)Specific preferred examples of the salt anion include tetrakis (pentafluorophenyl) borate ([ B (C)₆F₅)₄]^-) Tetra [ (trifluoromethyl) phenyl group]Borate ([ B (C) ]₆H₄CF₃)₄]^-) Difluoro bis (pentafluorophenyl) borate ([ (C)₆F₅)₂BF₂]^-) Trifluoro-pentafluorophenyl borate ([ (C)₆F₅)BF₃]^-) Tetrakis (difluorophenyl) borate ([ B (C) ]₆H₃F₂)₄]^-) And the like. Among them, tetrakis (pentafluorophenyl) borate ([ B (C) is particularly preferable₆F₅)₄]^-)。

As the photoacid generator of the second embodiment, there can be mentioned: 2, 4-bis (trichloromethyl) -6-piperonyl-1, 3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [ 2- (2-furyl) vinyl ] s-triazine, 2, 4-bis (trichloromethyl) -6- [ 2- (5-methyl-2-furyl) vinyl ] s-triazine, 2, 4-bis (trichloromethyl) -6- [ 2- (5-ethyl-2-furyl) vinyl ] s-triazine, 2, 4-bis (trichloromethyl) -6- [ 2- (5-propyl-2-furyl) vinyl ] s-triazine, 2, 4-bis (trichloromethyl) -6- [ 2- (3, 5-dimethoxyphenyl) vinyl ] s-triazine, 2, 4-bis (trichloromethyl) -6- [ 2- (3, 5-diethoxyphenyl) vinyl ] s-triazine, 2, 4-bis (trichloromethyl) -6- [ 2- (3, 5-Dipropyloxyphenyl) vinyl ] s-triazine, 2, 4-bis (trichloromethyl) -6- [ 2- (3-methoxy-5-ethoxyphenyl) vinyl ] s-triazine, 2, 4-bis (trichloromethyl) -6- [ 2- (3-methoxy-5-propoxyphenyl) vinyl ] s-triazine, 2, 4-bis (trichloromethyl) -6- [ 2- (3, 4-methylenedioxyphenyl) vinyl ] s-triazine, 2, 4-bis (trichloromethyl) -6- (3, 4-methylenedioxyphenyl) s-triazine, 2, 4-bis-trichloromethyl-6- (3-bromo-4-methoxy) phenyl s-triazine, 2, 4-bis-trichloromethyl-6- (2-bromo-4-methoxy) styrylphenyl s-triazine, 2, 4-bis-trichloromethyl-6- (3-bromo-4-methoxy) styrylphenyl s-triazine, 2- (4-methoxyphenyl) -4, 6-bis (trichloromethyl) -1, 3, 5-triazine, 2- (4-methoxynaphthyl) -4, 6-bis (trichloromethyl) -1, 3, 5-triazine, 2- [ 2- (2-furyl) vinyl ] -4, 6-bis (trichloromethyl) -1, 3, 5-triazine, 2- [ 2- (5-methyl-2-furyl) vinyl ] -4, 6-bis (trichloromethyl) -1, 3, 5-triazine, 2- [ 2- (3, 5-dimethoxyphenyl) vinyl ] -4, 6-bis (trichloromethyl) -1, 3, 5-triazine, 2- [ 2- (3, 4-dimethoxyphenyl) vinyl ] -4, 6-bis (trichloromethyl) -1, halogen-containing triazine compounds such as 3, 5-triazine, 2- (3, 4-methylenedioxyphenyl) -4, 6-bis (trichloromethyl) -1, 3, 5-triazine, tris (1, 3-dibromopropyl) -1, 3, 5-triazine, tris (2, 3-dibromopropyl) -1, 3, 5-triazine, and halogen-containing triazine compounds represented by the following formula (c3) such as tris (2, 3-dibromopropyl) isocyanurate.

[ CHEM 8 ]

In the above formula (c3), R^9c、R^10c、R^11cEach independently represents a haloalkyl group.

Examples of the photoacid generator of the third embodiment include α - (p-toluenesulfonyloxyimino) phenylacetonitrile, α - (benzenesulfonyloxyimino) -2, 4-dichlorophenylacetonitrile, α - (benzenesulfonyloxyimino) -2, 6-dichlorophenylacetonitrile, α - (2-chlorobenzenesulfonyloxyimino) -4-methoxyphenylacetonitrile, α - (ethylsulfonyloxyimino) -1-cyclopentenylacetonitrile, and a compound represented by the following formula (c4) containing an oxime sulfonate group.

[ CHEM 9]

In the above formula (c4), R^12cRepresents a 1-, 2-or 3-valent organic group, R^13cRepresents substituted or unsubstitutedThe saturated hydrocarbon group, the unsaturated hydrocarbon group or the aromatic compound group in (1), and n represents the number of repeating units in the structure in parentheses.

In the formula (c4), the aromatic compound group means a group of a compound showing physical and chemical properties peculiar to an aromatic compound, and examples thereof include: aryl groups such as phenyl and naphthyl; heteroaryl groups such as furyl and thienyl. These aromatic compound groups may have 1 or more suitable substituents such as halogen atoms, alkyl groups, alkoxy groups, and nitro groups on the ring. Furthermore, R^13cParticularly preferred is an alkyl group having 1 to 6 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group and a butyl group. Particular preference is given to R^12cIs an aromatic compound group and R^13cA compound having an alkyl group with 1 to 4 carbon atoms.

When n =1, the acid generator represented by the formula (c4) may be R^12cIs any one of phenyl, methylphenyl and methoxyphenyl and R^13cSpecific examples of the compound which is a methyl group include α - (methylsulfonoxyimino) -1-phenylacetonitrile, α - (methylsulfonoxyimino) -1- (p-methylphenyl) acetonitrile, α - (methylsulfonoxyimino) -1- (p-methoxyphenyl) acetonitrile, [ 2- (propylsulfonyloxyimino) -2, 3-dihydroxy-3-thienylene ] (o-tolyl) acetonitrile, and when n =2, specific examples of the photoacid generator represented by the above formula (c4) include a photoacid generator represented by the following formula.

[ CHEM 10 ]

Further, as the photoacid generator of the fourth embodiment, an onium salt having a naphthalene ring in the cation portion can be mentioned. The "having a naphthalene ring" means having a structure derived from naphthalene, and means maintaining the structure of at least 2 rings and their aromaticity. The naphthalene ring may have a substituent such as a linear or branched alkyl group having 1 to 6 carbon atoms, a hydroxyl group, or a linear or branched alkoxy group having 1 to 6 carbon atoms. The structure derived from the naphthalene ring may be a 1-valent group (free valence is 1) or a 2-valent group (free valence is 2) or more, but is preferably a 1-valent group (in this case, the value is obtained by calculating the free valence after removing a portion bonded to the substituent). The number of naphthalene rings is preferably 1 to 3.

The cation portion of the onium salt having a naphthalene ring in the cation portion is preferably a structure represented by the following formula (c 5).

[ CHEM 11 ]

In the above formula (c5), R^14c、R^15c、R^16cAt least one of them represents a group represented by the following formula (c6), and the rest R^14c、R^15c、R^16cRepresents a linear or branched alkyl group having 1 to 6 carbon atoms, a phenyl group which may have a substituent, a hydroxyl group, or a linear or branched alkoxy group having 1 to 6 carbon atoms. Or, R^14c、R^15c、R^16cOne of the groups is a group represented by the following formula (c6), the remaining two groups are each independently a linear or branched alkylene group having 1 to 6 carbon atoms, and R is^14c、R^15c、R^16cMay be bonded to form a ring.

[ CHEM 12 ]

In the above formula (c6), R^17c、R^18cEach independently represents a hydroxyl group, a linear or branched alkoxy group having 1 to 6 carbon atoms, or a linear or branched alkyl group having 1 to 6 carbon atoms, R^19cRepresents a single bond, or a linear or branched alkylene group having 1 to 6 carbon atoms which may have a substituent. 1 and m independently represent an integer of 0 to 2, and 1+ m is 3 or less. Wherein in the presence of a plurality of R^17cIn the case of (2), a plurality of R^17cMay be the same as or different from each other. In addition, in the presence of a plurality of R^18cIn the case of (2), a plurality of R^18cMay be the same as or different from each other.

In the above-mentioned R^14c、R^15c、R^16cIn the (b), the number of the groups represented by the above formula (c6) is preferably 1, and the remaining R is preferably 1, from the viewpoint of stability of the compound^14c、R^15c、R^16cIs a linear or branched alkylene group having 1 to 6 carbon atoms, R is^14c、R^15c、R^16cMay be bonded to form a ring. In this case, the 2 alkylene groups constitute a 3 to 9-membered ring including a sulfur atom. The number of atoms (including sulfur atoms) constituting the ring is preferably 5 to 6.

Examples of the substituent that the alkylene group may have include an oxygen atom (in this case, a carbonyl group is formed together with a carbon atom constituting the alkylene group), a hydroxyl group, and the like.

Examples of the substituent which the phenyl group may have include a hydroxyl group, a linear or branched alkoxy group having 1 to 6 carbon atoms, and a linear or branched alkyl group having 1 to 6 carbon atoms.

Preferable examples of the cation portion include structures represented by the following formulas (c7) and (c8), and particularly preferable is a structure represented by the following formula (c 8).

[ CHEM 13 ]

Such a cation portion may be an iodonium salt or a sulfonium salt, and a sulfonium salt is preferable from the viewpoint of acid generation efficiency and the like.

Therefore, as a preferable example of the anion portion of the onium salt having a naphthalene ring in the cation portion, an anion capable of forming a sulfonium salt is preferable.

The anion portion of such an acid generator is a fluoroalkyl sulfonic acid ion or aryl sulfonic acid ion in which a part or all of hydrogen atoms are fluorinated.

The alkyl group in the fluoroalkylsulfonic acid ion may be linear, branched or cyclic having 1 to 20 carbon atoms, and preferably has 1 to 10 carbon atoms in view of the volume size of the generated acid and the diffusion distance thereof. In particular, a branched or cyclic alkyl group is preferable because of its short diffusion distance. Further, methyl, ethyl, propyl, butyl, octyl and the like are preferable examples from the viewpoint of being able to synthesize at low cost.

The aryl group in the arylsulfonic acid ion is an aryl group having 6 to 20 carbon atoms, and examples thereof include a phenyl group and a naphthyl group which may be substituted or unsubstituted with an alkyl group or a halogen atom. Particularly, an aryl group having 6 to 10 carbon atoms is preferable because it can be synthesized at low cost. Specific examples of the preferred aryl group include a phenyl group, a tosyl group, an ethylphenyl group, a naphthyl group, and a methylnaphthyl group.

The fluorination rate when some or all of the hydrogen atoms of the fluoroalkyl sulfonic acid ion or aryl sulfonic acid ion are fluorinated is preferably 10 to 100%, more preferably 50 to 100%, and the acid strength when all of the hydrogen atoms are replaced with fluorine atoms is particularly strong, which is preferable. Specific examples of such a compound include trifluoromethanesulfonate, perfluorobutanesulfonate, perfluorooctanesulfonate, and perfluorobenzenesulfonate.

Among them, preferable examples of the anion portion include a structure represented by the following formula (c 9).

[ CHEM 14 ]

R^20cSO₃ ^-(c9)

In the above formula (c9), R^20cIs a group represented by the following formula (c10) or (c11) or a group represented by the following formula (c 12).

[ CHEM 15 ]

In the formula (c10), x represents an integer of 1 to 4. In the formula (c11), R is^21cRepresents a hydrogen atom, a hydroxyl group, a linear or branched alkyl group having 1 to 6 carbon atoms, or a linear or branched alkoxy group having 1 to 6 carbon atoms, and y represents an integer of 1 to 3. Among them, trifluoromethanesulfonate and perfluorobutanesulfonate are preferable from the viewpoint of safety.

Further, as the anion portion, a nitrogen-containing structure represented by the following formulae (c13) and (c14) may be used.

[ CHEM 16 ]

In the above formulae (c13) and (c14), X^cRepresents a linear or branched alkylene group in which at least 1 hydrogen atom is substituted with a fluorine atom, and the alkylene group has 2 to 6 carbon atoms, preferably 3 to 5 carbon atoms, and most preferably 3 carbon atoms. Furthermore, Y^c、Z^cEach independently represents a linear or branched alkyl group in which at least 1 hydrogen atom is substituted with a fluorine atom, and the number of carbon atoms in the alkyl group is 1 to 10, preferably 1 to 7, and more preferably 1 to 3.

X^cCarbon number of alkylene group of (2) or Y^c、Z^cThe smaller the number of carbon atoms of the alkyl group (b) is, the better the solubility in an organic solvent is, and therefore, the preferable range is.

In addition, in X^cAlkylene or Y of^c、Z^cIn the alkyl group of (3), the larger the number of hydrogen atoms substituted with fluorine atoms, the stronger the acid strength, and thus is preferred. The proportion of fluorine atoms in the alkylene group or alkyl group, that is, the fluorination rate, is preferably 70 to 100%, more preferably 90 to 100%, and most preferably a perfluoroalkylene group or perfluoroalkyl group in which all hydrogen atoms are substituted with fluorine atoms.

Preferred examples of such onium salts having a naphthalene ring in the cation portion include compounds represented by the following formulae (c15) and (c 16).

[ CHEM 17 ]

Examples of the photoacid generator of the fifth embodiment include bis (p-toluenesulfonyl) diazomethanes, bis (1, 1-dimethylethylsulfonyl) diazomethanes, bis (cyclohexylsulfonyl) diazomethanes, bis (2, 4-dimethylphenylsulfonyl) diazomethanes, and other bis-sulfonyl diazomethanes, nitrobenzyl derivatives such as 2-nitrobenzyl p-toluenesulfonate, 2, 6-dinitrobenzyl p-toluenesulfonate, nitrobenzyl tosylate, dinitrobenzyl tosylate, nitrobenzyl sulfonate, nitrobenzyl carbonate, dinitrobenzyl carbonate, and other nitrobenzyl derivatives, trifluoromethanesulfonates such as pyrogallol trimethinesulfonate, benzyl tosylate, benzyl sulfonate, N-methylsulfonyloxysuccinimide, N-trichloromethylsulfonyloxysuccinimide, N-phenylsulfonyloxybutylamide, and N-methylsulfonyloxyphthalimide, trifluoromethanesulfonates such as N-hydroxyphthalimide, trifluoromethanesulfonates such as iodonium hexafluoro, 4-methoxyphenyl phenyl iodonium phosphate, triphenylmethyl p-toluenesulfonyl bis (triphenylmethyl) sulfonium triflate, and other tosylate, trifluoromethanesulfonates such as (4-tolyliodonium) trifluoromethanesulfonates, triphenylsulfonium tosylate, trifluoromethanesulfonates, and other iodonium salts, and other tosylate salts.

Preferred examples of the thermal acid generator include oxime ester compounds of organic sulfonic acids, 2,4,4, 6-tetrabromocyclohexadiene, benzoin tosylate, 2-nitrobenzyl tosylate, and other alkyl organic sulfonates. Sulfonium salts, iodonium salts, benzothiazole salts, ammonium salts, phosphonium salts and other onium salts can also be suitably used as the thermal acid generator. Among them, oxime ester compounds of organic sulfonic acids are preferable in terms of excellent stability in an unheated state.

The content of the acid generator in the film-forming composition is not particularly limited as long as the object of the present invention is not impaired. The content of the acid generator in the film-forming composition is preferably 0.1 to 50 parts by mass, more preferably 0.5 to 30 parts by mass, and particularly preferably 1 to 20 parts by mass, based on 100 parts by mass of the total amount of the epoxy compounds in the film-forming composition.

Resin-containing composition for forming transparent insulating film

The components contained in the film-forming composition containing (a) a filler and (B2) a resin will be described below. Note that the description of the filler (a) is omitted.

[ (B2) resin ]

Since it is necessary to form a transparent insulating film using the film-forming composition, 1 or more species selected from the group consisting of silicone resins, polyamideimides, polyimides, polycarbonates, polyethers, polythioethers, and polymers of monomers having an ethylenically unsaturated double bond are used as the resin (B2) in the film-forming composition containing the resin from the viewpoint of transparency and film-forming properties. The content of the (B2) resin in the solid content of the film-forming composition is preferably 20 to 99 mass%, more preferably 30 to 80 mass%, and still more preferably 40 to 70 mass%.

Among the above-mentioned resins, preferred are polymers of monomers having an ethylenically unsaturated double bond, from the viewpoint of excellent film-forming properties and easy adjustment of the properties of the resin by selection of the monomers, examples of the monomers having an ethylenically unsaturated double bond include (meth) acrylic acid, (meth) acrylic acid esters, (meth) acrylamides, crotonic acid, anhydrides of maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, anhydrides of these dicarboxylic acids, allyl acetate, allyl caproate, allyl caprate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, allyl lactate, and allyloxyethanol, and allyl compounds 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, tetrahydrobenzyl vinyl ether, vinyl phenyl vinyl ether, 1-2-ethylbutyl vinyl ether, hydroxyethylvinyl ether, 1-chlorovinyl ether, 1-chloro vinyl ether, 1-3-chloro-4-chloro-phenyl vinyl ether, 1-chloro-3-chloro-2, 1-4-chloro-2, 3-chloro-2-4-chloro-methyl-ethyl vinyl acetate, 1-chloro-3-chloro-2, 1-chloro-2, 1-chloro-3-2, 1-chloro-2, 1-chloro-4-chloro-4-chloro-ethyl vinyl acetate, 1-chloro-3-chloro-3, 1-chloro-4-chloro-2, 1-chloro-2, 1-4-chloro-2, 1-chloro-3, 1-chloro-2, 1-chloro-4-chloro-2, 1-chloro-4-chloro-2, 1-chloro-2, 1-chloro-4-chloro-2, 1-chloro-4-.

As described later, by adding (D) a photopolymerizable compound and (E) a photopolymerization initiator to the film-forming composition containing (a) a filler and (B2) a resin, photosensitivity can be imparted to the film-forming composition. In particular, when the resin (B2) is an alkali-soluble resin, a patterned transparent insulating film can be formed by applying the filler (a), the resin (B2), the photopolymerizable compound (D), and the photopolymerization initiator (E) to a substrate to be formed into a transparent insulating film, and then selectively exposing and developing the applied film with an alkali developer such as a tetramethylammonium hydroxide aqueous solution. Therefore, when the film-forming composition is used as the photosensitive component, the (B2) resin is preferably alkali-soluble. In terms of alkali solubility and transparency, the resin (B2) contained in the photosensitive film-forming composition is preferably a resin containing a unit derived from an unsaturated carboxylic acid and a polymer of a monomer having an ethylenically unsaturated double bond.

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. The amount of the unit derived from an unsaturated carboxylic acid contained in the polymer of the monomer having an ethylenically unsaturated double bond used as the alkali-soluble resin is not particularly limited as long as the resin has desired alkali solubility. The amount of the unit derived from an unsaturated carboxylic acid in the resin used as the alkali-soluble resin is preferably 5 to 25% by mass, more preferably 8 to 16% by mass, based on the mass of the resin.

Among the polymers of 1 or more monomers selected from the monomers exemplified above, that is, the polymers of monomers having an ethylenically unsaturated double bond, the polymers of 1 or more monomers selected from (meth) acrylic acid and (meth) acrylic acid esters, polyethylene, polypropylene, polystyrene, and the like are preferable. Among them, from the viewpoint of improving the balance of mechanical properties such as transparency, film formability, and hardness, a polymer of 1 or more monomers selected from (meth) acrylic acid and (meth) acrylic esters is preferable. Hereinafter, a polymer of 1 or more monomers selected from (meth) acrylic acid and (meth) acrylic acid esters will be described.

The (meth) acrylate used for the preparation of the polymer of 1 or more monomers selected from (meth) acrylic acid and (meth) acrylic acid esters is not particularly limited as long as the object of the present invention is not impaired, and may be appropriately selected from known (meth) acrylates.

Preferred examples of the (meth) acrylic acid ester include: linear or branched alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, pentyl (meth) acrylate, and tert-octyl (meth) acrylate; chloroethyl (meth) acrylate, 2-dimethylhydroxypropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, trimethylolpropane mono (meth) acrylate, benzyl (meth) acrylate, furfuryl (meth) acrylate; (meth) acrylate having an epoxy-containing group; (meth) acrylate having a group having an alicyclic skeleton. The details of the (meth) acrylate having an epoxy group-containing group and the (meth) acrylate having a group having an alicyclic skeleton will be described below.

Among polymers of 1 or more monomers selected from (meth) acrylic acid and (meth) acrylic acid esters, a resin containing a unit derived from a (meth) acrylic acid ester having an epoxy group-containing group is preferable from the viewpoint of excellent adhesion of a transparent insulating film formed using the film-forming composition to a base material and excellent mechanical strength.

The (meth) acrylate having an epoxy group-containing group may be a (meth) acrylate having a chain aliphatic epoxy group-containing group, or may be a (meth) acrylate having an alicyclic epoxy group-containing group as described later.

The (meth) acrylate having an epoxy-containing group may contain an aromatic group. Examples of the aromatic ring constituting the aromatic group include a benzene ring and a naphthalene ring. Examples of the (meth) acrylate having an aromatic group and an epoxy group-containing 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.

From the viewpoint of transparency of a film formed using the film-forming composition, the (meth) acrylic acid having an epoxy-containing group preferably does not contain an aromatic group.

Examples of the (meth) acrylate having a group containing a chain-like aliphatic epoxy group include (meth) acrylates in which a chain-like aliphatic epoxy group is bonded to an oxy group (-O-) in an ester group (-O-CO-), such as an alkylene oxide (meth) acrylate and an alkylene oxide oxyalkyl (meth) acrylate. The chain aliphatic epoxy group of such a (meth) acrylate may contain 1 or more oxy groups (-O-) in the chain. The number of carbon atoms of the chain aliphatic epoxy group is not particularly limited, but is preferably 3 to 20, more preferably 3 to 15, and particularly preferably 3 to 10.

Specific examples of the (meth) acrylate having a group containing a chain-like aliphatic epoxy group include: epoxy alkyl (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-hexyl (meth) acrylate, and 6-glycidyloxy-n-hexyl (meth) acrylate

In the polymer containing 1 or more monomers selected from (meth) acrylic acid and (meth) acrylic acid esters and derived from a (meth) acrylic acid ester having an epoxy group-containing unit, the content of the unit derived from the (meth) acrylic acid ester having an epoxy group-containing group is preferably 1 to 95% by mass, more preferably 30 to 70% by mass, based on the weight of the resin.

Further, among the polymers of 1 or more monomers selected from the group consisting of (meth) acrylic acid and (meth) acrylic acid esters, a resin containing a unit derived from a (meth) acrylic acid ester having a group having an alicyclic skeleton is also preferable in terms of ease of use of the film-forming composition to form a transparent insulating film excellent in transparency.

In the (meth) acrylate having a group having an alicyclic skeleton, the group having an alicyclic skeleton may be a group having an alicyclic hydrocarbon group or a group having an alicyclic epoxy group. The alicyclic group constituting the alicyclic skeleton may be monocyclic or polycyclic. Examples of the monocyclic alicyclic group include cyclopentyl and cyclohexyl. Further, examples of the polycyclic alicyclic group include norbornyl, isobornyl, tricyclononyl, tricyclodecyl, tetracyclododecyl and the like.

Among the (meth) acrylates having a group having an alicyclic skeleton, examples of the (meth) acrylates having a group having an alicyclic hydrocarbon group include compounds represented by the following formulae (b 2-1) to (b 2-8). Among them, preferred are compounds represented by the following formulae (b 2-3) to (b 2-8), and more preferred are compounds represented by the following formulae (b 2-3) or (b 2-4).

[ CHEM 18 ]

[ CHEM 19]

In the above formula, R^b1Represents a hydrogen atom or a methyl group, R^b2Represents a single bond or a C1-6 aliphatic saturated hydrocarbon group having a valence of 2, R^b3Represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. As R^b2The alkylene group is preferably a single bond, a linear or branched alkylene group, and examples thereof include a methylene group, an ethylene group, a propylene group, a tetramethylene group, an ethylethylene group, a pentamethylene group and a hexamethylene group. As R^b3Methyl and ethyl are preferred.

Specific examples of the (meth) acrylate having a group having an alicyclic skeleton include compounds represented by the following formulae (b 3-1) to (b 3-16). Among them, in order to moderate the developability of the film-forming resin composition, compounds represented by the following formulae (b 3-1) to (b 3-6) are preferable, and compounds represented by the following formulae (b 3-1) to (b 3-4) are more preferable.

[ CHEM 20 ]

[ CHEM 21 ]

[ CHEM 22 ]

In the above formula, R^b4Represents a hydrogen atom or a methyl group, R^b5R represents a C1-6 aliphatic saturated hydrocarbon group having a valence of 2^b6Represents a C1-10 2-valent hydrocarbon group, and n represents an integer of 0-10. As R^b5The linear or branched alkylene group is preferably a methylene group, an ethylene group, a propylene group, a tetramethylene group, an ethylethylene group, a pentamethylene group or a hexamethylene group. As R^b6Preferred are, for example, methylene, ethylene, propylene, tetramethylene, ethylethylene, pentamethylene, hexamethylene, phenylene, cyclohexylene, -CH₂－Ph－CH₂- (Ph represents phenylene).

When the polymer of 1 or more monomers selected from the group consisting of (meth) acrylic acid and (meth) acrylic acid esters is a resin containing a unit derived from a (meth) acrylic acid ester having a group having an alicyclic skeleton, the amount of the unit derived from a (meth) acrylic acid ester having a group having an alicyclic skeleton in the resin is preferably 5 to 95% by mass, more preferably 10 to 90% by mass, and still more preferably 30 to 70% by mass.

Further, in the polymer containing 1 or more kinds of monomers selected from the group consisting of (meth) acrylic acid and (meth) acrylic acid esters derived from a (meth) acrylic acid ester having a group having an alicyclic skeleton, a resin containing a unit derived from (meth) acrylic acid and a unit derived from a (meth) acrylic acid ester having an alicyclic epoxy group is preferable. Such a resin has excellent adhesion to a substrate on which a transparent insulating film is formed. In addition, when such a resin is used, a spontaneous reaction between the carboxyl group contained in the resin and the alicyclic epoxy group can occur. Therefore, when a film-forming composition containing such a resin is used, a spontaneous reaction between a carboxyl group and an alicyclic epoxy group occurs by a method of heating the film, and the mechanical properties such as hardness of the formed transparent insulating film can be improved.

In the resin containing a unit derived from (meth) acrylic acid and a unit derived from a (meth) acrylate having an alicyclic epoxy group-containing group, the amount of the unit derived from (meth) acrylic acid in the resin is preferably 1 to 95% by mass, more preferably 10 to 50% by mass. In the resin containing a unit derived from (meth) acrylic acid and a unit derived from a (meth) acrylate having a group containing an alicyclic epoxy group, the amount of the unit derived from a (meth) acrylate having a group containing an alicyclic epoxy group in the resin is preferably 1 to 95% by mass, more preferably 30 to 70% by mass.

In the polymer containing 1 or more monomers selected from the group consisting of (meth) acrylic acid and (meth) acrylic acid esters, the polymer containing a unit derived from (meth) acrylic acid and a unit derived from a (meth) acrylic acid ester having an alicyclic epoxy group, a resin containing a unit derived from (meth) acrylic acid, a unit derived from a (meth) acrylic acid ester having an alicyclic hydrocarbon group, and a unit derived from a (meth) acrylic acid ester having an alicyclic epoxy group is preferable.

In the resin containing a unit derived from (meth) acrylic acid, a unit derived from a (meth) acrylate having an alicyclic hydrocarbon group, and a unit derived from a (meth) acrylate having an alicyclic epoxy group-containing group, the amount of the unit derived from (meth) acrylic acid in the resin is preferably 1 to 95% by mass, more preferably 10 to 50% by mass. In the resin containing a unit derived from (meth) acrylic acid, a unit derived from a (meth) acrylate having an alicyclic hydrocarbon group, and a unit derived from a (meth) acrylate having an alicyclic epoxy group-containing group, the amount of the unit derived from the (meth) acrylate having an alicyclic hydrocarbon group in the resin is preferably 1 to 95% by mass, more preferably 10 to 70% by mass. In the resin containing a unit derived from (meth) acrylic acid, a unit derived from a (meth) acrylate having an alicyclic hydrocarbon group, and a unit derived from a (meth) acrylate having an alicyclic epoxy group-containing group, the amount of the unit derived from the (meth) acrylate having an alicyclic epoxy group-containing group in the resin is preferably 1 to 95% by mass, more preferably 30 to 70% by mass.

[ (D) photopolymerizable Compound ]

The film-forming composition containing (a) a filler and (B2) a resin may contain (D) a photopolymerizable compound and (E) a photopolymerization initiator, and photosensitivity may be imparted to the film-forming composition. In particular, when the resin (B2) is an alkali-soluble resin, a patterned transparent insulating film can be formed by applying the filler (a), the resin (B2), the photopolymerizable compound (D), and the photopolymerization initiator (E) to a substrate to be formed into a transparent insulating film, and then selectively exposing and developing the applied film with an alkali developer such as a tetramethylammonium hydroxide aqueous solution.

As the photopolymerizable compound (D), a compound having an ethylenically unsaturated group can be preferably used. The compound having the ethylenically unsaturated group includes a monofunctional compound and a polyfunctional compound.

As monofunctional compounds, mention may be made of: (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 anhydride, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, crotonic acid, 2-acrylamido-2-methylpropanesulfonic acid, t-butylacrylamide sulfonic 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, methyl (meth) acrylate, N-methylol (meth) acrylamide, N-ethylmethacrylic (meth) acrylate, N-ethylhexylacrylate, N-ethyl, 2-hydroxybutyl (meth) acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2- (meth) acryloyloxy-2-hydroxypropyl phthalate, glycerol 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, half-esters of (meth) acrylic acid of phthalic acid derivatives, and the like. These monofunctional monomers may be used alone or in combination of 2 or more.

On the other hand, as the polyfunctional monomer, there can be mentioned: 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, butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerol 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-bis (4- (meth) acryloyloxydiethoxyphenyl) propane, propylene glycol di (meth) acrylate, butylene glycol, 2, 2-bis (4- (meth) acryloyloxypolyethoxyphenyl) propane, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, diglycidyl phthalate di (meth) acrylate, glycerol triacrylate, glycerol polyglycidyl ether poly (meth) acrylate, urethane (meth) acrylate (i.e., toluene diisocyanate), a reaction product of 2-hydroxyethyl (meth) acrylate such as trimethylhexamethylene diisocyanate and hexamethylene diisocyanate, methylenebis (meth) acrylamide, (meth) acrylamidomethylene ether, a condensate of a polyhydric alcohol and N-methylol (meth) acrylamide, a method for producing the same, and a pharmaceutical composition comprising the same, Triacryloxymethyl acetal, 2,4, 6-trioxahydro-1, 3, 5-triazine-1, 3, 5-triethanol triacrylate, and 2,4, 6-trioxahydro-1, 3, 5-triazine-1, 3, 5-triethanol diacrylate, etc. These polyfunctional monomers may be used alone or in combination of 2 or more.

Among these compounds having an ethylenically unsaturated group, a polyfunctional monomer having 3 or more functions is preferable in terms of obtaining a radiation-sensitive resin composition that forms a cured product excellent in both strength and adhesion to a substrate.

(D) The content of the photopolymerizable compound is preferably 5 to 60% by mass, more preferably 10 to 50% by mass, based on the solid content of the film-forming composition. When the content of the photopolymerizable compound (D) in the film-forming composition is in the above range, the balance among the sensitivity, developability, and resolution of the film-forming composition tends to be easily obtained.

[ (E) photopolymerization initiator ]

As the photopolymerization initiator (E) used together with the photopolymerizable compound (D), various photopolymerization initiators conventionally used as polymerization initiators for the photopolymerizable compound (D) can be used.

Specific examples of preferred (E) photopolymerization initiators include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [ 4- (2-hydroxyethoxy) phenyl ] -2-hydroxy-2-methyl-1-propane-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-dimethoxy-1, 2-diphenylethane-1-one, bis (4-dimethylaminophenyl) ketone, 2-methyl-1- [ 4- (methylthio) phenyl ] -2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane-1-one, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ], 1- (o-acetylbenzoin-butyryl) -triazine (N-phenyl) -6- (2-chloro-phenyl) -2-chloro-benzoyl) -2-4-chloro-phenyl-1-one, 2-chloro-2-phenyl-1-one, 2-dichloro-1-one, 2-phenyl-ethyl-2-chloro-2-bromo-2-phenyl-1-phenyl-1-one, 2-phenyl-1-phenyl-ketone, 2-phenyl-1-ketone, 2-phenyl-oxoethyl-2-chloro-phenyl-chloro-2-phenyl-ethyl-2-chloro-phenyl-ethyl-phenyl-2-phenyl-2-ethyl-phenyl-2-phenyl-2-phenyl-ethyl-2-phenyl-ethyl-phenyl-ethyl-phenyl-2-phenyl-ethyl-ketone, 2-phenyl-ethyl-phenyl-ethyl-4-phenyl-2-ethyl-phenyl-ethyl-phenyl-ethyl-phenyl-ethyl-phenyl-ketone, 2-ethyl-phenyl-ethyl-phenyl-ethyl-phenyl-4-phenyl-ethyl-phenyl-4-phenyl-ketone, 2-phenyl-ketone, 2-phenyl-ketone, 2-phenyl

In addition to the above-mentioned photopolymerization initiator, an oxime ester compound represented by the following formula (E1) or an oxime ester compound represented by the following formula (E2) is preferably used as the (E) photopolymerization initiator

[ CHEM 23 ]

(R^E11Is a group selected from 1-valent organic group, amino group, halogen, nitro group and cyano group, a is an integer of 0 to 4, b is 0 or 1, R^E12Is phenyl which may have substituents or carbazolyl which may have substituents, R^E13Is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. )

[ CHEM 24 ]

(d is an integer of 1 to 5, e is an integer of 1 to 8, f is an integer of 0 to (d +3), R^E21Is C1-11 alkyl which may have substituent or aryl which may have substituent, R^E22Is any one of substituents represented by the following formulae (E21) to (E23), R^E23Is C1-11 alkyl, R^E24Is aryl which may have a substituent, R^E25A hydrogen atom, an alkyl group or an aryl group having 1 to 10 carbon atoms which may have a substituent, R^E26Is an aryl group which may have a substituent. )

[ CHEM 25 ]

In the above-mentioned example of the photopolymerization initiator (E), an oxime ester compound represented by the following formula (E1) or an oxime ester compound represented by the following formula (E2) is preferable in that the film-forming composition can be easily used to form a transparent insulating film having excellent transparency. The oxime ester compound represented by the formula (E1) and the oxime ester compound represented by the formula (E2) are explained in this order.

(Oxime ester compound represented by the formula (E1))

Hereinafter, an oxime ester compound represented by the following formula (E1) which is preferable as the photopolymerization initiator (E) will be described.

[ CHEM 26 ]

(R^E11Is a group selected from 1-valent organic group, amino group, halogen, nitro group and cyano group, a is an integer of 0 to 4, b is 0 or 1, R^E12Is phenyl which may have a substituent or carbazolyl which may have a substituent, R^E13Is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. )

In the above formula (E1), R is^E11When it is a 1-valent organic group, R^E11In no way blockThe range of the object of the present invention is not particularly limited, and may be appropriately selected from various organic groups. As R^E11Preferred examples of organic groups include: 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 naphthyloxy group which may have a substituent, a naphthoyl group which may have a substituent, a naphthyloxycarbonyl group which may have a substituent, a naphthoyloxy group which may have a substituent, a naphthylalkyl group which may have a substituent, a heterocyclic group (heterocyclic group) which may have a substituent, an amino group substituted with 1 or 2 organic groups, a 1-morpholinyl group, a 1-piperazinyl group, and the like. When a is an integer of 2 to 4, R^E11May be the same or different. In addition, the carbon number of the substituent does not include the carbon number of the substituent further having the substituent.

At R^E11When the alkyl group is used, the carbon number is preferably 1 to 20, more preferably 1 to 6. In addition, in R^E11When the alkyl group is used, the alkyl group may be linear or branched. As R^E11Specific examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, tert-pentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, sec-octyl, tert-octyl, n-nonyl, isononyl, n-decyl, and isodecyl groups. In addition, in R^E11In the case of 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 methoxyethyl group, ethoxyethyl group, methoxyethoxyethyl group, ethoxyethoxyethyl group, propoxyethoxyethyl group, methoxypropyl group and the like

At R^E11When the alkoxy group is used, the carbon number is preferably 1 to 20, more preferably 1 to 6. In addition, in R^E11In the case of alkoxy, it may beThe polymer may be linear or branched. As R^E11Specific examples of the alkoxy group include: methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy, isopentoxy, sec-pentoxy, tert-pentoxy, n-hexoxy, n-heptoxy, n-octoxy, isooctoxy, sec-octoxy, tert-octoxy, n-nonoxy, isononyloxy, n-decyloxy, isodecyloxy and the like. In addition, in R^E11In the case of 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 propoxyethoxyethoxy group, a methoxypropoxy group, and the like.

At E^R11When the carbon number is cycloalkyl or cycloalkoxy, the carbon number is preferably 3 to 10, more preferably 3 to 6. As R^E11Specific examples of cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. As R^E11Specific examples of the cycloalkoxy group include a cyclopropyloxy group, a cyclobutyloxy group, a cyclopentyloxy group, a cyclohexyloxy group, a cycloheptyloxy group, and a cyclooctyloxy group.

At R^E11In the case of a saturated aliphatic acyl group or a saturated aliphatic acyloxy group, the number of carbon atoms is preferably 2 to 20, more preferably 2 to 7. As R^E11Specific examples of the saturated aliphatic acyl group include: acetyl, propionyl, n-butyryl, 2-methylpropionyl, n-pentanoyl, 2-dimethylpropionyl, n-hexanoyl, n-heptanoyl, n-octanoyl, n-nonanoyl, n-decanoyl, n-undecanoyl, n-dodecanoyl, n-tridecanoyl, n-tetradecanoyl, n-pentadecanoyl, n-hexadecanoyl, and the like. As R^E11Specific examples of the saturated aliphatic acyloxy group include: acetoxy, propionyloxy, n-butyryloxy, 2-methylpropionyloxy, n-valeryloxy, 2-dimethylpropionyloxy, n-hexanoyloxy, n-heptanoyloxy, n-octanoyloxy, n-nonanoyloxy, n-decanoyloxy, n-undecanoyloxy, n-decanoyloxy, nDialkanoyloxy, n-tridecanoyloxy, n-tetradecanoyloxy, n-pentadecanoyloxy, n-hexadecanoyloxy and the like.

At R^E11In the case of an alkoxycarbonyl group, the number of carbon atoms is preferably 2 to 20, more preferably 2 to 7. As R^E11Specific examples of the alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, a n-propoxycarbonyl group, an isopropoxycarbonyl group, a n-butoxycarbonyl group, an isobutoxycarbonyl group, a sec-butoxycarbonyl group, a tert-butoxycarbonyl group, a n-pentyloxycarbonyl group, an isopentyloxycarbonyl group, a sec-pentyloxycarbonyl group, a tert-pentyloxycarbonyl group, a n-hexyloxycarbonyl group, a n-heptyloxycarbonyl group, a n-octyloxycarbonyl group, an isooctyloxycarbonyl group, a sec-octyloxycarbonyl group, a tert-octyloxycarbonyl group, a n-nonyloxycarbonyl group, an isononyloxycarbonyl group, a n-decyloxycarbonyl group and an isodecyloxyca.

At R^E11In the case of phenylalkyl, the number of carbon atoms is preferably 7 to 20, more preferably 7 to 10. In addition, in R^E11In the case of a naphthyl alkyl group, the number of carbon atoms is preferably 11 to 20, more preferably 11 to 14. As R^E11Specific examples of phenylalkyl groups include benzyl, 2-phenylethyl, 3-phenylpropyl and 4-phenylbutyl. As R^E11Specific examples of naphthylalkyl groups include α -naphthylmethyl, β -naphthylmethyl, 2- (α -naphthyl) ethyl and 2- (β -naphthyl) ethyl^E11In the case of phenylalkyl or naphthylalkyl, R^E11May further have a substituent on the phenyl group or the naphthyl group.

At R^E11In the case of a heterocyclic group, the heterocyclic group is a 5-or 6-membered monocyclic ring containing 1 or more N, S, O atoms, or a heterocyclic group in which the monocyclic rings are condensed with each other or a heterocyclic group in which the monocyclic rings are condensed with a benzene ring. In the case where the heterocyclic group is a condensed ring, it is a heterocyclic group having a ring number of 3. Examples of the heterocyclic ring constituting the 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, indole, pyrazine, indole,carbazole, purine, quinoline, isoquinoline, quinazoline, phthalazine, cinnoline, quinoxaline, and the like. At R^E11In the case of a heterocyclic group, the heterocyclic group may further have a substituent.

At R^E11In the case of an amino group substituted with 1 or 2 organic groups, preferable 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, a heterocyclic group and the like. Specific examples of these preferred organic groups and R^E11Similarly, examples of the amino group substituted with 1 or 2 organic groups include a methylamino group, an ethylamino group, a diethylamino group, a n-propylamino group, a di-n-propylamino group, an isopropylamino group, a n-butylamino group, a di-n-butylamino group, a n-pentylamino group, a n-hexylamino group, a n-heptylamino group, a n-octylamino group, a n-nonylamino group, a n-decylamino group, a phenylamino group, a naphthylamino group, an acetylamino group, a propionylamino group, a n-butyrylamino group, a n-valerylamino group, a n-hexanoylamino group, a n-heptanoylamino group, a n-octanoylamino group, a n-decanoylamino group, a benzoylamino group, an α -naphthoylamino group, and a β.

As R^E11The substituents in the case where the phenyl group, naphthyl group and heterocyclic group contained in (1) further have a 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, a 1-morpholinyl group, a 1-piperazinyl group, a halogen, a nitro group and a cyano group. At R^E11When the phenyl group, naphthyl group and heterocyclic group contained in (1) further have a substituent, the number of the substituent is not limited within the range not to impair the object of the present invention, and is preferably 1 to 4. At R^E11The phenyl, naphthyl and heterocyclic group contained in (1)When there are a plurality of substituents, the plurality of substituents may be the same or different.

At R^E11Among them, from the viewpoint of chemical stability, small steric hindrance, easy synthesis of oxime ester compounds, high solubility in solvents, and the like, preferred are groups selected from nitro groups, alkyl groups having 1 to 6 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, and saturated aliphatic acyl groups having 2 to 7 carbon atoms, more preferred are nitro groups or alkyl groups having 1 to 6 carbon atoms, and particularly preferred are nitro groups or methyl groups.

For R^E11When the position of the bond between the phenyl group and the main skeleton of the oxime ester compound is 1-position and the position of the methyl group is 2-position, R represents a bonded phenyl group^E11The position bonded to the phenyl group is preferably the 4-or 5-position, more preferably the 5-position. Further, a is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and particularly preferably 0 or 1.

R^E12Is a phenyl group which may have a substituent or a carbazolyl group which may have a substituent. In addition, in R^E12When the substituted carbazolyl group is used, the nitrogen atom in the carbazolyl group may be substituted by an alkyl group having 1 to 6 carbon atoms.

R^E12In (3), the substituent group of the phenyl group or the carbazolyl group is not particularly limited insofar as it does not inhibit the object of the present invention. Examples of the preferable substituent which may be contained in the phenyl group or the carbazolyl group 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, and a naphthoxycarbonyl group which may have a substituent, Optionally substituted naphthoyloxy, optionally substituted C11-20 naphthaleneArylalkyl, a heterocyclic group which may have a substituent, a heterocyclic carbonyl group which may have a substituent, amino substituted with 1 or 2 organic groups, 1-morpholinyl and 1-piperazinyl, halogen, nitro, cyano and the like.

At R^E12In the case of the carbazolyl group, examples of preferable substituents which the carbazolyl group may have on a 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 naphthyloxycarbonyl group which may have a substituent, a naphthylalkyl group having 11 to 20 carbon atoms which may have a substituent, a heterocyclic group which may have a substituent, and a heterocyclic carbonyl group which may have a substituent. Among these substituents, 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.

Specific examples of the substituent which may be contained in the phenyl group or the carbazolyl group include 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, an optionally substituted phenylalkyl group, an optionally substituted naphthylalkyl group, an optionally substituted heterocyclic group and an amino group substituted with 1 or 2 organic groups, and R is^E11The same is true.

R^E12Among them, examples of the substituents when the phenyl group, naphthyl group and heterocyclic group contained in the substituents contained in the phenyl group or carbazolyl group further have a substituent include: an alkyl group having 1 to 6 carbon atoms; an alkoxy group having 1 to 6 carbon atoms; a C2-7 saturated aliphatic acyl group; an alkoxycarbonyl group having 2 to 7 carbon atoms; c2-7 saturated aliphatic acyloxy; a phenyl group; a naphthyl group; a benzoyl group; a naphthoyl group; benzoyl substituted by a group selected from alkyl having 1 to 6 carbon atoms, 1-morpholinyl, 1-piperazinyl and phenyl; 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; 1-morpholinyl(ii) a 1-piperazinyl; halogen; a nitro group; a cyano group. When the phenyl group, naphthyl group and heterocyclic group contained in the substituent group of the phenyl group or carbazolyl group further have a substituent group, the number of the substituent groups is not limited within the range not hindering the object of the present invention, and is preferably 1 to 4. In the case where the phenyl group, the naphthyl group and the heterocyclic group have a plurality of substituents, the plurality of substituents may be the same or different.

At R^E12Among them, from the viewpoint of providing the film-forming composition with excellent sensitivity, a group represented by the following formula (E11) or (E12) is preferable, a group represented by the following formula (E11) is more preferable, and a group represented by the following formula (E12) in which a is S is particularly preferable.

[ CHEM 27 ]

(R^E14Is a group selected from a 1-valent organic group, an amino group, a halogen, a nitro group and a cyano group, A is S or O, and c is an integer of 0 to 4. )

[ CHEM 28 ]

(R^E15And R^E16Are each a 1-valent organic group. )

R in the formula (E11)^E14In the case of an organic group, it may be selected from various organic groups within a range not to impair the object of the present invention. As R in the formula (E11)^E14Preferred examples of organic groups include: an alkyl group having 1 to 6 carbon atoms; an alkoxy group having 1 to 6 carbon atoms; a C2-7 saturated aliphatic acyl group; an alkoxycarbonyl group having 2 to 7 carbon atoms; c2-7 saturated aliphatic acyloxy; a phenyl group; a naphthyl group; a benzoyl group; a naphthoyl group; benzoyl substituted by a group selected from alkyl having 1 to 6 carbon atoms, 1-morpholinyl, 1-piperazinyl and phenyl; 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; 1-morpholinyl; 1-piperazinyl; halogen; a nitro group; a cyano group.

At E^R14Among them, it is preferable that: a benzoyl group; a naphthoyl group; benzoyl substituted by a group selected from alkyl having 1 to 6 carbon atoms, 1-morpholinyl, 1-piperazinyl and phenyl; a nitro group. More preferably: a benzoyl group; a naphthoyl group; 2-methylphenylcarbonyl; 4- (piperazin-1-yl) phenylcarbonyl; 4- (phenyl) phenylcarbonyl.

In the formula (E11), n is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and particularly preferably 0 or 1. In case n is 1, R^E14Is preferably relative to R^E14The bond between the bonded phenyl group and the sulfur atom is para.

R in the formula (E12)^E15May be selected from various organic groups within a range not hindering the object of the present invention. As R^E15Preferred examples of (d) 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 naphthyloxycarbonyl group which may have a substituent, a naphthylalkyl group having 11 to 20 carbon atoms which may have a substituent, a heterocyclic group which may have a substituent, and a heterocyclic carbonyl group which may have a substituent.

At R^E15Among 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.

R in the formula (E12)^E16The organic group is not particularly limited as long as the object of the present invention is not impaired, and may be selected from various organic groups. For as R^E16Specific examples of the preferable group include an alkyl group having 1 to 20 carbon atoms, an optionally substituted phenyl group, an optionally substituted naphthyl group, and an optionally substituted heterocyclic group. As R^E16Among these groups, phenyl groups which may have a substituent are more preferable, and 2-methylphenyl group is particularly preferable.

As R^E14、R^E15Or R^E16The substituents in the case where the phenyl group, naphthyl group and heterocyclic group contained in (1) further have a 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, a 1-morpholinyl group, a 1-piperazinyl group, a halogen, a nitro group and a cyano group. At R^E14、R^E15Or R^E16When the phenyl group, naphthyl group and heterocyclic group contained in (1) further have a substituent, the number of the substituent is not limited within the range not to impair the object of the present invention, and is preferably 1 to 4. At R^E14、R^E15Or R^E16When the phenyl group, naphthyl group and heterocyclic group contained in (1) have a plurality of substituents, the plurality of substituents may be the same or different.

R in the formula (E1)^E13Is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. As R^E13Preferably methyl or ethyl, more preferably methyl. At R^E13In the case of a methyl group, the photopolymerization initiator containing the compound represented by the formula (E1) is particularly excellent in sensitivity.

When b is 0, the oxime ester compound represented by formula (E1) can be synthesized, for example, according to the following scheme 1. Specifically, an aromatic compound represented by the following formula (E1-1) is acylated using a halocarbonyl compound represented by the following formula (E1-2) by a Friedel-crafts reaction to obtain a ketone compound represented by the following formula (E1-3), the obtained ketone compound (E1-3) is oximated using hydroxylamine to obtain an oxime compound represented by the following formula (E1-4), and then the oxime compound represented by the following formula (E1-4) is reacted with an acid anhydride ((R) represented by the following formula (E1-5) ((R)^E13CO)₂O) or an acid halide (R) represented by the following formula (E1-6)^E13COHal and Hal are halogens. ) The reaction was carried out to obtain an oxime ester compound represented by the following formula (E1-7). In addition, Hal in the following formula (E1-2) is halogen, and in the following formulae (E1-1), (E1-2), (E1-3), (E1-4) and (E1-7), R is^E11、R^E12、R^E13And a is the same as in formula (E1).

< route 1 >

[ CHEM 29 ]

When b is 1, the oxime ester compound represented by formula (E1) can be synthesized, for example, according to the following scheme 2. Specifically, a ketoxime compound represented by the following formula (E2-3) is obtained by reacting a nitrite (RONO, R is an alkyl group having 1 to 6 carbon atoms) represented by the following formula (E2-2) with a ketone compound represented by the following formula (E2-1) in the presence of hydrochloric acid, and then the ketoxime compound represented by the following formula (E2-3) and an acid anhydride ((R2-4) represented by the following formula (E2-4) are reacted with the ketoxime compound represented by the following formula (E2-3)^E13CO)₂O) or an acid halide (R) represented by the following formula (E2-5)^E13COHal and Hal are halogens. ) The reaction was carried out to obtain an oxime ester compound represented by the following formula (E2-6). In the following formulae (E2-1), (E2-3), (E2-4), (E2-5) and (E2-6), R^E11、R^E12、R^E13And a is the same as in formula (E1).

< route 2 >

[ CHEM 30 ]

In addition, where b is 1, RE¹¹Is methyl, relative to R^E11R for methyl bonded to the benzene ring to which it is bonded^E11In the case of bonding to the para position, the oxime ester compound represented by the formula (E1) can be synthesized by oximation and acylation of a compound represented by the following formula (E2-7) by the same method as in scheme 1, for example. In the following formula (E2-7), R^E12The same as in formula (E1).

[ CHEM 31 ]

Among the oxime ester compounds represented by the formula (E1), compounds represented by the following formula are particularly preferable.

[ CHEM 32 ]

[ CHEM 33 ]

[ CHEM 34 ]

[ CHEM 35 ]

[ CHEM 36 ]

[ CHEM 37 ]

(Oxime ester compound represented by the formula (E2))

Hereinafter, an oxime ester compound represented by the following formula (E2) which is preferable as the photopolymerization initiator (E) will be described.

[ CHEM 38 ]

(d is an integer of 1 to 5, e is an integer of 1 to 8, f is an integer of 0 to (d +3), R^E21Is C1-11 alkyl which may have substituent or aryl which may have substituent, R^E22Is any one of substituents represented by the following formulae (E21) to (E23), R^E23Is C1-11 alkyl, R^E24To be made availableAryl having a substituent R^E25A hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may have a substituent, or an aryl group, R^E26Is an aryl group which may have a substituent. )

[ CHEM 39 ]

In the formula (E2), d is preferably 1 to 3, more preferably 1 or 2. e is preferably 1 to 8, more preferably 1 to 4, and particularly preferably 2.

As at R^E21Examples of the substituent which may be contained in the alkyl group include phenyl and naphthyl. In addition, as in R^E21Examples of the substituent which may be contained in the aryl group include an alkyl group having 1 to 5 carbon atoms, an alkoxy group, and a halogen atom.

In the above formula (E2), R is^E21Preferred examples thereof include methyl, ethyl, propyl, isopropyl, butyl, phenyl, benzyl, methylphenyl, and naphthyl, and among these, methyl and phenyl are more preferred

In the above formula (E2), R is^E23Preferable examples thereof include methyl, ethyl, propyl, isopropyl, butyl, phenyl and the like, and among them, methyl is more preferable.

In the above formulae (E21) and (E22), R is^E24The substituent that the aryl group of (b) may have is preferably an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a halogen atom or the like. In the above formulae (E21) and (E22), R is^E25Examples of the substituent which may be contained in the alkyl group include alkoxy groups having 1 to 5 carbon atoms, phenyl groups, naphthyl groups, and the like.

In the above formulae (E21) and (E22), R is^E24Preferred examples thereof include phenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2-ethylphenyl, 3-ethylphenyl, 4-ethylphenyl, 2, 3-dimethylphenyl, 2, 4-dimethylphenyl, 2, 5-dimethylphenyl, 2, 6-dimethylphenyl, naphthyl, 2-methoxy-1-naphthyl and 9-anthryl.

In the above formulae (E21) and (E22), R is^E25Preferred examples thereofHydrogen atom, 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, phenyl group, 3-methylbutyl group, 3-methoxybutyl group and the like are shown, and among them, ethyl group is more preferable.

In the above formula (E23), R is^E26The aryl group of (1) may have a substituent, and examples thereof include an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, and a halogen atom. As R^E26Preferred examples thereof include phenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2-ethylphenyl, 3-ethylphenyl, 4-ethylphenyl, 2, 3-dimethylphenyl, 2, 4-dimethylphenyl, 2, 5-dimethylphenyl, 2, 6-dimethylphenyl, naphthyl, p-tert-butylphenyl and p-methoxyphenyl, and among these, phenyl is more preferred.

Among the oxime ester compounds represented by the formula (E2), particularly preferred examples include compounds represented by the following formulae.

[ CHEM 40 ]

The content of the photopolymerization initiator (E) in the film-forming composition is preferably 0.1 to 50 parts by mass, and more preferably 0.5 to 10 parts by mass, based on 100 parts by mass of the total solid content of the film-forming composition. By using the photopolymerization initiator (E) in an amount within the above range, the film-forming composition can be sufficiently cured by radiation, and a transparent insulating film having excellent transparency can be formed using the film-forming composition.

[ (S) solvent ]

The film-forming composition containing (a) a filler and (B2) a resin may contain (S) an organic solvent (hereinafter, also referred to as "component (S)") for the purpose of improving coatability or adjusting viscosity.

Specific examples of the organic solvent include: (poly) alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl 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, etc.; (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 (PGMEA), 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; alkyl lactate esters such as methyl 2-hydroxypropionate and ethyl 2-hydroxypropionate; other esters such as ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl glycolate, methyl 2-hydroxy-3-methylbutyrate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl formate, isoamyl 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; aromatic hydrocarbons such as toluene and xylene; amides such as N-methylpyrrolidone, N-dimethylformamide and N, N-dimethylacetamide. Among them, alkylene glycol monoalkyl ethers, alkylene glycol monoalkyl ether acetates, ethers other than the above, alkyl lactate esters, and esters other than the above are preferable, and alkylene glycol monoalkyl ether acetates, ethers other than the above, and esters other than the above are more preferable. These solvents may be used alone or in combination of 2 or more.

The content of the component (S) in the film-forming composition containing the filler (a) and the resin (B2) is not particularly limited. The content of the (S) component in the film-forming composition may be appropriately set according to the coating film thickness in an amount within a range in which the film-forming composition can be coated on a substrate to be a target for forming a transparent insulating film. Typically, the solid content concentration of the film-forming composition is preferably 1 to 50 mass%, more preferably 5 to 30 mass%, and still more preferably 5 to 15 mass%.

[ other Components ]

The film-forming composition containing the filler (a) and the resin (B2) may contain additives such as a surfactant, an adhesion improver, a thermal polymerization inhibitor, and an antifoaming agent, as required. Any of the additives may be any of those known in the art. Examples of the surfactant include anionic, cationic, and nonionic compounds, examples of the adhesion improving agent include conventionally known silane coupling agents, examples of the thermal polymerization inhibitor include hydroquinone and hydroquinone monoethyl ether, and examples of the defoaming agent include silicone compounds and fluorine compounds.

Method for producing composition for forming transparent insulating film

The method for producing the composition for forming a transparent insulating film is not particularly limited. The composition for forming a transparent insulating film can be produced by uniformly mixing the above-described components using a known mixing apparatus. When the composition for forming a transparent insulating film is a solid or a gel having a high viscosity at room temperature, the respective components can be mixed by using a melt kneading apparatus such as a kneader, a twin roll, or a three roll.

Method for forming transparent insulating film

After a film of the film-forming composition is formed on the surface of the substrate to be formed with the transparent insulating film using the composition for forming a transparent insulating film described above, the formed film is processed according to the composition of the film-forming composition, whereby a transparent insulating film can be formed. The method for forming a film of the film-forming composition on the surface of the substrate is not particularly limited. When the film-forming composition is a solid or a high-viscosity gel, a film of the film-forming composition can be formed by a method in which a predetermined amount of the film-forming composition is supplied onto a substrate and then the film-forming composition is pressed while being heated. When the film-forming composition is a liquid, a film of the film-forming composition can be formed by a method using a contact transfer type coating apparatus such as a roll coater, a reverse coater (reverse coater), a bar coater, or a slit coater, or a non-contact type coating apparatus such as a spinner (rotary coater) or a curtain coater, for example.

When the film-forming composition is a composition containing (a) a filler, (B1) a compound having an alicyclic epoxy group, and (C) an acid generator, the transparent insulating film can be formed by curing the film of the film-forming composition by a known method for curing an epoxy resin composition. Specifically, in the film of the film-forming composition, an acid is generated by an acid generator, thereby forming a transparent insulating film. The method of generating the acid may be selected from among the methods of irradiating the film-forming composition with light such as active energy rays such as ultraviolet rays or electron rays and heating the film-forming composition, depending on the type of the acid generator. As a light source for curing the coating film by irradiation with light, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a carbon arc lamp, a xenon lamp, a metal halide lamp, or the like can be used.

In addition, when a film of the film-forming composition is selectively exposed to light by a method such as exposure through a mask, a patterned transparent insulating film can be formed by developing the exposed film using an organic solvent or the like.

In the case where the film-forming composition is a composition containing (a) a filler, (B2) a resin and (S) a solvent, the transparent insulating film can be formed by applying the film-forming composition to a film and then removing the (S) solvent from the film by heating in the above-described method.

In the case where the film-forming composition is a solid or a highly viscous gel and does not contain a solvent, a film of the film-forming composition is formed by a method of pressing the film-forming composition while heating as described above, and then the formed film is cooled, whereby a transparent insulating film can be formed.

When the film-forming composition contains (a) a filler, (B2) a resin, (D) a photopolymerizable compound, and (E) a photopolymerization initiator, and the resin (B2) is an alkali-soluble resin, the film of the film-forming composition is selectively exposed to light through a mask and then developed with an alkali developer to form a patterned transparent insulating film by a method such as forming a film of the film-forming composition on a substrate to be formed into a transparent insulating film and then exposing the film to light through a mask.

Exposure by irradiation with ArF excimer laser, KrF excimer laser, F₂Excimer laser, Extreme Ultraviolet (EUV), Vacuum Ultraviolet (VUV), electron beam, X-ray, soft X-ray, and the like. The exposure amount varies depending on the composition of the film-forming composition, and is preferably 10 to 600 mJ/cm²Left and right.

The developing method is not particularly limited, and a dipping method, a spraying method, or the like can be used. Specific examples of the developer include: organic developer such as monoethanolamine, diethanolamine, triethanolamine and the like; aqueous solutions of sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia water, quaternary ammonium salts, and the like.

As described above, when the composition for forming a transparent insulating film of the present invention is used, the transparent insulating film can be formed by a simple method such as coating, spraying, and exposure. The transparent insulating film thus formed is excellent in transparency and high in dielectric constant, and therefore is suitable for use in the production of various types of display devices. From these advantages, the transparent insulating film formed in this manner is expected as a substitute material for a transparent insulating film containing silicon nitride, which has been conventionally used in display devices such as liquid crystal displays.

Examples

The present invention will be described with reference to examples, but the scope of the present invention is not limited to these examples.

Examples 1 to 8 and comparative examples 1 to 3

In examples 1 to 8 and comparative examples 1 to 3, the following compound 1 was used as the alicyclic epoxy compound.

[ CHEM 41 ]

In examples 1 to 8 and comparative examples 1 to 3, a compound of the following formula was used as an acid generator.

[ CHEM 42 ]

50 parts by mass of an alicyclic epoxy compound, 1.5 parts by mass of a photoacid generator, and 48.5 parts by mass of a filler of the type described in Table 1 or 2 were stirred at room temperature for 30 minutes to obtain film-forming compositions of examples 1 to 8 and comparative examples 1 to 3.

The transparent insulating films formed using the film-forming compositions obtained in examples and comparative examples were evaluated for transmittance, dielectric constant, and pencil hardness according to the following methods. The evaluation results thereof are recorded in table 1 or 2.

< transmittance >

The film-forming compositions of examples and comparative examples were spin-coated on a glass substrate. Subsequently, the coating film of the film-forming composition on the glass substrate was dried by heating at 80 ℃ for 120 seconds on a hot plate, and then exposed to broad band (broad band) light to form a cured film having a thickness of 2 μm.

The transmittance of the obtained transparent insulating film was measured at a measurement wavelength of 400nm using a spectrophotometer (MCPD-3000, available from Otsuka electronics Co., Ltd.).

Regarding the transmittance, 95% or more was judged as "◎", 90% or more and less than 95% was judged as "○", and less than 90% was judged as "x"

< dielectric constant >

A Si wafer (N-type in crystal plane direction (100), resistivity 0.01 to 0.03 α. omega. cm, manufactured by shin-Etsu semiconductor Co., Ltd.) was used as a substrate, the film-forming compositions of examples and comparative examples were spin-coated on the substrate to form a coating film, the coating film was cured in the same manner as in the transmittance measurement method to form a transparent insulating film having a film thickness of 0.9. mu.m, and the relative dielectric constant of the formed transparent insulating film was measured under a frequency of 0.1MHz using a dielectric constant measuring apparatus (SSM-495, manufactured by SEMILAB JAPAN.K.).

Regarding the dielectric constant (relative dielectric constant), 10 or more was judged as "◎", 7 or more and less than 10 were judged as "○", and less than 7 were judged as "x".

Hardness of pencil

The transparent insulating film formed in the same manner as in the measurement of the transmittance was subjected to a hardness test 5 times using an 8H pencil according to JIS K5600 under conditions of a load of 1kg, a 45-degree method, and a measurement distance of 30mm, and the presence or absence of a flaw after the application of the load was observed.

The case where no scar was present 3 or more times out of 5 tests was judged as "○", and the case where no scar was present 3 or more times was judged as "x".

[ TABLE 1 ]

[ TABLE 2 ]

As can be seen from examples 1 to 8, a transparent insulating film having both high transmittance and high dielectric constant can be formed as long as the film-forming composition contains (a) a filler containing an oxide of an element that holds electrons in the 4f orbital or the 5d orbital in the ground state, (B1) a compound having an alicyclic epoxy group, and (C) an acid generator.

As can be seen from comparative examples 1 and 2, BaTiO was used even when₃Or TiO₂The filler can form an insulating film having a high dielectric constant, and the insulating film has a high transparencyIs damaged. According to comparative example 3, even when an insulating film having excellent transparency can be formed using a filler such as ZrO2, an insulating film having a high dielectric constant cannot be formed.

Examples 9 to 16 and comparative examples 4 to 6

In examples 9 to 16 and comparative examples 4 to 6, resins containing structural units I to IV represented by the following formulae were used. In the following formula, the molar ratio (I/II/III/IV) of each constituent unit was 14/11/40/35. The mass average molecular weight of the resin used in examples 9 to 16 and comparative examples 4 to 6 was 12000.

[ CHEM 43 ]

M315 (manufactured by Toyo Seisaku-Sho Co., Ltd.) which is a mixture of 2,4, 6-trioxahydro-1, 3, 5-triazine-1, 3, 5-triethanol triacrylate and 2,4, 6-trioxahydro-1, 3, 5-triazine-1, 3, 5-triethanol diacrylate was used as the photopolymerizable compound.

As the photopolymerization initiator, IRGACURE OXE01 (manufactured by BASF) was used.

The film-forming compositions of examples 9 to 16 and comparative examples 4 to 6 were prepared by mixing 24.25 parts by mass of the filler of the type described in table 3 or 4, 15 parts by mass of the resin, 7 parts by mass of the photopolymerizable compound, 0.5 part by mass of the photopolymerization initiator, 15 parts by mass of propylene glycol monomethyl ether acetate, and 35 parts by mass of diethylene glycol monomethyl ether to prepare a uniform solution.

The transparent insulating films formed using the film-forming compositions of examples 9 to 16 and comparative examples 4 to 6 were evaluated for transmittance, dielectric constant, pencil hardness, and leakage current by the following methods. The evaluation results thereof are recorded in table 3 or 4.

< transmittance >

The film-forming compositions of examples and comparative examples were spin-coated on a glass substrate. Subsequently, the coating film of the film-forming composition on the glass substrate was dried by heating at 80 ℃ for 300 seconds on a hot plate, and then exposed to light at an exposure amount of 20 mJ/cm 2 using a Mirror Projection Alignment aligner (product name: TME-150 RTO, manufactured by TOPCON K.K.) to form a cured film having a film thickness of 2 μm.

The transmittance of the obtained transparent insulating film was measured at a measurement wavelength of 400nm using a spectrophotometer (MCPD-3000, available from Otsuka electronics Co., Ltd.).

Regarding the transmittance, 95% or more was judged as "◎", 90% or more and less than 95% was judged as "○", and less than 90% was judged as "x".

< dielectric constant >

A Si wafer (N-type in crystal plane direction (100), resistivity of 0.01 to 0.03. omega. cm, manufactured by shin-Etsu semiconductor Co., Ltd.) was used as a substrate. The film-forming compositions of examples and comparative examples were applied to a substrate by spin coating to form a coating film, and the coating film was cured in the same manner as in the transmittance measurement method to form a transparent insulating film having a film thickness of 0.9 μm. The relative dielectric constant of the formed transparent insulating film was measured using a dielectric constant measuring apparatus (manufactured by SSM-495, SEMILAB JAPAN k.k.) under a frequency of 0.1 mhz.

Regarding the dielectric constant (relative dielectric constant), 10 or more was judged as "◎", 7 or more and less than 10 were judged as "○", and less than 7 were judged as "x".

Hardness of pencil

The transparent insulating film formed in the same manner as in the measurement of the transmittance was subjected to a hardness test 5 times using an 8H pencil according to JIS K5600 under conditions of a load of 1kg, a 45-degree method, and a measurement distance of 30mm, and the presence or absence of a flaw after the application of the load was observed.

The case where no scar was present 3 or more times out of 5 tests was judged as "○", and the case where no scar was present 3 or more times was judged as "x".

< leakage Current >

Using the film-forming compositions of examples and comparative examples, an N-type film was formed on an Si wafer (crystal plane orientation (100)), and the electric resistance was measured by the same method as the measurement of dielectric constant0.01 to 0.03. omega. cm, manufactured by shin-Etsu semiconductor Co., Ltd.) is formed on the surface of the substrate with a transparent insulating film having a thickness of 0.9 μm. A voltage of 30 volts was applied to the formed insulating film, and a leakage current was measured. The leakage current value was set to 1.0X 10^-9A／cm²The following case was determined as "◎" and the leakage current value was set to exceed 1.0 × 10^-9A／cm²And 1.0X 10^-7A／cm²The following case was determined as "○" and the leakage current value was set to exceed 1.0 × 10^-7A／cm²And 1.0X 10^-6A／cm²The following case is determined as "△".

[ TABLE 3]

[ TABLE 4 ]

As can be seen from examples 9 to 16, a transparent insulating film having both high transmittance and high dielectric constant and low leakage current can be formed by using a film-forming composition containing (a) a filler containing an oxide of an element which holds electrons in the 4f orbital or 5d orbital in the ground state and (B2) a resin which is a copolymer of methacrylic acid and methacrylic acid ester.

As can be seen from comparative examples 4 and 5, BaTiO was used even when₃Or TiO₂Such a filler can form an insulating film having a high dielectric constant and a small leakage current, and the transparency of the insulating film is significantly impaired. According to comparative example 6, even when ZrO was used₂Such a filler can form an insulating film having excellent transparency, and cannot form an insulating film having a high dielectric constant.

[ examples 17 to 19]

Film-forming compositions of examples 17 to 19 were prepared in the same manner as in example 9, except that the ratio of the structural units I to IV of the resin used for preparing the film-forming composition was changed from the ratio of the resin used in example 9 to the ratio described in table 5 below. The transparent insulating films formed using the film-forming compositions of examples 17 to 19 were evaluated for transmittance, dielectric constant, pencil hardness, and leakage current in the same manner as in example 9. The evaluation results thereof are recorded in table 5.

[ TABLE 5 ]

It is understood from examples 17 to 19 that, even when a film-forming composition containing a resin having a different structural unit content from the resin used in example 9 was used, a transparent insulating film having both high transmittance and high dielectric constant and a small leakage current could be formed in the same manner as the film-forming composition used in example 9.

From examples 17 and 18, it is understood that when the resin contained in the film-forming composition contains a large amount of, for example, about 50 to 80% by mass of a unit derived from a (meth) acrylate having an alicyclic epoxy group-containing group such as a structural unit III, a high-quality transparent insulating film having a particularly small leakage current can be formed by using the film-forming composition.

Claims (9)

1. A composition for forming a transparent insulating film, which contains an oxide of an element that holds electrons in the 4f orbital or 5d orbital in the ground state as a filler (A) and can form a film having a transmittance of 90% or more for light having a wavelength of 400nm when measured using a sample having a thickness of 2 μm,

the filler (A) has a primary particle diameter of 200 [ mu ] m or less, the content of the filler (A) is 1 to 80 mass% based on the mass of the solid content in the composition for forming a transparent insulating film, and the oxide is selected from La₂O₃、CeO₂、Nd₂O₃、Gd₂O₃、Ho₂O₃、Lu₂O₃、HfO₂And Ta₂O₅At least one of the above-mentioned (B),

the composition for forming a transparent insulating film further contains (B1) a compound having an alicyclic epoxy group and (C) an acid generator, or a polymer containing a monomer having an ethylenically unsaturated double bond,

the content of the acid generator (C) is 0.1 to 50 parts by mass relative to 100 parts by mass of the total amount of the compound having an alicyclic epoxy group (B1) in the composition for forming a transparent insulating film,

the content of the polymer of the monomer having an ethylenically unsaturated double bond in the solid content in the composition for forming a transparent insulating film is 20 to 99% by mass.

2. The composition for forming a transparent insulating film according to claim 1, wherein the element contained in the filler (A) is an element in which the number of electrons contained in the 5d orbital is equal to or less than the number of electrons when the 5d orbital becomes a half-filled shell, or an element in which the number of electrons contained in the 4f orbital is equal to or less than the number of electrons when the 4f orbital becomes a half-filled shell.

3. The composition for forming a transparent insulating film according to claim 1, wherein the compound (B1) having an alicyclic epoxy group is a compound represented by the following formula (1),

in the formula (1), X is selected from single bond, -O-CO-, -S-, -SO₂－、－CH₂－、－C(CH₃)₂－、－CBr₂－、－C(CBr₃)₂－、－C(CF₃)₂-and-R¹⁹The 2-valent radical in-O-CO-, R¹⁹Is C1-C8 alkylene, R¹～R¹⁸Each independently is a group selected from a hydrogen atom, a halogen atom and an organic group.

4. The composition for forming a transparent insulating film according to claim 1 or 3, wherein the polymer of the monomer having an ethylenically unsaturated double bond is a polymer containing 1 or more kinds of monomers selected from (meth) acrylic acid and (meth) acrylic acid esters.

5. The composition for forming a transparent insulating film according to claim 4, wherein the polymer of the monomer having an ethylenically unsaturated double bond is a polymer containing 1 or more kinds of monomers selected from (meth) acrylic acid and (meth) acrylic acid esters, and is a resin containing a unit derived from a (meth) acrylic acid ester having an epoxy group-containing group.

6. The composition for forming a transparent insulating film according to claim 4, wherein the polymer of a monomer having an ethylenically unsaturated double bond is a polymer containing 1 or more kinds of monomers selected from (meth) acrylic acid and (meth) acrylic acid esters, and is a resin containing a unit derived from a (meth) acrylic acid ester having a group having an alicyclic skeleton.

7. The composition for forming a transparent insulating film according to claim 4, wherein the polymer of the monomer having an ethylenically unsaturated double bond is a polymer containing 1 or more monomers selected from the group consisting of (meth) acrylic acid and (meth) acrylic esters, and is a resin containing a unit derived from (meth) acrylic acid, a unit derived from a (meth) acrylic ester having an alicyclic hydrocarbon group, and a unit derived from a (meth) acrylic ester having an alicyclic epoxy group-containing group.

8. A transparent insulating film obtained by using the composition for forming a transparent insulating film according to claim 1.

9. A display device comprising the transparent insulating film according to claim 8.