KR20180048301A - Photosensitive resin composition for forming low refractive index film, low refractive index film, optical device, and method of producing low refractive index film - Google Patents

Abstract

The present invention relates to a photosensitive resin composition for forming a film with a low refractive index, the film with a low refractive index formed by curing the photosensitive resin composition, an optical device including the film with the low refractive index, and a method for using the photosensitive resin composition to form the film with the low refractive index. The photosensitive resin composition can be uniformly coated on a substrate and used to form the film with the low refractive index while enables the film to keep a smooth surface even when a protective film is attached to or detached from the same without leaving residue and even with low exposure dose. The photosensitive resin composition for forming the film with the low refractive index includes a resin (A), a photopolymerization compound (B), a photopolymerization initiator (C), and a filler (D) while additionally including 0.05-3 mass% of a fluorine-containing surfactant (E) with respect to the sum of the mass of the resin (A), the mass of the photopolymerization compound (B), and the mass of the filler (D).

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive resin composition for forming a low refractive index film, a low refractive index film, an optical device, and a method of manufacturing a low refractive index film. 2. Description of the Related Art Photothermographic materials,

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, an optical device including the low refractive index film, To a process for producing a low refractive index film using the composition.

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 covering an image sensor microlens or a low refractive index film for preventing reflection in a liquid crystal display, an organic EL element or the like is formed while patterning to a desired shape using a photosensitive resin composition.

The photosensitive resin composition capable of forming a patterned cured film that can be used as the antireflection low refractive index film includes a hollow or porous particle, a photopolymerization initiator, a polymerizable compound having alkali solubility, and a particle dispersing agent (Patent Document 1).

Japanese Patent Application Laid-Open No. 2009-271444

For example, when a surface of a microlens formed on a coloring film of RGB formed on a semiconductor substrate such as a silicon substrate is coated with a cured film (low refractive index film), a protective tape is attached to the surface of the low refractive index film, The substrate may be ground.

After such grinding, the protective tape is peeled off from the surface of the low refractive index film, but the surface of the low refractive index film is roughened by peeling of the protective tape, and the surface of the low refractive index film is likely to be roughened.

When the coated film of the photosensitive resin composition is exposed and cured, the surface of the low refractive index film is inhibited from being cured by oxygen, so that the surface of the low refractive index film has a slightly lower degree of curing. Therefore, it is considered that roughening of the surface of the low refractive index film due to peeling of the protective tape occurs.

For this reason, even when a low refractive index film is formed by using the photosensitive resin composition described in Patent Document 1, the problem that the surface of the low refractive index film becomes rough due to sticking and peeling of the protective tape to the low refractive index film . 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 by the protective tape is remarkable.

Since the low refractive index film is an optical functional layer, it is naturally desired that the surface thereof is smooth. For this reason, it is also required that the photosensitive resin composition for forming a low refractive index film can be uniformly coated on a substrate.

In the case of coating a microlens or the like in an image sensor, it is necessary to form a cured film as a low refractive index film with an exact dimension at a predetermined position. In the case of using the photosensitive composition described in Patent Document 1, The residue tends to be generated, and as a result, the apparent dimension of the pattern of the cured film may become larger than the desired dimension.

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and it is an object of the present invention to provide a protective tape which is uniformly applied on a substrate and which does not generate residues even in exposure with a low exposure dose, An optical device comprising the photosensitive resin composition for forming a low refractive index film capable of forming a low refractive index film, a low refractive index film formed by curing the photosensitive resin composition for forming the low refractive index film, and the low refractive index film, And a method for producing a low refractive index film using the photosensitive resin composition for forming a low refractive index film.

The inventors of the present invention have found that a photosensitive resin composition for forming a low refractive index film can be obtained by adding the resin (A), the photopolymerizable compound (B), the photopolymerization initiator (C)

The above problems can be solved by adding 0.05 to 3% by mass of the fluorine-containing surfactant (E) to the total of the mass of the resin (A), the mass of the photopolymerizable compound (B) and the mass of the filler The present inventors have completed the present invention. More specifically, the present invention provides the following.

A first aspect of the present invention is a resin composition containing a resin (A), a photopolymerizable compound (B), a photopolymerization initiator (C), a filler (D), and a fluorine-containing surfactant (E)

Wherein the content of the fluorine-containing surfactant (E) is 0.05 to 3% by mass relative to the sum of the mass of the resin (A), the mass of the photopolymerizable compound (B) and the mass of the filler (D) Based photosensitive resin composition.

A second aspect of the present invention is a low refractive index film formed by curing a 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 comprising a low refractive index film according to the second aspect.

The fourth aspect of the present invention is a method of forming a coating film of a photosensitive resin composition for forming a low refractive index film according to the first aspect,

Selectively exposing the coating film to a predetermined pattern in a predetermined pattern,

And developing the exposed coating film.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to form a low-refractive-index film which is uniformly applied on a substrate and is hardly roughened by peeling and peeling of a protective tape without generating residues even with exposure at a low exposure dose An optical device comprising the photosensitive resin composition for forming a low refractive index film, a low refractive index film formed by curing the photosensitive resin composition for forming the low refractive index film, the low refractive index film, and a photosensitive resin composition for forming the low refractive index film A low refractive index film can be provided.

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described based on preferred embodiments. In the present specification, " ~ " indicates an ideal (lower limit) to (less than) upper limit unless otherwise specified.

The term "photosensitive resin composition" simply refers to "photosensitive resin composition for forming a low refractive index film" unless otherwise described in the present specification.

In the present specification, the term "(meth) acrylate" includes both acrylate and methacrylate.

As used herein, the term " (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 is characterized in that in addition to the resin (A), the photopolymerizable compound (B), the photopolymerization initiator (C) and the filler (D) (E) a fluorine-containing surfactant in an amount of 0.05 to 3% by mass based on the sum of the mass of the polymerizable compound (B) and the mass of the filler (D).

The photosensitive resin composition contains the fluorine-containing surfactant (E) in an amount within the above-specified range so that the photosensitive resin composition can be uniformly coated on the substrate and the residue can be generated even with exposure at a low exposure dose , It is possible to form a low refractive index film which is less likely to be roughened even by attaching and peeling the protective tape.

Hereinafter, essential or optional components included 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 a pattern-forming photosensitive resin composition.

The resin (A) is not particularly limited as far as it is a resin conventionally compounded in the pattern-forming photosensitive resin composition. As the resin (A), an alkali-soluble resin is preferable in that it is easy to form a patterned cured film having a good shape.

The photosensitive resin composition containing an alkali-soluble resin is soluble in an alkali developing solution while the exposed photosensitive resin composition is cured. Therefore, when the coating film of the photosensitive resin composition exposed to the position selectively is developed using an alkali developer, only the unexposed portion is dissolved in the alkali developing solution, while the cured exposed portion remains, and the patterned cured film becomes a low refractive index film .

The alkali-soluble resin is a resin film having a thickness of 1 mu m formed on a substrate by a resin solution (solvent: propylene glycol monomethyl ether acetate) having a resin concentration of 20 mass%, and a tetramethylammonium hydroxide (TMAH) 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 (A1) having a cardo structure as an alkali-soluble resin, excellent heat resistance, mechanical properties, solvent resistance, chemical resistance and the like are well balanced and excellent low refractive index films are easily formed.

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

[Chemical Formula 1]

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

(2)

In the formula (a-2), R ^a1 independently represents a hydrogen atom, a hydrocarbon group of 1 to 6 carbon atoms, or a halogen atom, R ^a2 each 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).

(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 the dicarboxylic acid anhydride include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, anhydrous tetrahydrophthalic acid, anhydrous hexahydrophthalic acid, methylendomethylenetetrahydrophthalic anhydride, anhydrous chlorodic acid, Phthalic acid, and anhydrous glutaric acid.

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 the tetracarboxylic acid dianhydride include pyromellitic acid dianhydride, benzophenonetetracarboxylic acid dianhydride, biphenyltetracarboxylic acid dianhydride, and biphenyl ether tetracarboxylic acid dianhydride.

In the above formula (a-1), m represents an integer of 0 to 20.

The mass average molecular weight (Mw: measured value by gel permeation chromatography (GPC) in terms of polystyrene, the same in this specification) of the resin (A1) having a cardo structure is preferably 1000 to 40000, To 30,000. Within the above range, sufficient heat resistance and film strength can be obtained while obtaining good developing properties.

(A2), which is obtained by polymerizing at least (a1) an unsaturated carboxylic acid, can also be preferably used as an alkali-soluble resin in view of easy formation of a low refractive index film excellent in mechanical strength and adhesion to a substrate.

Examples of the unsaturated carboxylic acid (a1) include monocarboxylic acids such as (meth) acrylic acid and crotonic acid; Dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid and itaconic acid; Anhydrides of these dicarboxylic acids; And the like. Of these, (meth) acrylic acid and maleic anhydride are preferable from the viewpoints of copolymerization reactivity, alkali solubility of the resin to be obtained, ease of obtaining water, and the like. These (a1) unsaturated carboxylic acids may 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. The alicyclic epoxy group-containing unsaturated compound (a2) 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 alicyclic group of the polycyclic ring 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 may be used alone or in combination of two or more.

Specifically, (a2) the alicyclic epoxy group-containing unsaturated compound includes, for example, compounds represented by the following formulas (a2-1) to (a2-15). Among them, the compounds represented by the following formulas (a2-1) to (a2-5) are preferable, and the compounds represented by the following formulas (a2-1) to (a2-3) Do.

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

Wherein R ^a20 represents a hydrogen atom or a methyl group, R ^a21 represents a bivalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, R ^a22 represents a bivalent hydrocarbon group having 1 to 10 carbon atoms, t represents Represents an integer from 0 to 10. As R ^a21 , 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 and a hexamethylene group is preferable. Examples of R ^a22 include methylene, ethylene, propylene, tetramethylene, ethylethylene, pentamethylene, hexamethylene, phenylene, cyclohexylene, -CH ₂ -Ph-CH ₂ - And Ph represents a phenylene group).

The copolymer (A2) may be one obtained by copolymerizing the unsaturated carboxylic acid (a1) and the alicyclic group-containing unsaturated compound (a3) having no epoxy group together with the alicyclic epoxy group-containing unsaturated compound (a2).

(a3) The alicyclic group-containing unsaturated compound is not particularly limited as long as it is an unsaturated compound having an alicyclic group. The alicyclic group may be monocyclic or polycyclic. Examples of the monocyclic alicyclic group include a cyclopentyl group and a cyclohexyl group. Examples of the alicyclic group of the heterocyclic ring include adamantyl group, norbornyl group, isobornyl group, tricyclodonyl group, tricyclodecyl group and tetracyclododecyl group. These (a3) alicyclic group-containing unsaturated compounds may be used alone or in combination of two or more.

Specifically, examples of (a3) unsaturated alicyclic group-containing compounds include compounds represented by the following formulas (a3-1) to (a3-7). Among them, the compounds represented by the following formulas (a3-3) to (a3-8) are preferable and the compounds represented by the following formulas (a3-3) and (a3-4) Do.

(7)

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

The copolymer (A2) may be a polymer of a monomer containing the unsaturated carboxylic acid (a1) and the unsaturated compound (a4) having no alicyclic group.

Such a copolymer (A2)

May be a copolymer of the (a1) unsaturated carboxylic acid and the (a4) epoxy group-containing unsaturated compound,

May be a copolymer of the unsaturated carboxylic acid (a1), the unsaturated compound containing the alicyclic epoxy group (a2) and the unsaturated compound containing the epoxy group (a4)

May be a copolymer of the unsaturated carboxylic acid (a1), the unsaturated compound containing an alicyclic group (a3) and the unsaturated compound containing an epoxy group (a4)

A copolymer of the unsaturated carboxylic acid (a1) and the unsaturated compound containing the alicyclic epoxy group (a2) and the unsaturated compound containing the alicyclic group (a3) and the epoxy group-containing unsaturated compound (a4) may be used.

(a4) Examples of the epoxy group-containing unsaturated compound include glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, 6,7-epoxyheptyl (Meth) acrylic acid epoxyalkyl esters such as (meth) acrylate; ? -alkylacrylic acid epoxyalkyl esters such as glycidyl? -ethyl acrylate, glycidyl? -n-propyl acrylate, glycidyl? -n-butyl acrylate, and 6,7-epoxyheptyl? -ethylacrylate; And the like. Of these, glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, and 6,7-epoxyheptyl (meth) acrylate are preferable from the viewpoints of copolymerization reactivity, desirable. These (a4) epoxy group-containing unsaturated compounds may be used alone or in combination of two or more.

The copolymer (A2) may be a copolymer of the above (a1) unsaturated carboxylic acid and a monomer other than the above.

The copolymer (A2) is a copolymer comprising the unsaturated carboxylic acid (a1), the unsaturated compound containing the alicyclic epoxy group (a2), the unsaturated compound containing the alicyclic group (a3), and the unsaturated compound containing the epoxy group , And a copolymer of a monomer containing a compound other than the above.

Examples of other compounds include (meth) acrylic acid alkyl esters, (meth) acrylic acid hydroxyalkyl esters, (meth) acrylates having an ether bond, the other (meth) acrylates, (meth) acrylamides, Diethers, ethers, vinyl esters, styrenes, dicarboxylic acid diesters, conjugated diolefins, ditolyl group-containing polymerizable compounds, and chlorine-containing polymerizable compounds. These compounds may be used alone or in combination of two or more.

Examples of the (meth) acrylic acid alkyl ester include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, Octyl (meth) acrylate, and other linear or branched alkyl (meth) acrylates.

Examples of the (meth) acrylic acid hydroxyalkyl ester include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-dimethylhydroxypropyl (meth) acrylate, trimethylolpropane mono Methacrylate, and the like.

Examples of the (meth) acrylate having an ether bond include 2-methoxyethyl (meth) acrylate, methoxy triethylene glycol (meth) acrylate, 3-methoxybutyl (meth) acrylate, Acrylate, methoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate and tetrahydrofurfuryl (meth) acrylate, and 2-methoxyethyl (meth) Methoxytriethylene glycol (meth) acrylate is preferred.

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

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

Examples of the allyl compound include allyl esters such as allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, and allyl lactate; Allyloxyethanol; And the like.

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

Examples of the vinyl esters include vinyl acetate, vinyl butyrate, vinyl isobutyrate, vinyl trimethylacetate, vinyl diethyl acetate, vinyl valerate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxyacetate, vinyl butoxyacetate , Vinyl phenylacetate, vinyl acetoacetate, vinyl lactate, vinyl -? - phenyl butyrate, vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate and vinyl naphthoate.

Examples of the styrenes include styrene; Examples of the monomer include methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, isopropylstyrene, butylstyrene, hexylstyrene, cyclohexylstyrene, decylstyrene, benzylstyrene, chloromethylstyrene, trifluoromethylstyrene, , And acetoxymethylstyrene; Alkoxystyrene such as methoxystyrene, 4-methoxy-3-methylstyrene, and dimethoxystyrene; But are not limited to, chlorostyrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene, 2-bromo- Styrene, and 4-fluoro-3-trifluoromethylstyrene; And the like.

Examples of 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.

With respect to the copolymer (A2), among the copolymer of the unsaturated carboxylic acid (a1) and the monomer other than the above-mentioned other compound, the unsaturated carboxylic acid (a1) and the (meth) acrylate ≪ / RTI > is preferred.

In this case, the proportion of the constituent unit derived from (meth) acrylate having an ether bond in the copolymer (A2) is preferably 30 to 90% by mass, 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 from 1 to 50% by mass, and more preferably from 5 to 45% by mass.

When the copolymer (A2) contains the constitutional unit derived from the unsaturated compound containing the alicyclic epoxy group (a2) and the constitutional unit derived from the unsaturated compound containing the epoxy group (a4), the ratio of a2 ) Alicyclic epoxy group-containing unsaturated compound and the proportion of the constituent unit derived from the (a4) epoxy group-containing unsaturated compound is preferably 71% by mass or more, more preferably 71 to 95% by mass , And more preferably from 75 to 90 mass%. In particular, the proportion of the constituent units derived from the unsaturated compound (a2) in the copolymer (A2) is preferably 71% by mass or more, more preferably 71% to 80% by mass. By setting the proportion of the structural unit derived from the unsaturated compound containing an alicyclic epoxy group (a2) within the above range, the temporal stability of the photosensitive resin composition can be further improved.

When the copolymer (A2) contains (a3) a constituent unit derived from an alicyclic group-containing unsaturated compound, the proportion of the constituent units derived from the (a3) alicyclic group-containing unsaturated compound in the copolymer (A2) 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 from 2,000 to 200,000, more preferably from 3,000 to 30,000. When the amount is in the above range, the film forming ability of the photosensitive resin composition and the balance of developability after exposure tends to be easy to catch.

Examples of the alkali-soluble resin include (A3) a copolymer having at least a constituent unit derived from the (a1) unsaturated carboxylic acid and a constituent unit having a polymerizable moiety between a photopolymerizable compound (B) Or (A4) a structural unit derived from the (a1) unsaturated carboxylic acid, (a2) the alicyclic epoxy group-containing unsaturated compound and / or the (a4) epoxy group-containing unsaturated compound, A resin containing a copolymer having at least a constituent unit having a polymerizable portion with the compound (B) is also preferably used. When the alkali-soluble resin contains the copolymer (A3) or the copolymer (A4), the adhesion of the film formed using the photosensitive resin composition to the substrate and the mechanical strength of the low refractive film obtained using the photosensitive resin composition are increased .

The copolymer (A3) and the copolymer (A4) can be obtained by copolymerizing (meth) acrylic acid esters, (meth) acrylamides, allyl compounds, vinyl ethers, vinyl esters , Styrene, and the like may be further copolymerized.

The constituent unit having a polymerizable moiety with the photopolymerizable compound (B) preferably has an ethylenic unsaturated group as a polymerizable moiety with the photopolymerizable compound (B). The copolymerization with such a constituent unit can be carried out in the same manner as the copolymer (A3) except that at least a part of the carboxyl groups contained in the polymer containing the constituent unit derived from the unsaturated carboxylic acid (a1) , Or an epoxy group-containing unsaturated compound and / or (a4) epoxy group-containing unsaturated compound. The copolymer (A4) is a copolymer having a constituent unit derived from the unsaturated carboxylic acid (a1) and a constituent unit derived from the (a2) alicyclic epoxy group-containing unsaturated compound and / or the (a4) epoxy group- Can be prepared by reacting at least part of the epoxy group in the copolymer with (a1) an unsaturated carboxylic acid.

The proportion of the constituent unit derived from the unsaturated carboxylic acid (a1) in the copolymer (A3) is preferably from 1 to 50% by mass, more preferably from 5 to 45% by mass. The proportion of the constituent unit having a polymerizable moiety to the photopolymerizable compound (B) in the copolymer (A3) accounts for preferably from 1 to 45% by mass, more preferably from 5 to 40% by mass. When the copolymer (A3) contains each constituent unit in such a ratio, it is easy to obtain a photosensitive resin composition capable of forming a low refractive index film excellent in adhesion to a substrate.

 The proportion of the constituent unit derived from the unsaturated carboxylic acid (a1) in the copolymer (A4) is preferably from 1 to 50% by mass, and more preferably from 5 to 45% by mass. The proportion of the constituent units derived from the (a2) alicyclic epoxy group-containing unsaturated compound and / or the epoxy group-containing unsaturated compound in the copolymer (A4) accounts for 55% by mass or more, preferably 71% , And particularly preferably from 71 to 80 mass%.

The proportion of the constituent unit having a polymerizable moiety with the photopolymerizable compound (B) in the copolymer (A4) accounts for preferably from 1 to 45% by mass, more preferably from 5 to 40% by mass. When the copolymer (A4) contains each constituent unit in such a ratio, it is easy to obtain a photosensitive resin composition capable of forming a low refractive index film excellent in adhesion to a substrate.

The mass average molecular weight of the copolymer (A3) and the copolymer (A4) is preferably from 2,000 to 50,000, and more preferably from 5,000 to 30,000. When the amount is in the above range, the film forming ability of the photosensitive resin composition and the balance of developability after exposure tends to be easy to catch.

The content of the resin (A) in the photosensitive resin composition is preferably 20 to 85% by mass, more preferably 30 to 70% by mass with respect to the mass of the photosensitive resin composition excluding the mass of the filler (D) described later and the mass of the organic solvent (S) More preferably in mass%.

≪ Photopolymerizable compound (B) >

As the photopolymerizable compound (B), a monomer having an ethylenic unsaturated group can be preferably used. The monomers having an ethylenic unsaturated group include monofunctional monomers and polyfunctional monomers.

Examples of the monofunctional monomer include (meth) acrylamide, methylol (meth) acrylamide, methoxymethyl (meth) acrylamide, ethoxymethyl (meth) acrylamide, propoxymethyl (Meth) acrylamide, N-hydroxymethyl (meth) acrylamide, (meth) acrylic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, (Meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isopropyl (meth) acrylate, (Meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-hydroxyethyl 2-phenoxy-2-hydroxypropyl (meth) (Meth) acrylate, dimethylaminoethyl (meth) acrylate, glycidyl (meth) acrylate, ethylhexyl acrylate, (Meth) acrylate of 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, phthalic acid derivative, etc. . These monofunctional monomers may be used alone or in combination of two or more.

Examples of the polyfunctional monomer include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (Meth) acrylate, trimethyleneol propane tri (meth) acrylate, ethylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, neopentyl glycol di (Meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, 2,2-bis (4- (meth) acryloxy diethoxyphenyl) propane, 2,2- (Meth) acryloyloxypropyl (meth) acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, 2-hydroxy- (Meth) acrylates such as diethylene glycol diglycidyl ether di (meth) acrylate, phthalic acid diglycidyl ester di (meth) acrylate, glycerin triacrylate, glycerin polyglycidyl ether poly Acrylate such as methylenebis (meth) acrylamide, (meth) acrylamidomethyleneether, (meth) acrylamide (that is, a reaction product of tolylene diisocyanate, trimethylhexamethylene diisocyanate or hexamethylene diisocyanate and 2-hydroxyethyl , Polyfunctional monomers such as a condensation product of a polyhydric alcohol and N-methylol (meth) acrylamide, and triacryl formal. These polyfunctional monomers may be used alone or in combination of two or more.

Among these monomers having an ethylenically unsaturated group, a multifunctional monomer having three or more functional groups is preferable, and a multifunctional monomer having four or more functional groups is preferable because the adhesion of the photosensitive resin composition to the substrate and the strength after curing of the photosensitive resin composition tend to be enhanced. More preferred is a polyfunctional monomer having five or more functionalities.

It is particularly preferable that the photopolymerizable compound (B) comprises 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, highly crosslinking proceeds on the surface of the low refractive index film at the time of curing by exposure, so that a hard and tight low refractive index film It is easy to form.

Therefore, even if the protective tape is peeled off from the low refractive index film, the surface of the low refractive index film is hardly roughened.

It is also preferable that the photopolymerizable compound (B) contains a photopolymerizable compound having less than six functionalities together with a multifunctional compound having six or more functions.

When the polyfunctional compound having 6 or more functional groups is used alone, the effect of oxygen inhibition is small, and the degree of curing of the film surface can be improved. However, in this case, curing progresses to the unexposed portion due to the chain reaction, so that residues tend to be generated slightly after the development, or jaggies tend to occur in the pattern edge shape, although this is allowable.

On the other hand, when a photopolymerizable compound having less than six functionalities is used together with a polyfunctional compound having six or more functional groups, a good curing of the film surface, a small amount of residue after development, and a smooth pattern edge shape can be easily balanced.

The content of the photopolymerizable compound (B) in the photosensitive resin composition is preferably from 1 to 70% by mass, more preferably from 5 to 70% by mass, based on the mass of the photosensitive resin composition excluding the mass of the filler (D) described below and the mass of the organic solvent (S) To 60% by mass is more preferable. In the above range, a balance of sensitivity, developability and resolution tends to be easily obtained.

≪ Photopolymerization initiator (C) >

The photopolymerization initiator (C) is not particularly limited, and conventionally known photopolymerization initiators can be used.

Specific examples of the photopolymerization initiator (C) include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2-hydroxyethoxy 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- 2-methylpropan-1-one, 2,2-dimethoxy-1,2-diphenylethan-1-one, bis (4-dimethylaminophenyl) Methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, 2-benzyl- Acetyl-1- [6- (2-methylbenzoyl) -9-ethyl-9H-carbazol-3-yl] ethanone oxime, O- 9H-carbazol-3-yl] ethanone oxime, (9-ethyl-6-nitro- -2-methylphenyl] methanone A mixture of O-acetyl oxime, 2- (benzoyloxyimino) -1- [4- (phenylthio) phenyl] -1-octanone, 2,4,6-trimethylbenzoyl di Dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, butyl 4-dimethylaminobenzoate, 4-dimethylamino-2 -Benzyl dimethyl ketal, 1-phenyl-1,2-propanedioyl-2- (O-ethoxycarbonyl) Oxime, methyl o-benzoylbenzoate, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 1-chloro-4- propanedioxanthone, 2-chlorothioxanthene, 2,4-diethylthioxanthene, 2-methylthioxanthene, 2-isopropylthioxanthene, 2-ethyl anthraquinone, octamethylanthraquinone, , 2,3-diphenylanthraquinone, azobisisobutyronitrile, benzoyl peroxide, cumene hydroperoxide, 2-mercaptobenzoimidazole, 2-mercaptobenzooxazole, 2- (M-methoxyphenyl) -imidazolyl dimer, benzophenone, 2-chlorobenzophenone, p, p'-bisdimethyl Aminobenzophenone, 4,4'-bisdiethylaminobenzophenone, 4,4'-dichlorobenzophenone, 3,3-dimethyl-4-methoxybenzophenone, benzyl, benzoin, benzoin methyl ether, Ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, benzoin butyl ether, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, Propylphenone, p-tert-butyltrichloroacetophenone, p-tert-butyldichloroacetophenone, .alpha., .Alpha.-butyrolactophenone, dichloroacetophenone, trichloroacetophenone, -Dichloro-4-phenoxyacetophenone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, dibenzosuberone, pentyl- (9-acridinyl) pentane, 1,3-bis- (9-acridinyl) heptane, 1,5-bis Tri (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2 (Trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) ethenyl] -4,6- 4,6-bis (trichloromethyl) -s-triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] (Trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) ethenyl] -4,6-bis Bis (trichloromethyl) -s-triazine, bis (trichloromethyl) -s-triazine, 2- (4-ethoxystyryl) (Trichloromethyl) -s-triazine, 2,4-bis-trichloromethyl-6- (3-bromo-4- methoxy) phenyl- - bis-trichloromethyl-6- (2-bromo 4-methoxy) phenyl-s-triazine, 2,4-bis-trichloromethyl-6- (3-bromo- -Trichloromethyl-6- (2-bromo-4-methoxy) styrylphenyl-s-triazine. These photopolymerization initiators may be used alone or in combination of two or more.

Among them, it is particularly preferable to use an oxime ester compound as the photopolymerization initiator (C) in terms of sensitivity. Examples of preferred oxime ester compounds are O-acetyl-1- [6- (2-methylbenzoyl) -9-ethyl-9H-carbazol- Yl) ethanone oxime, and 2- (benzoyloxyimino) -1- [4- (phenylthio) phenyl] -1 - octanone.

When the oxime ester compound is used as the photopolymerization initiator (C), it is also preferable to use an oxime ester compound in combination with a photopolymerization initiator other than the oxime ester compound.

When the oxime ester compound and another photopolymerization initiator are used in combination, it is easy to adjust the sensitivity of the photosensitive resin composition to an appropriate range. Therefore, it is difficult to form a patterned low-refractive-index film having a width wider than the desired width since it is difficult for excessive curing to proceed by exposure.

As another photopolymerization initiator to be used in combination with the oxime ester compound, a? -Aminoalkylphenone-based photopolymerization initiator is preferable. Preferable examples of the? -aminoalkylphenone based photopolymerization initiator include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one (IRGACURE 907 (Irgacure 369E (IR-369E), trade name, manufactured by BASF), 2-benzyl-2-dimethylamino-1- ).

It is also preferable to use an oxime ester compound represented by the following formula (c1) as the oxime ester compound.

[Chemical Formula 8]

(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 the formula (c1), R ^c1 is not particularly limited within a range that does not impair the object of the present invention, and is appropriately selected from various organic media. Preferable examples of R ^{c1 in the} case where R ^c1 is an organic group include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, a saturated aliphatic acyloxy group, an alkoxycarbonyl group, a phenyl group which may have a substituent, A benzoyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, a benzoyloxy group which may have a substituent, a phenylalkyl group which may have a substituent, a naphthyl group which may have a substituent, a naphthyl group which may have a substituent A naphthoyl group which may have a substituent, a naphthoxycarbonyl group which may have a substituent, a naphthoyloxy group which may have a substituent, a naphthylalkyl group which may have a substituent, a heterocyclyl group which may have a substituent, , An amino group substituted with an organic group of 1 or 2, a morpholin-1-yl group, and a piperazin-1-yl group, a halogen, a nitro group, And the like groups. When n1 is an integer of 2 to 4, ^Rc1 may be the same or different. The number of carbon atoms of the substituent does not include the number of carbon atoms of the substituent further having a substituent.

When R ^c1 is an alkyl group, the number of carbon atoms is preferably from 1 to 20, and more preferably from 1 to 6 carbon atoms. When R ^c1 is an alkyl group, it may be a linear chain or a branched chain. Concrete examples of the case where R ^c1 is an alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec- N-hexyl group, n-heptyl group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, n-nonyl group, isononyl group, n-decyl, and isodecyl. When R ^c1 is an alkyl group, the alkyl group may contain an ether bond (-O-) in the carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include a methoxyethyl group, an ethoxyethyl group, a methoxyethoxyethyl group, an ethoxyethoxyethyl group, a propyloxyethoxyethyl group, and a methoxypropyl group.

When R ^c1 is an alkoxy group, the number of carbon atoms is preferably from 1 to 20, and more preferably from 1 to 6 carbon atoms. When R ^c1 is an alkoxy group, it may be a linear chain or a branched chain. Specific examples of R ^{c1 in the} case where R ^c1 is an alkoxy group include methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, sec- An n-pentyloxy group, an isopentyloxy group, a sec-pentyloxy group, a tert-pentyloxy group, a n-hexyloxy 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 contain an ether bond (-O-) in the carbon chain. Examples of the alkoxy group having an ether bond in the carbon chain include a methoxyethoxy group, an ethoxyethoxy group, a methoxyethoxyethoxy group, an ethoxyethoxyethoxy group, a propoxyoxyethoxyethoxy group, and And a methoxypropyloxy group.

When R ^c1 is a cycloalkyl group or a cycloalkoxy group, the number of carbon atoms is preferably from 3 to 10, more preferably from 3 to 6. Specific examples of the case where R ^c1 is a cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Concrete examples of 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, the number of carbon atoms is preferably 2 to 20, and more preferably 2 to 7 carbon atoms. Specific examples of the case where R ^c1 is a saturated aliphatic acyl group include an acetyl group, a propanoyl group, an n-butanoyl group, a 2-methylpropanoyl group, an n-pentanoyl group, a 2,2-dimethylpropanoyl group, Heptanoyl, n-octanoyl, n-nonanoyl, n-decanoyl, n-undecanoyl, n-dodecanoyl, n-tridecanoyl, n-pentadecanoyl group, and n-hexadecanoyl group. Specific examples of the case where R ^c1 is a saturated aliphatic acyloxy group include an acetyloxy group, propanoyloxy group, n-butanoyloxy group, 2-methylpropanoyloxy group, n-pentanoyloxy group, N-hexanoyloxy, n-heptanoyloxy, n-octanoyloxy, n-nonanoyloxy, n-decanoyloxy, n-undecanoyloxy, n-dodecanoyloxy , n-tridecanoyloxy group, n-tetradecanoyloxy group, n-pentadecanoyloxy group, and n-hexadecanoyloxy group.

When R ^c1 is an alkoxycarbonyl group, the number of carbon atoms is preferably 2 to 20, and more preferably 2 to 7 carbon atoms. Specific examples of when R ^c1 is an alkoxycarbonyl group include methoxycarbonyl, ethoxycarbonyl, n-propyloxycarbonyl, isopropyloxycarbonyl, n-butyloxycarbonyl, isobutyloxycarbonyl, sec- An n-pentyloxycarbonyl group, an n-pentyloxycarbonyl group, an n-pentyloxycarbonyl group, an isopentyloxycarbonyl group, a sec-pentyloxycarbonyl group, a tert-pentyloxycarbonyl group, , a sec-octyloxycarbonyl group, a tert-octyloxycarbonyl group, an n-nonyloxycarbonyl group, an isononyloxycarbonyl group, a n-decyloxycarbonyl group, and an isodecyloxycarbonyl group.

When R ^c1 is a phenylalkyl group, the number of carbon atoms is preferably 7 to 20, more preferably 7 to 10 carbon atoms. When ^Rc1 is a naphthylalkyl group, the number of carbon atoms is preferably from 11 to 20, more preferably from 11 to 14 carbon atoms. Specific examples of 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? -Naphthylmethyl group, a? -Naphthylmethyl group, a 2- (? -Naphthyl) ethyl group and a 2- (? -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 the naphthyl group.

When R ^c1 is a heterocyclyl group, the heterocyclyl group may be a 5- or 6-membered monocyclic ring containing one or more N, S, O, or a heterocyclyl group condensed with such monocyclic ring and benzene ring . When the heterocyclyl group is a condensed ring, the number of rings is 3 or less. Examples of the heterocyclic ring constituting the heterocyclyl group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, Benzoimidazole, benzothiazole, benzothiazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, isoindoline, quinazoline, Phthalazine, cinnolin, 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 1 or 2 organic groups, preferred examples of the organic group include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a saturated An aliphatic acyl group, a phenyl group which may have a substituent, a benzoyl group which may have a substituent, a phenylalkyl group having 7 to 20 carbon atoms which may have a substituent, a naphthyl group which may have a substituent, , A naphthylalkyl group having from 11 to 20 carbon atoms which may have a substituent, and a heterocyclyl group. Specific examples of these preferred organic ^groups are the same as R ^c1 . Specific examples of the amino group substituted with 1 or 2 organic groups include a methylamino group, ethylamino group, diethylamino group, n-propylamino group, di-n-propylamino group, isopropylamino group, n- N-pentylamino group, n-pentylamino group, n-hexylamino group, n-heptylamino group, n-octylamino group, N-hexanoylamino group, n-heptanoylamino group, n-octanoylamino group, n-decanoylamino group, benzoylamino group,? -Naphthoylamino group and? -Naphthoylamino group And the like.

Examples of the substituents on the case, a phenyl group, a naphthyl group, and the heterocyclyl included in R ^c1 group having a substituent in addition, the carbon atom number of the alkyl group of 1 to 6, the number of alkoxy groups, the carbon atoms of the carbon atoms 1-6 2 A saturated aliphatic acyl group having 1 to 7 carbon atoms, an alkoxycarbonyl group having 2 to 7 carbon atoms, a saturated aliphatic acyloxy group having 2 to 7 carbon atoms, a monoalkylamino group having an alkyl group having 1 to 6 carbon atoms, A dialkylamino group having an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, a halogen atom, a nitro group and a cyano group. When the phenyl group, the naphthyl group, and the heterocyclyl group contained in R ^c1 further have a substituent, the number of the substituent is not limited to the range not hindering the object of the present invention, but is preferably 1 to 4. When the phenyl group, the naphthyl group, and the heterocyclyl group contained in R ^c1 have plural substituents, a plurality of substituents may be the same or different.

R ^c1 is chemically stable, has few steric hindrance, and is easy to synthesize an oxime ester compound. The alkyl group having 1 to 6 carbon atoms, the alkoxy group having 1 to 6 carbon atoms, and the carbon atom number 2 A saturated aliphatic acyl group of 1 to 7 carbon atoms, more preferably an alkyl of 1 to 6 carbon atoms, and particularly preferably a methyl group.

R ^c1 is a position, R ^c1 is the bonding position of the phenyl group and the oxime ester compound week combination the position of the hand in the first position, and a methyl group of a skeleton of for the phenyl group bonded to the phenyl group in the case of a two-position, the 4 Position, or 5 position is preferable, and 5 position 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 which may have a substituent, the nitrogen atom on the carbazolyl group may be substituted with an alkyl group having 1 to 6 carbon atoms.

In R ^c2 , the substituent of the phenyl group or the carbazolyl group is not particularly limited within the range not hindering the object of the present invention. Examples of preferable substituents which 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, a cycloalkyl group having 3 to 10 carbon atoms, A cycloalkoxy group having 3 to 10 carbon atoms, a saturated aliphatic acyl group having 2 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, a saturated aliphatic acyloxy group having 2 to 20 carbon atoms, A phenoxy group which may have a substituent, a phenylthio which may have a substituent, a benzoyl group which may have a substituent, a phenoxycarbonyl which may have a substituent, a benzoyloxy group which may have a substituent, A phenylalkyl group having 7 to 20 carbon atoms, 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 naphthoyloxy group which may have a substituent, a naphthylalkyl group having a carbon number of 11 to 20 which may have a substituent, a heterocyclyl group which may have a substituent, a heterocyclylcarbonyl group which may have a substituent, An amino group, an amino group substituted with an organic group of 1 or 2, a morpholin-1-yl group, and a piperazin-1-yl group, a halogen atom, a nitro group, and a cyano group.

When R ^c2 is a carbazolyl group, examples of the preferable substituent which the carbazolyl group may have on the nitrogen atom include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, An alkoxycarbonyl group having 2 to 20 carbon atoms, a phenyl group which may have a substituent, a benzoyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, a carbonyl group having 7 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 a carbon number of 11 to 20 which may have a substituent, A heterocyclyl group which may be substituted, and a heterocyclylcarbonyl group which may have a substituent. Among these substituents, an alkyl group having 1 to 20 carbon atoms is preferable, an alkyl group having 1 to 6 carbon atoms is more preferable, and an ethyl group is particularly preferable.

Specific examples of the substituent which 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, , A naphthylalkyl group which may have a substituent, a heterocyclyl group which may have a substituent, and an amino group substituted by 1 or 2 organic groups are the same as R ^c1 .

Examples of the substituent when the phenyl group, naphthyl group and heterocyclyl group contained in the substituent of the phenyl group or the carbazolyl group 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; Naphthyl group; Benzoyl group; A naphthoyl group; A benzoyl group substituted by a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, and a phenyl group; A monoalkylamino group having an alkyl group of 1 to 6 carbon atoms; A dialkylamino group having an alkyl group of 1 to 6 carbon atoms; Morpholin-1-yl group; Piperazin-1-yl group; Halogen; A nitro group; And cyano group. When the phenyl group, the naphthyl group, and the heterocyclyl group contained in the substituent of the phenyl group or the carbazolyl group further have a substituent, the number of the substituent is not limited to the range not hindering the object of the present invention, ~ 4 is preferred. When the phenyl group, the naphthyl group, and the heterocyclyl group have a plurality of substituents, the plurality of substituents may be the same or different.

R ^c2 is preferably a group represented by the following formula (c2) or (c3), more preferably a group represented by the following formula (c2) , A group in which A is S is particularly preferable.

[Chemical Formula 9]

(R ^c4 is a group selected from the group consisting of a monovalent organic group, an amino group, a halogen atom, a nitro group and a cyano group, A is S or O, and n 3 is an integer of 0 to 4)

[Chemical formula 10]

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

When R ^c4 in the formula (c2) is an organic group, it can be selected from a variety of organic groups within the range not hindering the object of the present invention. In the formula (c2), when R ^c4 is an organic group, preferred examples thereof 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; Naphthyl group; Benzoyl group; A naphthoyl group; A benzoyl group substituted by a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, and a phenyl group; A monoalkylamino group having an alkyl group of 1 to 6 carbon atoms; A dialkylamino group having an alkyl group of 1 to 6 carbon atoms; Morpholin-1-yl group; Piperazin-1-yl group; Halogen; A nitro group; And cyano group.

Among R ^c4 , a benzoyl group; A naphthoyl group; A benzoyl group substituted by a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, and a phenyl group; A nitro group is preferable, a benzoyl group; A naphthoyl group; A 2-methylphenylcarbonyl group; 4- (piperazin-1-yl) phenylcarbonyl group; And a 4- (phenyl) phenylcarbonyl group is more preferable.

In the 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, the binding position of R ^c4 is a phenyl group which is bonded R ^c4 is preferably a para position relative to the bonding hands binding to the oxygen atom or a sulfur atom.

R ^c5 in the formula (c3) can be selected from various organic groups within the range not hindering the object of the present invention. 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, an alkoxycarbonyl group having 2 to 20 carbon atoms, A phenyl group which may have a substituent, a benzoyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, a phenylalkyl group having 7 to 20 carbon atoms which may have a substituent, a naphthyl group which may have a substituent, A naphthoyl group, a naphthoxycarbonyl group which may have a substituent, a naphthylalkyl group having 11 to 20 carbon atoms which may have a substituent, a heterocyclyl group which may have a substituent, and a heterocyclylcarbonyl group which may have a substituent .

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.

The R ^c6 in the formula (c3) is not particularly limited within a range that does not impair the object of the present invention, and can be selected from various organic groups. Specific examples of the group represented by 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 heterocyclyl group which may have a substituent. As R ^c6 , among these groups, a phenyl group which may have a substituent is more preferable, and a 2-methylphenyl group is particularly preferable.

The substituent in the case where the phenyl group, the naphthyl group and the heterocyclyl group have further substituents included in R ^c4 , R ^c5 or R ^c6 includes an alkyl group having 1 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms An alkoxy group, 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 monoalkyl having 1 to 6 carbon atoms An amino 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 atom, a nitro group and a cyano group. When the phenyl group, the naphthyl group, and the heterocyclyl group contained in R ^c4 , R ^c5 , or R ^c6 further have a substituent, the number of the substituent is not limited to the extent that the object of the present invention is not impaired, 1 to 4 is preferable. When a phenyl group, a naphthyl group, and a heterocyclyl group contained in R ^c4 , R ^c5 , or R ^c6 have a plurality of substituents, a plurality of substituents may be the same or different.

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

The oxime ester compound represented by formula (c1) can be synthesized, for example, according to scheme 1 below when p is 0. 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) to obtain the following formula (C1-3) is oximated with hydroxylamine to obtain an oxime compound represented by the following formula (c1-4), and then the oxime compound of the formula (c1-4) is obtained , The oxime ester compound represented by the following formula (c1-7) can be obtained. As the acylating agent, an acid anhydride ((R ^c3 CO) ₂ O) represented by the following formula (c1-5) or an acid halide (R ^c3 COHal and Hal used as a halogen) represented by the following formula (c1-6) . In the following formula (c1-2), Hal is halogen and is represented by the following formulas (c1-1), (c1-2), (c1-3), (c1-4) , R ^c1 , R ^c2 , R ^c3 , and n1 are the same as in the formula (c1).

<Scheme 1>

(11)

The oxime ester compound represented by formula (c1) can be synthesized, for example, according to Scheme 2 below when n2 is 1. Specifically, a ketone compound represented by the following formula (c2-1) is reacted with a nitrite ester represented by the following formula (c2-2) (RONO, R is an alkyl group having 1 to 6 carbon atoms) in the presence of hydrochloric acid To obtain a ketooxime compound represented by the following formula (c2-3), followed by acylating the hydroxy group in the ketooxime compound represented by the following formula (c2-3) to obtain an oxime ester compound represented by the following formula Can be obtained. As the acylating agent, an acid anhydride ((R ^c3 CO) ₂ O) represented by the following formula (c2-4) or an acid halide (R ^c3 COHal and Hal used for a halogen) represented by the following formula (c2-5) . R ^c1 , R ^c2 , R ^c3 and n1 in the following formulas (c2-1), (c2-3), (c2-4), (c2-5) and (c2-6) Is the same as the formula (c1).

<Scheme 2>

[Chemical Formula 12]

The oxime ester compound represented by the formula (c1) is, n2 is 1, and R ^c1 is a methyl group and, for the methyl group bonded to the benzene ring which is bonded R ^c1 R ^c1 is a case, for example, combining the para position The compound represented by the following formula (c2-7) can also be synthesized by oximation and acylation in the same manner as scheme 1. In the following formula (c2-7), R ^c2 is the same as in formula (c1).

[Chemical Formula 13]

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

[Chemical Formula 14]

[Chemical Formula 15]

[Chemical Formula 16]

[Chemical Formula 17]

[Chemical Formula 18]

[Chemical Formula 19]

The oxime ester compound represented by the following formula (c4) is also preferable as the photopolymerization initiator.

[Chemical Formula 20]

(R ^c7 is a hydrogen atom, a nitro group or a monovalent organic group, R ^c8 and R ^c9 are each a chained alkyl group which may have a substituent, a cyclic organic group which may have a substituent, or a hydrogen atom, R ^c8 And R ^c9 may be bonded to each other to form a ring, R ^c10 is a monovalent organic group, R ^c11 is a hydrogen atom, an alkyl group having 1 to 11 carbon atoms which may have a substituent, N4 is an integer of 0 to 4, and n5 is 0 or 1.)

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

[Chemical Formula 21]

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

In the formulas (c4) and (c5), R ^c7 is a hydrogen atom, a nitro group or a monovalent organic group. R ^c7 on the fluorene ring of formula (c4) is bonded to a six-atom ring which is different from the six-atom ring which is bonded to the group represented by - (CO) _n5 -. In formula (c4), the bonding position of R ^{c7 to} the fluorene ring is not particularly limited. When the compound represented by the formula (c4) having one or more R ^c7, etc. formula (c4) that the synthesis is easy of a compound represented by, it is desirable to combine the 2-position of the fluorene ring have one of one or more of R ^c7 . When there are a plurality of R ^{c7 s} , a plurality of R ^{c7 s} may be the same or different.

When R ^c7 is an organic group, R ^c7 is not particularly limited as long as it does not impair the object of the present invention, and is appropriately selected from various organic groups. Preferable examples of R ^{c7 in the} case where R ^c7 is an organic group include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, a saturated aliphatic acyloxy group, an alkoxycarbonyl group, a phenyl group which may have a substituent, A benzoyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, a benzoyloxy group which may have a substituent, a phenylalkyl group which may have a substituent, a naphthyl group which may have a substituent, a naphthyl group which may have a substituent A naphthoyl group which may have a substituent, a naphthoxycarbonyl group which may have a substituent, a naphthoyloxy group which may have a substituent, a naphthylalkyl group which may have a substituent, a heterocyclyl group which may have a substituent, , An amino group substituted with an organic group of 1 or 2, a morpholin-1-yl group, and a piperazine Gin may be mentioned 1-yl group and the like.

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

When R ^c7 is an alkoxy group, the number of carbon atoms of the alkoxy group is preferably from 1 to 20, more preferably from 1 to 6. When R ^c7 is an alkoxy group, it may be a linear chain or a branched chain. Specific examples of the case where R ^c7 is an alkoxy group include methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, sec- An n-pentyloxy group, an isopentyloxy group, a sec-pentyloxy group, a tert-pentyloxy group, a n-hexyloxy 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 contain an ether bond (-O-) in the carbon chain. Examples of the alkoxy group having an ether bond in the carbon chain include a methoxyethoxy group, an ethoxyethoxy group, a methoxyethoxyethoxy group, an ethoxyethoxyethoxy group, a propoxyoxyethoxyethoxy group, and 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 from 3 to 10, more preferably from 3 to 6. Specific examples of the case where R ^c7 is a cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Concrete examples of the case where 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, more preferably 2 to 7. Specific examples of the case where R ^c7 is a saturated aliphatic acyl group include acetyl, propanoyl, n-butanoyl, 2-methylpropanoyl, n-pentanoyl, Heptanoyl, n-octanoyl, n-nonanoyl, n-decanoyl, n-undecanoyl, n-dodecanoyl, n-tridecanoyl, n-pentadecanoyl group, and n-hexadecanoyl group. Specific examples of the case where R ^c7 is a saturated aliphatic acyloxy group include an acetyloxy group, propanoyloxy group, n-butanoyloxy group, 2-methylpropanoyloxy group, n-pentanoyloxy group, 2,2- N-hexanoyloxy, n-heptanoyloxy, n-octanoyloxy, n-nonanoyloxy, n-decanoyloxy, n-undecanoyloxy, n-dodecanoyloxy , n-tridecanoyloxy group, n-tetradecanoyloxy group, n-pentadecanoyloxy group, and n-hexadecanoyloxy group.

When R ^c7 is an alkoxycarbonyl group, the number of carbon atoms of the alkoxycarbonyl group is preferably from 2 to 20, more preferably from 2 to 7. Specific examples of when R ^c7 is an alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, an n-propyloxycarbonyl group, an isopropyloxycarbonyl group, an n-butyloxycarbonyl group, an isobutyloxycarbonyl group, An n-pentyloxycarbonyl group, an n-pentyloxycarbonyl group, an n-pentyloxycarbonyl group, an isopentyloxycarbonyl group, a sec-pentyloxycarbonyl group, a tert-pentyloxycarbonyl group, , a sec-octyloxycarbonyl group, a tert-octyloxycarbonyl group, an n-nonyloxycarbonyl group, an isononyloxycarbonyl group, a 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, more preferably 7 to 10. When R ^c7 is a naphthylalkyl group, the number of carbon atoms of the naphthylalkyl group is preferably from 11 to 20, and more preferably from 11 to 14. Specific examples of the case where R ^c7 is a phenylalkyl group include a benzyl group, a 2-phenylethyl group, a 3-phenylpropyl group, and a 4-phenylbutyl group. Specific examples of the case where R ^c7 is a naphthylalkyl group include an? -Naphthylmethyl group,? -Naphthylmethyl group, 2- (? -Naphthyl) ethyl group and 2- (? -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 the naphthyl group.

When R ^c7 is a heterocyclyl group, the heterocyclyl group may be a 5- or 6-membered monocyclic ring containing 1 or more N, S, O, or a heterocyclyl group condensed with such a monocyclic ring and a benzene ring . When the heterocyclyl group is a condensed ring, the number of rings is 3 or less. The heterocyclyl group may be an aromatic group (heteroaryl group) or a nonaromatic group. Examples of the heterocyclic ring constituting the heterocyclyl group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, Benzoimidazole, benzothiazole, benzothiazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, isoindoline, quinazoline, Phthalazine, cinnoline, quinoxaline, piperidine, piperazine, morpholine, piperidine, tetrahydropyran, tetrahydrofuran and the like. 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 the case where R ^c7 is a heterocyclyl group.

When R ^c7 is an amino group substituted with 1 or 2 organic groups, preferred examples of the organic group include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a saturated aliphatic group having 2 to 21 carbon atoms An acyl group, a phenyl group which may have a substituent, a benzoyl group which may have a substituent, a phenylalkyl group having 7 to 20 carbon atoms which may have a substituent, a naphthyl group which may have a substituent, a naphthoyl group which may have a substituent, A naphthylalkyl group having 11 to 20 carbon atoms which may have a substituent, and a heterocyclyl group. Specific examples of these preferred organic ^groups are the same as R ^c7 . Specific examples of the amino group substituted with 1 or 2 organic groups include a methylamino group, ethylamino group, diethylamino group, n-propylamino group, di-n-propylamino group, isopropylamino group, n- N-pentylamino group, n-pentylamino group, n-hexylamino group, n-heptylamino group, n-octylamino group, N-hexanoylamino group, n-heptanoylamino group, n-octanoylamino group, n-decanoylamino group, benzoylamino group,? -Naphthoylamino group and? -Naphthoylamino group And the like.

^Examples of the substituent in the case where the phenyl group, the naphthyl group, and the heterocyclyl group have a substituent further include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkyl group having 2 to 2 carbon atoms A saturated aliphatic acyl group having 1 to 7 carbon atoms, an alkoxycarbonyl group having 2 to 7 carbon atoms, a saturated aliphatic acyloxy group having 2 to 7 carbon atoms, a monoalkylamino group having an alkyl group having 1 to 6 carbon atoms, A dialkylamino group having an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, a halogen atom, a nitro group and a cyano group. When the phenyl group, the naphthyl group, and the heterocyclyl group contained in R ^c7 further have a substituent, the number of the substituent is not limited to the range not hindering the object of the present invention, but is preferably 1 to 4. When the phenyl group, the naphthyl group, and the heterocyclyl group contained in R ^c7 have a plurality of substituents, the plurality of substituents may be the same or different.

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 it does not impair the object of the present invention, and can be selected from various organic devices. Examples of a preferable group as R ^c12 include an alkyl group having 1 to 20 carbon atoms, a phenyl group which may have a substituent, a naphthyl group which may have a substituent, and a heterocyclyl group which may have a substituent. As R ^c12 , among these groups, 2-methylphenyl group, thiophen-2-yl group and? -Naphthyl group are particularly preferable.

When R ^c7 is a hydrogen atom, transparency tends to be good, which is preferable. Furthermore, when R ^c7 is a hydrogen atom and R ^c10 is a group represented by the formula (c4a) or (c4b) described later, the transparency tends to be better.

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

When R ^c8 and R ^c9 are a chained alkyl group having no substituent, the number of carbon atoms of the chained alkyl group is preferably from 1 to 20, more preferably from 1 to 10, and particularly preferably from 1 to 6. Specific examples of R ^c8 and R ^c9 in the case of a chain alkyl group include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec- N-hexyl group, n-heptyl group, n-octyl group, iso-octyl group, sec-octyl group, tert-octyl group, n-nonyl group , An isononyl group, an n-decyl group, and an isodecyl group. 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 a chained alkyl group having a substituent, the number of carbon atoms of the chained alkyl group is preferably from 1 to 20, more preferably from 1 to 10, and particularly preferably from 1 to 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 chained alkyl group having a substituent is preferably a linear chain.

The substituent that the alkyl group may have is not particularly limited within the range not hindering the object of the present invention. Preferable examples of the substituent include a cyano group, a halogen atom, a cyclic organic group, and an alkoxycarbonyl group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Of 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 in the case where R ^c7 is a heterocyclyl group. When R ^c7 is an alkoxycarbonyl group, the alkoxy group contained in the alkoxycarbonyl group may be either linear or branched, and preferably is linear. The number of carbon atoms of the alkoxy group contained in the alkoxycarbonyl group is preferably 1 to 10, more preferably 1 to 6.

When the chained 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 of the chained alkyl group. The number of substituents is typically 1 to 20, preferably 1 to 10, and more preferably 1 to 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 the case where R ^c8 and R ^c9 are a chained alkyl group.

When R ^c8 and R ^c9 are aromatic hydrocarbon groups, the aromatic hydrocarbon group is preferably a phenyl group or a group formed by bonding a plurality of benzene rings via a carbon-carbon bond, or a group in which a plurality of benzene rings are formed by condensation . When the aromatic hydrocarbon group is a phenyl group or a group formed by bonding or condensing a plurality of benzene rings, the number of rings of the benzene ring included in the aromatic hydrocarbon group is not particularly limited and is preferably 3 or less, more preferably 2 or less, 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. The number of carbon atoms of the aliphatic cyclic hydrocarbon group is not particularly limited, but is preferably 3 to 20, more preferably 3 to 10. Examples of monocyclic cyclic hydrocarbon groups include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, norbornyl group, isobornyl group, tricyclononyl group, tricyclo A decyl group, a tetracyclododecyl group, and an adamantyl group.

When R ^c8 and R ^c9 are a heterocyclyl group, the heterocyclyl group may be a 5- or 6-membered monocyclic ring containing 1 or more N, S, O, or a heterocyclic ring containing such a monocyclic ring and a benzene ring-condensed hetero Cyclohexyl group. When the heterocyclyl group is a condensed ring, the number of rings is 3 or less. The heterocyclyl group may be an aromatic group (heteroaryl group) or a nonaromatic group. Examples of the heterocyclic ring constituting the heterocyclyl group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, Benzoimidazole, benzothiazole, benzothiazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, isoindoline, quinazoline, Phthalazine, cinnoline, quinoxaline, piperidine, piperazine, morpholine, piperidine, tetrahydropyran, tetrahydrofuran and the like.

R ^c8 and R ^c9 may be bonded to each other to form a ring. The cyclic group 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, 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 which may be condensed with a cycloalkylidene group include a benzene ring, a naphthalene ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a furan ring, a thiophene ring, A ring, a pyrazine ring, and a pyrimidine ring.

Among the groups R ^c8 and R ^c9 described above, preferred examples of the groups include groups represented by the formula -A ¹ -A ² . Wherein 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 of the straight chain alkylene group of A ¹ is preferably from 1 to 10, more preferably from 1 to 6. When A ² is an alkoxy group, the alkoxy group may be of a linear type, a branched type, or a linear type. The number of carbon atoms of the alkoxy group is preferably from 1 to 10, more preferably from 1 to 6. 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 and 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 cyclic organic groups are the same as the cyclic organic groups having R ^c8 and R ^c9 as substituents. When A ² is an alkoxycarbonyl group, examples of the alkoxycarbonyl group are the same as the alkoxycarbonyl group having R ^c8 and R ^c9 as a substituent.

Preferable examples of R ^c8 and R ^c9 include alkyl groups such as an ethyl group, an n-propyl group, an n-butyl group, an n-hexyl group, an n-heptyl group, and an n-octyl group; Methoxy-n-butyl group, 5-methoxy-n-pentyl group, 6-methoxy-n-hexyl group, 7-methoxy ethoxy-n-propyl group, 4-ethoxy-n-butyl group, 5-ethoxy-n-pentyl group, Ethoxy-n-hexyl group, 7-ethoxy-n-heptyl group, and 8-ethoxy-n-octyl group; N-propyl group, 4-cyano-n-butyl group, 5-cyano-n-pentyl group, 6-cyano- n-heptyl group, and 8-cyano-n-octyl group; Phenyl-n-pentyl group, 6-phenyl-n-hexyl group, 7-phenyl-n-heptyl group, And a phenylalkyl group such as an 8-phenyl-n-octyl group; Cyclohexyl-n-propyl group, 4-cyclohexyl-n-butyl group, 5-cyclohexyl-n-pentyl group, 6-cyclohexyl n-hexyl group, 7-cyclohexyl cyclopentyl-n-propyl group, 4-cyclopentyl-n-butyl group, 5-cyclopentyl-n-pentyl group, Cycloalkylalkyl groups such as a t-butyl group, a 6-cyclopentyl-n-hexyl group, a 7-cyclopentyl-n-heptyl group and an 8-cyclopentyl-n-octyl group; Methoxycarbonyl-n-propyl group, 4-methoxycarbonyl-n-butyl group, 5-methoxycarbonyl-n-pentyl group, 6-methoxycarbonyl n-hexyl group, 7-methoxycarbonyl-n-heptyl group, 8-methoxycarbonyl-n-octyl group, 2-ethoxycarbonylethyl group, 3-ethoxycarbonyl- Ethoxycarbonyl-n-butyl group, 5-ethoxycarbonyl-n-pentyl group, 6-ethoxycarbonyl-n-hexyl group, An alkoxycarbonylalkyl group such as an ethoxycarbonyl-n-octyl group; Chloro-n-pentyl group, 6-chloro-n-hexyl group, 7-chloro- n-heptyl group, Propyl group, 4-bromo-n-butyl group, 5-bromo-n-pentyl group, 6-bromo- hexyl group, 7-bromo-n-heptyl group, 8-bromo-n-octyl group, 3,3,3-trifluoropropyl group, and 3,3,4,4,5,5, And a 5-heptafluoro-n-pentyl group.

Preferred among R ^c8 and R ^c9 among the above groups are an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, a 2-methoxyethyl group, a 2-cyanoethyl group, a 2-phenylethyl group, a 2-cyclohexylethyl group , 2-methoxycarbonylethyl group, 2-chloroethyl group, 2-bromoethyl group, 3,3,3-trifluoropropyl group, and 3,3,4,4,5,5,5-heptafluoro n-pentyl group.

Examples of preferred organic groups of R ^c10 is, R ^c7, and similarly, an alkyl group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, an alkoxycarbonyl group, a saturated aliphatic acyloxy group, a phenyl group which may have a substituent, a substituent A phenoxy group which may have a substituent, a phenoxycarbonyl group which may have a substituent, a benzoyloxy group which may have a substituent, a phenylalkyl group which may have a substituent, a naphthyl group which may have a substituent, A naphthoyl group which may have a substituent, a naphthoyl group which may have a substituent, a naphthoylcarbonyl group which may have a substituent, a naphthoyloxy group which may have a substituent, a naphthylalkyl group which may have a substituent, A heterocyclylcarbonyl group which may have a substituent, an amino group substituted by an organic group of 1 or 2, morpholin-1-yl Group, a piperazin-1-yl group, and the like. Specific examples of these groups are the same as those described for R ^c7 . Also, R ^c10 is 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 phenoxyalkyl group and the substituent which the phenylthioalkyl group may have are the same as the substituent which the phenyl group contained in R ^c7 may have.

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

Also, R ^c10 is preferably a group represented by -A ³ -CO-OA ⁴ . A ³ is a divalent organic group, preferably a divalent hydrocarbon group, and is preferably an alkylene group. A ⁴ is a monovalent organic group and is preferably a monovalent hydrocarbon group.

When A &lt; ³ &gt; is an alkylene group, the alkylene group may be linear or branched, and preferably is linear. When A ³ is an alkylene group, the number of carbon atoms of the alkylene group is preferably from 1 to 10, more preferably from 1 to 6, and particularly preferably from 1 to 4.

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. Specific examples of A ⁴ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec- , A phenyl group, a naphthyl group, a benzyl group, a phenethyl group, an a-naphthylmethyl group, and a -naphthylmethyl group.

Specific examples of the group represented by -A ³ -CO-OA ⁴ include 2-methoxycarbonylethyl group, 2-ethoxycarbonylethyl group, 2-n-propyloxycarbonylethyl group, 2-n- N-hexyloxycarbonylethyl group, 2-benzyloxycarbonylethyl group, 2-phenoxycarbonylethyl group, 3-methoxycarbonyl-n-pentyloxycarbonylethyl group, Propyloxycarbonyl-n-propyl group, 3-n-butyloxycarbonyl-n-propyl group, 3-n-pentyloxycar N-propyl group, 3-n-hexyloxycarbonyl-n-propyl group, 3-benzyloxycarbonyl-n-propyl group and 3-phenoxycarbonyl- have.

Above has been described for the R ^c10, R ^c10, it is preferable group represented by the following formula (c4a) or (c4b).

[Chemical Formula 22]

(Formula (a c4a) and (c4b) of, R ^c13 and R ^c14 are each an organic group, n6 is the case for an integer of 0 ~ 4, R ^c13 and R ⁸ is present on the adjacent positions on the benzene ring, R ^c13 and R ^c14 is to form a ring by combining to each other, n7 is an integer of 1 ~ 8, n8 represents an integer of 1 ~ 5, n9 is an integer of 0 ~ (n8 + 3), R c15 is an organic group .)

Examples of organic ^groups for R ^c13 and R ^c14 in formula (c4a) are the same as R ^c7 . As R ^c13 , an alkyl group or a phenyl group is preferable. When R ^c13 is an alkyl group, the number of carbon atoms is preferably from 1 to 10, more preferably from 1 to 5, particularly preferably from 1 to 3, most preferably 1. In short, R ^c13 is most preferably a methyl group. When R ^c13 and R ^c14 are bonded 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 naphthalene-1-yl group, a 1,2,3,4-tetrahydronaphthalen-5- . In the formula (c4a), n6 is an integer of 0 to 4, preferably 0 or 1, and more preferably 0.

In the formula (c4b), R ^c15 is an organic group. As the organic group, there can be mentioned the same group as the organic group described for R ^c7 . Among the organic groups, an alkyl group is preferable. The alkyl group may be linear or branched. The number of carbon atoms in the alkyl group is preferably from 1 to 10, more preferably from 1 to 5, and particularly preferably from 1 to 3. 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 the formula (c4b), n8 is an integer of 1 to 5, preferably an integer of 1 to 3, more preferably 1 or 2. In the formula (c4b), n9 is 0 to (n8 + 3), preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and particularly preferably 0. In the formula (c4b), n7 is an integer of 1 to 8, preferably an integer of 1 to 5, more preferably an integer of 1 to 3, and particularly preferably 1 or 2.

In the formula (c4), R ^c11 is a hydrogen atom, an alkyl group having 1 to 11 carbon atoms which may have a substituent, or an aryl group which may have a substituent. As the substituent which may be taken when R ^c11 is an alkyl group, a phenyl group, a naphthyl group and the like are preferably exemplified. As the substituent which may be taken when R ^c7 is an aryl group, an alkyl group, an alkoxy group, a halogen atom and the like having 1 to 5 carbon atoms are preferably exemplified.

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

The compound represented by the formula (c4) includes a step of converting an oxime group (> C = N-OH) contained in the compound represented by the above formula (c5) into oxime ester groups represented by> ^C═NO -COR ^c11 . &Lt; / RTI &gt; R ^c11 is the same as R ^c11 in the formula (c4).

Conversion of the oxime group (> C = N-OH) to an oxime ester group represented by> ^C═NO -COR ^c11 is carried out by reacting the compound represented by the above formula (c5) with an acylating agent.

Acylating agents giving an acyl group represented by -COR ^c11 include an acid anhydride represented by (R ^c11 CO) ₂ O and an acid halide represented by R ^c11 COHal (Hal is a halogen atom).

When n5 is 0, the compound represented by the general formula (c4) can be synthesized, for example, according to the following Scheme 3. 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, a fluorene derivative represented by the formula (c3-1) is obtained by reacting a 9-position fluorene derivative substituted with R ^c8 and R ^c9 with a substituent R ^c7 . In the case where R ^c8 and R ^c9 are alkyl groups, for example, the fluorene derivative substituted at the 9-position with R ^c8 and R ^c9 , in the presence of an alkali metal hydroxide, as described in JP-A-06-234668, Can be obtained by reacting fluorene with an alkylating agent in an aprotic polar organic solvent. An alkylation reaction such as an alkyl halide, an aqueous solution of an alkali metal hydroxide and an interphase transfer catalyst such as tetrabutylammonium iodide or potassium tert-butoxide are added to an organic solvent solution of fluorene to obtain an alkylene halide of formula 9-alkyl substituted fluorene can be obtained.

The fluorene derivative represented by the formula (c3-1) is obtained by introducing an acyl group represented by -CO-R ^c10 into a fluorene derivative represented by the formula (c3-1) by a Friedel-Crafts acylation reaction. 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 the 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 appropriately changing the conditions of the Friedel-Crafts reaction or by protecting or deprotecting the position of the acylation site.

Subsequently, a group represented by -CO-R ^c10 in the resulting fluorene derivative represented by the formula (c3-3) is converted into a group represented by -C (= N-OH) -R ^c10 to obtain oxime Compound. The method of converting a group represented by -CO-R ^c10 into a group represented by -C (= N-OH) -R ^c10 is not particularly limited, but oxime formation with hydroxylamine is preferable. An oxime compound of the formula (c3-4), an acid anhydride (R ^c11 CO) ₂ O represented by the following formula (c3-5), or an acid halide represented by the formula (c3-6) (R ^c11 COHal, Hal Is a halogen atom) to obtain a compound represented by the following formula (c3-7).

Further, in the formula (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 in the formula (c4).

In Scheme 3, R ^c10 contained in each of the formulas (c3-2), (c3-3) and (c3-4) may be the same or different. In short, R ^c10 in the formula (c3-2), the formula (c3-3) and the formula (c3-4) may be chemically modified in the synthesis process represented by the scheme 3. Examples of chemical formulas include esterification, etherification, acylation, amidation, halogenation, and substitution of hydrogen atoms in an amino group by an organic group. The chemical formulas that R &lt; ^c10 &gt; may receive are not limited to these.

<Scheme 3>

(23)

When n5 is 1, the compound represented by formula (c4) can be synthesized, for example, according to scheme 4 below. 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) can be produced by reacting the compound represented by the formula (c3-1) with an acyl group represented by -CO-CH ₂ -R ^c10 by the Friedel-Crafts reaction . As the acylating agent, a carboxylic acid halide represented by the formula (c3-8): Hal-CO-CH ₂ -R ^c10 is preferable. Next, the methylene group present between R ^c10 and the carbonyl group in the compound represented by the formula (c4-1) is oxidized to obtain a ketooxime compound represented by the following formula (c4-3). The method of oxymering the methylene group is not particularly limited, but a method of reacting a nitrite ester represented by the following general formula (c4-2) (RONO, R is an alkyl group having 1 to 6 carbon atoms) in the presence of hydrochloric acid is preferable . Subsequently, a ketooxime 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 an acid halide represented by the formula (c4-5) ^c11 COHal, Hal is a halogen atom) to obtain a compound represented by the following formula (c4-6). In the formulas (c4-1), (c4-3), (c4-4), (c4-5) and (c4-6) shown below, R ^c7 , R ^c8 , R ^c9 , R ^c10 and R ^c11 is the same as that of the formula (c4).

When n5 is 1, generation of foreign matter in a pattern formed by using the photosensitive resin composition containing the compound represented by the formula (c4) tends to be further reduced.

In addition, it may be in the scheme 4, the formula (c3-8), formula (c4-1), and the formula (c4-3) R ^c10 included in each of which may be identical or different. In short, R ^c10 in the formula (c3-8), the formula (c4-1) and the formula (c4-3) may be chemically modified in the synthesis process represented by the scheme 4. Examples of chemical formulas include esterification, etherification, acylation, amidation, halogenation, and substitution of hydrogen atoms in an amino group by an organic group. The chemical formulas that R &lt; ^c10 &gt; may receive are not limited to these.

<Scheme 4>

&Lt; EMI ID =

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

(25)

(26)

The content of the photopolymerization initiator (C) is preferably from 0.5 to 30 mass%, more preferably from 1 to 20 mass%, based on the mass of the photosensitive resin composition excluding the mass of the organic solvent (S) described below. When the content of the photopolymerization initiator (C) is within the above range, a photosensitive resin composition having good curability and hardly causing defects in the pattern shape can be obtained.

When the oxime ester compound and the photopolymerization initiator other than the oxime ester compound are used in combination as the photopolymerization initiator (C), the ratio of the mass of the oxime ester compound to the mass of the photopolymerization initiator (C) is preferably 50 mass% or less , More preferably 1 mass% or more and 50 mass% or less, particularly preferably 3 mass% or more and 30 mass% or less, and most preferably 5 mass% or more and 20 mass% or less.

When an oxime ester compound in an amount within this range is contained in the photopolymerization initiator (C), it is difficult to form a patterned low refractive index film having a width wider than a desired width.

A photoinitiator may be combined with the photo-polymerization initiator (C). Examples of the photoinitiator include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate , Benzoic acid 2-dimethylaminoethyl, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone, 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9 Diethoxyanthracene, 2-mercapto benzothiazole, 2-mercaptobenzooxazole, 2-mercaptobenzoimidazole, 2-mercapto-5- And thiol compounds such as methoxybenzothiazole, 3-mercaptopropionic acid, methyl 3-mercaptopropionate, pentaerythritol tetramercaptoacetate, and 3-mercaptopropionate. These photoinitiator aids may be used alone or in combination of two or more.

<Filler (D)>

The photosensitive resin composition includes a filler (D) to form a low refractive index film exhibiting a refractive index as low as desired. The filler (D) is appropriately selected from the fillers conventionally blended with the photosensitive resin composition used for forming the low refractive index film, so long as the object of the present invention is not impaired. As such a filler (D), hollow particles or porous particles are preferable.

As the filler (D), one kind of particles may be used, or two or more kinds of particles may be used in combination. As the filler (D), hollow particles and porous particles may be used in combination.

Hollow particles refer to particles having cavities enclosed by an outer shell. The porous particle refers to a porous particle having a plurality of voids therein.

The porosity of the hollow particles or the porous particles is preferably 10 to 80%, more preferably 20 to 60%, and most preferably 30 to 50% in view of good durability of the filler (D) and easy formation of a low refractive index with a low refractive index. To 60% is particularly preferable.

In the hollow particles and the porous particles, hollow particles are more preferable because they can easily lower the refractive index of the low refractive index film.

For example, the refractive index of the hollow silica particles is significantly lower than the refractive index of ordinary silica of 1.46. This is because the hollow silica particles contain air inside which exhibits a low refractive index of 1.0.

The average particle diameter of the filler (D) is not particularly limited within the range not hindering the object of the present invention. The average particle diameter of the filler (D) is preferably 1 to 200 nm, more preferably 10 to 100 nm.

The average particle diameter of the filler (D) is obtained from an image obtained by observing the dispersed filler particles with a transmission electron microscope. More specifically, the following steps 1) to 3)

1) Calculate the projected area for each of a plurality of filler particles.

2) Calculate the circle equivalent diameter of each filler particle from the obtained projected area.

3) Calculate the number average value of the circle equivalent diameters of a plurality of filler particles, and determine the average particle size of the filler (D).

Further, the measurement of the average particle diameter is typically performed on at least 300 filler particles.

The specific surface area of the filler (D) is preferably 10 to 2000 m 2 / g, more preferably 20 to 1800 m 2 / g, and particularly preferably 50 to 1500 m 2 / g.

When the filler (D) is a hollow particle or a porous particle, the refractive index thereof is preferably from 1.10 to 1.40, more preferably from 1.15 to 1.35, and particularly preferably from 1.15 to 1.30. Here, the refractive index is the refractive index of the whole particle, and when the particle is a hollow particle, it does not represent the refractive index of only the outer angle forming the hollow particle. When the particles are porous particles, the refractive index of the porous particles can be measured using an Abbe's refractive index meter (manufactured by Atago).

The material of the hollow particles or the porous particles is preferably an inorganic material in view of lowering the refractive index of the low refractive index film. Examples of such an inorganic material include particles of magnesium fluoride and silica. The inorganic material may be a crystalline material or an amorphous material.

Hollow silica particles or porous silica particles are preferable as the hollow particles or porous particles made of an inorganic material because they are easy to form a low refractive index film having a low refractive index and are easy to be stably dispersed in the photosensitive resin composition .

The average primary particle size of the inorganic hollow particles or inorganic porous particles is preferably 1 to 100 nm, more preferably 1 to 60 nm.

The hollow inorganic particles or the porous silica particles may be monodisperse particles or may contain aggregates of aggregated primary particles.

In the case where the filler (D) is an inorganic particle, it is possible to improve dispersion stability of the filler (D) in the photosensitive resin composition or to improve dispersion stability of the filler (D) The surface of the inorganic particles may be subjected to a physical surface treatment such as a plasma discharge treatment or a corona discharge treatment or a chemical surface treatment with a surfactant or a coupling agent.

Among these surface treatments, chemical surface treatment using a coupling agent is preferred.

As the coupling agent, a titanium coupling agent, a silane coupling agent and the like are preferable, and a silane coupling agent is more preferable.

For example, when the silica particles are treated with a silane coupling agent, the organosilyl group binds to the surface of the silica particles by the reaction between the silane coupling agent and the silanol group on the surface of the silica particles.

Examples of the organic group introduced by the treatment with the silane coupling agent include a hydrocarbon group of 1 to 18 carbon atoms which may have an unsaturated bond and a halogenated hydrocarbon group of 1 to 18 carbon atoms which may have an unsaturated bond .

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. The filler (D) may be surface-treated by adding a coupling agent to the photosensitive resin composition.

The filler (D) such as an inorganic particle is preferably dispersed in the medium in advance before preparing the photosensitive resin composition in order to prevent aggregation and to facilitate dispersion in the photosensitive composition.

When silica particles are used as the filler (D), commercially available silica particles can be preferably used.

Specific examples of the commercially available silica particles include, for example, Surulia series (isopropanol (IPA) dispersion, 4-methyl-2-pentanone (MIBK) dispersion and the like) manufactured by Nikki Catalysts Co., Ltd.; OSCAL series manufactured by Nikki Catalysts Co., Ltd.; (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 , An ethyl acetate dispersion, a butyl acetate dispersion, a xylene-n-butanol dispersion, a toluene dispersion, etc.); Syriacus manufactured by Nittsu Mining Co., Ltd.; PL series (IPA dispersion, toluene dispersion, propylene glycol monomethyl ether dispersion, methyl ethyl ketone dispersion, etc.) manufactured by Fuso Kagaku Kogyo Co., Ltd.; Aerosil series (propylene glycol acetate dispersion, ethylene glycol dispersion, MIBK dispersion, etc.) manufactured by EVONIK; .

As described above, the filler (D) is preferably blended in the photosensitive resin composition as a dispersion liquid dispersed in the medium.

When the silica particles are incorporated in the photosensitive resin composition as a dispersion, the content of the silica particles in the dispersion is preferably 10 to 50% by mass, more preferably 15 to 40% by mass, and particularly preferably 15 to 30% by mass.

When the filler (D) is dispersed in the medium or in the photosensitive resin composition, a dispersant may be used.

Specific examples of the dispersing agent include polyamide amines, salts of polyamide amines, polycarboxylic acids, polycarboxylates, high molecular weight unsaturated acid esters, modified polyurethanes, modified polyesters, modified poly (meth) acrylates, Methacrylic copolymer, and naphthalenesulfonic acid formalin condensate.

In addition, compounds such as polyoxyethylene alkyl phosphate ester, polyoxyethylene alkylamine, alkanolamine and the like can be used as a dispersant.

Among the above dispersants, a dispersion resin is preferable. The dispersion resin can be classified into a linear polymer, a terminal modified polymer, a graft polymer, and a block polymer from the structure.

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, graft polymer, and block polymer having an anchor site to the surface of the filler particle are preferable structures.

The mass average molecular weight (polystyrene conversion value measured by the GPC method) of the dispersion resin is preferably from 1,000 to 200,000, more preferably from 2,000 to 100,000, and particularly preferably from 5,000 to 50,000.

The dispersion resin is available as a commercial product.

As specific examples of the commercially available dispersion resin,

Disperbyk-101 (polyamide amine phosphate), Disperbyk-107 (carboxylic acid ester), Disperbyk-110 (copolymer containing an acid group), Disperbyk-111 (polyamide), Disperbyk-130 Disperbyk-163 (Polymer Copolymer), Disperbyk-163 (Polymer Copolymer), Disperbyk-163 (Polymer Copolymer), Disperbyk-163 (Polymer Copolymer) -166 (Polymer Copolymer), Disperbyk-170 (Polymer Copolymer), BYK-P104 (High Molecular Weight Unsaturated Polycarboxylic Acid), BYK-P105 (High Molecular Weight Unsaturated Polycarboxylic Acid);

EFKA4050 (polyurethane), EFKA4050 to 4010 to 4165 (polyurethane), EFKA4330 to 4340 (block copolymer), EFKA4400 to 4402 (modified polyacrylate), EFKA5010 (polyester amide), EFKA5765 Molecular weight polycarboxylate), EFKA6220 (fatty acid polyester), EFKA6745 (phthalocyanine derivative), EFKA6750 (azo pigment derivative);

Ajisper PB821, Ajisper PB822 manufactured by Ajinomoto Fine Techno Co., Ltd.;

Flowen TG-710 (urethane oligomer), Polyflow No.50E (acrylic copolymer), Polyflow No.300 (acrylic copolymer) manufactured by Kyowa Chemical Industry Co., Ltd.;

Disperon KS-860 (polymeric polyester amine salt), Disperon KS-873SN (polymeric polyester amine salt), Disperon KS-874 (polymeric polyester amine salt), Disperon 2150 (manufactured by Kusumoto Chemical Co., (Polyetherester), Dysperon DA-703-50, Dysperon DA-705, Dysperon DA-725;

(Aromatic sulfonic acid formalin polycondensate), Demol C (aromatic sulfonic acid formalin polycondensate), Demol SN-B (polycondensation product of aromatic sulfonic acid and formaldehyde), decolin N (naphthalenesulfonic acid formalin polycondensate) Emeralgen 920 (polyoxyethylene nonylphenyl ether), EMULGEN 930 (polyoxyethylene nonylphenyl ether), EMULGEN 935 (polyoxyethylene nonylphenyl ether), and the like. Ethylenonylphenyl ether), EMULGEN 985 (polyoxyethylene nonylphenyl ether), acetamine 86 (stearylamine acetate);

Sol Spurs 3000 (terminal modified polymer), Sol Spurs 17000 (terminal modified polymer), and Solpfer 3000 (terminal modified polymer) manufactured by Lubrizol Corporation, Sol Spurs 5000 (phthalocyanine derivative), Solspus 22000 (azo pigment derivative) Sol Spurs 27000 (terminal modified polymer), Sol Spurs 24000 (graft polymer), Sol Spurs 28000 (graft polymer), Sol Spurs 32000 (graft polymer), Sol Spurs 38500 (graft polymer);

NIKOL T106 (polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene monostearate), manufactured by Nikko Chemical Co., Ltd.;

46, EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450, manufactured by Morishita Industrial Co.,

Disperse AID 6, Disperse Aid 8, Disperse Aid 15, Disperse Aid 9100, manufactured by Sanopkos;

.

As the dispersing agent, nonionic, anionic, cationic surfactants can be used. These surfactants are commercially available.

As specific examples of commercially available surfactants,

EFKA-745 manufactured by EFKA;

Organosiloxane polymer KP341 manufactured by Shin-Etsu Chemical Co., Ltd.;

Polymer Polyflow No. 75 manufactured by Kyowa Chemical Industry Co., Ltd., Polymer Polyflow No. 90, Polymer Polyflow No. 95;

W001, W004, W005, W017, manufactured by Yusoh Corp.;

Sol Spurs 3000, Sol Spurs 5000, Sol Spurs 9000, Sol Spurs 12000, Sol Spurs 13240, Sol Spurs 13940, Sol Spurs 17000, Sol Spurs 24000, Sol Spurs 26000, and Sol Spurs 28000 manufactured by Nippon Lubrizol Corporation;

Adekafluronic L64, adecafluronic L38, adecafluronic L42, adecafluronic L64, adecafluronic L64, adecafluronic L64, adecafluronic L42, Nick F68, Adeka fluroonic L72, Adeka fluroonic P95, Adeka fluroonic F77, Adeka fluroonic P84, Adeka fluroonic F87, Adeka fluroonic P94, Adeka fluroonic L101, adecafluronic P103, adecafluronic F108, adecafluronic L121, adecafluronic P-123;

Isonet S-20 manufactured by Sanyo Chemical Industries, Ltd.;

Hinoact T-8000E manufactured by Kawaken Fine Chemicals Co., Ltd.;

ELEBASE BA-200, ELEBASE BCP-2, ELEBASE BUB-3, ELEBASE BUB-4, ELEBASE CP-800K, ELEBASE EDP-475, ELEBASE HEB-5 manufactured by Aoki Kasei Kogyo Co., 204, BLAUNON DSP-12.5, BLAUNON DT-03, BLAUNON L-205, BLAUNON LPE-1007, BLAUNON O-205, BLAUNON S- Uonon S-207, Blaonon S-205T;

Emulsion A-500, Emergen PP-290, Amide 102, Amide 105, Amide 302, Amide 320, Amison PK-02S, Emanon CH-25, Emergene 104P, 108, Emergen 404, Emergen 408, Emergen A-60, Emergen A-90, Emergen B-66, Emergen LS-106, Emergen LS-114, Leodol 430V, Leodol 440V, Leodol 460V, Leodol TW-S106, Leodol TW-S120V, Leodol Super TW-L120, Phospanol ML-200, Emal 20T, Emal E-27, Neopellex GS, Pelex NBL, Pelex SS- Pelex SS-L, POIS 532A, LAMELEL ASK, LAMEL E-118B, LAMEL E-150;

Newarken FS-3PG, Newcargen FE-7 PG, Pionin D-6414, Pionin A-24-EA, Pionin A-28-B, Pionin A -29-M, Pionin A-44-B, Pionin A-44TW;

Dynol 604, Olin PD-002W, Surfinol 2502, Surfinol 440, Surfinol 465, Surfinol 485, Surfinol 61 manufactured by Nissin Chemical Industry Co., Ltd.;

EMULSOGEN COL-020 manufactured by Clariant, EMULSOGEN 070, EMULSOGEN 080,

Flysurf A208B, Flysurf A210B, Flysurf A210G, Flysurf A219B, Flysurf AL, Lavelle FC-45 manufactured by Daiichi Kogyo Seiyaku Co., Ltd.;

AKYPO ECT-3, AKYPO ECT-7, Hosten HLP, Hosten HLP-1, Hosten HLP-TEA, AKYPO RLM45,

.

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 based on the mass of the filler. When the dispersing agent is a dispersing resin, the amount of the dispersing agent to be used is preferably 5 to 100% by mass, 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) to be used in the photosensitive resin composition is not particularly limited within the range not hindering the object of the present invention. The content of the filler (D) in the photosensitive resin composition is preferably 80% by mass or less, more preferably 20 to 80% by mass, based on the mass of the photosensitive resin composition excluding the mass of the organic solvent (S) And particularly preferably from 30 to 70% by mass.

<Fluorine-Containing Surfactant (E)>

The photosensitive resin composition essentially contains a fluorine-containing surfactant (E). The content of the fluorine-containing surfactant (E) in the photosensitive resin composition is preferably such that the sum of the mass of the resin (A) in the photosensitive resin composition, the mass of the photopolymerizable compound (B), and the mass of the filler 0.05 to 3% by mass.

Since the photosensitive resin composition contains the fluorine-containing surfactant (E) in an amount within this range, the photosensitive resin composition can be uniformly coated on the substrate, and even when exposed at a low exposure dose, And a low refractive index film which is less prone to surface roughening can be formed 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 any of anionic surfactants, cationic surfactants and nonionic surfactants may be used.

The fluorine-containing surfactant (E) may be used in combination of two or more.

Specific examples of the fluorine-containing surfactant include BM-1000, BM-1100 (all manufactured by BM Chemical), Megafac F142D, Megafac F172, Megafac F173, Megafac F183 (all manufactured by Dainippon Ink and Chemicals, Inc.) (All from Sumitomo 3M), Surfron S-112, Surfron S-113, Surfron S-131, Surfle FC-430, Fluorad FC-430 and Fluorad FC- (Available from Asahi Glass Co., Ltd.), SH-28PA, SH-190, SH-193, SZ-6032 and SF-8428 Surfactants, and the like, but are not limited thereto.

As the fluorine-containing surfactant, a compound having a fluoroalkyl group in the 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 the formulas (e-1) and (e-2), x1 is an integer of 0 to 7.

In the formula (e-3), x2 is an integer of 0 to 8.

In the formula (e-4), x3 is an integer of 6 to 20.

(27)

(28)

[Chemical Formula 29]

The content of the fluorine-containing surfactant (E) is 0.05 to 3% by mass based on the sum of the mass of the resin (A) in the photosensitive composition, the mass of the photopolymerizable compound (B) and the mass of the filler (D) Is preferably 0.05 to 2% by mass, more preferably 0.10 to 1.5% by mass, most preferably 0.15 to 1% by mass.

&Lt; Polymerization inhibitor (F) &gt;

The photosensitive resin composition preferably contains a polymerization inhibitor (F), if 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 the polymerization inhibitor (F) is not particularly limited, and a compound conventionally used as a polymerization inhibitor for inhibiting polymerization of a compound having 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. Although the reason is unclear, the photosensitive resin composition contains a hindered phenol compound having a molecular weight within the above-mentioned predetermined range as the polymerization inhibitor (F), so that at a wide exposure dose, It is easy to form the pattern into a desired dimension.

If the molecular weight of the polymerization inhibitor (F) is too low, residues tend to form at the time of pattern formation. If the molecular weight of the polymerization inhibitor (F) is excessive, the polymerization inhibitor (F) is localized in the photosensitive resin composition, so that it may be difficult to obtain the desired effect by using the polymerization inhibitor (F).

Hindered phenols are those having at least one hydrogen atom and a bulky substituent other than a methyl group at two ortho positions of the phenolic hydroxyl group. Examples of bulky substituents include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a substituted amino group, a thioalkyl group and a thiophenyl group other than the methyl group.

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 the hindered phenol compound 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- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (1177.6), N, N'-hexane- (3,5-di-tert-butyl-4-hydroxyphenyl) propionamide] (637.0), 1,3,5-tris (3,5- (1H, 3H, 5H) -triene (784.1), 4,4 ', 4 "- (1-methylpropanyl- (6-tert-butyl-m-cresol (544.8), 6,6'-di-tert-butyl-4,4'-butyrylidene-m-cresol (382.6), octadecyl 3 - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate (530.9) Methylphenyl) propionyloxy] -1,1-dimethylethyl} -2,4,8,10-tetraoxaspiro [5.5] undecane (741.0), 1,3,5-tris -Butyl-4-hydro (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,2'-thiodiethylbis [3- (642.9), isooctyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate (390.6), calcium bis [3,5- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionic acid] [ethylene bis (oxyethylene)] (586.8), 1,6 (6-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).

Values in parentheses immediately after each compound name are the molecular weights of the respective compounds.

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 compounds such as hydroquinone, methylhydroquinone, 2,5-di-t-butylhydroquinone, and t-butylhydroquinone; benzoquinone compounds such as p-benzoquinone, methyl-p-benzoquinone, t-butylbenzoquinone, and 2,5-diphenyl-p-benzoquinone; Benzotriazole-based compounds such as 2- (2-hydroxy-5-methylphenyl) benzotriazole; Nitrosopamine-based compounds such as N-nitrosophenylhydroxylamine and N-nitrosophenylhydroxylamine aluminum salt; Organic sulfur compounds such as phenothiazine, dithiobenzoyl sulfide and dibenzyltetrasulfide; Bis (1,1-dimethylethyl) -4-hydroxyphenyl} methyl] butyl malonate, and the like. A dodamine compound; aromatic amines such as p-phenylenediamine and N, N-diphenyl-p-phenylenediamine; Phosphorous compounds such as tris (2,4-di-t-butylphenyl) phosphite and tetrakis (2,4-di-tert- butylphenyl) [1,1-biphenyl] -4,4'- And the like.

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 phenolic compound having a molecular weight of 230 to 1500 in the polymerization inhibitor (F) is not particularly limited within the range not hindering the object of the present invention. 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, Most preferably 100% by mass.

The content of the polymerization inhibitor (F) in the photosensitive resin composition is not particularly limited within the range not hindering the object of the present invention. The content of the polymerization inhibitor (F) is preferably 0.001 to 1% by mass, more preferably 0.01 to 1% by mass relative to the mass of the photosensitive resin composition excluding the mass of the filler (D) and the mass of the organic solvent (S) Is more preferable. By setting the content of the polymerization inhibitor (F) within the above range, it is easy to suppress the dimension of the patterned low refractive index film from becoming larger than a desired dimension while keeping the curing property of the photosensitive resin composition in a good range.

&Lt; Organic solvent (S) &gt;

The photosensitive resin composition preferably contains an organic solvent (S) in order to improve the coating property and adjust 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- -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- Propylene glycol mono-n-butyl ether, dipropylene glycol mono-n-butyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether , Tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether and the like (poly) alkylene glycol monoalkyl Ketoethers; (Propylene glycol monomethyl ether acetate), ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate (PGMEA) Alkylene glycol monoalkyl ether acetates; Other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether and tetrahydrofuran; Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone and 3-heptanone; Lactic acid alkyl esters such as methyl 2-hydroxypropionate and ethyl 2-hydroxypropionate; Ethoxyacetonate, ethyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate, n-propyl acetate, isopropyl acetate, Propyl acetate, isopropyl acetate, n-butyl acetate, i-butyl acetate, n-pentyl formate, i-pentyl acetate, benzyl acetate, n-butyl propionate, ethyl butyrate, , Other esters such as methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, and ethyl 2-oxobutanoate; Aromatic hydrocarbons such as toluene and xylene; N, N-dimethylacetamide, N, N-dimethylisobutylamide, N, N-diethylacetamide, N, N-diethyl Nitrogen-containing polar organic solvents such as formamide, N-methylcaprolactam, 1,3-dimethyl-2-imidazolidinone, pyridine, and N, N, N ', N'-tetramethylurea; And the like.

Of these, preferred are the alkane monools, the alkylene glycol monoalkyl ethers, the alkylene glycol monoalkyl ether acetates, the other ethers described above, the lactic acid alkyl esters and the other esters described above, and the alkylene glycol mono The above-described other esters such as alkyl ether acetates, the above-mentioned other ethers, and benzyl acetate are more preferable.

It is also preferable that the organic solvent (S) contains a nitrogen-containing polar organic solvent in view of the solubility of each component. As the nitrogen-containing polar organic solvent, N, N, N ', N'-tetramethylurea and the like can be used.

These solvents may be used alone or in combination of two or more.

The content of the organic solvent (S) is not particularly limited and is appropriately set in accordance with the coating film thickness at a concentration applicable to a substrate or the like. 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. The solid content concentration of the photosensitive resin composition is preferably 1 to 50% by mass, more preferably 1 to 20% by mass.

<Other ingredients>

Additives such as surfactants, photoacid generators, adhesion improvers, thermal polymerization inhibitors, antifoaming agents, coloring agents and silane coupling agents other than the above-mentioned fluorine-containing surfactants may be contained in the photosensitive resin composition, if necessary. Any additive may be any conventionally known one.

When the coating film of the photosensitive resin composition is exposed and cured, the surface of the low refractive index film is inhibited from being cured by oxygen, so that the surface of the low refractive index film has a slightly lower degree of curing. Therefore, when the protective tape is attached to the surface of the low refractive index film having a slightly lower surface hardening degree, the surface of the low refractive index film tends to be roughened when the protective tape is peeled off.

However, when the photosensitive resin composition contains a resin having a functional group capable of crosslinking by the action of an acid such as an epoxy group, if the photosensitive resin composition contains an acid generator, the acid generated by the exposure causes the crosslinkable group Crosslinking also proceeds on the surface of the low refractive index film, so that the surface of the low refractive index film is sufficiently cured.

Therefore, even if the protective tape is peeled off 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 in that it has a good shape and is easy to form a low refractive index film excellent in adhesion to a substrate. As the silane coupling agent, conventionally known ones can be used without particular limitation.

Examples of the surfactant include compounds such as anionic, cationic and nonionic systems. Examples of the thermal polymerization inhibitor include hydroquinone, hydroquinone monoethyl ether and the like. Examples of the defoaming agent include silicone compounds, fluorine compounds And the like.

&Lt; Preparation method of photosensitive resin composition &gt;

The above-described photosensitive resin composition is obtained by mixing each of the above-mentioned respective components in a predetermined amount and then uniformly mixing them with an agitator. It may also be filtered using a filter so that the resulting mixture becomes more uniform.

&Lt; Method of producing low refractive index film &

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

As a preferable production method of the low refractive index film,

Forming a coating film of the above-mentioned photosensitive resin composition,

A method of selectively exposing the coating film to a predetermined pattern,

And developing the exposed coating film.

In order to form a low refractive index film using the photosensitive resin composition, a photosensitive resin composition is first applied on a substrate selected according to the use of the low refractive index film to form a coating film.

As the substrate, in the case of forming an image sensor, for example, a substrate having a coloring film of RGB on a semiconductor layer such as silicon and having a microlens on the coloring film is used.

The method of forming the coating film is not particularly limited, and is carried out using a non-contact type coating device such as a contact transfer type coating device such as a roll coater, a reverse coater, a bar coater, a spinner (rotary coating device), or a curtain flow coater.

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

Subsequently, exposure to the coating film is performed. The exposure is carried out by irradiating active energy rays such as ultraviolet rays and excimer laser rays. The exposure is performed in a positional manner, for example, by a method of performing exposure through a negative type mask.

After the coated film is subjected to positional selective exposure, the exposed film is developed with a developer to dissolve the unexposed portion in the developing solution, and a patterned cured film is formed. The developing method is not particularly limited, and for example, a dipping method, a spraying method, or the like can be used. The developer is appropriately selected according to the composition of the photosensitive resin composition. As the developer, a basic aqueous solution such as sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia or quaternary ammonium salt can be used.

Then, the patterned cured film may be baked (post-baked). The baking temperature is not particularly limited, but is preferably 180 to 250 占 폚, more preferably 220 to 230 占 폚. 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 is obtained.

The cured film thus formed can be preferably 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 캜) of the low refractive index film is preferably 1.35 or less, more preferably 1.23 to 1.34, and particularly preferably 1.25 to 1.33.

It is preferable that the contact angle of the surface of the low refractive index film with respect to water is larger than 60 degrees. In this case, the protective tape can be adhered to and peeled off from the surface of the low-refractive-index film, in particular, without roughening the surface of the low-refractive-index film.

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, for example. In the image sensor, when the low-refractive-index film is used as a coating layer covering a microlens formed on a coloring film of R, G, and B, reflection of light incident on the microlens becomes good, thereby suppressing flare in the image sensor.

In the optical device, a protective tape is preferably adhered to the surface of the low refractive index film. A protective tape is provided on the surface of the low refractive index film. In the optical device having the protective tape, the semiconductor layer located on the surface opposite to the surface of the protective tape is subjected to grinding.

Since the optical device has the low refractive index film formed by using the photosensitive resin composition described above, the surface smoothness of the low refractive index film is maintained even if the protective tape is peeled off after the grinding process.

Example

 Hereinafter, the present invention will be described in more detail with reference to examples, but the scope of the present invention is not limited to these examples.

[Examples 1 to 11 and Comparative Examples 1 to 3]

(A) having the type and amount described in Table 1, a photopolymerizable compound (B) of the kind and amount shown in Table 1, a photopolymerization initiator (C) of the kind and amount described in Table 1, The amount of the following filler (D), the fluorine-containing surfactant (E) in the amount shown in Table 1 and the polymerization inhibitor (F) in the amount shown in Table 1 were mixed with the organic solvent (S) Thereby obtaining photosensitive resin compositions of Examples and Comparative Examples.

In Examples 1 to 3, Examples 5 and 11, and Comparative Example 1, 92.7 mass% of propylene glycol monomethyl ether, 3.3 mass% of 3-methoxybutyl acetate, and 3 mass% of 3- A mixed solvent consisting of 3.3% by mass methoxy-n-butanol and 0.7% by mass methanol was used to prepare a photosensitive resin composition having a solid content concentration of 13.5% by mass.

In Example 4, 6 to 10, Comparative Examples 2 and 3, 96.3% by mass of propylene glycol monomethyl ether, 3.0% by mass of propylene glycol monomethyl ether acetate, and 0.7% by mass of methanol % By mass was used to prepare a photosensitive resin composition such that the solid concentration was 10.90% by mass.

In Example 4, Examples 6 to 10, Comparative Example 2 and Comparative Example 3, 1 part by mass of 3-glycidoxypropyltrimethoxysilane as an adhesion enhancer was further added at the time of preparing the photosensitive resin composition.

In the examples and comparative examples, the following resins A1 and A2 were used as the resin (component (A)).

A1:

(30)

A2:

(31)

As the photopolymerizable compound (component (B)), the following B1 and B2 were used.

B1: Ethylene oxide-modified trimethylolpropane triacrylate (3 moles of ethylene oxide)

B2: dipentaerythritol hexaacrylate

As the photopolymerization initiator (component (C)), the following C1 and C2 were used.

C1: 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-

C2: 2- (Benzoyloxyimino) -1- [4- (phenylthio) phenyl] -1-octanone

C3: 1-Hydroxy-cyclohexyl-phenyl-ketone

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

As the surfactant (component (E)), the following fluorine-based surfactants were used.

(32)

As the polymerization inhibitor (component (F)), the following F1 was used.

F1: pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (molecular weight: 1177.6)

Using the photosensitive resin compositions of the respective Examples and Comparative Examples thus obtained, a low refractive index film was prepared by the following method. The refractive indices of the obtained low refractive index films were measured. As a result, the refractive index values of the cured films formed using the photosensitive resin compositions of Examples and Comparative Examples were within the range of 1.32 to 1.40.

(Measurement of refractive index)

The photosensitive resin composition was coated on a silicon wafer using a spin coater so that the coating film thickness became 800 nm. The formed coating film was heated by a hot plate at 90 DEG C for 2 minutes, and then exposed selectively at 500 mJ / cm2 in an i-line stepper.

The coated film after exposure was developed with a tetramethylammonium hydroxide aqueous solution having a concentration of 0.2 mass% for 1 minute. The patterned film obtained by development was heated by a hot plate at 220 캜 for 5 minutes to obtain a low refractive index film. The refractive index of the obtained low refractive index film was measured using a refractive index measuring apparatus (spectroscopic ellipsometer) VUV-VASE VU-302 manufactured by J. A. Woollam.

Using the photosensitive resin compositions of each of the examples and comparative examples, the resolution, the remaining film ratio, the amount of exposure not generating residue, the amount of exposure capable of peeling off the protective tape, and the coating uniformity were evaluated according to the following method. The evaluation results are shown in Table 2.

(50 占 퐉 resolution evaluation)

When the pattern was formed in the same manner as in the measurement of the refractive index, and the line pattern having a line width of 50 mu m was able to be resolved, the symbol was marked as &amp; cir &amp;

(Residual film ratio evaluation)

The pattern was formed in the same manner as in the measurement of the refractive index, and the film thickness after development when the film thickness after pre-baking was 100% was regarded as the film residual ratio.

(Evaluation of exposure dose with no residue)

A pattern was formed in the same manner as in the measurement of the refractive index except that the exposure amount was varied, and the maximum exposure amount capable of developing the pattern without generating the residue was determined.

For example, in the case of Example 1, when exposed at 175 mJ / cm 2 or more, residues are generated but when exposed at 175 mJ / cm 2 or less, no residue is produced.

(Protective tape peelable exposure amount)

A pattern was formed in the same manner as in the measurement of the refractive index except that the amount of exposure was changed. When a protective tape was attached to the cured film after curing, the minimum exposure dose at which no film adhered to the tape was obtained.

(Uniformity of application)

The photosensitive resin compositions of the examples and comparative examples were spin-coated on a Si substrate to form a coating film. The coating film thus formed was uniformly coated with naked eye and microscopic observation without observing radial streaks or color unevenness.

Further, regarding the photosensitive resin composition of Comparative Example 1, since the coating film formed was remarkably non-uniform, no detailed evaluation was performed other than the coating uniformity.

In the photosensitive resin compositions of Comparative Example 2 and Comparative Example 3, no detailed evaluation of the protective tape peelable exposure amount was performed because the formed coating film had streaks or irregularities.

As can be seen from Table 2, the amount of the fluorine-containing surfactant (F (meth) acrylate) of 0.05 to 3% by mass relative to the sum of the mass of the resin (A), the mass of the photopolymerizable compound ) Can be coated well on a substrate and a cured film which is less likely to be roughened even when the protective tape is applied and peeled can be formed even with exposure at a low exposure amount .

In the embodiment, exposure is performed at an exposure amount between the lower limit value of the protective tape peelable exposure amount and the upper limit value of the remaining amount of non-generated exposure, in which the upper limit value of the residual exposure unexposed exposure amount is larger than the lower limit value of the protective tape peelable exposure amount It is possible to form a cured film which is less likely to be roughened even when the protection tape is attached and peeled while suppressing the occurrence of residues during development.

On the other hand, in the case of a comparative example which does not contain the fluorine-containing surfactant (F) in an amount of 0.05 to 3% by mass based on the sum of the mass of the resin (A), the mass of the photopolymerizable compound (B) and the mass of the filler It can be seen that the photosensitive resin composition is difficult to uniformly coat on the substrate before the problem of whether or not a cured film which is hard to be roughened even by attaching and peeling the protective tape can be formed.

In Comparative Example 1, the upper limit value of the residue-unexposed exposure amount and the lower limit value of the protective tape peelable exposure amount were compared. However, the upper limit value of the residual unexposed exposure amount was smaller than the lower limit value of the protective tape peelable exposure amount. In short, in the photosensitive resin composition of Comparative Example 1, there is no range of the exposure dose capable of satisfactorily suppressing the generation of residues and forming a cured film which is less likely to be roughened even by attaching and peeling the protective tape.

Claims (11)

A photocurable composition containing a resin (A), a photopolymerizable compound (B), a photopolymerization initiator (C), a filler (D), and a fluorine-containing surfactant (E)
Wherein the content of the fluorine-containing surfactant (E) is 0.05 to 3% by mass relative to the sum 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. The method according to claim 1,
And a polymerization inhibitor (F). The method according to claim 1,
The photosensitive resin composition for forming a low refractive index film, wherein the photopolymerization initiator (C) comprises an oxime ester compound. The method according to claim 1,
The photosensitive resin composition for forming a low refractive index film, wherein the photopolymerizable compound (B) comprises a compound having 6 or more polymerizable functional groups. 5. The method of claim 4,
The photosensitive resin composition for forming a low refractive index film, wherein the photopolymerizable compound (B) further comprises a compound having a polymerizable functional group of less than 6. A low refractive index film formed by curing the photosensitive resin composition for forming a low refractive index film according to any one of claims 1 to 5. The method according to claim 6,
And has a surface roughness Ra of 30 nm or less. The method according to claim 6,
A low refractive index film having a contact angle to water greater than 60 degrees. 7. An optical device comprising the low-refractive-index film according to claim 6. 10. The method of claim 9,
And a protective tape on the low refractive index film. A method of 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 in a position-selective manner according to a predetermined pattern,
And developing the exposed coating film to form a patterned low-refractive-index film.