JP2018072634A - Photosensitive resin composition for low refractive index film formation, low refractive index film, optical device, and method for producing low refractive index film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition for low refractive index film formation which can be uniformly applied onto a substrate and can form a low refractive index film that prevents generation of a residue even with low light exposure and hardly causes roughness of a surface by adhesion and peeling of a protective tape; a low refractive index film formed by curing the photosensitive resin composition for low refractive index film formation; an optical device having the low refractive index film; and a method for producing a low refractive index film using the photosensitive resin composition for low refractive index film formation.SOLUTION: A photosensitive resin composition for low refractive index film formation is blended with 0.05-3 mass% of a fluorine-containing surfactant (E) with respect to the total of a mass of a resin (A), a mass of a photopolymerizable compound (B) and a mass of a filler (D), in addition to the resin (A), the photopolymerizable compound (B), a photopolymerization initiator (C) and a filler (D).SELECTED DRAWING: None

Description

  The present invention relates to a photosensitive resin composition for forming a low refractive index film, a low refractive index film formed by curing the photosensitive resin composition for forming a low refractive index film, and an optical device comprising the low refractive index film. And a method for producing a low refractive index film using the above-described photosensitive resin composition for forming a low refractive index film.

Conventionally, various functional films such as an insulating film, a protective film, and an antireflection film have been formed using a photosensitive resin composition.
Specifically, a low refractive index film for coating a microlens for an image sensor, or a low refractive index film for antireflection in a liquid crystal display, an organic EL element, or the like is formed into a desired shape using a photosensitive resin composition. It is formed while being patterned.

  As a photosensitive resin composition capable of forming a patterned cured film that can be used as a low-refractive index film for antireflection, hollow or porous particles, a photopolymerization initiator, and an alkali-soluble polymerizability A photosensitive resin composition containing a compound and a particle dispersant has been proposed (Patent Document 1).

JP 2009-271444 A

For example, when the surface of a microlens formed on an RGB colored film formed on a semiconductor substrate such as a silicon substrate is coated with a cured film (low refractive index film), a protective tape is applied to the surface of the low refractive index film. The semiconductor substrate may be ground in the pasted state.
After such grinding, the protective tape is peeled off from the surface of the low refractive index film. However, the surface of the low refractive index film is easily roughened due to the peeling of the protective tape.
When the coating film of the photosensitive resin composition is exposed and cured, the curing of the surface of the low refractive index film is somewhat low due to the inhibition of curing by oxygen on the surface of the low refractive index film. For this reason, it seems that the surface of the low refractive index film is roughened by peeling off the protective tape.
For these reasons, even when the low refractive index film is formed using the photosensitive resin composition described in Patent Document 1, the low refractive index film is formed by attaching and peeling the protective tape to the low refractive index film. There is a problem that the surface of the surface becomes rough. When the low refractive index film is formed with a low exposure amount, the problem of roughening the surface of the low refractive index film with a protective tape is significant.
Moreover, since the low refractive index film is an optical functional layer, it is naturally desirable that the surface thereof be smooth. For this reason, the photosensitive resin composition for forming a low refractive index film is also required to be able to be applied uniformly on a substrate.
Furthermore, in the microlens coating or the like in the image sensor, it is necessary to form a cured film as a low refractive index film with an accurate dimension at a predetermined position. When used, residues are likely to occur near the pattern after development, and as a result, the apparent dimension of the pattern of the cured film may be larger than the desired dimension.

  The present invention has been made in view of the above-described problems, and can be applied uniformly on a substrate, and can be applied by peeling and applying a protective tape without producing a residue even when exposed at a low exposure amount. A low-refractive-index film-forming photosensitive resin composition capable of forming a low-refractive-index film that does not easily roughen the surface, a low-refractive-index film formed by curing the low-refractive-index film-forming photosensitive resin composition, An object of the present invention is to provide an optical device including a low refractive index film and a method for producing a low refractive index film using the above-described photosensitive resin composition for forming a low refractive index film.

In addition to the resin (A), the photopolymerizable compound (B), the photopolymerization initiator (C), and the filler (D), the present inventors have made a photosensitive resin composition for forming a low refractive index film. And
0.05-3 mass% fluorine-containing surfactant (E) is mix | blended with respect to the sum total of the mass of resin (A), the mass of a photopolymerizable compound (B), and the mass of a filler (D). As a result, the present inventors have found that the above problems can be solved, and have completed the present invention. More specifically, the present invention provides the following.

The first aspect of the present invention comprises a resin (A), a photopolymerizable compound (B), a photopolymerization initiator (C), a filler (D), and a fluorine-containing surfactant (E). Contains,
Content of fluorine-containing surfactant (E) is 0.05-3 with respect to the sum total of the mass of resin (A), the mass of a photopolymerizable compound (B), and the mass of a filler (D). It is a photosensitive resin composition for forming a low refractive index film, which is mass%.

  The second aspect of the present invention is a low refractive index film formed by curing the photosensitive resin composition for forming a low refractive index film according to the first aspect.

  A third aspect of the present invention is an optical device including the low refractive index film according to the second aspect.

According to a fourth aspect of the present invention, there is provided a coating film of the photosensitive resin composition for forming a low refractive index film according to the first aspect;
Exposing the coating film selectively according to a predetermined pattern;
Developing the exposed coating film, and manufacturing a patterned low refractive index film.

  According to the present invention, a low-refractive-index film that can be uniformly applied on a substrate and does not cause a residue even when exposed at a low exposure amount, and is less likely to be roughened by attaching and peeling a protective tape. A low-refractive index film-forming photosensitive resin composition, a low-refractive-index film formed by curing the low-refractive-index film-forming photosensitive resin composition, and an optical device including the low-refractive index film, It is possible to provide a method for producing a low refractive index film using the above-described photosensitive resin composition for forming a low refractive index film.

Hereinafter, the present invention will be described based on preferred embodiments. In the present specification, “to” represents the above (lower limit) to the following (upper limit) unless otherwise specified.
In the present specification, when simply described as “photosensitive resin composition”, it means “photosensitive resin composition for forming a low refractive index film” unless otherwise specified.
In the present specification, “(meth) acrylate” includes both acrylate and methacrylate.
In the present specification, “(meth) acryl” includes both acryl and methacryl.
In the present specification, “(meth) acryloyl” includes both acryloyl and methacryloyl.

<< Photosensitive resin composition for forming a low refractive index film >>
The photosensitive resin composition for forming a low refractive index film comprises a resin (A), a photopolymerizable compound (B), a photopolymerization initiator (C), and a filler (D). The fluorine-containing surfactant (E) is included in an amount of 0.05 to 3% by mass with respect to the total of the mass of the photopolymerizable compound (B) and the mass of the filler (D).
When the photosensitive resin composition contains the fluorine-containing surfactant (E) in an amount within the above predetermined range, the photosensitive resin composition can be uniformly applied on the substrate, and exposure with a low exposure amount is possible. However, it is possible to form a low-refractive-index film whose surface is hardly roughened by applying and peeling off the protective tape without generating a residue.
Hereinafter, essential or optional components contained in the photosensitive resin composition for forming a low refractive index film will be described.

<Resin (A)>
The photosensitive resin composition for forming a low refractive index film contains a resin (A). Resin (A) is a component that imparts a film-forming property capable of forming a coating film and a patterned film to the photosensitive resin composition for pattern formation.
The resin (A) is not particularly limited as long as it is a resin that has been conventionally blended in a photosensitive resin composition for pattern formation. As the resin (A), an alkali-soluble resin is preferable because a patterned cured film having a good shape can be easily formed.
While the photosensitive resin composition containing an alkali-soluble resin is soluble in an alkali developer, the exposed photosensitive resin composition is cured. For this reason, when the coating film of the photosensitive resin composition that has been selectively exposed is developed using an alkali developer, only the unexposed portion is dissolved in the alkali developer, while the cured exposed portion remains, A patterned cured film is formed as a low refractive index film.

  The alkali-soluble resin is a resin film having a resin concentration of 20% by mass (solvent: propylene glycol monomethyl ether acetate) and a resin film having a thickness of 1 μm is formed on the substrate, and tetramethylammonium hydroxide having a concentration of 0.05% by mass. (TMAH) A solution that dissolves in a thickness of 0.01 μm or more when immersed in an aqueous solution for 1 minute.

  Preferable examples of the alkali-soluble resin include a resin (A1) having a cardo structure. By using a photosensitive resin composition containing a resin having a cardo structure (A1) as an alkali-soluble resin, a low refractive index film having excellent balance of heat resistance, mechanical properties, solvent resistance, chemical resistance, etc. Easy to form.

  The resin (A1) having a cardo structure is not particularly limited, and conventionally known resins can be used. Among these, the resin represented by the following formula (a-1) is preferable.

In the formula ^{(a-1), X} a represents a group represented by the following formula (a-2).

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

In the formula (a-1), Y ^a represents a residue obtained by removing an acid anhydride group (—CO—O—CO—) from a dicarboxylic acid anhydride. Examples of dicarboxylic acid anhydrides include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, chlorendic anhydride, methyltetrahydro Examples thereof include phthalic anhydride and glutaric anhydride.

Further, in the above formula ^(a-1), Z a represents a residue obtained by removing two acid anhydride groups from a tetracarboxylic acid dianhydride. Examples of tetracarboxylic dianhydrides include pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, biphenyl ether tetracarboxylic dianhydride, and the like.
Moreover, in said formula (a-1), m shows the integer of 0-20.

  The mass average molecular weight of the resin (A1) having a cardo structure (Mw: measured value by gel permeation chromatography (GPC) in terms of polystyrene. The same applies in the present specification) is preferably 1000 to 40000, and preferably 2000 to 30000. It is more preferable that By setting it as the above range, sufficient heat resistance and film strength can be obtained while obtaining good developability.

  Since it is easy to form a low refractive index film excellent in mechanical strength and adhesion to the substrate, (a1) a copolymer (A2) obtained by polymerizing at least an unsaturated carboxylic acid is also preferably used as an alkali-soluble resin. be able to.

  (A1) Examples of unsaturated carboxylic acids include monocarboxylic acids such as (meth) acrylic acid and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, and itaconic acid; and anhydrides of these dicarboxylic acids; Etc. Among these, (meth) acrylic acid and maleic anhydride are preferable in terms of copolymerization reactivity, alkali solubility of the resulting resin, availability, and the like. These (a1) unsaturated carboxylic acids can be used alone or in combination of two or more.

  The copolymer (A2) may be a copolymer of (a1) an unsaturated carboxylic acid and (a2) an alicyclic epoxy group-containing unsaturated compound. (A2) The unsaturated compound having an alicyclic epoxy group is not particularly limited as long as it is an unsaturated compound having an alicyclic epoxy group. The alicyclic group constituting the alicyclic epoxy group may be monocyclic or polycyclic. Examples of the monocyclic alicyclic group include a cyclopentyl group and a cyclohexyl group. Examples of the polycyclic alicyclic group include a norbornyl group, an isobornyl group, a tricyclononyl group, a tricyclodecyl group, and a tetracyclododecyl group. These (a2) alicyclic epoxy group-containing unsaturated compounds can be used alone or in combination of two or more.

  Specifically, examples of the (a2) alicyclic epoxy group-containing unsaturated compound include compounds represented by the following formulas (a2-1) to (a2-15). Among these, in order to moderate developability, compounds represented by the following formulas (a2-1) to (a2-5) are preferable, and in the following formulas (a2-1) to (a2-3) The compounds represented are more preferred.

In the above formula, R ^a20 represents a hydrogen atom or a methyl group, R ^a21 represents a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, and R ^a22 represents a divalent having 1 to 10 carbon atoms. A hydrocarbon group is shown, t shows the integer of 0-10. R ^a21 is preferably a linear or branched alkylene group such as a methylene group, an ethylene group, a propylene group, a tetramethylene group, an ethylethylene group, a pentamethylene group, or a hexamethylene group. As R ^a22 , for example, a methylene group, an ethylene group, a propylene group, a tetramethylene group, an ethylethylene group, a pentamethylene group, a hexamethylene group, a phenylene group, a cyclohexylene group, —CH ₂ —Ph—CH ₂ — (Ph is A phenylene group) is preferred.

The copolymer (A2) comprises (a3) an unsaturated carboxylic acid containing (a1) an unsaturated carboxylic acid and (a2) an alicyclic group-containing unsaturated compound having no epoxy group together with the alicyclic epoxy group-containing unsaturated compound. It may be copolymerized.
The (a3) alicyclic group-containing unsaturated compound is not particularly limited as long as it is an unsaturated compound having an alicyclic group. The alicyclic group may be monocyclic or polycyclic. Examples of the monocyclic alicyclic group include a cyclopentyl group and a cyclohexyl group. Examples of the polycyclic alicyclic group include an adamantyl group, a norbornyl group, an isobornyl group, a tricyclononyl group, a tricyclodecyl group, and a tetracyclododecyl group. These (a3) alicyclic group-containing unsaturated compounds can be used alone or in combination of two or more.

  Specifically, examples of the (a3) alicyclic group-containing unsaturated compound include compounds represented by the following formulas (a3-1) to (a3-7). Among these, in order to moderate developability, compounds represented by the following formulas (a3-3) to (a3-8) are preferable, and in the following formulas (a3-3) and (a3-4) The compounds represented are more preferred.

In the above formula, R ^a23 represents a hydrogen atom or a methyl group, R ^a24 represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, and R ^a25 represents a hydrogen atom or 1 carbon atom. Represents an alkyl group of ~ 5. R ^a24 is preferably a single bond or a linear or branched alkylene group such as a methylene group, an ethylene group, a propylene group, a tetramethylene group, an ethylethylene group, a pentamethylene group, or a hexamethylene group. As R ^a25 , for example, a methyl group and an ethyl group are preferable.

Further, the copolymer (A2) may be a monomer polymer containing the above (a1) unsaturated carboxylic acid and (a4) an epoxy group-containing unsaturated compound having no alicyclic group. Good.
Such a copolymer (A2) is
It may be a copolymer of the above (a1) unsaturated carboxylic acid and (a4) an epoxy group-containing unsaturated compound,
It may be a copolymer of (a1) unsaturated carboxylic acid, (a2) alicyclic epoxy group-containing unsaturated compound and (a4) epoxy group-containing unsaturated compound,
It may be a copolymer of the above (a1) unsaturated carboxylic acid, the above (a3) alicyclic group-containing unsaturated compound, and (a4) an epoxy group-containing unsaturated compound,
Copolymer of (a1) unsaturated carboxylic acid, (a2) alicyclic epoxy group-containing unsaturated compound, (a3) alicyclic group-containing unsaturated compound and (a4) epoxy group-containing unsaturated compound It may be.

  (A4) Examples of the epoxy group-containing unsaturated compound include glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, and 6,7-epoxyheptyl (meth) acrylate. (Meth) acrylic acid epoxy alkyl esters; α-ethyl glycidyl acrylate, α-n-propyl acrylate glycidyl, α-n-butyl acrylate glycidyl, α-ethyl acrylate 6,7-epoxyheptyl, etc. And alkylacrylic acid epoxy alkyl esters. Among these, glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, and 6,7-epoxyheptyl (meth) acrylate are preferable from the viewpoint of copolymerization reactivity and the strength of the cured resin. These (a4) epoxy group-containing unsaturated compounds can be used alone or in combination of two or more.

The copolymer (A2) may be a monomer copolymer containing the (a1) unsaturated carboxylic acid and a compound other than the above.
The copolymer (A2) comprises the above (a1) unsaturated carboxylic acid, the above (a2) alicyclic epoxy group-containing unsaturated compound, the above (a3) alicyclic group-containing unsaturated compound, and the above (a4). It may be a copolymer of monomers containing one or more monomers selected from the group consisting of epoxy group-containing unsaturated compounds and other compounds than the above.

  Other compounds include (meth) acrylic acid alkyl ester, (meth) acrylic acid hydroxyalkyl ester, (meth) acrylate having an ether bond, other (meth) acrylates described above, (meth) acrylamides, allyl compounds, Examples include vinyl ethers, vinyl esters, styrenes, dicarboxylic acid diesters, conjugated olefins, nitrile group-containing polymerizable compounds, and chlorine-containing polymerizable compounds. These compounds can be used alone or in combination of two or more.

  Examples of (meth) acrylic acid alkyl esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, amyl (meth) acrylate, and tert-octyl (meth). Examples thereof include linear or branched alkyl (meth) acrylate such as acrylate.

  Examples of (meth) acrylic acid hydroxyalkyl esters include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-dimethylhydroxypropyl (meth) acrylate, and trimethylolpropane mono (meth) acrylate. It is done.

  Examples of the (meth) acrylate having an ether bond include 2-methoxyethyl (meth) acrylate, methoxytriethylene glycol (meth) acrylate, 3-methoxybutyl (meth) acrylate, ethyl carbitol (meth) acrylate, phenoxypolyethylene glycol ( Examples include meth) acrylate, methoxypolypropylene glycol (meth) acrylate, and tetrahydrofurfuryl (meth) acrylate, with 2-methoxyethyl (meth) acrylate and methoxytriethylene glycol (meth) acrylate being preferred.

  Examples of the other (meth) acrylates include chloroethyl (meth) acrylate, benzyl (meth) acrylate, and phenyl (meth) acrylate.

  (Meth) acrylamides include (meth) acrylamide, N-alkyl (meth) acrylamide, N-aryl (meth) acrylamide, N, N-dialkyl (meth) acrylamide, N, N-aryl (meth) acrylamide, N -Methyl-N-phenyl (meth) acrylamide, N-hydroxyethyl-N-methyl (meth) acrylamide and the like.

  Examples of the allyl compound include allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, allyl lactate, etc .; allyloxyethanol; Can be mentioned.

  Examples of vinyl ethers include hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethyl hexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl ether, 2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether. Alkyl vinyl ethers such as diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether; vinyl phenyl ether, vinyl tolyl ether, vinyl chlorophenyl ether, vinyl-2,4-dichloropheny And the like; ethers, vinyl naphthyl ether, vinyl aryl ethers such as vinyl anthranyl ether.

  Vinyl esters include vinyl acetate, vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl valerate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxyacetate, vinyl butoxyacetate Vinyl phenyl acetate, vinyl acetoacetate, vinyl lactate, vinyl-β-phenylbutyrate, vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, vinyl naphthoate and the like.

  Styrenes include: styrene; methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, isopropyl styrene, butyl styrene, hexyl styrene, cyclohexyl styrene, decyl styrene, benzyl styrene, chloromethyl styrene, trifluoromethyl styrene, ethoxy Alkyl styrene such as methyl styrene and acetoxymethyl styrene; alkoxy styrene such as methoxy styrene, 4-methoxy-3-methyl styrene and dimethoxy styrene; chlorostyrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, Dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethyl Styrene, halostyrenes such as 4-fluoro-3-trifluoromethyl styrene; and the like.

  Dicarboxylic acid diesters include diethyl maleate and dibutyl fumarate.

  Examples of the conjugated diolefin include butadiene and isoprene.

  Examples of the nitrile group-containing polymerizable compound include (meth) acrylonitrile.

  Examples of the chlorine-containing polymerizable compound include vinyl chloride and vinylidene chloride.

As for the copolymer (A2), among the copolymers of monomers containing the above (a1) unsaturated carboxylic acid and a compound other than the above, the above (a1) unsaturated carboxylic acid and the above ether bond A copolymer of a monomer containing (meth) acrylate having the above is preferable.
In this case, the proportion of the structural unit derived from (meth) acrylate having an ether bond in the copolymer (A2) is preferably 30 to 90% by mass, and more preferably 40 to 80% by mass.

The proportion of the structural unit derived from the (a1) unsaturated carboxylic acid in the copolymer (A2) is preferably 1 to 50% by mass, and more preferably 5 to 45% by mass.
In the case where the copolymer (A2) contains a structural unit derived from the above (a2) alicyclic epoxy group-containing unsaturated compound and a structural unit derived from the above (a4) epoxy group-containing unsaturated compound, The sum of the proportion of the structural unit derived from the (a2) alicyclic epoxy group-containing unsaturated compound and the proportion of the structural unit derived from the (a4) epoxy group-containing unsaturated compound in the combined (A2) is 71% by mass or more. It is preferable that it is 71-95 mass%, it is more preferable that it is 75-90 mass%. In particular, the proportion of the structural unit derived from the (a2) alicyclic epoxy group-containing unsaturated compound in the copolymer (A2) is preferably 71% by mass or more, and preferably 71 to 80% by mass. Is more preferable. By setting the proportion of the structural unit derived from the (a2) alicyclic epoxy group-containing unsaturated compound within the above range, the temporal stability of the photosensitive resin composition can be further improved.
In addition, when the copolymer (A2) contains a structural unit derived from the (a3) alicyclic group-containing unsaturated compound, the above (a3) alicyclic group-containing unsaturated compound in the copolymer (A2) The proportion of the derived structural unit is preferably 1 to 30% by mass, and more preferably 5 to 20% by mass.

  The mass average molecular weight of the copolymer (A2) is preferably 2000 to 200000, and more preferably 3000 to 30000. By setting it as the above range, the film forming ability of the photosensitive resin composition and the developability after exposure tend to be easily balanced.

  The alkali-soluble resin includes (A3) a copolymer having at least a structural unit derived from the above (a1) unsaturated carboxylic acid and a structural unit having a polymerizable site with the photopolymerizable compound (B) described later. A polymer, or (A4) a structural unit derived from the (a1) unsaturated carboxylic acid, and (a2) an alicyclic epoxy group-containing unsaturated compound and / or (a4) an epoxy group-containing unsaturated compound. A resin containing a copolymer having at least a structural unit and a structural unit having a polymerizable portion with the photopolymerizable compound (B) described later can also be used suitably. When alkali-soluble resin contains a copolymer (A3) or a copolymer (A4), the adhesiveness to the board | substrate of the film | membrane formed using a photosensitive resin composition, or a photosensitive resin composition is used. The mechanical strength of the resulting low refractive index film can be increased.

  Copolymer (A3) and copolymer (A4) are described as other compounds for copolymer (A2), (meth) acrylic acid esters, (meth) acrylamides, allyl compounds, vinyl ethers , Vinyl esters, styrenes and the like may be further copolymerized.

  The structural unit having a site that can be polymerized with the photopolymerizable compound (B) preferably has an ethylenically unsaturated group as a site that can be polymerized with the photopolymerizable compound (B). In the copolymerization having such a constitutional unit, for the copolymer (A3), at least a part of the carboxyl group contained in the polymer containing the constitutional unit derived from the above (a1) unsaturated carboxylic acid, It can be prepared by reacting the above (a2) alicyclic epoxy group-containing unsaturated compound and / or (a4) an epoxy group-containing unsaturated compound. In addition, the copolymer (A4) is composed of (a1) a structural unit derived from an unsaturated carboxylic acid, (a2) an alicyclic epoxy group-containing unsaturated compound and / or (a4) an epoxy group-containing unsaturated compound. It can be prepared by reacting at least a part of an epoxy group in a copolymer having a derived structural unit with (a1) an unsaturated carboxylic acid.

  The proportion of the structural unit derived from the (a1) unsaturated carboxylic acid in the copolymer (A3) is preferably 1 to 50 mass%, more preferably 5 to 45 mass%. In the copolymer (A3), the proportion of the structural unit having a site polymerizable with the photopolymerizable compound (B) is preferably 1 to 45% by mass, and more preferably 5 to 40% by mass. When copolymer (A3) contains each structural unit in such a ratio, it is easy to obtain the photosensitive resin composition which can form the low refractive index film | membrane excellent in adhesiveness with a board | substrate.

1-50 mass% is preferable and, as for the ratio for which the structural unit derived from (a1) unsaturated carboxylic acid in a copolymer (A4) accounts, 5-45 mass% is more preferable. The proportion of the structural unit derived from the (a2) alicyclic epoxy group-containing unsaturated compound and / or (a4) the epoxy group-containing unsaturated compound in the copolymer (A4) is preferably 55% by mass or more, 71 More preferably, it is more preferably 71 to 80% by mass.
In the copolymer (A4), the proportion of the structural unit having a site polymerizable with the photopolymerizable compound (B) is preferably 1 to 45% by mass, and more preferably 5 to 40% by mass. When a copolymer (A4) contains each structural unit in such a ratio, it is easy to obtain the photosensitive resin composition which can form the low refractive index film | membrane excellent in adhesiveness with a board | substrate.

  The mass average molecular weight of the copolymer (A3) and the copolymer (A4) is preferably 2000 to 50000, and more preferably 5000 to 30000. By setting it as the above range, the film forming ability of the photosensitive resin composition and the developability after exposure tend to be easily balanced.

  Content in the photosensitive resin composition of resin (A) is 20-85 mass with respect to the mass of the photosensitive resin composition except the mass of the filler (D) mentioned later and the mass of the organic solvent (S). %, And more preferably 30 to 70% by mass.

<Photopolymerizable compound (B)>
As the photopolymerizable compound (B), a monomer having an ethylenically unsaturated group can be preferably used. Monomers having an ethylenically unsaturated group include monofunctional monomers and polyfunctional monomers.

  Monofunctional monomers include (meth) acrylamide, methylol (meth) acrylamide, methoxymethyl (meth) acrylamide, ethoxymethyl (meth) acrylamide, propoxymethyl (meth) acrylamide, butoxymethoxymethyl (meth) acrylamide, N-methylol ( (Meth) acrylamide, N-hydroxymethyl (meth) acrylamide, (meth) acrylic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, crotonic acid, 2-acrylamide- 2-methylpropane sulfonic acid, tert-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, 2-hydroxybutyl (meth) acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2- (Meth) acryloyloxy-2-hydroxypropyl phthalate, glycerin mono (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dimethylaminoethyl (meth) acrylate, glycidyl (meth) acrylate, 2,2,2-trifluoroethyl Examples include (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, and half (meth) acrylate of a phthalic acid derivative. These monofunctional monomers can be used alone or in combination of two or more.

  On the other hand, as the polyfunctional monomer, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butylene glycol Di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexane glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate, glycerin di ( (Meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) Acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 2,2-bis (4- (meth) acryloxydiethoxyphenyl) propane, 2,2-bis (4- (meth) Acryloxypolyethoxyphenyl) propane, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, diglycidyl phthalate Ester di (meth) acrylate, glycerin triacrylate, glycerin polyglycidyl ether poly (meth) acrylate, urethane (meth) acrylate (ie, tolylene diisocyanate, trimer Reaction product of 2-hexoxymethylene diisocyanate or hexamethylene diisocyanate and 2-bidoxyethyl (meth) acrylate), methylenebis (meth) acrylamide, (meth) acrylamide methylene ether, polyhydric alcohol and N-methylol (meth) acrylamide Examples include polyfunctional monomers such as condensates, triacryl formal, and the like. These polyfunctional monomers can be used alone or in combination of two or more.

  Among these monomers having an ethylenically unsaturated group, a trifunctional or higher polyfunctional monomer has a tendency to increase the adhesion of the photosensitive resin composition to the substrate and the strength after curing of the photosensitive resin composition. Are preferred, polyfunctional monomers having 4 or more functional groups are more preferable, and polyfunctional monomers having 5 or more functional groups are more preferable.

Moreover, it is particularly preferable that the photopolymerizable compound (B) contains a polyfunctional compound having 6 or more functional groups.
When the photosensitive resin composition contains a photopolymerizable compound (B) containing a polyfunctional compound having 6 or more functional groups, a high degree of crosslinking proceeds on the surface of the low refractive index film at the time of curing by exposure. It is easy to form a low refractive index film.
For this reason, even if the protective tape is peeled from the low refractive index film, the surface of the low refractive index film is hardly roughened.

Furthermore, the photopolymerizable compound (B) preferably contains a photopolymerizable compound having a functionality of less than 6 with a polyfunctional compound having a functionality of 6 or more.
When a polyfunctional compound having six or more functional groups is used alone, the influence of oxygen inhibition is small and the degree of curing of the film surface can be improved. However, in this case, the curing progresses to the unexposed area by a chain reaction, and although it is acceptable, a post-development residue is likely to occur or the pattern edge shape is likely to be rattled.
On the other hand, when a photopolymerizable compound of less than 6 functions is used together with a polyfunctional compound of 6 or more functions, the balance between good curing of the film surface, a small amount of residue after development, and a smooth pattern edge shape is achieved. Easy to take.

  Content in the photosensitive resin composition of a photopolymerizable compound (B) is 1 with respect to the mass of the photosensitive resin composition except the mass of the filler (D) mentioned later and the mass of the organic solvent (S). -70 mass% is preferable, and 5-60 mass% is more preferable. By setting it as the above range, it tends to be easy to balance sensitivity, developability, and resolution.

<Photopolymerization initiator (C)>
It does not specifically limit as a photoinitiator (C), A conventionally well-known photoinitiator can be used.

  Specific examples of the photopolymerization initiator (C) include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and 1- [4- (2-hydroxyethoxy) phenyl]. 2-hydroxy-2-methyl-1-propan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4-dodecylphenyl) -2- Hydroxy-2-methylpropan-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one, bis (4-dimethylaminophenyl) ketone, 2-methyl-1- [4- (methylthio) Phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, O Acetyl-1- [6- (2-methylbenzoyl) -9-ethyl-9H-carbazol-3-yl] ethanone oxime, O-acetyl-1- [6- (pyrrol-2-ylcarbonyl) -9- Ethyl-9Hcarbazol-3-yl] ethanone oxime, (9-ethyl-6-nitro-9H-carbazol-3-yl) [4- (2-methoxy-1-methylethoxy) -2-methylphenyl] methanone O-acetyloxime, 2- (benzoyloxyimino) -1- [4- (phenylthio) phenyl] -1-octanone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 4-benzoyl-4′-methyldimethylsulfide 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, -Butyl dimethylaminobenzoate, 4-dimethylamino-2-ethylhexylbenzoic acid, 4-dimethylamino-2-isoamylbenzoic acid, benzyl-β-methoxyethyl acetal, benzyldimethyl ketal, 1-phenyl-1,2-propane Dione-2- (O-ethoxycarbonyl) oxime, methyl o-benzoylbenzoate, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 1-chloro-4-propoxythioxanthone, thioxanthene, 2-chlorothioxanthene, 2,4-diethylthioxanthene, 2-methylthioxanthene, 2-isopropylthioxanthene, 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-diphenyla Traquinone, azobisisobutyronitrile, benzoyl peroxide, cumene hydroperoxide, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2- (o-chlorophenyl) -4,5-di (m -Methoxyphenyl) -imidazolyl dimer, benzophenone, 2-chlorobenzophenone, p, p'-bisdimethylaminobenzophenone, 4,4'-bisdiethylaminobenzophenone, 4,4'-dichlorobenzophenone, 3,3-dimethyl- 4-methoxybenzophenone, benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, benzoin Ether, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p-tert-butylacetophenone, p-dimethylaminoacetophenone, p-tert-butyltrichloro Acetophenone, p-tert-butyldichloroacetophenone, α, α-dichloro-4-phenoxyacetophenone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, dibenzosuberone, pentyl-4-dimethylaminobenzoate, 9-phenylacridine, 1,7-bis- (9-acridinyl) heptane, 1,5-bis- (9-acridinyl) pentane, 1,3-bis- (9-acridinyl) propyl Bread, p-methoxytriazine, 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2- [2- (5-methyl) Furan-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s- Triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4-dimethoxyphenyl) ethenyl]- 4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-n-butoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-bis-trichloromethyl-6 -(3-Bromo-4-methoxy) phenyl-s-triazine, 2,4-bis-trichloromethyl-6- (2-bromo-4-methoxy) phenyl-s-triazine, 2,4-bis-trichloromethyl Examples include -6- (3-bromo-4-methoxy) styrylphenyl-s-triazine, 2,4-bis-trichloromethyl-6- (2-bromo-4-methoxy) styrylphenyl-s-triazine, and the like. These photopolymerization initiators can be used alone or in combination of two or more.

  Among these, it is particularly preferable in terms of sensitivity to use an oxime ester compound as the photopolymerization initiator (C). Preferred examples of the oxime ester compound include O-acetyl-1- [6- (2-methylbenzoyl) -9-ethyl-9H-carbazol-3-yl] ethanone oxime, O-acetyl-1- [6- (Pyrrole-2-ylcarbonyl) -9-ethyl-9Hcarbazol-3-yl] ethanone oxime and 2- (benzoyloxyimino) -1- [4- (phenylthio) phenyl] -1- Octanone is mentioned.

When using an oxime ester compound as a photoinitiator (C), it is also preferable to use together an oxime ester compound and other photoinitiators other than an oxime ester compound.
When using an oxime ester compound and another photoinitiator together, it is easy to adjust the sensitivity of the photosensitive resin composition to an appropriate range. For this reason, since the progress of excessive curing due to exposure hardly occurs, it is difficult to form a patterned low refractive index film having a width wider than a desired width.
As another photopolymerization initiator used in combination with the oxime ester compound, an α-aminoalkylphenone photopolymerization initiator is preferable. Preferred examples of the α-aminoalkylphenone-based photopolymerization initiator include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (IRGACURE 907 (IR-907)). , Trade name, manufactured by BASF), and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one (Irgacure 369E (IR-369E), trade name, manufactured by BASF) Is mentioned.

（Ｒ^ｃ１は、１価の有機基、アミノ基、ハロゲン、ニトロ基、及びシアノ基からなる群より選択される基であり、
ｎ１は０〜４の整数であり、
ｎ２は０、又は１であり、
Ｒ^ｃ２は、置換基を有してもよいフェニル基、又は置換基を有してもよいカルバゾリル基であり、
Ｒ^ｃ３は、水素原子、又は炭素原子数１〜６のアルキル基である。） Moreover, it is also preferable to use the oxime ester compound represented by a following formula (c1) as an oxime ester compound.

(R ^c1 is a group selected from the group consisting of a monovalent organic group, an amino group, a halogen, a nitro group, and a cyano group;
n1 is an integer of 0 to 4,
n2 is 0 or 1,
R ^c2 is a phenyl group which may have a substituent, or a carbazolyl group which may have a substituent,
R ^c3 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. )

In formula (c1), R ^c1 is not particularly limited as long as the object of the present invention is not impaired, and is appropriately selected from various organic groups. Preferred examples when R ^c1 is an organic group include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, a saturated aliphatic acyloxy group, an alkoxycarbonyl group, and a substituent. An optionally substituted phenyl group, an optionally substituted phenoxy group, an optionally substituted benzoyl group, an optionally substituted phenoxycarbonyl group, an optionally substituted benzoyloxy A group, a phenylalkyl group which may have a substituent, a naphthyl group which may have a substituent, a naphthoxy group which may have a substituent, a naphthoyl group which may have a substituent, a substituent A naphthoxycarbonyl group which may have a naphthyloxy group which may have a substituent, a naphthylalkyl group which may have a substituent, a heterocyclyl group which may have a substituent, Examples include an amino group substituted with an mino group, 1 or 2 organic groups, a morpholin-1-yl group, a piperazin-1-yl group, a halogen, a nitro group, and a cyano group. When n1 is an integer of 2 to 4, R ^c1 may be the same or different. Further, the number of carbon atoms of the substituent does not include the number of carbon atoms of the substituent that the substituent further has.

When R ^c1 is an alkyl group, 1 to 20 carbon atoms are preferable, and 1 to 6 carbon atoms are more preferable. Further, when R ^c1 is an alkyl group, it may be linear or branched. Specific examples when R ^c1 is an alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, and an n-pentyl group. , Isopentyl group, sec-pentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, n-nonyl group, isononyl group, An n-decyl group, an isodecyl group, etc. are mentioned. When R ^c1 is an alkyl group, the alkyl group may include an ether bond (—O—) in the carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include a methoxyethyl group, an ethoxyethyl group, a methoxyethoxyethyl group, an ethoxyethoxyethyl group, a propyloxyethoxyethyl group, and a methoxypropyl group.

When R ^c1 is an alkoxy group, 1 to 20 carbon atoms are preferable, and 1 to 6 carbon atoms are more preferable. Further, when R ^c1 is an alkoxy group, it may be linear or branched. Specific examples when R ^c1 is an alkoxy group include methoxy group, ethoxy group, n-propyloxy group, isopropyloxy group, n-butyloxy group, isobutyloxy group, sec-butyloxy group, tert-butyloxy group, n -Pentyloxy group, isopentyloxy group, sec-pentyloxy group, tert-pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, isooctyloxy group, sec-octyloxy group Tert-octyloxy group, n-nonyloxy group, isononyloxy group, n-decyloxy group, and isodecyloxy group. When R ^c1 is an alkoxy group, the alkoxy group may include an ether bond (—O—) in the carbon chain. Examples of the alkoxy group having an ether bond in the carbon chain include a methoxyethoxy group, an ethoxyethoxy group, a methoxyethoxyethoxy group, an ethoxyethoxyethoxy group, a propyloxyethoxyethoxy group, and a methoxypropyloxy group.

When R ^c1 is a cycloalkyl group or a cycloalkoxy group, 3 to 10 carbon atoms are preferable, and 3 to 6 carbon atoms are more preferable. Specific examples in the case where R ^c1 is a cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Specific examples in the case where R ^c1 is a cycloalkoxy group include a cyclopropyloxy group, a cyclobutyloxy group, a cyclopentyloxy group, a cyclohexyloxy group, a cycloheptyloxy group, and a cyclooctyloxy group.

When R ^c1 is a saturated aliphatic acyl group or a saturated aliphatic acyloxy group, 2 to 20 carbon atoms are preferable, and 2 to 7 carbon atoms are more preferable. Specific examples when R ^c1 is a saturated aliphatic acyl group include acetyl group, propanoyl group, n-butanoyl group, 2-methylpropanoyl group, n-pentanoyl group, 2,2-dimethylpropanoyl group, n -Hexanoyl group, n-heptanoyl group, n-octanoyl group, n-nonanoyl group, n-decanoyl group, n-undecanoyl group, n-dodecanoyl group, n-tridecanoyl group, n-tetradecanoyl group, n-pentadecanyl group Examples include a noyl group and an n-hexadecanoyl group. Specific examples when R ^c1 is a saturated aliphatic acyloxy group include acetyloxy group, propanoyloxy group, n-butanoyloxy group, 2-methylpropanoyloxy group, n-pentanoyloxy group, 2, 2-dimethylpropanoyloxy group, n-hexanoyloxy group, n-heptanoyloxy group, n-octanoyloxy group, n-nonanoyloxy group, n-decanoyloxy group, n-undecanoyloxy group, n -Dodecanoyloxy group, n-tridecanoyloxy group, n-tetradecanoyloxy group, n-pentadecanoyloxy group, n-hexadecanoyloxy group and the like.

When R ^c1 is an alkoxycarbonyl group, 2 to 20 carbon atoms are preferable, and 2 to 7 carbon atoms are more preferable. Specific examples when R ^c1 is an alkoxycarbonyl group include methoxycarbonyl group, ethoxycarbonyl group, n-propyloxycarbonyl group, isopropyloxycarbonyl group, n-butyloxycarbonyl group, isobutyloxycarbonyl group, sec-butyl. Oxycarbonyl group, tert-butyloxycarbonyl group, n-pentyloxycarbonyl group, isopentyloxycarbonyl group, sec-pentyloxycarbonyl group, tert-pentyloxycarbonyl group, n-hexyloxycarbonyl group, n-heptyloxycarbonyl Group, n-octyloxycarbonyl group, isooctyloxycarbonyl group, sec-octyloxylcarbonyl group, tert-octyloxycarbonyl group, n-nonyloxycarbonyl group , Isononyloxycarbonyl group, n-decyloxycarbonyl group, isodecyloxycarbonyl group and the like.

When R ^c1 is a phenylalkyl group, 7 to 20 carbon atoms are preferable, and 7 to 10 carbon atoms are more preferable. Further, when R ^c1 is a naphthylalkyl group, the number of carbon atoms is preferably 11 to 20, and more preferably 11 to 14 carbon atoms. Specific examples when R ^c1 is a phenylalkyl group include a benzyl group, a 2-phenylethyl group, a 3-phenylpropyl group, and a 4-phenylbutyl group. Specific examples of when R ^c1 is a naphthylalkyl group include an α-naphthylmethyl group, a β-naphthylmethyl group, a 2- (α-naphthyl) ethyl group, and a 2- (β-naphthyl) ethyl group. . When R ^c1 is a phenylalkyl group or a naphthylalkyl group, R ^c1 may further have a substituent on the phenyl group or naphthyl group.

When R ^c1 is a heterocyclyl group, the heterocyclyl group is a 5-membered or 6-membered monocycle containing 1 or more of N, S, and O, or such monocycles or such monocycles and a benzene ring are condensed. Heterocyclyl group. When the heterocyclyl group is a condensed ring, the ring number is up to 3. Examples of the heterocyclic ring constituting the heterocyclyl group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, pyridazine, benzofuran, benzothiophene, indole, Examples include isoindole, indolizine, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalazine, cinnoline, and quinoxaline. When R ^c1 is a heterocyclyl group, the heterocyclyl group may further have a substituent.

When R ^c1 is an amino group substituted with an organic group of 1 or 2, suitable examples of the organic group include alkyl groups having 1 to 20 carbon atoms, cycloalkyl groups having 3 to 10 carbon atoms, carbon A saturated aliphatic acyl group having 2 to 20 atoms, a phenyl group which may have a substituent, a benzoyl group which may have a substituent, a phenyl having 7 to 20 carbon atoms which may have a substituent Examples thereof include an alkyl group, an optionally substituted naphthyl group, an optionally substituted naphthoyl group, an optionally substituted naphthylalkyl group having 11 to 20 carbon atoms, and a heterocyclyl group. It is done. Specific examples of these suitable organic groups are the same as those for R ^c1 . Specific examples of the amino group substituted with 1 or 2 organic groups include methylamino group, ethylamino group, diethylamino group, n-propylamino group, di-n-propylamino group, isopropylamino group, n- Butylamino group, di-n-butylamino group, n-pentylamino group, n-hexylamino group, n-heptylamino group, n-octylamino group, n-nonylamino group, n-decylamino group, phenylamino group, Naphthylamino group, acetylamino group, propanoylamino group, n-butanoylamino group, n-pentanoylamino group, n-hexanoylamino group, n-heptanoylamino group, n-octanoylamino group, n- Examples include a decanoylamino group, a benzoylamino group, an α-naphthoylamino group, and a β-naphthoylamino group.

In the case where the phenyl group, naphthyl group, and heterocyclyl group contained in R ^c1 further have a substituent, the substituent is as follows: an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a carbon atom A monoalkylamino group having 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, and an alkyl group having 1 to 6 carbon atoms And a dialkylamino group having an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, a halogen, a nitro group, and a cyano group. When the phenyl group, naphthyl group, and heterocyclyl group included in R ^c1 further have a substituent, the number of the substituent is not limited as long as the object of the present invention is not impaired, but 1 to 4 is preferable. When the phenyl group, naphthyl group, and heterocyclyl group included in R ^c1 have a plurality of substituents, the plurality of substituents may be the same or different.

Among R ^c1 , since it is chemically stable, has few steric hindrances, and is easy to synthesize an oxime ester compound, an alkyl group having 1 to 6 carbon atoms, 1 to 1 carbon atoms, and the like. A group selected from the group consisting of 6 alkoxy groups and saturated aliphatic acyl groups having 2 to 7 carbon atoms is preferred, alkyls having 1 to 6 carbon atoms are more preferred, and methyl groups are particularly preferred.

Position R ^c1 is bonded to the phenyl group, the phenyl group R ^c1 are attached the position of the bond to the main chain of the phenyl group and the oxime ester compound as a 1-position, if the 2-position of the position of the methyl group 4th or 5th is preferable, and 5th is more preferable. N1 is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and particularly preferably 0 or 1.

R ^c2 is a phenyl group which may have a substituent, or a carbazolyl group which may have a substituent. When R ^c2 is a carbazolyl group that may have a substituent, the nitrogen atom on the carbazolyl group may be substituted with an alkyl group having 1 to 6 carbon atoms.

In R ^c2 , the substituent that the phenyl group or carbazolyl group has is not particularly limited as long as the object of the present invention is not impaired. Examples of suitable substituents that the phenyl group or carbazolyl group may have on the carbon atom include an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and 3 carbon atoms. -10 cycloalkyl group, C3-C10 cycloalkoxy group, C2-C20 saturated aliphatic acyl group, C2-C20 alkoxycarbonyl group, C2-C20 saturated Aliphatic acyloxy group, optionally substituted phenyl group, optionally substituted phenoxy group, optionally substituted phenylthio group, optionally substituted benzoyl group, substituted A phenoxycarbonyl group which may have a group, a benzoyloxy group which may have a substituent, a phenylalkyl group having 7 to 20 carbon atoms which may have a substituent, and a substituent. Naphthyl A naphthoxy group which may have a substituent, a naphthoyl group which may have a substituent, a naphthoxycarbonyl group which may have a substituent, a naphthoyloxy group which may have a substituent, a substituent A naphthylalkyl group having 11 to 20 carbon atoms which may have a group, a heterocyclyl group which may have a substituent, a heterocyclylcarbonyl group which may have a substituent, an amino group, 1 or 2 organic groups Examples include an amino group substituted with a group, a morpholin-1-yl group, a piperazin-1-yl group, a halogen, a nitro group, and a cyano group.

When R ^c2 is a carbazolyl group, examples of suitable substituents that the carbazolyl group may have on the nitrogen atom include alkyl groups having 1 to 20 carbon atoms and cycloalkyl groups 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, and a substituent. A phenoxycarbonyl group which may have, a phenylalkyl group having 7 to 20 carbon atoms which may have a substituent, a naphthyl group which may have a substituent, a naphthoyl group which may have a substituent, A naphthoxycarbonyl group which may have a substituent, a naphthylalkyl group having 11 to 20 carbon atoms which may have a substituent, a heterocyclyl group which may have a substituent, and a substituent; Heterogeneity And a krylcarbonyl group. 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 that the phenyl group or carbazolyl group may have 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, and a substituent. With respect to an optionally substituted phenylalkyl group, an optionally substituted naphthylalkyl group, an optionally substituted heterocyclyl group, and an amino group substituted with one or two organic groups , R ^c1 .

Examples of the substituent in the case where the phenyl group, the naphthyl group, and the heterocyclyl group included in the substituent that the phenyl group or the carbazolyl group has in R ^c2 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 phenyl group; Benzoyl group; benzoyl group; benzoyl substituted by a group selected from the group consisting of alkyl groups having 1 to 6 carbon atoms, morpholin-1-yl group, piperazin-1-yl group, and phenyl group; A monoalkylamino group having an alkyl group having 1 to 6 carbon atoms; a dialkylamino group having an alkyl group having 1 to 6 carbon atoms; Examples include a holin-1-yl group; a piperazin-1-yl group; a halogen; a nitro group; and a cyano group. When the phenyl group, the naphthyl group, and the heterocyclyl group included in the substituent of the phenyl group or carbazolyl group further have a substituent, the number of the substituent is not limited as long as the object of the present invention is not impaired. 1-4 are preferable. When the phenyl group, naphthyl group, and heterocyclyl group have a plurality of substituents, the plurality of substituents may be the same or different.

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

（Ｒ^ｃ４は、１価の有機基、アミノ基、ハロゲン、ニトロ基、及びシアノ基からなる群より選択される基であり、ＡはＳ又はＯであり、ｎ３は、０〜４の整数である。）

(R ^c4 is a group selected from the group consisting of a monovalent organic group, amino group, halogen, nitro group, and cyano group, A is S or O, and n3 is an integer of 0 to 4. is there.)

（Ｒ^ｃ５及びＲ^ｃ６は、それぞれ、１価の有機基である。）

(R ^c5 and R ^c6 are each a monovalent organic group.)

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

In ^Rc4 , substituted with a group selected from the group consisting of a benzoyl group; a naphthoyl group; an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, and a phenyl group Benzoyl group; nitro group is preferred, benzoyl group; naphthoyl group; 2-methylphenylcarbonyl group; 4- (piperazin-1-yl) phenylcarbonyl group; 4- (phenyl) phenylcarbonyl group is more preferred.

In formula (c2), n3 is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and particularly preferably 0 or 1. If n3 is 1, binding position of R ^c4, to the bond to the phenyl group R ^c4 is bonded is bonded to an oxygen atom or a sulfur atom, it is preferably in the para position.

R ^c5 in formula (c3) can be selected from various organic groups as long as the object of the present invention is not ^impaired . Preferable examples of R ^c5 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, and 2 to 20 carbon atoms. Alkoxycarbonyl group, phenyl group which may have a substituent, benzoyl group which may have a substituent, phenoxycarbonyl group which may have a substituent, carbon atoms which may have a substituent 7 ~ 20 phenylalkyl group, optionally substituted naphthyl group, optionally substituted naphthoyl group, optionally substituted naphthoxycarbonyl group, optionally substituted Examples thereof include a naphthylalkyl group having 11 to 20 carbon atoms, a heterocyclyl group which may have a substituent, and a heterocyclylcarbonyl group which may have a substituent.

Among R ^c5 , an alkyl group having 1 to 20 carbon atoms is preferable, an alkyl group having 1 to 6 carbon atoms is more preferable, and an ethyl group is particularly preferable.

R ^c6 in formula (c3) is not particularly limited as long as the object of the present invention is not impaired, and can be selected from various organic groups. Specific examples of the group suitable as R ^c6 include an alkyl group having 1 to 20 carbon atoms, a phenyl group which may have a substituent, a naphthyl group which may have a substituent, and a substituent. The heterocyclyl group which may be sufficient is mentioned. Among these groups, R ^c6 is more preferably a phenyl group which may have a substituent, and particularly preferably a 2-methylphenyl group.

^Examples of the substituent when the phenyl group, naphthyl group, and heterocyclyl group contained in R ^c4 , R ^c5 , or R ^c6 further have a substituent include an alkyl group having 1 to 6 carbon atoms, and 1 to 1 carbon atom. 6 alkoxy groups, saturated aliphatic acyl groups having 2 to 7 carbon atoms, alkoxycarbonyl groups having 2 to 7 carbon atoms, saturated aliphatic acyloxy groups having 2 to 7 carbon atoms, alkyl having 1 to 6 carbon atoms And a monoalkylamino group having a group, a dialkylamino group having an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, a halogen, a nitro group, and a cyano group. When the phenyl group, naphthyl group, and heterocyclyl group contained in R ^c4 , R ^c5 , or R ^c6 further have a substituent, the number of the substituent is not limited as long as the object of the present invention is not impaired, 1-4 are preferable. When the phenyl group, naphthyl group, and heterocyclyl group contained in R ^c4 , R ^c5 , or R ^c6 have a plurality of substituents, the plurality of substituents may be the same or different.

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

When p is 0, the oxime ester compound represented by the formula (c1) can be synthesized according to the following scheme 1, for example. Specifically, an aromatic compound represented by the following formula (c1-1) is acylated by a Friedel-Crafts reaction using a halocarbonyl compound represented by the following formula (c1-2), and the following formula: A ketone compound represented by (c1-3) is obtained, and the resulting ketone compound (c1-3) is oximed with hydroxylamine to obtain an oxime compound represented by the following formula (c1-4), and then the formula The hydroxy group in the oxime compound of (c1-4) can be acylated to obtain an oxime ester compound represented by the following formula (c1-7). As an acylating agent, an acid anhydride (R ^c3 COHal, Hal represented by the following formula (c 1-6) or an acid anhydride ((R ^c3 CO) ₂ O) represented by the following formula (c 1-5) Is preferably halogen.). In the following formula (c1-2), Hal is halogen, and in the following formulas (c1-1), (c1-2), (c1-3), (c1-4), and (c1-7) , R ^c1 , R ^c2 , R ^c3 , and n1 are the same as those in the formula (c1).

<Scheme 1>

When n2 is 1, the oxime ester compound represented by the formula (c1) can be synthesized according to the following scheme 2, for example. Specifically, a ketone compound represented by the following formula (c2-1) is added to a nitrite ester (RONO, R is represented by 1 to 6 carbon atoms) represented by the following formula (c2-2) in the presence of hydrochloric acid. To obtain a ketoxime compound represented by the following formula (c2-3), and then acylate the hydroxy group in the ketoxime compound represented by the following formula (c2-3). An oxime ester compound represented by the following formula (c2-6) can be obtained. As an acylating agent, an acid anhydride (R ^c3 COHal, Hal represented by the following formula ( ^c 2-5) or an acid anhydride (R ^c3 CO) ₂ O represented by the following formula (c2-4) Is preferably halogen.). In the following formulas (c2-1), (c2-3), (c2-4), (c2-5), and (c2-6), R ^c1 , R ^c2 , R ^c3 , and n1 are formulas Same as (c1).

<Scheme 2>

Further, the oxime ester compound represented by the formula (c1) is, n2 is ^1, and ^{R c1} is a methyl ^group, with respect to methyl groups attached to the benzene ring ^{to which R c1} are ^{attached, R c1} para In the case of bonding to a position, for example, a compound represented by the following formula (c2-7) can be synthesized by oximation and acylation in the same manner as in Scheme 1. In the following formula (c2-7), R ^c2 is the same as in formula (c1).

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

  Moreover, the oxime ester compound represented by a following formula (c4) is also preferable as a photoinitiator.

（Ｒ^ｃ７は水素原子、ニトロ基又は１価の有機基であり、Ｒ^ｃ８及びＲ^ｃ９は、それぞれ、置換基を有してもよい鎖状アルキル基、置換基を有してもよい環状有機基、又は水素原子であり、Ｒ^ｃ８とＲ^ｃ９とは相互に結合して環を形成してもよく、Ｒ^ｃ１０は１価の有機基であり、Ｒ^ｃ１１は、水素原子、置換基を有してもよい炭素原子数１〜１１のアルキル基、又は置換基を有してもよいアリール基であり、ｎ４は０〜４の整数であり、ｎ５は０又は１である。）

(R ^c7 is a hydrogen atom, a nitro group or a monovalent organic group, and R ^c8 and R ^c9 are each a chain alkyl group which may have a substituent, or a cyclic organic which may have a substituent. R ^c8 and R ^c9 may be bonded to each other to form a ring, R ^c10 is a monovalent organic group, and R ^c11 has a hydrogen atom or a substituent. An alkyl group having 1 to 11 carbon atoms, or an aryl group which may have a substituent, n4 is an integer of 0 to 4, and n5 is 0 or 1.)

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

（Ｒ^ｃ７、Ｒ^ｃ８、Ｒ^ｃ９、Ｒ^ｃ１０、ｎ４、及びｎ５は、式（ｃ４）と同様である。）

(R ^c7 , R ^c8 , R ^c9 , R ^c10 , n4, and n5 are the same as in formula (c4).)

In formulas (c4) and (c5), R ^c7 is a hydrogen atom, a nitro group, or a monovalent organic group. R ^c7 is bonded to a 6-membered aromatic ring different from the 6-membered aromatic ring bonded to the group represented by — (CO) _n5 — on the fluorene ring in the formula (c4). In formula (c4), the bonding position of R ^{c7 to} the fluorene ring is not particularly limited. When the compound represented by the formula (c4) has one or more R ^c7 , one of the one or more R ^c7 is a fluorene ring because synthesis of the compound represented by the formula (c4) is easy. Bonding at the 2-position is preferable. If R ^c7 is more, a plurality of R ^c7 is independently in may be the same or different.

When R ^c7 is an organic group, R ^c7 is not particularly limited as long as the object of the present invention is not ^{impaired, and} is appropriately selected from various organic groups. Preferred examples when R ^c7 is an organic group include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, a saturated aliphatic acyloxy group, an alkoxycarbonyl group, and a substituent. An optionally substituted phenyl group, an optionally substituted phenoxy group, an optionally substituted benzoyl group, an optionally substituted phenoxycarbonyl group, an optionally substituted benzoyloxy A group, a phenylalkyl group which may have a substituent, a naphthyl group which may have a substituent, a naphthoxy group which may have a substituent, a naphthoyl group which may have a substituent, a substituent An optionally substituted naphthoxycarbonyl group, an optionally substituted naphthoyloxy group, an optionally substituted naphthylalkyl group, an optionally substituted heterocyclyl group, Examples include a heterocyclylcarbonyl group which may have a substituent, an amino group substituted with 1 or 2 organic groups, a morpholin-1-yl group, and a piperazin-1-yl group.

When R ^c7 is an alkyl group, the number of carbon atoms of the alkyl group is preferably 1-20, and more preferably 1-6. Further, when R ^c7 is an alkyl group, it may be linear or branched. Specific examples when R ^c7 is an alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, and an n-pentyl group. , Isopentyl group, sec-pentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, n-nonyl group, isononyl group, An n-decyl group, an isodecyl group, etc. are mentioned. When R ^c7 is an alkyl group, the alkyl group may include an ether bond (—O—) in the carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include a methoxyethyl group, an ethoxyethyl group, a methoxyethoxyethyl group, an ethoxyethoxyethyl group, a propyloxyethoxyethyl group, and a methoxypropyl group.

When R ^c7 is an alkoxy group, the alkoxy group preferably has 1 to 20 carbon atoms, and more preferably 1 to 6 carbon atoms. Further, when R ^c7 is an alkoxy group, it may be linear or branched. Specific examples when R ^c7 is an alkoxy group include methoxy group, ethoxy group, n-propyloxy group, isopropyloxy group, n-butyloxy group, isobutyloxy group, sec-butyloxy group, tert-butyloxy group, n -Pentyloxy group, isopentyloxy group, sec-pentyloxy group, tert-pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, isooctyloxy group, sec-octyloxy group Tert-octyloxy group, n-nonyloxy group, isononyloxy group, n-decyloxy group, and isodecyloxy group. When R ^c7 is an alkoxy group, the alkoxy group may include an ether bond (—O—) in the carbon chain. Examples of the alkoxy group having an ether bond in the carbon chain include a methoxyethoxy group, an ethoxyethoxy group, a methoxyethoxyethoxy group, an ethoxyethoxyethoxy group, a propyloxyethoxyethoxy group, and a methoxypropyloxy group.

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

When R ^c7 is a saturated aliphatic acyl group or a saturated aliphatic acyloxy group, the number of carbon atoms of the saturated aliphatic acyl group or the saturated aliphatic acyloxy group is preferably 2 to 21, and more preferably 2 to 7. Specific examples when R ^c7 is a saturated aliphatic acyl group include acetyl group, propanoyl group, n-butanoyl group, 2-methylpropanoyl group, n-pentanoyl group, 2,2-dimethylpropanoyl group, n -Hexanoyl group, n-heptanoyl group, n-octanoyl group, n-nonanoyl group, n-decanoyl group, n-undecanoyl group, n-dodecanoyl group, n-tridecanoyl group, n-tetradecanoyl group, n-pentadecane Examples include a noyl group and an n-hexadecanoyl group. Specific examples when R ^c7 is a saturated aliphatic acyloxy group include acetyloxy group, propanoyloxy group, n-butanoyloxy group, 2-methylpropanoyloxy group, n-pentanoyloxy group, 2, 2-dimethylpropanoyloxy group, n-hexanoyloxy group, n-heptanoyloxy group, n-octanoyloxy group, n-nonanoyloxy group, n-decanoyloxy group, n-undecanoyloxy group, n -Dodecanoyloxy group, n-tridecanoyloxy group, n-tetradecanoyloxy group, n-pentadecanoyloxy group, n-hexadecanoyloxy group and the like.

When R ^c7 is an alkoxycarbonyl group, the number of carbon atoms of the alkoxycarbonyl group is preferably 2-20, and more preferably 2-7. Specific examples when R ^c7 is an alkoxycarbonyl group include methoxycarbonyl group, ethoxycarbonyl group, n-propyloxycarbonyl group, isopropyloxycarbonyl group, n-butyloxycarbonyl group, isobutyloxycarbonyl group, sec-butyl. Oxycarbonyl group, tert-butyloxycarbonyl group, n-pentyloxycarbonyl group, isopentyloxycarbonyl group, sec-pentyloxycarbonyl group, tert-pentyloxycarbonyl group, n-hexyloxycarbonyl group, n-heptyloxycarbonyl Group, n-octyloxycarbonyl group, isooctyloxycarbonyl group, sec-octyloxycarbonyl group, tert-octyloxycarbonyl group, n-nonyloxycarbonyl group, Examples include an isononyloxycarbonyl group, an n-decyloxycarbonyl group, and an isodecyloxycarbonyl group.

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

When R ^c7 is a heterocyclyl group, the heterocyclyl group is a 5-membered or 6-membered monocycle containing 1 or more of N, S, and O, or such monocycles or such monocycles and a benzene ring are condensed. Heterocyclyl group. When the heterocyclyl group is a condensed ring, the ring number is up to 3. The heterocyclyl group may be an aromatic group (heteroaryl group) or a non-aromatic group. Examples of the heterocyclic ring constituting the heterocyclyl group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, pyridazine, benzofuran, benzothiophene, indole, Examples include isoindole, indolizine, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalazine, cinnoline, quinoxaline, piperidine, piperazine, morpholine, piperidine, tetrahydropyran, and tetrahydrofuran. It is done. When R ^c7 is a heterocyclyl group, the heterocyclyl group may further have a substituent.

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

When R ^c7 is an amino group substituted with 1 or 2 organic groups, suitable examples of the organic group include alkyl groups having 1 to 20 carbon atoms, cycloalkyl groups having 3 to 10 carbon atoms, and carbon atoms. A saturated aliphatic acyl group having 2 to 21 carbon atoms, a phenyl group which may have a substituent, a benzoyl group which may have a substituent, a phenylalkyl having 7 to 20 carbon atoms which may have a substituent A naphthyl group which may have a substituent, a naphthyl group which may have a substituent, a naphthylalkyl group having 11 to 20 carbon atoms which may have a substituent, a heterocyclyl group, and the like. . Specific examples of these suitable organic groups are the same as those for R ^c7 . Specific examples of the amino group substituted with 1 or 2 organic groups include methylamino group, ethylamino group, diethylamino group, n-propylamino group, di-n-propylamino group, isopropylamino group, n- Butylamino group, di-n-butylamino group, n-pentylamino group, n-hexylamino group, n-heptylamino group, n-octylamino group, n-nonylamino group, n-decylamino group, phenylamino group, Naphthylamino group, acetylamino group, propanoylamino group, n-butanoylamino group, n-pentanoylamino group, n-hexanoylamino group, n-heptanoylamino group, n-octanoylamino group, n- Examples include a decanoylamino group, a benzoylamino group, an α-naphthoylamino group, and a β-naphthoylamino group.

In the case where the phenyl group, the naphthyl group, and the heterocyclyl group included in R ^c7 further have a substituent, the substituent includes an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and a carbon atom. A monoalkylamino group having 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, and an alkyl group having 1 to 6 carbon atoms And a dialkylamino group having an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, a halogen, a nitro group, and a cyano group. When the phenyl group, naphthyl group, and heterocyclyl group contained in R ^c7 further have a substituent, the number of the substituent is not limited as long as the object of the present invention is not impaired, but 1 to 4 is preferable. When the phenyl group, naphthyl group, and heterocyclyl group included in R ^c7 have a plurality of substituents, the plurality of substituents may be the same or different.

Among the groups described above, R ^c7 is preferably a nitro group or a group represented by R ^c12 —CO— because the sensitivity tends to be improved. R ^c12 is not particularly limited as long as the object of the present invention is not ^impaired , and can be selected from various organic groups. Examples of groups suitable as R ^c12 include an alkyl group having 1 to 20 carbon atoms, a phenyl group which may have a substituent, a naphthyl group which may have a substituent, and a substituent. Or a heterocyclyl group that may be used. As R ^c12 , among these groups, a 2-methylphenyl group, a thiophen-2-yl group, and an α-naphthyl group are particularly preferable.
Moreover, it is preferable that R ^c7 is a hydrogen atom because transparency tends to be good. When R ^c7 is a hydrogen atom and R ^c10 is a group represented by the following formula (c4a) or (c4b), the transparency tends to be better.

In formula (c4), R ^c8 and R ^c9 each represent a chain alkyl group that may have a substituent, a cyclic organic group that may have a substituent, or a hydrogen atom. R ^c8 and R ^c9 may be bonded to each other to form a ring. Among these groups, as R ^c8 and R ^c9 , a chain alkyl group which may have a substituent is preferable. When R ^c8 and R ^c9 are chain alkyl groups which may have a substituent, the chain alkyl group may be a straight chain alkyl group or a branched chain alkyl group.

When R ^c8 and R ^c9 are chain alkyl groups having no substituent, the number of carbon atoms of the chain alkyl group is preferably 1-20, more preferably 1-10, and particularly preferably 1-6. Specific examples when R ^c8 and R ^c9 are chain alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, and tert-butyl group. N-pentyl group, isopentyl group, sec-pentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, n-nonyl Group, isononyl group, n-decyl group, isodecyl group and the like. When R ^c8 and R ^c9 are alkyl groups, the alkyl group may contain an ether bond (—O—) in the carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include a methoxyethyl group, an ethoxyethyl group, a methoxyethoxyethyl group, an ethoxyethoxyethyl group, a propyloxyethoxyethyl group, and a methoxypropyl group.

When R ^c8 and R ^c9 are chain alkyl groups having a substituent, the number of carbon atoms of the chain alkyl group is preferably 1-20, more preferably 1-10, and particularly preferably 1-6. In this case, the number of carbon atoms of the substituent is not included in the number of carbon atoms of the chain alkyl group. The chain alkyl group having a substituent is preferably linear.
The substituent that the alkyl group may have is not particularly limited as long as the object of the present invention is not impaired. Preferable examples of the substituent include a cyano group, a halogen atom, a cyclic organic group, and an alkoxycarbonyl group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. In these, a fluorine atom, a chlorine atom, and a bromine atom are preferable. Examples of the cyclic organic group include a cycloalkyl group, an aromatic hydrocarbon group, and a heterocyclyl group. Specific examples of the cycloalkyl group are the same as the preferred examples in the case where R ^c7 is a cycloalkyl group. Specific examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, a biphenylyl group, an anthryl group, and a phenanthryl group. Specific examples of the heterocyclyl group are the same as the preferred examples when R ^c7 is a heterocyclyl group. When R ^c7 is an alkoxycarbonyl group, the alkoxy group contained in the alkoxycarbonyl group may be linear or branched, and is preferably linear. 1-10 are preferable and, as for the carbon atom number of the alkoxy group contained in an alkoxycarbonyl group, 1-6 are more preferable.

  When the chain alkyl group has a substituent, the number of substituents is not particularly limited. The number of preferred substituents varies depending on the number of carbon atoms in the chain alkyl group. The number of substituents is typically 1-20, preferably 1-10, and more preferably 1-6.

When R ^c8 and R ^c9 are cyclic organic groups, the cyclic organic group may be an alicyclic group or an aromatic group. Examples of the cyclic organic group include an aliphatic cyclic hydrocarbon group, an aromatic hydrocarbon group, and a heterocyclyl group. When R ^c8 and R ^c9 are cyclic organic groups, the substituent that the cyclic organic group may have is the same as when R ^c8 and R ^c9 are chain alkyl groups.

When R ^c8 and R ^c9 are aromatic hydrocarbon groups, is the aromatic hydrocarbon group a phenyl group or a group formed by bonding a plurality of benzene rings via a carbon-carbon bond? A group formed by condensation of a plurality of benzene rings is preferred. When the aromatic hydrocarbon group is a phenyl group or a group formed by combining or condensing a plurality of benzene rings, the number of benzene rings contained in the aromatic hydrocarbon group is not particularly limited, 3 or less is preferable, 2 or less is more preferable, and 1 is particularly preferable. Preferable specific examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, a biphenylyl group, an anthryl group, and a phenanthryl group.

When R ^c8 and R ^c9 are aliphatic cyclic hydrocarbon groups, the aliphatic cyclic hydrocarbon group may be monocyclic or polycyclic. Although the carbon atom number of an aliphatic cyclic hydrocarbon group is not specifically limited, 3-20 are preferable and 3-10 are more preferable. Examples of monocyclic cyclic hydrocarbon groups are cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, norbornyl, isobornyl, tricyclononyl, tricyclodecyl, Examples include a tetracyclododecyl group and an adamantyl group.

When R ^c8 and R ^c9 are a heterocyclyl group, the heterocyclyl group is a 5-membered or 6-membered monocycle containing one or more N, S, O, such monocycles, or such monocycles and a benzene ring. And a condensed heterocyclyl group. When the heterocyclyl group is a condensed ring, the ring number is up to 3. The heterocyclyl group may be an aromatic group (heteroaryl group) or a non-aromatic group. Examples of the heterocyclic ring constituting the heterocyclyl group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, pyridazine, benzofuran, benzothiophene, indole, Examples include isoindole, indolizine, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalazine, cinnoline, quinoxaline, piperidine, piperazine, morpholine, piperidine, tetrahydropyran, and tetrahydrofuran. It is done.

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

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

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

The number of carbon atoms in a straight chain alkylene group A ¹ is 1 to 10 preferably 1 to 6 is more preferable. When A ² is an alkoxy group, the alkoxy group may be linear or branched, and is preferably linear. 1-10 are preferable and, as for the carbon atom number of an alkoxy group, 1-6 are more preferable. When A ² is a halogen atom, a fluorine atom, a chlorine atom, a bromine atom and an iodine atom are preferable, and a fluorine atom, a chlorine atom and a bromine atom are more preferable. When A ² is a halogenated alkyl group, the halogen atom contained in the halogenated alkyl group is preferably a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, and more preferably a fluorine atom, a chlorine atom, or a bromine atom. The halogenated alkyl group may be linear or branched, and is preferably linear. When A ² is a cyclic organic group, examples of the cyclic organic group are the same as the cyclic organic group that R ^c8 and R ^c9 have as a substituent. When A ² is an alkoxycarbonyl group, examples of the alkoxycarbonyl group are the same as the alkoxycarbonyl group that R ^c8 and R ^c9 have as a substituent.

Preferable specific examples of R ^c8 and R ^c9 include alkyl groups such as ethyl group, n-propyl group, n-butyl group, n-hexyl group, n-heptyl group, and n-octyl group; 2-methoxyethyl Group, 3-methoxy-n-propyl group, 4-methoxy-n-butyl group, 5-methoxy-n-pentyl group, 6-methoxy-n-hexyl group, 7-methoxy-n-heptyl group, 8-methoxy -N-octyl group, 2-ethoxyethyl group, 3-ethoxy-n-propyl group, 4-ethoxy-n-butyl group, 5-ethoxy-n-pentyl group, 6-ethoxy-n-hexyl group, 7- Alkoxyalkyl groups such as ethoxy-n-heptyl group and 8-ethoxy-n-octyl group; 2-cyanoethyl group, 3-cyano-n-propyl group, 4-cyano-n-butyl group, 5-cyano-n − Cyanoalkyl groups such as an nyl group, a 6-cyano-n-hexyl group, a 7-cyano-n-heptyl group, and an 8-cyano-n-octyl group; a 2-phenylethyl group, a 3-phenyl-n-propyl group Phenylalkyl such as 4-phenyl-n-butyl group, 5-phenyl-n-pentyl group, 6-phenyl-n-hexyl group, 7-phenyl-n-heptyl group, and 8-phenyl-n-octyl group Groups: 2-cyclohexylethyl group, 3-cyclohexyl-n-propyl group, 4-cyclohexyl-n-butyl group, 5-cyclohexyl-n-pentyl group, 6-cyclohexyl-n-hexyl group, 7-cyclohexyl-n- Heptyl, 8-cyclohexyl-n-octyl, 2-cyclopentylethyl, 3-cyclopentyl-n-propyl, 4-cyclopent Cycloalkylalkyl groups such as ru-n-butyl, 5-cyclopentyl-n-pentyl, 6-cyclopentyl-n-hexyl, 7-cyclopentyl-n-heptyl, and 8-cyclopentyl-n-octyl; 2-methoxycarbonylethyl group, 3-methoxycarbonyl-n-propyl group, 4-methoxycarbonyl-n-butyl group, 5-methoxycarbonyl-n-pentyl group, 6-methoxycarbonyl-n-hexyl group, 7-methoxy Carbonyl-n-heptyl group, 8-methoxycarbonyl-n-octyl group, 2-ethoxycarbonylethyl group, 3-ethoxycarbonyl-n-propyl group, 4-ethoxycarbonyl-n-butyl group, 5-ethoxycarbonyl-n -Pentyl group, 6-ethoxycarbonyl-n-hexyl group, 7-ethoxy Alkoxycarbonylalkyl groups such as rubonyl-n-heptyl and 8-ethoxycarbonyl-n-octyl; 2-chloroethyl, 3-chloro-n-propyl, 4-chloro-n-butyl, 5-chloro -N-pentyl group, 6-chloro-n-hexyl group, 7-chloro-n-heptyl group, 8-chloro-n-octyl group, 2-bromoethyl group, 3-bromo-n-propyl group, 4-bromo -N-butyl group, 5-bromo-n-pentyl group, 6-bromo-n-hexyl group, 7-bromo-n-heptyl group, 8-bromo-n-octyl group, 3,3,3-trifluoro Examples thereof include a propyl group and a halogenated alkyl group such as 3,3,4,4,5,5,5-heptafluoro-n-pentyl group.

Among R ^c8 and R ^c9 , preferred groups among the above are ethyl group, n-propyl group, n-butyl group, n-pentyl group, 2-methoxyethyl group, 2-cyanoethyl group, 2-phenylethyl group, 2-cyclohexylethyl group, 2-methoxycarbonylethyl group, 2-chloroethyl group, 2-bromoethyl group, 3,3,3-trifluoropropyl group, and 3,3,4,4,5,5,5-hepta A fluoro-n-pentyl group;

Examples of suitable organic groups for R ^c10 are the same as for R ^c7 , alkyl groups, alkoxy groups, cycloalkyl groups, cycloalkoxy groups, saturated aliphatic acyl groups, alkoxycarbonyl groups, saturated aliphatic acyloxy groups, substituents. 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, and a substituent A good benzoyloxy group, a phenylalkyl group which may have a substituent, a naphthyl group which may have a substituent, a naphthoxy group which may have a substituent, a naphthoyl group which may have a substituent, A naphthoxycarbonyl group which may have a substituent, a naphthoyloxy group which may have a substituent, a naphthylalkyl group which may have a substituent, a heterocycle which may have a substituent Group, an optionally substituted heterocyclyl group, 1, or an amino group substituted with two organic groups, morpholin-1-yl group, and piperazine-1-yl group. Specific examples of these groups are the same as those described for R ^c7 . R ^c10 is also preferably a cycloalkylalkyl group, a phenoxyalkyl group which may have a substituent on the aromatic ring, or a phenylthioalkyl group which may have a substituent on the aromatic ring. The substituent that the phenoxyalkyl group and the phenylthioalkyl group may have is the same as the substituent that the phenyl group contained in R ^c7 may have.

Among organic groups, as R ^c10 , an alkyl group, a cycloalkyl group, a phenyl group which may have a substituent, a cycloalkylalkyl group, or a phenylthio which may have a substituent on an aromatic ring. Alkyl groups are preferred. As the alkyl group, an alkyl group having 1 to 20 carbon atoms is preferable, an alkyl group having 1 to 8 carbon atoms is more preferable, an alkyl group having 1 to 4 carbon atoms is particularly preferable, and a methyl group is most preferable. Among the phenyl groups that may have a substituent, a methylphenyl group is preferable, and a 2-methylphenyl group is more preferable. The number of carbon atoms of the cycloalkyl group contained in the cycloalkylalkyl group is preferably 5 to 10, more preferably 5 to 8, and particularly preferably 5 or 6. 1-8 are preferable, as for the carbon atom number of the alkylene group contained in a cycloalkylalkyl group, 1-4 are more preferable, and 2 is especially preferable. Of the cycloalkylalkyl groups, a cyclopentylethyl group is preferred. 1-8 are preferable, as for the carbon atom number of the alkylene group contained in the phenylthioalkyl group which may have a substituent on an aromatic ring, 1-4 are more preferable, and 2 is especially preferable. Among the phenylthioalkyl groups which may have a substituent on the aromatic ring, a 2- (4-chlorophenylthio) ethyl group is preferable.

In addition, as R ^c10 , a group represented by —A ³ —CO—O—A ⁴ is also preferable. A ³ is a divalent organic group, preferably a divalent hydrocarbon group, and preferably an alkylene group. A ⁴ is a monovalent organic group, and is preferably a monovalent hydrocarbon group.

When A ³ is an alkylene group, the alkylene group may be linear or branched, and is preferably linear. If A ³ is an alkylene group, number of carbon atoms in the alkylene group is preferably 1 to 10, more preferably 1 to 6, 1 to 4 are particularly preferred.

Preferable examples of A ⁴ include an alkyl group having 1 to 10 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, and an aromatic hydrocarbon group having 6 to 20 carbon atoms. Preferred examples of A ⁴ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, and n-hexyl. Group, phenyl group, naphthyl group, benzyl group, phenethyl group, α-naphthylmethyl group, β-naphthylmethyl group and the like.

Preferred examples of the group represented by —A ³ —CO—O—A ⁴ include 2-methoxycarbonylethyl group, 2-ethoxycarbonylethyl group, 2-n-propyloxycarbonylethyl group, 2-n -Butyloxycarbonylethyl group, 2-n-pentyloxycarbonylethyl group, 2-n-hexyloxycarbonylethyl group, 2-benzyloxycarbonylethyl group, 2-phenoxycarbonylethyl group, 3-methoxycarbonyl-n-propyl Group, 3-ethoxycarbonyl-n-propyl group, 3-n-propyloxycarbonyl-n-propyl group, 3-n-butyloxycarbonyl-n-propyl group, 3-n-pentyloxycarbonyl-n-propyl group , 3-n-hexyloxycarbonyl-n-propyl group, 3-benzyloxycarbonyl -n- propyl group, and 3-phenoxycarbonyl -n- propyl group and the like.

（式（ｃ４ａ）及び（ｃ４ｂ）中、Ｒ^ｃ１３及びＲ^ｃ１４はそれぞれ有機基であり、ｎ６は０〜４の整数であり、Ｒ^ｃ１３及びＲ^８がベンゼン環上の隣接する位置に存在する場合、Ｒ^ｃ１３とＲ^ｃ１４とが互いに結合して環を形成してもよく、ｎ７は１〜８の整数であり、ｎ８は１〜５の整数であり、ｎ９は０〜（ｎ８＋３）の整数であり、Ｒ^ｃ１５は有機基である。） ^Having described ^{R c10,} as the ^{R c10,} preferably a group represented by the following formula (C4a) or (C4b).

(In the formulas (c4a) and (c4b), R ^c13 and R ^c14 are each an organic group, n6 is an integer of 0 to 4, and R ^c13 and R ⁸ are present at adjacent positions on the benzene ring. R ^c13 and R ^c14 may be bonded to each other to form a ring, n7 is an integer of 1 to 8, n8 is an integer of 1 to 5, and n9 is an integer of 0 to (n8 + 3). And R ^c15 is an organic group.)

Examples of the organic group for R ^c13 and R ^{c14 in} formula (c4a) are the same as those for R ^c7 . R ^c13 is preferably an alkyl group or a phenyl group. When R ^c13 is an alkyl group, the number of carbon atoms is preferably 1 to 10, more preferably 1 to 5, particularly preferably 1 to 3, and most preferably 1. That is, R ^c13 is most preferably a methyl group. When R ^c13 and R ^c14 combine to form a ring, the ring may be an aromatic ring or an aliphatic ring. Preferred examples of the group represented by the formula (c4a) in which R ^c13 and R ^c14 form a ring include a naphthalen-1-yl group, 1,2,3,4- And tetrahydronaphthalen-5-yl group. In said formula (c4a), n6 is an integer of 0-4, It is preferable that it is 0 or 1, and it is more preferable that it is 0.

In the above formula (c4b), R ^c15 is an organic group. ^Examples of the organic group include the same groups as those described for R ^c7 . Of the organic groups, an alkyl group is preferred. The alkyl group may be linear or branched. 1-10 are preferable, as for the carbon atom number of an alkyl group, 1-5 are more preferable, and 1-3 are especially preferable. As R ^c15 , a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group and the like are preferably exemplified, and among these, a methyl group is more preferable.

  In said formula (c4b), n8 is an integer of 1-5, the integer of 1-3 is preferable and 1 or 2 is more preferable. In said formula (c4b), n9 is 0- (n8 + 3), the integer of 0-3 is preferable, the integer of 0-2 is more preferable, and 0 is especially preferable. In said formula (c4b), n7 is an integer of 1-8, the integer of 1-5 is preferable, the integer of 1-3 is more preferable, and 1 or 2 is especially preferable.

In formula (c4), R ^c11 represents a hydrogen atom, an alkyl group having 1 to 11 carbon atoms which may have a substituent, or an aryl group which may have a substituent. Preferred examples of the substituent that may be present when R ^c11 is an alkyl group include a phenyl group and a naphthyl group. In addition, preferred examples of the substituent that may be present when R ^c7 is an aryl group include an alkyl group having 1 to 5 carbon atoms, an alkoxy group, and a halogen atom.

In formula (c4), R ^c11 is preferably a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a phenyl group, a benzyl group, a methylphenyl group, a naphthyl group, or the like. Among these, a methyl group or a phenyl group is more preferable.

The compound represented by the formula (c4) represents an oxime group (> C═N—OH) contained in the compound represented by the above formula (c5) by> C═N—O—COR ^c11. It is produced by a method including a step of converting to an oxime ester group. R ^c11 are the same as ^{R c11} in formula (c4).

The conversion of the oxime group (> C═N—OH) to the oxime ester group represented by> C═N—O—COR ^c11 involves conversion of the compound represented by the above formula (c5), an acylating agent, It is performed by reacting.
The acylating agent to give the acyl group represented by -COR ^{c11, (R c11} _CO) or an acid anhydride represented by ₂ ^O, R c11 COHal (Hal is a halogen atom) include acid halide represented by It is done.

When n5 is 0, the compound represented by the general formula (c4) can be synthesized according to the following scheme 3, for example. In Scheme 3, a fluorene derivative represented by the following formula (c3-1) is used as a raw material. When R ^c7 is a nitro group or a monovalent organic group, the fluorene derivative represented by the formula (c3-1) is converted into a fluorene derivative substituted at the 9-position with R ^c8 and R ^c9 by a known method. It can be obtained by introducing the substituent R ^c7 . The fluorene derivative substituted at the 9-position with R ^c8 and R ^c9 is, for example, an alkali metal hydroxide as described in JP-A No. 06-234668 when R ^c8 and R ^c9 are alkyl groups. It can be obtained by reacting fluorene with an alkylating agent in the presence of an aprotic polar organic solvent. In addition, an alkylating agent such as an alkyl halide, an aqueous solution of an alkali metal hydroxide, and a phase transfer catalyst such as tetrabutylammonium iodide or potassium tert-butoxide are added to an organic solvent solution of fluorene. By performing the alkylation reaction, 9,9-alkyl-substituted fluorene can be obtained.

An acyl group represented by —CO—R ^c10 is introduced into the fluorene derivative represented by the formula (c3-1) by Friedel-Crafts acylation reaction, and the fluorene derivative represented by the formula (c3-3) can get. The acylating agent for introducing an acyl group represented by —CO—R ^c10 may be a halocarbonyl compound or an acid anhydride. As the acylating agent, a halocarbonyl compound represented by the formula (c3-2) is preferable. In formula (c3-2), Hal is a halogen atom. The position at which the acyl group is introduced on the fluorene ring can be selected by changing the Friedel-Crafts reaction conditions as appropriate, or by performing protection and deprotection at other positions where acylation is performed. it can.

Next, the group represented by —CO—R ^c10 in the fluorene derivative represented by the formula (c3-3) to be obtained is converted into a group represented by —C (═N—OH) —R ^c10 , An oxime compound represented by the formula (c3-4) is obtained. The method for converting the group represented by —CO—R ^c10 to the group represented by —C (═N—OH) —R ^c10 is not particularly limited, but oximation with hydroxylamine is preferred. An oxime compound of the formula (c3-4) and an acid anhydride ((R ^c11 CO) ₂ O) represented by the following formula (c3-5) or an acid halide represented by the following formula (c3-6) ( R ^c11 COHal, Hal is a halogen atom) and a compound represented by the following formula (c3-7) can be obtained.

In formulas (c3-1), (c3-2), (c3-3), (c3-4), (c3-5), (c3-6), and (c3-7), R ^c7 , R ^c8 , R ^c9 , R ^c10 , and R ^c11 are the same as those in formula (c4).

In Scheme 3, R ^c10 contained in each of formula (c3-2), formula (c3-3), and formula (c3-4) may be the same or different. That is, R ^c10 in formula (c3-2), formula (c3-3), and formula (c3-4) may undergo chemical modification in the synthesis process shown as Scheme 3. Examples of chemical modification include esterification, etherification, acylation, amidation, halogenation, substitution of a hydrogen atom in an amino group with an organic group, and the like. The chemical modification that R ^c10 may undergo is not limited thereto.

<Scheme 3>

When n5 is 1, the compound represented by the formula (c4) can be synthesized according to the following scheme 4, for example. In Scheme 4, a fluorene derivative represented by the following formula (c4-1) is used as a raw material. The fluorene derivative represented by the formula (c4-1) is represented by —CO—CH ₂ —R ^c10 by a Friedel-Crafts reaction to a compound represented by the formula (c3-1) by the same method as in Scheme 3. It is obtained by introducing an acyl group. The acylating agent of the formula (C3-8): carboxylic acid halide is preferably represented by ^{_{Hal-CO-CH 2 -R c10}} . Subsequently, the methylene group present between R ^c10 and the carbonyl group in the compound represented by the formula (c4-1) is oximed to obtain a ketoxime compound represented by the following formula (c4-3). The method for oximation of the methylene group is not particularly limited, but a nitrite ester (RONO, R is an alkyl group having 1 to 6 carbon atoms) represented by the following general formula (c4-2) in the presence of hydrochloric acid. A reaction method is preferred. Next, a ketoxime compound represented by the following formula (c4-3) and an acid anhydride (R ^c11 CO) ₂ O) represented by the following formula (c4-4) or the following formula (c4-5) The compound represented by the following formula (c4-6) can be obtained by reacting with an acid halide (R ^c11 COHal, Hal is a halogen atom). In the following formulas (c4-1), (c4-3), (c4-4), (c4-5), and (c4-6), R ^c7 , R ^c8 , R ^c9 , R ^c10 , and R ^c11 is the same as that of Formula (c4).
When n5 is 1, there exists a tendency which can reduce more the generation | occurrence | production of the foreign material in the pattern formed using the photosensitive resin composition containing the compound represented by Formula (c4).

In scheme 4, R ^c10 contained in each of formula (c3-8), formula (c4-1), and formula (c4-3) may be the same or different. That is, R ^c10 in formula (c3-8), formula (c4-1), and formula (c4-3) may undergo chemical modification in the synthesis process shown as Scheme 4. Examples of chemical modification include esterification, etherification, acylation, amidation, halogenation, substitution of a hydrogen atom in an amino group with an organic group, and the like. The chemical modification that R ^c10 may undergo is not limited thereto.

<Scheme 4>

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

  It is preferable that content of a photoinitiator (C) is 0.5-30 mass% with respect to the mass of the photosensitive resin composition except the mass of the organic solvent (S) mentioned later, More preferably, it is 20 mass%. By setting the content of the photopolymerization initiator (C) within the above range, it is possible to obtain a photosensitive resin composition that has good curability and is less likely to have a defective pattern shape.

As a photopolymerization initiator (C), when the oxime ester compound and a photopolymerization initiator other than the oxime ester compound are used in combination, the ratio of the mass of the oxime ester compound to the mass of the photopolymerization initiator (C) is: 50 mass% or less is preferable, 1 mass% or more and 50 mass% or less are more preferable, 3 mass% or more and 30 mass% or less are especially preferable, and 5 mass% or more and 20 mass% or less are the most preferable.
When the oxime ester compound is contained in an amount within the range of the photopolymerization initiator (C), it is difficult to form a patterned low refractive index film having a width wider than a desired width.

  You may combine a photoinitiator adjuvant with a photoinitiator (C). Examples of the photoinitiator include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminobenzoic acid 2- Ethylhexyl, 2-dimethylaminoethyl benzoate, N, N-dimethylparatoluidine, 4,4′-bis (dimethylamino) benzophenone, 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9, 10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-5-methoxybenzothiazole 3-mercaptopropionic acid, 3-mercaptopropionic acid methyl, pentaerythritol tetra-mercapto acetate, thiol compounds such as 3-mercapto propionate. These photoinitiation assistants can be used alone or in combination of two or more.

<Filler (D)>
The photosensitive resin composition contains a filler (D) in order to form a low refractive index film having a refractive index as low as desired. A filler (D) is suitably selected from the fillers mix | blended with the photosensitive resin composition conventionally used for formation of a low refractive index film in the range which does not inhibit the objective of this invention. As the filler (D), hollow particles or porous particles are preferable.
As the filler (D), one type of particle may be used, or two or more types of particles may be combined and used. Moreover, you may use combining a hollow particle and a porous particle as a filler (D).

A hollow particle refers to a particle having a cavity surrounded by an outer shell. The porous particle refers to a porous particle having a large number of voids inside.
The void ratio of the hollow particles or porous particles is preferably 10 to 80%, preferably 20 to 60% from the viewpoint that the durability of the filler (D) is good and the low refractive index having a low refractive index is easily formed. % Is more preferable, and 30 to 60% is particularly preferable.

The hollow particles and the porous particles are more preferably hollow particles because the refractive index of the low refractive index film is likely to be lowered.
For example, the refractive index of hollow silica particles is significantly lower than the refractive index of 1.46 of ordinary silica. This is because the hollow silica particles contain air having a low refractive index of 1.0 inside.

The average particle diameter of a filler (D) is not specifically limited in the range which does not inhibit the objective of this invention. 1-200 nm is preferable and, as for the average particle diameter of a filler (D), 10-100 nm is more preferable.
The average particle diameter of the filler (D) is determined from an image obtained by observing the dispersed filler particles with a transmission electron microscope. Specifically, the following procedures 1) to 3)
1) A projected area is obtained for each of a plurality of filler particles.
2) The equivalent circle diameter of each filler particle is obtained from the obtained projected area.
3) The number average value of the equivalent circle diameters of a plurality of filler particles is calculated and used as the average particle diameter of the filler (D).
The average particle diameter is typically measured for 300 or more filler particles.

The specific surface area of the filler (D) is preferably from 10~2000m ² / g, more preferably ^{20~1800m 2 / g, 50~1500m 2 /} g is particularly preferred.

  When the filler (D) is a hollow particle or a porous particle, the refractive index is preferably 1.10 to 1.40, more preferably 1.15 to 1.35, and particularly preferably 1.15 to 1.30. preferable. The refractive index here is the refractive index of the entire particle, and when the particle is a hollow particle, it does not represent the refractive index of only the outer shell forming the hollow particle. When the particles are porous particles, the refractive index of the porous particles can be measured using an Abbe refractometer (manufactured by Atago Co., Ltd.).

The material of the hollow particles or porous particles is preferably an inorganic material from the viewpoint of lowering the refractive index of the low refractive index film. Such inorganic materials include magnesium fluoride and silica particles. The inorganic material may be a crystalline material or an amorphous material.
As hollow particles or porous particles made of an inorganic material, it is easy to form a low refractive index film having a low refractive index, is easily dispersed stably in the photosensitive resin composition, and is inexpensive. Hollow silica particles or porous silica particles are preferred.
1-100 nm is preferable and, as for the average primary particle diameter of an inorganic hollow particle or an inorganic porous particle, 1-60 nm is more preferable.
The inorganic hollow particles or the porous silica particles may be monodispersed particles or may contain an aggregate in which primary particles are aggregated.

In the case where the filler (D) is an inorganic particle, the purpose of improving the dispersion stability of the filler (D) in the dispersion liquid of the filler (D) or in the photosensitive resin composition, or a component such as the resin (A) In order to increase the affinity and binding properties, the surface of the inorganic particles may be subjected to a physical surface treatment such as plasma discharge treatment or corona discharge treatment, or a chemical surface treatment such as a surfactant or a coupling agent. Good.
Among such surface treatments, a chemical surface treatment using a coupling agent is preferable.
As a coupling agent, a titanium coupling agent, a silane coupling agent, etc. are preferable, and a silane coupling agent is more preferable.

For example, when silica particles are treated with a silane coupling agent, an organosilyl group is bonded to the surface of the silica particles by a reaction between the silane coupling agent and a silanol group on the surface of the silica particles.
The organic group introduced by the treatment with the silane coupling agent is a hydrocarbon group having 1 to 18 carbon atoms which may have an unsaturated bond, or 1 carbon atom which may have an unsaturated bond. -18 halogenated hydrocarbon groups and the like.
The surface treatment with the coupling agent may be performed before the inorganic particles as the filler (D) are blended in the photosensitive resin composition. Moreover, you may surface-treat a filler (D) by adding a coupling agent to the photosensitive resin composition.

  Since the filler (D) such as inorganic particles prevents aggregation and is easily dispersed in the photosensitive composition, it is preliminarily dispersed in the medium before preparing the photosensitive resin composition. preferable.

When silica particles are used as the filler (D), commercially available silica particles can be suitably used.
Specific examples of the commercially available silica particles include, for example, Julia Catalytic Chemical's Thululia series (isopropanol (IPA) dispersion, 4-methyl-2-pentanone (MIBK) dispersion, etc.); OSCAL series manufactured by Nissan Chemical Co., Ltd. Snowtex series (IPA dispersion, ethylene glycol dispersion, methyl ethyl ketone (MEK) dispersion, dimethylacetamide dispersion, MIBK dispersion, propylene glycol monomethyl acetate dispersion, Propylene glycol monomethyl ether dispersion, methanol dispersion, ethyl acetate dispersion, butyl acetate dispersion, xylene-n-butanol dispersion, toluene dispersion, etc.); Silinax manufactured by Nittetsu Mining Co., Ltd .; Fuso Chemical Industry ( PL series (IPA dispersion, toluene dispersion) , Propylene glycol monomethyl ether dispersion, methyl ethyl ketone dispersion, etc.); EVONIK manufactured by Aerosil series (propylene glycol acetate dispersions, ethylene glycol dispersion, MIBK dispersion, etc.); and the like.

As described above, the filler (D) is preferably blended in the photosensitive resin composition as a dispersion liquid dispersed in a medium.
When the silica particles are blended in the photosensitive resin composition as a dispersion, the content of silica particles in the dispersion is preferably 10 to 50% by mass, more preferably 15 to 40% by mass, and 15 to 30% by mass. Particularly preferred.

When the filler (D) is dispersed in the medium or the photosensitive resin composition, a dispersant may be used.
Specific examples of the dispersant include polyamidoamine, polyamidoamine salt, polycarboxylic acid, polycarboxylate, high molecular weight unsaturated acid ester, modified polyurethane, modified polyester, modified poly (meth) acrylate, (meth) acrylic Examples thereof include dispersion resins such as copolymers and naphthalenesulfonic acid formalin condensate.
In addition, compounds such as polyoxyethylene alkyl phosphate esters, polyoxyethylene alkyl amines, and alkanol amines can be used as the dispersant.
Among the above dispersants, a dispersion resin is preferable. Dispersing resins can be classified into linear polymers, terminal-modified polymers, graft polymers, and block polymers from their structures.

  The dispersion resin is adsorbed on the surface of the filler particles and acts to prevent aggregation of the filler particles. For this reason, a terminal modified polymer, a graft polymer, and a block polymer having an anchor site to the filler particle surface can be cited as preferred structures.

  1000-200000 are preferable, as for the mass average molecular weight (polystyrene conversion value measured by GPC method) of dispersion resin, 2000-100000 are more preferable, and 5000-50000 are especially preferable.

The dispersion resin is available as a commercial product.
As specific examples of commercially available dispersion resins,
BYKChemie's Disperbyk-101 (polyamideamine phosphate), Disperbyk-107 (carboxylic acid ester), Disperbyk-110 (copolymer containing an acid group), Disperbyk-111 (polyamide), Disperbyk-130 (polyamide) Disperbyk-161 (polymer copolymer), Disperbyk-162 (polymer copolymer), Disperbyk-163 (polymer copolymer), Disperbyk-164 (polymer copolymer), Disperbyk-165 (high Molecular copolymer), Disperbyk-166 (polymer copolymer), Disperbyk-170 (polymer copolymer), BYK-P104 (high molecular weight unsaturated polycarboxylic acid), BYK-P105 (high molecular weight unsaturated) Polycarboxylic acid);
EFKA 4047 (polyurethane), EFKA 4050-4010-4165 (polyurethane), EFKA 4330-4340 (block copolymer), EFKA 4400-4402 (modified polyacrylate), EFKA5010 (polyesteramide), EFKA5765 (high molecular weight polycarboxylic acid) manufactured by EFKA Acid salt), EFKA 6220 (fatty acid polyester), EFKA 6745 (phthalocyanine derivative), EFKA 6750 (azo pigment derivative);
Ajinomoto Fan Techno Co., Ajisper PB821, Ajisper PB822;
Fluorene TG-710 (urethane oligomer), Polyflow No. 50E (acrylic copolymer), Polyflow No. 300 (acrylic copolymer);
Disparon KS-860 (polymer polyesteramine salt), Disparon KS-873SN (polymer polyesteramine salt), Disparon KS-874 (polymer polyesteramine salt), Dispalon 2150 (aliphatic polyvalent carboxylic acid) manufactured by Enomoto Kasei Co., Ltd. Acid), Disparon 7004 (polyetherester), Disparon DA-703-50, Disparon DA-705, Disparon DA-725;
Demol RN (Naphthalenesulfonic acid formalin polycondensate), Demol N (Naphthalenesulfonic acid formalin polycondensate), Demol MS (aromatic sulfonic acid formalin polycondensate), Demol C (aromatic sulfonic acid formalin) manufactured by Kao Polycondensate), demole SN-B (aromatic sulfonic acid formalin polycondensate), homogenol L-18 (polymer polycarboxylic acid), emulgen 920 (polyoxyethylene nonylphenyl ether), emulgen 930 (polyoxyethylene nonyl) Phenyl ether), emulgen 935 (polyoxyethylene nonyl phenyl ether), emulgen 985 (polyoxyethylene nonyl phenyl ether), acetamine 86 (stearylamine acetate);
Solsperse 5000 (phthalocyanine derivative), Solsperse 22000 (azo pigment derivative), Solsperse 13240 (polyesteramine), Solsperse 3000 (terminal modified polymer), Solsperse 17000 (terminal modified polymer), Solsperse 27000 (terminal modified polymer) manufactured by Lubrizol ), Solsperse 24000 (graft polymer), Solsperse 28000 (graft polymer), Solsperse 32000 (graft polymer), Solsperse 38500 (graft polymer);
Nikkor T106 (polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene monostearate) manufactured by Nikko Chemical Co .;
EFKA-46, EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450 manufactured by Morishita Sangyo Co., Ltd .;
Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, Disperse Aid 9100 from San Nopco
Is mentioned.

Moreover, nonionic, anionic, and cationic sea surface active agents can be used as the dispersant. These surfactants are commercially available.
Specific examples of commercially available surfactants include:
EFKA-745 manufactured by EFKA;
Organosiloxane polymer KP341 manufactured by Shin-Etsu Chemical Co., Ltd .;
Polymer Polyflow No. manufactured by Kyoeisha Yushi Chemical Co., Ltd. 75, polymer polyflow no. 90, polymer polyflow no. 95;
W001, W004, W005, W017 made by Yushosha;
Solsperse 3000, Solsperse 5000, Solsperse 9000, Solsperse 12000, Solsperse 13240, Solsperse 13940, Solsperse 17000, Solsperse 24000, Solsperse 26000, Solsperse 28000 manufactured by Nippon Lubrizol Corporation;
Adeka Pluronic L31, Adeka Pluronic F38, Adeka Pluronic L42, Adeka Pluronic L44, Adeka Pluronic L61, Adeka Pluronic L64, Adeka Pluronic F68, Adeka Pluronic L72, Adeka Pluronic F95, Adeka Pluronic F77, Adeka Pluronic F77 F87, Adeka Pluronic P94, Adeka Pluronic L101, Adeka Pluronic P103, Adeka Pluronic F108, Adeka Pluronic L121, Adeka Pluronic P-123;
ISONET S-20 manufactured by Sanyo Chemical Industries;
Hinoact T-8000E manufactured by Kawaken Fine Chemicals;
ELEBASE BA-100, ELEBASE BA-200, ELEBASE BCP-2, ELEBASE BUB-3, ELEBASE BUB-4, ELEBASE CP-800K, ELEBASE EDP-475, ELEBASE HEB-5, Fine Surf 270, manufactured by Aoki Yushi Kogyo Co., Ltd. Finesurf 7045, Finesurf 7085, Brownon DSP-12.5, Brownon DT-03, Brownon L-205, Brownon LPE-1007, Brownon O-205, Brownon S-202, Brownon S-204, Brownon S-207, Braunon S-205T;
Emulgen A-500, Emulgen PP-290, Amate 102, Amate 105, Amit 302, Amit 320, Aminone PK-02S, Emanon CH-25, Emulgen 104P, Emulgen 108, Emulgen 404, Emulgen 408, Emulgen A -60, Emulgen A-90, Emulgen B-66, Emulgen LS-106, Emulgen LS-114, Rheodor 430V, Rheodor 440V, Rheodor 460V, Rheodor TW-S106, Rheodor TW-S120V, Rheodor Super TW-L120, Foss Phanol ML-200, Emar 20T, Emar E-27, Neoperex GS, Perex NBL, Perex SS-H, Perex SS-L, Poise 532A, Ramtel AS , Ramuteru E-118B, Ramuteru E-150;
New Calgen 3000S, New Calgen FS-3PG, New Calgen FE-7PG, Pionin D-6414, Pionin A-24-EA, Pionin A-28-B, Pionin A-29-M, Pionin A- 44-B, Pionein A-44TW;
Dinol 604, Olfin PD-002W, Surfinol 2502, Surfinol 440, Surfinol 465, Surfinol 485, Surfinol 61 manufactured by Nissin Chemical Industry Co., Ltd .;
Clariant's EMULSOGEN COL-020, EMULSOGEN 070, EMULSOGEN 080,
Plysurf A208B, Plysurf A210B, Plysurf A210G, Plysurf A219B, Plysurf AL, Labelin FC-45 manufactured by Daiichi Kogyo Seiyaku Co., Ltd .;
AKYPO RLM100NV, AKYPO RLM45, AKYPO RLM45NV, AKYPO ECT-3, AKYPO ECT-3NEX, AKYPO ECT-7, Hosten HLP, Hosten HLP-1, Host Store HLP-TEA;
Is mentioned.
These dispersants may be used alone or in combination of two or more.

  The content of the dispersant in the photosensitive resin composition is preferably 1 to 100% by mass, more preferably 5 to 80% by mass, and particularly preferably 10 to 60% by mass with respect to the mass of the filler. . When the dispersant is a dispersion resin, the amount of the dispersant used is preferably 5 to 100% by mass and more preferably 10 to 80% by mass with respect to the mass of the filler.

  When the photosensitive resin composition contains the filler (D), the amount of the filler (D) used in the photosensitive resin composition is not particularly limited as long as the object of the present invention is not impaired. 80 mass% or less is preferable with respect to the mass of the photosensitive resin composition except the mass of the organic solvent (S) mentioned later, and content of the filler (D) in the photosensitive resin composition is 20-80 mass%. Is more preferable, and 30 to 70% by mass is particularly preferable.

<Fluorine-containing surfactant (E)>
The photosensitive resin composition essentially contains a fluorine-containing surfactant (E). Content of the fluorine-containing surfactant (E) in the photosensitive resin composition is the mass of the resin (A), the mass of the photopolymerizable compound (B), and the filler (D) in the photosensitive resin composition. It is 0.05-3 mass% with respect to the sum total with a mass.
When the photosensitive resin composition contains the fluorine-containing surfactant (E) in an amount in such a range, the photosensitive resin composition can be uniformly applied on the substrate, and the residue can be removed even with low exposure exposure. Without generation, it is possible to form a low-refractive-index film that hardly causes surface roughness by peeling off the protective tape.
The fluorine-containing surfactant (E) is not particularly limited as long as it is a surfactant containing a fluorine atom, and may be any of an anionic surfactant, a cationic surfactant, and a nonionic surfactant.
Two or more fluorine-containing surfactants (E) may be used in combination.

  Specific examples of the fluorine-containing surfactant include BM-1000, BM-1100 (all manufactured by BM Chemie), MegaFuck F142D, MegaFuck F172, MegaFuck F173, MegaFak F183 (all Dainippon Ink and Chemicals, Inc.) ), Fluorado FC-135, Fluorado FC-170C, Fluorado FC-430, Fluorado FC-431 (all manufactured by Sumitomo 3M), Surflon S-112, Surflon S-113, Surflon S-131, Surflon S- 141, Surflon S-145 (all manufactured by Asahi Glass Co., Ltd.), SH-28PA, SH-190, SH-193, SZ-6032, SF-8428 (all manufactured by Toray Silicone Co., Ltd.) However, it is not limited to these.

Moreover, as a fluorine-containing surfactant, the compound which has a fluoroalkyl group in a side chain is also preferable.
Examples of the compound having a fluoroalkyl group in the side chain include compounds represented by the following formulas (e-1) to (e-3).
In Formula (e-1) and Formula (e-2), x1 is an integer of 0-7.
In formula (e-3), x2 is an integer of 0-8.
In formula (e-4), x3 is an integer of 6-20.

  Content of a fluorine-containing surfactant (E) is with respect to the sum total of the mass of resin (A) in a photosensitive composition, the mass of a photopolymerizable compound (B), and the mass of a filler (D). 0.05 to 3 mass%, preferably 0.05 to 2 mass%, more preferably 0.10 to 1.5 mass%, and most preferably 0.15 to 1 mass%.

<Polymerization inhibitor (F)>
It is preferable that the photosensitive resin composition contains a polymerization inhibitor (F) as necessary. By including the polymerization inhibitor in the photosensitive resin composition, it is easy to suppress the width of the patterned low refractive index film from becoming larger than a predetermined dimension.
The kind of polymerization inhibitor (F) is not specifically limited, The compound conventionally used as a polymerization inhibitor for prohibiting superposition | polymerization of the compound which has an unsaturated double bond can be used.

As the polymerization inhibitor (F), a hindered phenol compound having a molecular weight of 230 to 1500 is preferable. The reason is unknown, but the photosensitive resin composition contains a hindered phenol compound having a molecular weight within the above-mentioned predetermined range as a polymerization inhibitor (F), so that a residue is generated at a wide exposure amount. Therefore, it is easy to form a pattern having a good shape with a desired dimension.
If the molecular weight of the polymerization inhibitor (F) is too small, a residue is likely to occur during pattern formation. When the molecular weight of the polymerization inhibitor (F) is excessive, the polymerization inhibitor (F) is localized in the photosensitive resin composition, so that a desired effect by using the polymerization inhibitor (F) is obtained. It may be difficult.

  The hindered phenol has a bulky substituent other than a hydrogen atom and a methyl group in at least one of two ortho positions of the phenolic hydroxyl group. Examples of bulky substituents include alkyl groups other than methyl groups, alkenyl groups, alkynyl groups, aryl groups, heterocyclic groups, alkoxy groups, aryloxy groups, substituted amino groups, thioalkyl groups, thiophenyl groups, and the like.

The hindered phenol compound having a molecular weight of 230 to 1500 is not particularly limited as long as it is a hindered phenol compound having a molecular weight within a predetermined range and exhibiting an action as a polymerization inhibitor.
Specific examples of hindered phenol compounds having a molecular weight of 230 to 1500 include 2,5-bis (1,1,3,3-tetramethylbutyl) hydroquinone (334.5), 2,5-bis (1, 1-dimethylbutyl) hydroquinone (250.4), pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (1177.6), N, N′-hexane- 1,6-diylbis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionamide] (637.0), 1,3,5-tris (3,5-di-tert-butyl -4-hydroxybenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione (784.1), 4,4 ', 4 "-(1-methylpropyl) Panyl-3-ylidene) tris (6-tert-butyl-m-cresol (544.8), 6,6′-di-tert-butyl-4,4′-butylidenedi-m-cresol (382.6), Octadecyl 3- (3,5-di-tetr-butyl-4-hydroxyphenyl) propionate (530.9), 3,9-bis {2- [3- (3-tert-butyl-4-hydroxy-5- Methylphenyl) propionyloxy] -1,1-dimethylethyl} -2,4,8,10-tetraoxaspiro [5.5] undecane (741.0), 1,3,5-tris (3,5- Di-tert-butyl-4-hydroxyphenylmethyl) -2,4,6-trimethylbenzene (775.2), 2,2′-thiodiethylbis [3- (3,5-di-tert-butyl-4 Hydroxyphenyl) propionate] (642.9), isooctyl 3- (3,5-di-tetra-butyl-4-hydroxyphenyl) propionate (390.6), calcium bis [3,5-di (tert-butyl) -4-hydroxybenzyl (ethoxy) phosphinate] (692.8), bis [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionic acid] [ethylenebis (oxyethylene)] (586. 8), 1,6-hexanediol bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (638.9), and 4-[[4,6-bis (octylthio) -1,3,5-triazin-2-yl] amino] -2,6-di-tert-butylphenol (589.0) It is below.
The numerical value in parentheses immediately after each compound name is the molecular weight of each compound.
The polymerization inhibitor (F) may contain a combination of two or more hindered phenol compounds having a molecular weight of 230 to 1500.

The polymerization inhibitor (F) may contain a polymerization inhibitor other than the hindered phenol compound having a molecular weight of 230 to 1500.
Specific examples of other polymerization inhibitors include 2,6-di-tert-butyl-p-cresol (BHT); hydroquinone, methylhydroquinone, 2,5-di-t-butylhydroquinone, t-butylhydroquinone, etc. Hydroquinone compounds; benzoquinone compounds such as p-benzoquinone, methyl-p-benzoquinone, t-butylbenzoquinone and 2,5-diphenyl-p-benzoquinone; benzotriazo- such as 2- (2-hydroxy-5-methylphenyl) benzotriazole Nitrosamine compounds such as N-nitrosophenylhydroxylamine and N-nitrosophenylhydroxylamine aluminum salts; organic sulfur compounds such as phenothiazine, dithiobenzoyl sulfide and dibenzyltetrasulfide; bis (1,2,2,6) , Hindered amine compounds such as -pentamethyl-4-piperidyl) [{3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl} methyl] butylmalonate; p-phenylenediamine, N, N- Aromatic amines such as diphenyl-p-phenylenediamine; tris (2,4-di-tert-butylphenyl) phosphite, tetrakis (2,4-di-tert-butylphenyl) [1,1-biphenyl] -4 , 4'-diylbisphosphonate and other phosphorus compounds.
The polymerization inhibitor (D) may contain a combination of two or more polymerization inhibitors other than the hindered phenol compound having a molecular weight of 230 to 1500.

  The content of the hindered phenol compound having a molecular weight of 230 to 1500 in the polymerization inhibitor (F) is not particularly limited as long as the object of the present invention is not impaired. The content of the hindered phenol compound having a molecular weight of 230 to 1500 in the polymerization inhibitor (F) is preferably 70% by mass or more, more preferably 80% by mass or more, particularly preferably 90% by mass or more, and 100% by mass. Most preferably.

  The content of the polymerization inhibitor (F) in the photosensitive resin composition is not particularly limited as long as the object of the present invention is not impaired. The content of the polymerization inhibitor (F) is 0.001 to 1% by mass with respect to the mass of the photosensitive resin composition excluding the mass of the filler (D) and the mass of the organic solvent (S). It is preferable that it is 0.01-1 mass%. By setting the content of the polymerization inhibitor (F) in the above range, the dimension of the patterned low refractive index film is more than the desired dimension while maintaining the curability of the photosensitive resin composition in a favorable range. It is easy to suppress the increase.

<Organic solvent (S)>
The photosensitive resin composition preferably contains an organic solvent (S) for improving coating properties and adjusting the viscosity.

  Specific examples of the organic solvent (S) include alkane monools such as methanol, ethanol, n-propanol, isopropanol, and n-butanol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, Ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, Propylene glycol monoethyl ether, propylene glycol mono-n-propyl Pill ether, propylene glycol mono-n-butyl ether, 3-methoxy-n-butanol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether , (Poly) alkylene glycol monoalkyl ethers such as tripropylene glycol monomethyl ether and tripropylene glycol monoethyl ether; 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 (PG (EA), (poly) alkylene glycol monoalkyl ether acetates such as propylene glycol monoethyl ether acetate; other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran; methyl ethyl ketone, cyclohexanone, 2-heptanone, Ketones such as 3-heptanone; alkyl lactates such as methyl 2-hydroxypropionate and ethyl 2-hydroxypropionate; ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, 3-methoxypropione Ethyl acetate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate , Methyl 2-hydroxy-3-methylbutanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, ethyl acetate, n-propyl acetate, acetic acid i -Propyl, n-butyl acetate, i-butyl acetate, n-pentyl formate, i-pentyl acetate, benzyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, i-propyl butyrate, n-butyl butyrate, Other esters such as methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxobutanoate; aromatic hydrocarbons such as toluene, xylene; N-methyl-2 -Pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, N, N-dimethyl Sobutyramide, N, N-diethylacetamide, N, N-diethylformamide, N-methylcaprolactam, 1,3-dimethyl-2-imidazolidinone, pyridine, N, N, N ′, N′-tetramethylurea, etc. Nitrogen-containing polar organic solvent; and the like.

Among these, alkane monools, alkylene glycol monoalkyl ethers, alkylene glycol monoalkyl ether acetates, other ethers described above, lactic acid alkyl esters, and other esters described above are preferable, alkylene glycol monoalkyl ether acetates , Other ethers mentioned above, and other esters mentioned above such as benzyl acetate are more preferred.
Moreover, it is preferable that the organic solvent (S) contains a nitrogen-containing polar organic solvent in terms of the solubility of each component. As the nitrogen-containing polar organic solvent, N, N, N ′, N′-tetramethylurea or the like can be used.
These solvents can be used alone or in combination of two or more.

  Content of an organic solvent (S) is not specifically limited, It is a density | concentration which can be apply | coated to a board | substrate etc., and is suitably set according to a coating film thickness. For example, the viscosity of the photosensitive resin composition is preferably 1 to 500 cp, more preferably 1 to 50 cp, and even more preferably 1 to 30 cp. Moreover, it is preferable that the solid content density | concentration of the photosensitive resin composition is 1-50 mass%, and it is more preferable that it is 1-20 mass%.

<Other ingredients>
For the photosensitive resin composition, if necessary, surfactants other than the aforementioned fluorine-containing surfactants, photoacid generators, adhesion improvers, thermal polymerization inhibitors, antifoaming agents, colorants, silane cups Additives such as ring agents can be included. Any additive can be used as the additive.

When the coating film of the photosensitive resin composition is exposed and cured, the curing of the surface of the low refractive index film is somewhat low due to the inhibition of curing by oxygen on the surface of the low refractive index film. For this reason, if a protective tape is affixed on the surface of the low refractive index film | membrane with a slightly low degree of surface hardening, when the protective tape is peeled off, the surface of the low refractive index film is likely to be roughened.
However, when the photosensitive resin composition contains a resin having a functional group that can be cross-linked by the action of an acid such as an epoxy group, if the photosensitive resin composition contains an acid generator, the cross-linkability is caused by the acid generated by exposure. Cross-linking between groups also proceeds on the surface of the low refractive index film, and the surface of the low refractive index film is sufficiently cured.
For this reason, even if the protective tape is peeled from the low refractive index film, the surface of the low refractive index film is hardly roughened.

  The photosensitive resin composition preferably contains a silane coupling agent because it has a good shape and can easily form a low refractive index film having excellent adhesion to a substrate. A conventionally known silane coupling agent can be used without particular limitation.

  Examples of the surfactant include anionic, cationic, and nonionic compounds, examples of the thermal polymerization inhibitor include hydroquinone and hydroquinone monoethyl ether, and examples of the antifoaming agent include silicone and fluorine. Compounds and the like.

<Method for preparing photosensitive resin composition>
The photosensitive resin composition described above can be obtained by mixing each of the above components in a predetermined amount and then uniformly mixing with a stirrer. In addition, you may filter using a filter so that the obtained mixture may become a more uniform thing.

≪Low refractive index film manufacturing method≫
As a method for producing a low refractive index film, a conventionally known method for producing a low refractive index film using a photosensitive resin composition containing a photopolymerizable compound (B) can be employed without any particular limitation.

As a suitable manufacturing method of the low refractive index film,
Forming a coating film of the photosensitive resin composition described above;
Exposing the coating film in a position-selective manner according to a predetermined pattern;
And developing the exposed coating film.

In order to form a low refractive index film using a photosensitive resin composition, first, the photosensitive resin composition is applied onto a substrate selected according to the use of the low refractive index film to form a coating film. To do.
When the image sensor is formed as the substrate, for example, a substrate including an RGB colored film on a semiconductor layer such as silicon and a microlens on the colored film is used.

  The method for forming the coating film is not particularly limited. For example, the coating film is formed using a contact transfer type coating device such as a roll coater, a reverse coater, or a bar coater, or a non-contact type coating device such as a spinner (rotary coating device) or a curtain flow coater. Is called.

  The applied photosensitive resin composition is dried as necessary to form a coating film. The drying method is not particularly limited. For example, (1) a method of drying on a hot plate at 80 to 120 ° C., preferably 90 to 100 ° C. for 60 to 120 seconds, (2) several hours at room temperature Examples include a method of leaving for several days, and (3) a method of removing the solvent by putting it in a warm air heater or an infrared heater for several tens of minutes to several hours.

  Next, the coating film is exposed. The exposure is performed by irradiating active energy rays such as ultraviolet rays and excimer laser light. The exposure is performed position-selectively by, for example, a method of performing exposure through a negative mask.

  After the coating film is selectively exposed to position, the exposed film is developed with a developing solution, whereby the unexposed portion is dissolved and removed in the developing solution to form a patterned cured film. The development method is not particularly limited, and for example, an immersion method, a spray method, or the like can be used. The developer is appropriately selected according to the composition of the photosensitive resin composition. As the developer, for example, a basic aqueous solution such as sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, or a quaternary ammonium salt can be used.

Next, the patterned cured film may be baked (post-baked). The baking temperature is not particularly limited, but is preferably 180 to 250 ° C, more preferably 220 to 230 ° C. The baking time is typically 10 to 90 minutes, preferably 20 to 60 minutes.
By baking as described above, a cured film of the photosensitive resin composition can be obtained.

The cured film thus formed can be suitably used as a low refractive index film. When the cured film is used as a low refractive index film, the refractive index (wavelength 633 nm, measurement temperature 25 ° C.) of the low refractive index film is preferably 1.35 or less, more preferably 1.23-1.34. 25 to 1.33 is particularly preferable.
Further, the contact angle of water on the surface of the low refractive index film is preferably larger than 60 °. In such a case, in particular, the protective tape can be attached to and peeled from the surface of the low refractive index film without roughening the surface of the low refractive index film.
Furthermore, the surface roughness Ra of the low refractive index film is preferably 30 nm or less.

  The low refractive index film can be preferably used in an optical device such as an image sensor. In the image sensor, when the low refractive index film is applied as a coating layer for covering the microlens formed on the RGB colored film, the reflection of light incident on the microlens is improved. Is suppressed.

In the above optical device, a protective tape is preferably applied to the surface of the low refractive index film. A protective tape is provided on the surface of the low refractive index film. In an optical device including a protective tape, a grinding process is performed on a semiconductor layer located on a surface opposite to the surface of the protective tape.
Since the optical device includes the low refractive index film formed using the above-described photosensitive resin composition, the smoothness of the surface of the low refractive index film is maintained even if the protective tape is peeled off after grinding. The

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the scope of the present invention is not limited to these examples.

[Examples 1 to 11 and Comparative Examples 1 to 3]
The type and amount of the resin (A) described in Table 1, the type and amount of the photopolymerizable compound (B) described in Table 1, and the type and amount of the photopolymerization initiator (C) described in Table 1. The following filler (D) in the amount shown in Table 1, the fluorine-containing surfactant (E) in the amount shown in Table 1, and the polymerization inhibitor (F) in the amount shown in Table 1 are organically mixed. It mixed with the solvent (S) and the photosensitive resin composition of each Example and the comparative example was obtained.

In Examples 1-3, Example 5, Example 11, and Comparative Example 1, as the organic solvent (S), 92.7% by mass of propylene glycol monomethyl ether, 3.3% by mass of 3-methoxybutyl acetate, A photosensitive resin composition was prepared using a mixed solvent consisting of 3.3% by mass of 3-methoxy-n-butanol and 0.7% by mass of methanol so that the solid content concentration was 13.5% by mass. .
In Example 4, Examples 6 to 10, Comparative Example 2, and Comparative Example 3, as the organic solvent (S), 96.3% by mass of propylene glycol monomethyl ether, 3.0% by mass of propylene glycol monomethyl ether acetate, The photosensitive resin composition was prepared using the mixed solvent which consists of methanol 0.7 mass% so that solid content concentration might be 10.90 mass%.

  In Example 4, Examples 6 to 10, Comparative Example 2, and Comparative Example 3, 1 part by mass of 3-glycidoxypropyltrimethoxysilane, which is an adhesion enhancer, was further added during the preparation of the photosensitive resin composition. It was.

  In Examples and Comparative Examples, the following A1 and A2 were used as the resin (component (A)).

A1:

A2:

The following B1 and B2 were used as the photopolymerizable compound (component (B)).
B1: Ethylene oxide modified trimethylolpropane triacrylate (3 mol addition of ethylene oxide)
B2: Dipentaerythritol hexaacrylate

The following C1 and C2 were used as the photopolymerization initiator (component (C)).
C1: 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one C2: 2- (benzoyloxyimino) -1- [4- (phenylthio) phenyl] -1-octanone C3: 1-hydroxy-cyclohexyl-phenyl-ketone

  As the filler (component (D)), A2SL-03TO (product name, manufactured by JGC Catalysts & Chemicals Co., Ltd., dispersion of hollow silica particles having an average primary particle size of 60 nm, solid content concentration of 20% by mass) was used.

As the surfactant (component (E)), the following fluorosurfactant was used.

The following F1 was used as a polymerization inhibitor (component (F)).
F1: pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (molecular weight: 1177.6),

Using the obtained photosensitive resin compositions of Examples and Comparative Examples, low refractive index films were produced according to the following method. When the refractive index of the obtained low refractive index film was measured, the value of the refractive index of the cured film formed using the photosensitive resin composition of any of Examples and Comparative Examples was 1.32 to 1.40. It was in the range.
(Measurement of refractive index)
The photosensitive resin composition was applied on a silicon wafer using a spin coater so that the applied film thickness was 800 nm. The formed coating film was heated with a hot plate at 90 ° C. for 2 minutes, and then exposed selectively with an i-line stepper at 500 mJ / cm ² .
The coated film after exposure was developed for 1 minute with an aqueous tetramethylammonium hydroxide solution having a concentration of 0.2% by mass. The patterned film obtained by development was heated on a hot plate at 220 ° C. for 5 minutes to obtain a low refractive index film. The refractive index of the obtained low refractive index film is measured using a refractive index measuring device (spectral ellipsometer). A. It measured using Woollam VUV-VASE VU-302.

  In addition, using the photosensitive resin compositions of the examples and comparative examples, 50 μm resolution, residual film ratio, residual non-occurrence exposure, protective tape peelable exposure, and coating uniformity were evaluated according to the following methods. did. These evaluation results are shown in Table 2.

(50 μm resolution evaluation)
A pattern was formed by the same method as the measurement of the refractive index, and a case where a line pattern having a line width of 50 μm could be resolved was marked with ◯, and a case where the pattern could not be resolved was marked with x.

(Residual film rate evaluation)
A pattern was formed by the same method as the measurement of the refractive index, and the film thickness after development when the film thickness after pre-baking was 100% was taken as the remaining film ratio.

(Evaluation of exposure amount without residue)
Other than changing the exposure amount, a pattern was formed by the same method as the measurement of the refractive index, and the maximum exposure amount capable of developing the pattern without generating a residue was determined.
For example, in the case of Example 1, a residue appears when exposed at 175 mJ / cm ² or more, but no residue appears when exposed at 175 mJ / cm ² or less.

(Exposure that can be peeled off the protective tape)

  Except for changing the exposure amount, when forming a pattern in the same way as the refractive index measurement, after curing, when applying a protective tape to the cured film and peeling it off, the minimum exposure amount at which the film does not stick to the tape is set. Asked.

(Coating uniformity)
The photosensitive resin composition of each Example and the comparative example was spin-coated on the Si substrate, and the coating film was formed. The case where the formed coating film could be uniformly applied without visual observation of radial streaks and color unevenness by visual observation and microscopic observation was marked with ◯, and the others were marked with x.
In addition, about the photosensitive resin composition of the comparative example 1, since the formed coating film was remarkably non-uniform | heterogenous, detailed evaluation other than application | coating uniformity was not performed.
Moreover, about the photosensitive resin composition of the comparative example 2 and the comparative example 3, since the streaks and the nonuniformity produced in the coating film when it formed, detailed evaluation of the exposure amount which can peel off a protective tape was not performed.

As can be seen from Table 2, 0.05 to 3% by mass of the fluorine-containing surface activity with respect to the total of the mass of the resin (A), the mass of the photopolymerizable compound (B), and the mass of the filler (D). The photosensitive resin composition of the example containing the agent (F) can be satisfactorily coated on the substrate, and a cured film whose surface is not easily roughened even by exposure to a low exposure amount or by attaching and peeling of a protective tape. It can be seen that it can be formed.
Further, in the examples, the upper limit value of the residual exposure amount where the residue is not generated is larger than the lower limit value of the protective tape peelable exposure amount, the lower limit value of the protective tape peelable exposure amount, and the upper limit value of the residual residue occurrence amount. It can be seen that by performing exposure with an exposure amount between 2 and 1, it is possible to form a cured film whose surface is hardly roughened even by applying and peeling off the protective tape while suppressing the generation of residues during development.

On the other hand, 0.05-3 mass% fluorine-containing surfactant (F) with respect to the sum total of the mass of resin (A), the mass of a photopolymerizable compound (B), and the mass of a filler (D). The photosensitive resin composition of the comparative example that does not contain the resin is difficult to uniformly apply on the substrate before the problem of whether or not a cured film that does not roughen the surface can be formed even by applying and peeling the protective tape. I understand that.
In addition, about the comparative example 1, although the upper limit of the residue non-occurrence exposure amount and the lower limit of the exposure amount that can be peeled off the protective tape were compared, It was smaller than the lower limit of. That is, in the photosensitive resin composition of Comparative Example 1, there is no range of exposure amount that can achieve both good suppression of residue generation and formation of a cured film that does not roughen the surface even when the protective tape is applied and peeled off. .

Claims (11)

A resin (A), a photopolymerizable compound (B), a photopolymerization initiator (C), a filler (D), and a fluorine-containing surfactant (E);
The content of the fluorine-containing surfactant (E) is 0 with respect to the total of the mass of the resin (A), the mass of the photopolymerizable compound (B), and the mass of the filler (D). A photosensitive resin composition for forming a low refractive index film, which is 0.05 to 3% by mass.   The photosensitive resin composition for low-refractive-index film formation of Claim 1 containing a polymerization inhibitor (F).   The photosensitive resin composition for low refractive index film formation according to claim 1 or 2, wherein the photopolymerization initiator (C) contains an oxime ester compound.   The photosensitive resin composition for low refractive index film | membrane formation of any one of Claims 1-3 in which the said photopolymerizable compound (B) contains the compound which has a 6 or more polymerizable functional group.   The photosensitive resin composition for forming a low refractive index film according to claim 4, wherein the photopolymerizable compound (B) further comprises a compound having a polymerizable functional group of less than 6.   The low-refractive-index film formed by hardening the photosensitive resin composition for low-refractive-index film formation of any one of Claims 1-5.   The low refractive index film according to claim 6, which is patterned and has a surface roughness Ra of 30 nm or less.   The low refractive index film according to claim 6 or 7, wherein a contact angle with water is larger than 60 °.   An optical device provided with the low-refractive-index film of any one of Claims 6-8.   The optical device according to claim 9, further comprising a protective tape on the low refractive index film. Forming a coating film of the photosensitive resin composition for forming a low refractive index film according to any one of claims 1 to 5,
Exposing the coating film selectively according to a predetermined pattern;
Developing the exposed coating film, and producing a patterned low refractive index film.