KR20210116281A - Photosensitive composition, transparent body and method of manufacturing transparent body - Google Patents

Abstract

An objective of the present invention is to provide a photosensitive composition, a transparent body formed of the photosensitive composition, and a method of manufacturing the transparent body, capable of forming a patterned cured product having excellent adhesion to a substrate and having a tapered cross section having an appropriate taper angle. The photosensitive composition includes: an alkali-soluble resin (A); a photopolymerizable monomer (B); a photopolymerization initiator (C); and a solvent (S), wherein the photopolymerization initiator (C) includes: a fluorene-based oxime ester compound (C1); a fluorene-based oxime ester compound (C2); and at least one compound (C3) selected from a phosphine oxide-based compound and an amino ketone-based compound, the fluorene-based oxime ester compound (C1) has a nitro group, and the fluorene-based oxime ester compound (C2) does not have a nitro group.

Description

A photosensitive composition, a transparent body, and the manufacturing method of a transparent body {PHOTOSENSITIVE COMPOSITION, TRANSPARENT BODY AND METHOD OF MANUFACTURING TRANSPARENT body}

The present invention relates to a photosensitive composition, a transparent body comprising the photosensitive composition, and a method for producing the transparent body.

In a display device such as a liquid crystal display device, it is necessary for a material such as an insulating film or a spacer to efficiently transmit light generated from a light source such as a backlight. For this reason, in order to form patterned transparent objects, such as an insulating film and a spacer, the photosensitive composition which provides a transparent hardened|cured material (transparent object) by exposure is used. By selectively exposing such a photosensitive composition to light, a transparent patterned cured product can be formed.

As a photosensitive composition which can form a transparent hardened|cured material (transparent body), the composition containing resin, a polymeric compound, the polymerization initiator of a specific structure, and a solvent is proposed, for example (patent document 1). Specifically, in the Example of Patent Document 1, a copolymer of methacrylic acid and an acrylate having an alicyclic epoxy group, dipentaerythritol hexaacrylate, a polymerization initiator represented by any one of the following formulas, and 3-methoxy A photosensitive composition comprising a mixed solvent consisting of -1-butanol, propylene glycol monomethyl ether acetate, ethyl 3-ethoxypropionate, and 3-methoxy butyl acetate is disclosed.

Japanese Patent Laid-Open No. 2012-58728

When a cured product patterned on a line is formed as a transparent cured product, as shown in Fig. 1(a), the cross section 1, which is a cross section in the width direction of the pattern, is more positive than the width of the base 1a. In some cases, it is preferable that the (頂邊) 1b has a slightly narrow trapezoidal shape (that is, a tapered shape having an appropriate taper angle). At this time, the angle θ formed between the cross section 1 of the pattern and the substrate (not shown) on which the pattern is provided is 70° or more and 85° or less.

However, when a conventional photosensitive composition as described in Patent Document 1 is used, as shown in FIG. Undercuts 21 may be formed at both ends of the bottom 2a in the end face 2 . In addition, when the width of the positive side 1b is larger than the width of the bottom side 1a and a narrow trapezoidal shape is obtained, or the width of the positive side 1b is slightly narrower than the width of the bottom side 1a, but the trapezoidal shape is hardly changed sometimes it becomes Incidentally, when the undercut 21 is formed, the angle θ between the end face 2 of the pattern and the substrate (not shown) becomes an obtuse angle. In addition, when the width of the positive side 1b is larger than the width of the bottom side 1a and a narrow trapezoidal shape is formed, the angle θ becomes a small angle. In addition, when the width of the positive side 1b is slightly narrower than the width of the base side 1a, but almost unchanged, the trapezoidal shape makes the angle θ close to 90°.

In any of these cases, a pattern having a trapezoidal cross section in which the width of the front side 1b is slightly narrower than the width of the bottom side 1a is not formed.

When an undercut occurs in the pattern, for example, when a display device using such a pattern as an insulating film or a spacer is produced, the image quality of the display device deteriorates due to air bubbles remaining in the undercut portion.

In addition, if the width of the positive side 1b is larger than the width of the base 1a and narrow trapezoidal shape, or the width of the positive side 1b is slightly narrower than the width of the bottom side 1a, but almost unchanged, the insulating film However, there is a fear that the function as a spacer may be impaired.

For this reason, it is preferable that the cross section can form the tapered pattern which has an appropriate taper angle.

Moreover, when manufacturing a display device, after forming transparent hardened|cured material, such as an insulating film and a spacer, on a board|substrate, it may heat. In this case, it becomes a problem that transparent hardened|cured material, such as an insulating film and a spacer, peels easily from a board|substrate by heating.

For this reason, it is preferable that hardened|cured material excellent in the adhesiveness to a board|substrate can be formed.

The present invention has been made in view of the above problems, and is excellent in adhesion to a substrate and capable of forming a patterned cured product having a tapered cross section having an appropriate taper angle, and a transparent body comprising the photosensitive composition And it aims to provide the manufacturing method of the said transparent body.

MEANS TO SOLVE THE PROBLEM As a result of repeating research earnestly in order to achieve the said objective, the present inventors contain alkali-soluble resin (A), a photopolymerizable monomer (B), a photoinitiator (C), and a solvent (S), A photoinitiator (C) discovered that the said subject was solvable with the photosensitive composition containing the compound of a specific structure, and came to complete this invention. Specifically, the present invention provides the following.

A 1st aspect of this invention contains alkali-soluble resin (A), a photopolymerizable monomer (B), a photoinitiator (C), and a solvent (S),

The photopolymerization initiator (C) is at least one compound (C3) selected from a fluorene-based oxime ester compound (C1), a fluorene-based oxime ester compound (C2), a phosphine oxide-based compound, and an amino ketone-based compound ) containing,

The fluorene-based oxime ester compound (C1) has a nitro group,

It is a photosensitive composition in which the said fluorene type oxime ester compound (C2) does not have a nitro group.

A 2nd aspect of this invention is a transparent body which consists of hardened|cured material of the photosensitive composition which concerns on 1st aspect.

A third aspect of the present invention comprises the steps of applying the photosensitive composition according to the first aspect to form a coating film;

It is a manufacturing method of a transparent body including the process of exposing the said coating film.

A fourth aspect of the present invention comprises the steps of applying the photosensitive composition according to the first aspect to form a coating film;

a step of positionally selectively exposing the coating film;

It is a manufacturing method of the patterned transparent body including the process of developing the said coating film after exposure.

ADVANTAGE OF THE INVENTION According to this invention, the photosensitive composition which is excellent in adhesiveness to a board|substrate, and can form the patterned hardened|cured material which has a tapered cross section with an appropriate taper angle, the transparent body which consists of the said photosensitive composition, and the manufacturing method of the said transparent body can provide

(FIG. 1) It is a schematic diagram which shows the cross-sectional shape of the width direction of the pattern formed using the photosensitive composition.

«Photosensitive composition»

The photosensitive composition of this invention contains alkali-soluble resin (A), a photopolymerizable monomer (B), a photoinitiator (C), and a solvent (S). The photoinitiator (C) is at least one compound (C3) selected from a fluorene-based oxime ester compound (C1), a fluorene-based oxime ester compound (C2), a phosphine oxide-based compound, and an aminoketone-based compound The fluorene-based oxime ester compound (C1) has a nitro group, and the fluorene-based oxime ester compound (C2) does not have a nitro group.

A photosensitive composition is an alkali-soluble resin (A), a photopolymerizable monomer (B), and a solvent (S), The fluorene-type oxime ester compound (C1) which has a nitro group, and a fluorene-type oxime ester compound which does not have a nitro group ( By containing C2) and a phosphine oxide-based compound or an aminoketone-based compound, a cured product having excellent adhesion to a substrate can be formed as shown in Examples to be described later, and a tapered shape having an appropriate taper angle A patterned cured product having a cross-section of can be formed. That the cross section has an appropriate tapered shape indicates that the angle θ between the cross section of the patterned cured product and the substrate on which the patterned cured product is provided is 70° or more and 85° or less.

Since hardened|cured material is excellent in adhesiveness to a board|substrate, even if it heats, it is hard to peel from a board|substrate.

Moreover, defects which arise when it is not a taper shape which has an appropriate taper angle can be suppressed. For example, it can suppress that the image quality of the display apparatus using the hardened|cured material of the photosensitive composition as an insulating film or a spacer falls by the bubble which arises in an undercut location.

Moreover, the hardened|cured material of the said photosensitive composition can be used suitably as a transparent body. In the transparent body, the transmittance at one or more wavelengths in the visible light region (380 to 750 nm) is preferably 90% or more, more preferably 95% or more, and still more preferably 98% or more.

Moreover, the said photosensitive composition can suppress generation|occurrence|production of the foreign material in hardened|cured material.

The said photosensitive composition gives hardened|cured material with a low optical density (OD value). For example, the OD value per 1 micrometer in thickness of the hardened|cured material of the said photosensitive composition is 0.05 or less, Preferably it is 0.01 or less.

The said photosensitive composition gives the patterned hardened|cured material excellent in straightness.

The said photosensitive composition can suppress peeling of the patterned hardened|cured material at the time of image development.

Hereinafter, the essential component and optional component which the photosensitive composition contains, and the preparation method of the photosensitive composition are demonstrated in order.

<Alkali-soluble resin (A)>

The photosensitive composition contains alkali-soluble resin (A) (henceforth (A) component.). By mix|blending alkali-soluble resin (A) with the photosensitive composition, alkali developability can be provided to the photosensitive composition.

In the present specification, alkali-soluble resin refers to a resin film having a film thickness of 1 µm formed on a substrate with a resin solution (solvent: propylene glycol monomethyl ether acetate) having a resin concentration of 20% by mass, and added to a KOH aqueous solution having a concentration of 0.05% by mass. When immersed for 1 minute, it means to melt|dissolve 0.01 micrometer or more of film thickness.

As alkali-soluble resin (A), alkali-soluble resin represented by a following formula (a-1) is mentioned.

In formula (a-1), X ^a is the following formula (a-2):

represents a group represented by . t1 represents an integer of 0 or more and 20 or less.

In formula (a-2), R ^a1 each independently represents a hydrogen atom, a hydrocarbon group having 1 or more and 7 or less carbon atoms, or a halogen atom. R ^a2 each independently represents a hydrogen atom or a methyl group. R ^a3 each independently represents a linear or branched alkylene group. t2 represents 0 or 1 each independently.

W ^a is the following formula (a-3):

represents a group represented by .

Ring A in Formula (a-3) represents the aliphatic ring which may be condensed with an aromatic ring, or may have a substituent.

R ^a0 represents a hydrogen atom or a group represented by ^{-CO-Y a -COOH, and Y a} represents a residue obtained by removing an acid anhydride group from dicarboxylic acid anhydride.

Z ^a represents a residue obtained by removing two acid anhydride groups from tetracarboxylic dianhydride.

Alkali-soluble resin represented by said Formula (a-1) is cardo resin which has a cardo structure in the structure. The cardo structure refers to a structure in which a second cyclic structure and a third cyclic structure are bonded to one ring carbon atom constituting the first cyclic structure. In addition, the 2nd cyclic structure and the 3rd cyclic structure may be the same structure or different structures may be sufficient as them.

As a typical example of the cardo structure, the structure etc. which two aromatic rings (for example, a benzene ring) couple|bonded with the 9th-position carbon atom of a fluorene ring are mentioned.

In the formula (a-2), ^{as the hydrocarbon group having 1 to 7 carbon atoms as R a1} , a methyl group, an ethyl group, a propyl group, an isopropyl group, n-butyl group, an isobutyl group, a tert-butyl group, and n- Alkyl groups, such as a pentyl group, an isopentyl group, a neopentyl group, n-hexyl group, and n-heptyl group, a phenyl group, a methylphenyl group, etc. are mentioned.

^Examples of the halogen atom as R a1 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

In formula (a-2), R ^a3 is preferably an alkylene group having 1 or more and 20 or less carbon atoms, more preferably an alkylene group having 1 or more and 10 or less carbon atoms, and alkyl having 1 or more and 6 or less carbon atoms. A lene group is particularly preferred, and an ethane-1,2-diyl group, a propane-1,2-diyl group, and a propane-1,3-diyl group are most preferred.

Ring A in Formula (a-3) represents the aliphatic ring which may have an aromatic ring and the substituent which may be condensed. The aliphatic ring may be an aliphatic hydrocarbon ring or an aliphatic heterocyclic ring.

Examples of the aliphatic ring include monocycloalkane, bicycloalkane, tricycloalkane and tetracycloalkane.

Specifically, monocycloalkanes, such as cyclopentane, cyclohexane, cycloheptane, and cyclooctane, adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, etc. are mentioned.

An aromatic hydrocarbon ring or an aromatic heterocyclic ring may be sufficient as the aromatic ring which may be condensed to an aliphatic ring, and an aromatic hydrocarbon ring is preferable. Specifically, a benzene ring and a naphthalene ring are preferable.

The following group is mentioned as a suitable example of the bivalent group represented by Formula (a-3).

The divalent group X ^a in the formula (a-1) is alkali-soluble represented by the formula (a-1) by reacting the tetracarboxylic dianhydride giving the ^{residue Z a with a diol compound represented by the following formula (a-2a).} introduced into the resin.

In the formula (a-2a), R ^a1 , R ^a2 , R ^a3 , and t2 are as described for the formula (a-2). The ring A in the formula (a-2a) is as described for the formula (a-3).

The diol compound represented by Formula (a-2a) can be manufactured with the following method, for example.

First, a hydrogen atom in the phenolic hydroxyl group of a diol compound represented by the following formula (a-2b) is replaced with a group represented by ^{-R a3 -OH according to a conventional method if necessary, followed by epichlorohydrin or the like.} It is glycidylated and the epoxy compound represented by a following formula (a-2c) is obtained.

Then, the diol compound represented by Formula (a-2a) can be obtained by making the epoxy compound represented by Formula (a-2c) react with acrylic acid or methacrylic acid.

In formulas (a-2b) and (a-2c), R ^a1 , R ^a3 , and t2 are as described for formula (a-2). The ring A in the formulas (a-2b) and (a-2c) is as described for the formula (a-3).

In addition, the manufacturing method of the diol compound represented by Formula (a-2a) is not limited to said method.

The following diol compounds are mentioned as a suitable example of the diol compound represented by Formula (a-2b).

In the formula (a-1), R ^a0 is a hydrogen atom or a group represented by ^{-CO-Y a -COOH.} Here, Y ^a represents the residue remove|excluding the acid anhydride group (-CO-O-CO-) from dicarboxylic acid anhydride.

Examples of dicarboxylic anhydride include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, chlorendic anhydride, methyltetrahydrophthalic anhydride, Anhydrous glutaric acid etc. are mentioned.

The dicarboxylic acid anhydride may contain the fluorine atom. Examples of the dicarboxylic anhydride containing a fluorine atom include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylendomethylene tetrahydrophthalic anhydride, chlorendic anhydride, methyl The compound etc. which 1 or more fluorine atom or a fluorine-containing substituent were introduce|transduced into dicarboxylic acid anhydrides, such as tetrahydrophthalic anhydride and glutaric anhydride, are mentioned.

In addition, in said Formula (a-1), Z ^a represents the residue which removed two acid anhydride groups from tetracarboxylic dianhydride.

As an example of tetracarboxylic dianhydride, tetracarboxylic dianhydride represented by following formula (a-4), pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, biphenyl ether tetracarboxylic acid 2 Anhydride etc. are mentioned. Especially, pyromellitic dianhydride or biphenyltetracarboxylic dianhydride is preferable.

In formula (a-4), R ^a4 , R ^a5 , and R ^a6 each independently represent one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and a fluorine atom, and t3 is , an integer of 0 or more and 12 or less.

The alkyl group which can be selected as ^{R a4} in formula (a-4) is a C1-C10 alkyl group. By setting the number of carbon atoms included in the alkyl group within this range, the heat resistance of the resulting carboxylic acid ester can be further improved. When R ^a4 is an alkyl group, the number of carbon atoms is preferably 1 or more and 6 or less, more preferably 1 or more and 5 or less, and still more preferably 1 or more and 4 or less from the viewpoint of easily obtaining an alkali-soluble resin excellent in heat resistance. and 1 or more and 3 or less are particularly preferable.

When R ^a4 is an alkyl group, the alkyl group may be linear or branched.

^{R a4} in the formula (a-4) is more preferably a hydrogen atom or an alkyl group having 1 or more and 10 or less carbon atoms, each independently from the viewpoint of easily obtaining an alkali-soluble resin excellent in heat resistance. ^{R a4} in the formula (a-4) is more preferably a hydrogen atom, a methyl group, an ethyl group, an n-propyl group or an isopropyl group, and particularly preferably a hydrogen atom or a methyl group.

^{It is preferable that the some R a4} in Formula (a-4) is the same group because preparation of highly purified tetracarboxylic dianhydride is easy.

t3 in Formula (a-4) represents the integer of 0 or more and 12 or less. By setting the value of t3 to 12 or less, purification of tetracarboxylic dianhydride can be facilitated.

From the point that refinement|purification of tetracarboxylic dianhydride is easy, 5 is preferable and, as for the upper limit of t3, 3 is more preferable.

From the point of the chemical stability of tetracarboxylic dianhydride, 1 is preferable and, as for the minimum of t3, 2 is more preferable.

As for t3 in Formula (a-4), 2 or 3 is especially preferable.

The alkyl group having 1 to 10 carbon atoms which can be selected as ^{R a5} and R ^a6 in the formula (a-4) is the same as the alkyl group having 1 to 10 carbon atoms that can be selected as ^{R a4 .}

R ^a5 and R ^a6 are hydrogen atoms, or 1 or more and 10 or less carbon atoms (preferably 1 or more and 6 or less, more preferably 1 or more and 5 or less, more preferably 1 or more and 5 or less, more Preferably it is 1 or more and 4 or less, Especially preferably, it is 1 or more and 3 or less), it is preferable that it is an alkyl group, and it is especially preferable that it is a hydrogen atom or a methyl group.

As tetracarboxylic dianhydride represented by Formula (a-4), it is norbornane-2-spiro-α-cyclopentanone-α'-spiro-2''- norbornane-5,5'', for example. ,6,6''-tetracarboxylic dianhydride (alias "norbornane-2-spiro-2'-cyclopentanone-5'-spiro-2''-norbornane-5,5'', 6, 6''-tetracarboxylic dianhydride"), methylnorbornane-2-spiro-α-cyclopentanone-α'-spiro-2''-(methylnorbornane)-5,5'', 6, 6''-tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclohexanone-α'-spiro-2''-norbornane-5,5'', 6,6''-tetracarboxylic acid dianhydride (alias "norbornane-2-spiro-2'-cyclohexanone-6'-spiro-2''-norbornane-5,5'',6,6''-tetracarboxylic dianhydride" ), methylnorbornane-2-spiro-α-cyclohexanone-α'-spiro-2''-(methylnorbornane)-5,5'', 6,6''-tetracarboxylic dianhydride, Norbornane-2-spiro-α-cyclopropanone-α'-spiro-2''-norbornane-5,5'',6,6''-tetracarboxylic dianhydride, norbornane-2- Spiro-α-cyclobutanone-α′-spiro-2′′-norbornane-5,5′′,6,6′′-tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclohep Thanone-α'-spiro-2''-norbornane-5,5'',6,6''-tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclooctanone-α'-spiro -2''-norbornane-5,5'', 6,6''-tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclononanone-α'-spiro-2''-nor Bornane-5,5'', 6,6''-tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclodecanone-α'-spiro-2''-norbornane-5,5 '', 6,6''-tetracarboxylic dianhydride, norbornane-2-spiro-α-cycloundecanone-α'-spiro-2''-norbornane-5,5'', 6,6 ''-tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclododecanone-α'-spiro-2''-norbornane-5,5'',6,6''-tetracarboxylic acid 2 Anhydride, norbornane-2- Spiro-α-cyclotridecanone-α'-spiro-2''-norbornane-5,5'',6,6''-tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclo Tetradecanone-α'-spiro-2''-norbornane-5,5'', 6,6''-tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclopentadecanone-α '-spiro-2''-norbornane-5,5'',6,6''-tetracarboxylic dianhydride, norbornane-2-spiro-α-(methylcyclopentanone)-α'-spiro -2''-norbornane-5,5'', 6,6''-tetracarboxylic dianhydride, norbornane-2-spiro-α-(methylcyclohexanone)-α'-spiro-2' '- norbornane-5,5'', 6,6''-tetracarboxylic dianhydride, etc. are mentioned.

In said formula (a-1), t1 represents the integer of 0 or more and 20. It is preferable that t1 is an integer of 1 or more and 20 or less.

1000 or more and 40,000 or less are preferable and, as for the mass average molecular weight (Mw) of alkali-soluble resin represented by Formula (a-1), 2000 or more and 30000 or less are more preferable.

In this specification, a mass average molecular weight (Mw) is a measured value by polystyrene conversion of gel permeation chromatography (GPC).

80 mass % or more is preferable, as for content of alkali-soluble resin represented by Formula (a-1) in alkali-soluble resin (A), 90 mass % or more is more preferable, and its 100 mass % is especially preferable.

As alkali-soluble resin (A) other than alkali-soluble resin represented by the said Formula (a-1), from the point excellent in film forming property, the thing which is easy to adjust the characteristic of resin by selection of a monomer, etc., an ethylenically unsaturated double bond and polymers of monomers having Examples of the monomer having an ethylenically unsaturated double bond include (meth)acrylic acid; (meth)acrylic acid ester; (meth)acrylic acid amide; crotonic acid; maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, and anhydrides of these dicarboxylic acids; aryl compounds such as aryl acetate, aryl caproate, aryl caprylate, aryl laurate, aryl palmitate, aryl stearate, aryl benzoate, aryl acetoacetate, aryl lactate, and aryloxyethanol; Hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl ether, 2-ethyl butyl vinyl ether, hydroxyethyl vinyl ether, diethyleneglycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether, vinyl phenyl ether, vinyl ethers such as vinyl tolyl ether, vinyl chlorophenyl ether, vinyl-2,4-dichlorophenyl ether, vinyl naphthyl ether, and vinyl anthranyl ether; vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl valate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxy acetate, vinyl butoxy acetate, vinyl phenyl acetate, vinyl aceto acetate, vinyl esters such as vinyl lactate, vinyl-β-phenylbutyrate, vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, and vinyl naphthoate; styrene; Methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, isopropyl styrene, butyl styrene, hexyl styrene, cyclohexyl styrene, decyl styrene, benzyl styrene, chloromethyl styrene, trifluoromethyl styrene, ethoxymethyl styrene , acetoxymethylstyrene, methoxystyrene, 4-methoxy-3-methylstyrene, dimethoxystyrene, chlorostyrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene , styrene or styrene derivatives such as iodostyrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethylstyrene, and 4-fluoro-3-trifluoromethylstyrene; Ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4- Methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, olefins such as 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene; and the like.

The polymer of the monomer which has an ethylenically unsaturated double bond as alkali-soluble resin (A) contains the unit derived from an unsaturated carboxylic acid normally. Examples of the unsaturated carboxylic acid include (meth)acrylic acid; (meth)acrylic acid amide; crotonic acid; Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, anhydrides of these dicarboxylic acids, etc. are mentioned. The amount of the unit derived from the unsaturated carboxylic acid contained in the polymer of the monomer having an ethylenically unsaturated double bond used as the alkali-soluble resin is not particularly limited as long as the resin has a desired alkali solubility. 5 mass % or more and 25 mass % or less are preferable with respect to the mass of resin, and, as for the quantity of the unit derived from an unsaturated carboxylic acid in resin used as alkali-soluble resin, 8 mass % or more and 16 mass % or less are more preferable.

Among the polymers of a monomer having an ethylenically unsaturated double bond, which is a polymer of one or more monomers selected from the monomers exemplified above, a polymer of one or more monomers selected from (meth)acrylic acid and (meth)acrylic acid ester is preferable. . Hereinafter, the polymer of 1 or more types of monomers chosen from (meth)acrylic acid and (meth)acrylic acid ester is demonstrated.

The (meth)acrylic acid ester used for the preparation of a polymer of one or more monomers selected from (meth)acrylic acid and (meth)acrylic acid ester is not particularly limited as far as the object of the present invention is not impaired, and known ( It is appropriately selected from meth)acrylic acid esters.

Suitable examples of the (meth)acrylic acid ester include linear or branched alkyl (meth)acrylate; Chloro ethyl (meth) acrylate, 2,2-dimethyl hydroxypropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, trimethylolpropane mono (meth) acrylate, benzyl (meth) acrylate, puffril (meth)acrylate; (meth)acrylic acid ester having a group having an epoxy group; (meth)acrylic acid ester etc. which have group which has alicyclic skeleton are mentioned. The detail of the (meth)acrylic acid ester which has group which has an epoxy group, and (meth)acrylic acid ester which has group which has alicyclic skeleton is mentioned later.

Among the polymers of one or more monomers selected from (meth)acrylic acid and (meth)acrylic acid ester, the cured product formed using the photosensitive composition has excellent adhesion and mechanical strength to the substrate, ) A resin containing a unit derived from an acrylic acid ester is preferable.

The (meth)acrylic acid ester having a group having an epoxy group may be a (meth)acrylic acid ester having a group having a chain aliphatic epoxy group, or may be a (meth)acrylic acid ester having a group having an alicyclic epoxy group as described later.

The (meth)acrylic acid ester which has group which has an epoxy group may contain the aromatic group. A benzene ring and a naphthalene ring are mentioned as an example of the aromatic ring which comprises an aromatic group. As an example of the (meth)acrylic acid ester which has an aromatic group and has a group which has an epoxy group, 4-glycidyloxy phenyl (meth)acrylate, 3-glycidyloxy phenyl (meth)acrylate, 2-glycidyloxy Phenyl (meth)acrylate, 4-glycidyloxy phenylmethyl (meth)acrylate, 3-glycidyloxy phenylmethyl (meth)acrylate, and 2-glycidyloxy phenylmethyl (meth)acrylate, etc. can be heard

When the hardened|cured material formed using the photosensitive composition requires high transparency, it is preferable that (meth)acrylic acid which has a group which has an epoxy group does not contain an aromatic group.

Examples of the (meth)acrylic acid ester having a group having a chain aliphatic epoxy group include an oxy group (-O-CO-) in the ester group (-O-CO-), such as epoxy alkyl (meth) acrylate and epoxy alkyloxy alkyl (meth) acrylate. and (meth)acrylic acid esters in which a chain aliphatic epoxy group is bonded to O-). The chain|strand-shaped aliphatic epoxy group which such (meth)acrylic acid ester has may contain 1 or several oxy group (-O-) in a chain|strand. Although the number of carbon atoms of a chain|strand-shaped aliphatic epoxy group is not specifically limited, 3 or more and 20 or less are preferable, 3 or more and 15 or less are more preferable, 3 or more and 10 or less are especially preferable.

Specific examples of the (meth)acrylic acid ester having a group having a chain aliphatic epoxy group include glycidyl (meth)acrylate, 2-methylglycidyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, 6 Epoxy alkyl (meth)acrylates, such as 7-epoxyheptyl (meth)acrylate; 2-Glycidyloxy ethyl (meth)acrylate, 3-glycidyloxy-n-propyl (meth)acrylate, 4-glycidyloxy-n-butyl (meth)acrylate, 5-glycidyl Epoxy alkyloxy alkyl (meth)acrylates, such as oxy-n-hexyl (meth)acrylate and 6-glycidyloxy-n-hexyl (meth)acrylate, etc. are mentioned.

(meth)acrylic acid having a group having an epoxy group in a polymer of one or more monomers selected from (meth)acrylic acid and (meth)acrylic acid ester containing a unit derived from (meth)acrylic acid ester having a group having an epoxy group 1 mass % or more and 95 mass % or less are preferable with respect to the weight of resin, and, as for content of the unit derived from ester, 40 mass % or more and 80 mass % or less are more preferable.

In addition, among the polymers of one or more monomers selected from (meth)acrylic acid and (meth)acrylic acid ester, it is easy to form a cured product having excellent transparency using the photosensitive composition, so that (meth) having a group having an alicyclic skeleton (meth) ) A resin containing a unit derived from an acrylic acid ester is preferable.

In the (meth)acrylic acid ester having a group having an alicyclic skeleton, the group having an alicyclic skeleton may be a group having an alicyclic hydrocarbon group or a group having an alicyclic epoxy group. The alicyclic group constituting the alicyclic skeleton may be monocyclic or polycyclic. Examples of the monocyclic alicyclic group include a cyclopentyl group and a cyclohexyl group. Moreover, as a polycyclic alicyclic group, a norbornyl group, an isobornyl group, a tricyclononyl group, a tricyclodecyl group, tetracyclododecyl group, etc. are mentioned.

Among the (meth)acrylic acid esters having a group having an alicyclic skeleton, examples of the (meth)acrylic acid ester having a group having an alicyclic hydrocarbon group include compounds represented by the following formulas (a1-1) to (a1-8). have. Among these, the compounds represented by the following formulas (a1-3) to (a1-8) are preferable, and the compounds represented by the following formulas (a1-3) or (a1-4) are more preferable.

In the formula, R ^a11 represents a hydrogen atom or a methyl group, R ^a12 represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, and R ^a13 is a hydrogen atom or 1 to 5 carbon atoms represents an alkyl group of As R ^a12 , a single bond, a linear or branched alkylene group, for example, a methylene group, an ethylene group, a propylene group, a tetramethylene group, an ethylethylene group, a pentamethylene group, or a hexamethylene group is preferable. R ^a13 is preferably a methyl group or an ethyl group.

Among the (meth)acrylic acid esters having a group having an alicyclic skeleton, specific examples of the (meth)acrylic acid ester having a group having an alicyclic epoxy group include, for example, compounds represented by the following formulas (a2-1) to (a2-16) can be heard Among these, in order to make the developability of a photosensitive composition into a suitable level, the compound represented by following formula (a2-1) - (a2-6) is preferable, and is represented by following formula (a2-1) - (a2-4) A compound is more preferable.

In the formula, R ^a14 represents a hydrogen atom or a methyl group, R ^a15 represents a divalent aliphatic saturated hydrocarbon group having 1 to 6 ^{carbon atoms, and R a16} represents a divalent hydrocarbon group having 1 to 10 carbon atoms , n represents an integer of 0 or more and 10 or less. As R ^a15 , a linear or branched alkylene group, for example, a methylene group, an ethylene group, a propylene group, a tetramethylene group, an ethylethylene group, a pentamethylene group, or a hexamethylene group is preferable. As R ^a16 , for example, a methylene group, an ethylene group, a propylene group, a tetramethylene group, an ethyl ethylene group, a pentamethylene group, a hexamethylene group, a phenylene group, a cyclohexylene group, -CH ₂ -Ph-CH ₂ -( Ph represents a phenylene group) is preferable.

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

In addition, in the polymer of one or more monomers selected from (meth)acrylic acid and (meth)acrylic acid ester containing a unit derived from (meth)acrylic acid ester having a group having an alicyclic skeleton, (meth)acrylic acid derived A resin containing a unit derived from a unit to be used and a unit derived from (meth)acrylic acid ester having a group having an alicyclic epoxy group is preferable. The film formed using the photosensitive composition containing such alkali-soluble resin is excellent in adhesiveness to a base material. In addition, when using such a resin, it is possible to cause a self-reaction between the carboxyl group contained in the resin and the alicyclic epoxy group. For this reason, when a photosensitive composition containing such a resin is used, mechanical properties such as hardness of the formed film can be improved by causing a self-reaction between the carboxyl group and the alicyclic epoxy group using a method for heating the film or the like. .

Resin containing a unit derived from (meth)acrylic acid and a unit derived from (meth)acrylic acid ester having a group having an alicyclic epoxy group WHEREIN: The quantity of the unit derived from (meth)acrylic acid in resin is 1 mass % 95 mass % or more is preferable, and 10 mass % or more and 50 mass % or less are more preferable. In a resin comprising a unit derived from (meth)acrylic acid and a unit derived from (meth)acrylic acid ester having a group having an alicyclic epoxy group, derived from (meth)acrylic acid ester having a group having an alicyclic epoxy group in the resin 1 mass % or more and 95 mass % or less are preferable, and, as for the quantity of the unit to make, 30 mass % or more and 70 mass % or less are more preferable.

In a polymer of one or more monomers selected from (meth)acrylic acid and (meth)acrylic acid ester, comprising a unit derived from (meth)acrylic acid and a unit derived from (meth)acrylic acid ester having a group having an alicyclic epoxy group is preferably a resin comprising a unit derived from (meth)acrylic acid, a unit derived from (meth)acrylic acid ester having an alicyclic hydrocarbon group, and a unit derived from (meth)acrylic acid ester having a group having an alicyclic epoxy group. do.

In a resin comprising a unit derived from (meth)acrylic acid, a unit derived from (meth)acrylic acid ester having an alicyclic hydrocarbon group, and a unit derived from (meth)acrylic acid ester having a group having an alicyclic epoxy group, the resin 1 mass % or more and 95 mass % or less are preferable, and, as for the quantity of the unit derived from (meth)acrylic acid, 10 mass % or more and 50 mass % or less are more preferable. In a resin comprising a unit derived from (meth)acrylic acid, a unit derived from (meth)acrylic acid ester having an alicyclic hydrocarbon group, and a unit derived from (meth)acrylic acid ester having a group having an alicyclic epoxy group, the resin 1 mass % or more and 95 mass % or less are preferable, and, as for the quantity of the unit derived from (meth)acrylic acid ester which has an alicyclic hydrocarbon group, 10 mass % or more and 70 mass % or less are more preferable. In a resin comprising a unit derived from (meth)acrylic acid, a unit derived from (meth)acrylic acid ester having an alicyclic hydrocarbon group, and a unit derived from (meth)acrylic acid ester having a group having an alicyclic epoxy group, the resin 1 mass % or more and 95 mass % or less are preferable, and, as for the quantity of the unit derived from (meth)acrylic acid ester which has a group which has an alicyclic epoxy group, 30 mass % or more and 80 mass % or less are more preferable.

2000 or more and 200000 or less are preferable and, as for the mass average molecular weights of alkali-soluble resins (A) other than alkali-soluble resin represented by said Formula (a-1), 2000 or more and 18000 or less are more preferable. By setting it as said range, there exists a tendency for the balance of the film-forming ability of a photosensitive composition and the developability after exposure to be easy to obtain.

15 mass % or more and 90 mass % or less are preferable in solid content of the photosensitive composition, as for content of alkali-soluble resin (A) in the photosensitive composition, 35 mass % or more and 85 mass % or less are more preferable, 50 mass % or more and 70 mass % % or less is particularly preferred. In addition, in this specification, solid content shows the total of components other than the solvent contained in the photosensitive composition.

<Photopolymerizable monomer (B)>

The photopolymerizable monomer (B) (it is also referred to as (B) component hereafter.) which the photosensitive composition contains is not specifically limited, A conventionally well-known photopolymerizable monomer can be used. Especially, the monomer which has an ethylenically unsaturated group is preferable.

Monofunctional monomers and polyfunctional monomers exist in the monomer which has an ethylenically unsaturated group. Hereinafter, a monofunctional monomer and a polyfunctional monomer are demonstrated in order.

Examples of the monofunctional monomer include (meth)acrylamide, methylol (meth)acrylamide, methoxymethyl (meth)acrylamide, ethoxymethyl (meth)acrylamide, propoxymethyl (meth)acrylamide, butoxymethyl Toxymethyl (meth)acrylamide, N-methylol (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, (meth)acrylic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citracone Acid, citraconic anhydride, crotonic acid, 2-acrylamido-2-methylpropane sulfonic acid, tert-butylacrylamide sulfonic acid, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acryl Rate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth) Acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2- (meth) acryloyloxy-2-hydroxypropyl phthalate, glycerin mono (meth) acrylate, tetrahydrofurfuryl (meth) ) acrylate, dimethylamino (meth) acrylate, glycidyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl ( and meth)acrylate and half (meth)acrylate of a phthalic acid derivative. These monofunctional monomers may be used independently and may be used in combination of 2 or more type.

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. Acrylate, butylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexaneglycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, glycerin di(meth)acrylate ) acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth) ) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 2,2-bis (4- (meth) acryloxy diene Toxyphenyl) propane, 2,2-bis (4- (meth) acryloxy polyethoxyphenyl) propane, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, ethylene glycol diglycol Cidyl ether di(meth)acrylate, diethylene glycol diglycidyl ether di(meth)acrylate, phthalic acid diglycidyl ester di(meth)acrylate, glycerin triacrylate, glycerin polyglycidyl ether poly (meth)acrylate, urethane (meth)acrylate (ie, tolylene diisocyanate), trimethylhexamethylene diisocyanate, hexamethylene diisocyanate and 2-hydroxyethyl (meth) acrylate, methylene bis (meth) ) Polyfunctional monomers, such as a condensate of acrylamide, (meth)acrylamide methylene ether, polyhydric alcohol, and N-methylol (meth)acrylamide, triacryl formal, etc. are mentioned. These polyfunctional monomers may be used independently and may be used in combination of 2 or more type.

The content of the photopolymerizable monomer (B) in the photosensitive composition is preferably 5 mass % or more and 60 mass % or less, more preferably 10 mass % or more and 50 mass % or less, 15 mass % or more and 40 mass % or more in solid content of the photosensitive composition. % or less is particularly preferred.

<Photoinitiator (C)>

The photopolymerization initiator (C) containing the photosensitive composition (hereinafter also referred to as component (C)) is a fluorene-based oxime ester compound (C1), a fluorene-based oxime ester compound (C2), a phosphine oxide-based compound, and At least one compound (C3) selected from aminoketone compounds is contained, the fluorene-based oxime ester compound (C1) has a nitro group, and the fluorene-based oxime ester compound (C2) does not have a nitro group.

[Fluorene-based oxime ester compound (C1)]

A fluorene-type oxime ester compound (C1) is a compound which has a nitro group, a fluorene ring, and the bond represented by >C=N-O-CO-.

As a fluorene type oxime ester compound (C1), the compound represented, for example by a following formula (c1-1) is mentioned.

(In formula (c1-1), R ^c1 is a nitro group, R ^c2 and R ^c3 are each a chain alkyl group which may have a substituent, a cyclic organic group which may have a substituent, or a hydrogen atom, and R ^c2 and R ^c3 may be bonded to each other to form a ring, R ^c4 is a monovalent organic ^{group, R c5} is a hydrogen atom, an alkyl group having 1 to 11 carbon atoms which may have a substituent, or an aryl which may have a substituent group, n1 is an integer of 1 or more and 4 or less, and m1 is 0 or 1.)

In formula (c1-1), R ^c1 is a nitro group. R ^c1 is bonded to a 6-membered aromatic ring different from the 6-membered aromatic ring bonded to the group represented by _{-(CO) m1} - on the fluorene ring in formula (c1-1). In the formula (c1-1), the bonding position of ^{R c1 to} the fluorene ring as long as it is bonded to a 6-membered aromatic ring different from the 6-membered aromatic ring bonded to the group represented _{by -(CO) m1 - on the fluorene ring.} is not particularly limited. Expression when having the (c1-1) compound is one or more of R ^c1 represented by the formula from binding (c1-1) will be easily obtained by synthesizing the compound represented by the formula or the like, over two of the one of the one or more of R ^c1 fluorene ring It is preferable to do When R ^c1 is a plurality, the plurality of R ^c1 are may be the same or different.

In formula (c1-1), R ^c2 and R ^c3 each represent a chain alkyl group which may have a substituent, a cyclic organic group which may have a substituent, or a hydrogen atom. R ^c2 and R ^c3 may combine with each other to form a ring. Among these groups, as R ^c2 and R ^c3 , a chain alkyl group which may have a substituent is preferable. When R ^c2 and R ^c3 are a chain alkyl group which may have a substituent, the chain alkyl group may be a straight chain alkyl group or a branched chain alkyl group.

When R ^c2 and R ^c3 are a chain alkyl group having no substituent, the number of carbon atoms in the chain alkyl group is preferably 1 or more and 20 or less, more preferably 1 or more and 10 or less, and still more preferably 1 or more and 6 or less. Specific examples when R ^c2 and R ^c3 are a chain alkyl group include a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group , isopentyl group, sec-pentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, n-nonyl group, isono A nyl group, an n-decyl group, an isodecyl group, etc. are mentioned. In addition, when R ^c2 and R ^c3 are 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 ^c2 and R ^c3 are a chain alkyl group having a substituent, the number of carbon atoms in the chain alkyl group is preferably 1 or more and 20 or less, more preferably 1 or more and 10 or less, and particularly preferably 1 or more and 6 or less. In this case, the number of carbon atoms of the substituent is not included in the number of carbon atoms of the chain alkyl group. It is preferable that the linear alkyl group which has a substituent is linear.

The substituent which the alkyl group may have is not specifically limited in the range which does not impair the objective of this invention. Suitable examples of the substituent include a cyano group, a halogen atom, a cyclic organic group, and an alkoxycarbonyl group.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Among these, a fluorine atom, a chlorine atom, a bromine atom, etc. are preferable.

Examples of the cyclic organic group include a cycloalkyl group, an aromatic hydrocarbon group, and a heterocyclyl group. 3 or more and 10 or less are preferable and, as for carbon atom number of a cycloalkyl group, 3 or more and 6 or less are more preferable. Specific examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl 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. The heterocyclyl group is a 5-membered or 6-membered monocyclic ring containing one or more N, S, and O, or a group obtained by condensing such monocyclic rings or such a monocyclic ring and a benzene ring. When the heterocyclyl group is a condensed ring, the number of condensed monocyclic rings is 3 or less. The heterocyclyl group may be an aromatic group (heteroaryl group) or a non-aromatic group. As a heterocycle constituting such a heterocyclyl group, furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyridine Midin, pyridazine, benzofuran, benzothiophene, indole, isoindole, indolizine, benzoimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, pr and talazine, cinnoline, quinoxarine, piperidine, piperazine, morpholine, tetrahydropyran, and tetrahydrofuran.

2 or more and 20 or less are preferable and, as for the number of carbon atoms of an alkoxycarbonyl group, 2 or more and 7 or less are more preferable. Specific examples of the alkoxycarbonyl group include methoxycarbonyl group, ethoxycarbonyl group, n-propyloxycarbonyl group, isopropyloxycarbonyl group, n-butyloxycarbonyl group, isobutyloxycarbonyl group, sec-butyloxycarbonyl group, tert-butyloxycarbonyl group, n- pentyloxycarbonyl group, isopentyloxycarbonyl group, sec-pentyloxycarbonyl group, tert-pentyloxycarbonyl group, n-hexyloxycarbonyl group, n-heptyloxycarbonyl group, n-octyloxycarbonyl group, isooctyloxycarbonyl group, sec-octyloxycarbonyl group, tert-octyloxycarbonyl group, n-nonyloxycarbonyl group, isononyloxycarbonyl group, n-decyloxycarbonyl group, isodecyloxycarbonyl group, etc. are mentioned.

When the chain alkyl group has a substituent, the number of the substituents is not particularly limited. The preferred number of substituents changes depending on the number of carbon atoms in the chain alkyl group. The number of substituents is typically 1 or more and 20 or less, 1 or more and 10 or less are preferable, and 1 or more and 6 or less are more preferable.

When R ^c2 and R ^c3 are a cyclic organic group, 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 ^c2 and R ^c3 are a cyclic organic group, the substituents which the cyclic organic group may have are the ^{same as when R c2} and R ^c3 are a chain alkyl group.

When R ^c2 and R ^c3 are aromatic hydrocarbon groups, the aromatic hydrocarbon group is preferably a phenyl group, a group formed by bonding a plurality of benzene rings through a carbon-carbon bond, or a group formed by condensation of a plurality of benzene rings. 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, preferably 3 or less, more preferably 2 or less, and 1 is particularly desirable. 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 ^c2 and R ^c3 are an aliphatic cyclic hydrocarbon group, the alicyclic hydrocarbon group may be monocyclic or polycyclic. Although the number of carbon atoms of an aliphatic cyclic hydrocarbon group is not specifically limited, 3 or more and 20 or less are preferable, and 3 or more and 10 or less are more preferable. Examples of the monocyclic cyclic hydrocarbon group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a norbornyl group, an isobornyl group, a tricyclononyl group, and a tricyclodecyl group. , a tetracyclododecyl group, and an adamantyl group.

When R ^c2 and R ^c3 are a heterocyclyl group, the heterocyclyl group is a 5-membered or 6-membered monocyclic ring containing one or more N, S, and O, or a heterocycle in which such monocyclic rings are condensed with a benzene ring. it's the weather When the heterocyclyl group is a condensed ring, the number of condensed rings is 3 or less. The heterocyclyl group may be an aromatic group (heteroaryl group) or a non-aromatic group. As a heterocycle constituting such a heterocyclyl group, furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyridine Midin, pyridazine, benzofuran, benzothiophene, indole, isoindole, indolizine, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, pr and talazine, cinnoline, quinoxarine, piperidine, piperazine, morpholine, tetrahydropyran, and tetrahydrofuran.

R ^c2 and R ^c3 may combine with each other to form a ring. The group consisting of a ring formed by ^{R c2} and R ^{c3 is preferably a cycloalkylidene group.} When R ^c2 and R ^c3 combine to form a cycloalkylidene group, the ring constituting the cycloalkylidene group is preferably a 5-membered ring or a 6-membered ring, more preferably a 5-membered ring.

When ^{the group formed by bonding of R c2} and R ^c3 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 the 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 pyrrole ring, a pyridine ring, A pyrazine ring, a pyrimidine ring, etc. are mentioned.

Suitable specific examples of R ^c2 and R ^c3 include an alkyl group such as an ethyl group, n-propyl group, n-butyl group, n-hexyl group, n-heptyl group, and n-octyl group; 2-methoxyethyl group, 3-methoxy-n-propyl group, 4-methoxy-n-butyl group, 5-methoxy-n-pentyl group, 6-methoxy-n-hexyl group, 7-methoxy group -n-heptyl group, 8-methoxy-n-octyl group, 2-ethoxy ethyl group, 3-ethoxy-n-propyl group, 4-ethoxy-n-butyl group, 5-ethoxy-n-phene alkoxy alkyl groups such as a tyl group, a 6-ethoxy-n-hexyl group, a 7-ethoxy-n-heptyl group, and an 8-ethoxy-n-octyl group; 2-cyanoethyl group, 3-cyano-n-propyl group, 4-cyano-n-butyl group, 5-cyano-n-pentyl group, 6-cyano-n-hexyl group, 7-cyano group cyanoalkyl groups such as -n-heptyl and 8-cyano-n-octyl; 2-phenyl ethyl group, 3-phenyl-n-propyl group, 4-phenyl-n-butyl group, 5-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; 2-cyclohexyl ethyl group, 3-cyclohexyl-n-propyl group, 4-cyclohexyl-n-butyl group, 5-cyclohexyl-n-pentyl group, 6-cyclohexyl-n-hexyl group, 7-cyclohexyl group -n-heptyl group, 8-cyclohexyl-n-octyl group, 2-cyclopentyl ethyl group, 3-cyclopentyl-n-propyl group, 4-cyclopentyl-n-butyl group, 5-cyclopentyl-n-pene cycloalkyl alkyl groups such as a tyl group, a 6-cyclopentyl-n-hexyl group, a 7-cyclopentyl-n-heptyl group, and an 8-cyclopentyl-n-octyl group; 2-Methoxycarbonyl-ethyl group, 3-methoxycarbonyl-n-propyl group, 4-methoxycarbonyl-n-butyl group, 5-methoxycarbonyl-n-pentyl group, 6-methoxycar Bornyl-n-hexyl group, 7-methoxycarbonyl-n-heptyl group, 8-methoxycarbonyl-n-octyl group, 2-ethoxycarbonyl-ethyl group, 3-ethoxycarbonyl-n-propyl group group, 4-ethoxycarbonyl-n-butyl group, 5-ethoxycarbonyl-n-pentyl group, 6-ethoxycarbonyl-n-hexyl group, 7-ethoxycarbonyl-n-heptyl group, and alkoxycarbonyl alkyl groups such as 8-ethoxycarbonyl-n-octyl group; 2-chloro ethyl group, 3-chloro-n-propyl group, 4-chloro-n-butyl group, 5-chloro-n-pentyl group, 6-chloro-n-hexyl group, 7-chloro-n-heptyl group, 8-chloro-n-octyl group, 2-bromoethyl group, 3-bromo-n-propyl group, 4-bromo-n-butyl group, 5-bromo-n-pentyl group, 6-bromo- n-hexyl group, 7-bromo-n-heptyl group, 8-bromo-n-octyl group, 3,3,3-trifluoropropyl group, and 3,3,4,4,5,5; Halogenated alkyl groups, such as 5-heptafluoro-n-pentyl group, etc. are mentioned.

As R ^c2 and R ^c3 , suitable groups among the above are ethyl group, n-propyl group, n-butyl group, n-pentyl group, 2-methoxyethyl group, 2-cyanoethyl group, 2-phenyl ethyl group, 2-cyclohexyl group Ethyl group, 2-methoxycarbonyl-ethyl group, 2-chloro ethyl group, 2-bromoethyl group, 3,3,3-trifluoropropyl group, and 3,3,4,4,5,5,5-hepta It is a fluoro-n-pentyl group.

Examples of suitable organic groups for R ^c4 include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, an alkoxycarbonyl group, a saturated aliphatic acyloxy group, an optionally substituted phenyl group, an optionally substituted phenoxy group, The benzoyl group which may have a substituent, the phenoxycarbonyl group which may have a substituent, the benzoyloxy group which may have a substituent, the phenylalkyl group which may have a substituent, the naphthyl group which may have a substituent, the naphthoxy group which may have a substituent , a naphthoyl group which may have a substituent, a naphthoxycarbonyl group which may have a substituent, a naphthoyloxy group which may have a substituent, a naphthylalkyl group which may have a substituent, a heterocyclyl group which may have a substituent, a substituent and a heterocyclylcarbonyl group optionally substituted with 1 or 2 organic groups, a morpholin-1-yl group, and a piperazin-1-yl group. Specific examples of these groups are the same as the specific examples of these groups described for ^{R c1 .} Moreover, as R<^c4> , a cycloalkyl alkyl group, the phenoxy alkyl group which may have a substituent on the aromatic ring, and the phenylthio alkyl group which may have a substituent on the aromatic ring are also preferable. The substituent which the phenoxyalkyl group and the phenylthioalkyl group may have is the same as the substituent which the phenyl group contained in ^{Rc1 may have.}

When R ^c4 is an alkyl group, 1 or more and 20 or less are preferable and, as for the number of carbon atoms of an alkyl group, 1 or more and 6 or less are more preferable. Further, when R ^c4 is an alkyl group, it may be linear or branched. Specific examples when R ^c4 is an alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, and an isopentyl group. , sec-pentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, n-nonyl group, isononyl group, n- A decyl group, an isodecyl group, etc. are mentioned. In addition, when R ^c4 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 ^c4 is an alkoxy group, 1 or more and 20 or less are preferable and, as for the number of carbon atoms, 1 or more and 6 or less are more preferable. Further, when R ^c4 is an alkoxy group, it may be linear or branched. Specific examples when R ^c4 is an alkoxy group include a methoxy group, an ethoxy group, n-propyloxy group, isopropyloxy group, n-butyloxy group, isobutyloxy group, sec-butyloxy group, tert-butyloxy group, n-pentyloxy group, isopentyloxy group, sec-pentyloxy group, tert-pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, isooctyloxy group, sec-octyloxy group , tert-octyloxy group, n-nonyloxy group, isononyloxy group, n-decyloxy group, isodecyloxy group, and the like. In addition, when R ^c4 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 methoxy ethoxy group, an ethoxy ethoxy group, a methoxy ethoxy ethoxy group, an ethoxy ethoxy ethoxy group, a propyloxy ethoxy ethoxy group, and a methoxy propyloxy group. can be heard

When R ^c4 is a cycloalkyl group or a cycloalkoxy group, 3 or more and 10 or less are preferable and, as for the number of carbon atoms of a cycloalkyl group or a cycloalkoxy group, 3 or more and 6 or less are more preferable. Specific examples of the case where R ^c4 is a cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Specific examples in the case where R ^c4 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 ^c4 is a saturated aliphatic acyl group or a saturated aliphatic acyloxy group, the number of carbon atoms in the saturated aliphatic acyl group or saturated aliphatic acyloxy group is preferably 2 or more and 20 or less, and more preferably 2 or more and 7 or less. Specific examples when R ^c4 is a saturated aliphatic acyl group include acetyl group, propanoyl group, n-butanoyl group, 2-methylpropanoyl group, n-pentanoyl group, 2,2-dimethylpropanoyl group, n-hexanoyl group, n-heptanoyl group, n-octanoyl group, n-nonanoyl group, n-decanoyl group, n-undecanoyl group, n-dodecanoyl group, n-tridecanoyl group, n-tetradecanoyl group, n- A pentadecanoyl group, n-hexadecanoyl group, etc. are mentioned. Specific examples in the case where R ^c4 is a saturated aliphatic acyloxy group include acetyloxy group, propanoyloxy group, n-butanoyloxy group, 2-methylpropanoyloxy group, n-pentanoyloxy group, and 2,2-dimethylpropanoyloxy group. Period, n-hexanoyloxy group, n-heptanoyloxy group, n-octanoyloxy group, n-nonanoyloxy group, n-decanoyloxy group, n-undecanoyloxy group, n-dodecanoyloxy group, n -tridecanoyloxy group, n-tetradecanoyloxy group, n-pentadecanoyloxy group, n-hexadecanoyloxy group, etc. are mentioned.

When R ^c4 is an alkoxycarbonyl group, the number of carbon atoms in the alkoxycarbonyl group is preferably 2 or more and 20 or less, more preferably 2 or more and 7 or less ^{Specific examples when R c4} is an alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group , n-propyloxycarbonyl group, isopropyloxycarbonyl group, n-butyloxycarbonyl group, isobutyloxycarbonyl group, sec-butyloxycarbonyl group, tert-butyloxycarbonyl group, n-pentyloxycarbonyl group, isopentyloxycarbonyl group, sec-pentyloxy group Carbonyl group, tert-pentyloxycarbonyl group, n-hexyloxycarbonyl group, n-heptyloxycarbonyl group, n-octyloxycarbonyl group, isooctyloxycarbonyl group, sec-octyloxycarbonyl group, tert-octyloxycarbonyl group, n-nonyloxycarbonyl group, iso Nonyloxycarbonyl group, n-decyloxycarbonyl group, isodecyloxycarbonyl group, etc. are mentioned.

When R ^c4 is a phenyl alkyl group, 7 or more and 20 or less are preferable, and, as for the number of carbon atoms of a phenyl alkyl group, 7 or more and 10 or less are more preferable. Moreover, when R<^c4> is a naphthylalkyl group, 11 or more and 20 or less are preferable and, as for the number of carbon atoms of a naphthylalkyl group, 11 or more and 14 or less are more preferable. Specific examples of the case where R ^c4 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 ^c4 is a naphthylalkyl group include an α-naphthylmethyl group, a β-naphthylmethyl group, a 2-(α-naphthyl)ethyl group, and a 2-(β-naphthyl)ethyl group. When R ^c4 is a phenylalkyl group or a naphthylalkyl group, R ^c4 may further have a substituent on the phenyl group or the naphthyl group.

When R ^c4 is a heterocyclyl group, the heterocyclyl group is a 5-membered or 6-membered monocyclic ring containing one or more N, S, and O, or a heterocyclyl group obtained by condensing such monocyclic rings or such a monocyclic ring and a benzene ring. When the heterocyclyl group is a condensed ring, the number of condensed monocyclic rings is 3 or less. The heterocyclyl group may be an aromatic group (heteroaryl group) or a non-aromatic group. As a heterocycle constituting such a heterocyclyl group, furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyridine Midin, pyridazine, benzofuran, benzothiophene, indole, isoindole, indolizine, benzoimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, pr and talazine, cinnoline, quinoxarine, piperidine, piperazine, morpholine, tetrahydropyran, and tetrahydrofuran. When R ^c4 is a heterocyclyl group, the heterocyclyl group may further have a substituent.

When R ^c4 is a heterocyclylcarbonyl group, the heterocyclyl group included in the heterocyclylcarbonyl group is the ^{same as when R c4} is a heterocyclyl group.

When R ^c4 is an amino group substituted with an organic group of 1 or 2, suitable examples of the organic group include an alkyl group having 1 or more and 20 or less carbon atoms, a cycloalkyl group having 3 or more and 10 or less carbon atoms, and 2 or more and 21 or less carbon atoms. A saturated aliphatic acyl group of A naphthoyl group, a C11-C20 naphthylalkyl group which may have a substituent, a heterocyclyl group, etc. are mentioned. Specific examples of these suitable organic groups are the same as the organic group as ^{R c4 .} Specific examples of the amino group substituted with 1 or 2 organic groups include methylamino group, ethylamino group, diethylamino group, n-propylamino group, di-n-propylamino group, isopropylamino group, n-butylamino group, di-n-butyl Amino group, n-pentylamino group, n-hexylamino group, n-heptylamino group, n-octylamino group, n-nonylamino group, n-decylamino group, phenylamino group, naphthylamino group, acetylamino group, propanoylamino group, n-buta noylamino group, n-pentanoylamino group, n-hexanoylamino group, n-heptanoylamino group, n-octanoylamino group, n-decanoylamino group, benzoylamino group, α-naphthoylamino group, and β-naphthoylamino group can be heard

^Examples of the substituent when the phenyl group, naphthyl group, and heterocyclyl group contained in R c4 further have a substituent include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and the number of carbon atoms. A monoalkylamino group having 2 or more and 7 or less saturated aliphatic acyl group, an alkoxycarbonyl group having 2 or more and 7 or less carbon atoms, a saturated aliphatic acyloxy group having 2 or more and 7 or less carbon atoms, or an alkyl group having 1 or more and 6 or less carbon atoms, and a dialkylamino group, a morpholin-1-yl group, a piperazin-1-yl group, a halogen, a nitro group, and a cyano group having an alkyl group having 1 to 6 carbon atoms. When the ^{phenyl group, naphthyl group, and heterocyclyl group included in R c4} further have a substituent, the number of the substituents is not limited within a range that does not impair the object of the present invention, but preferably 1 or more and 4 or less . When the ^{phenyl group, naphthyl group, and heterocyclyl group included in R c4} have a plurality of substituents, the plurality of substituents may be the same or different.

Moreover, as R<^c4> , a cycloalkyl alkyl group, the phenoxy alkyl group which may have a substituent on the aromatic ring, and the phenylthioalkyl group which may have a substituent on the aromatic ring are preferable. The substituent which the phenoxyalkyl group and the phenylthioalkyl group may have is the same as the substituent which the phenyl group contained in ^{Rc4 may have.}

Among the organic ^{groups, R c4 is preferably an} alkyl group, a cycloalkyl group, a phenyl group which may have a substituent, or a cycloalkyl alkyl group or a phenylthioalkyl group which may have a substituent on the aromatic ring. As the alkyl group, an alkyl group having 1 to 20 carbon atoms is preferable, an alkyl group having 1 to 8 carbon atoms is more preferable, an alkyl group having 1 to 4 carbon atoms is particularly preferable, and a methyl group is most preferable. Among the phenyl groups which may have a substituent, a methylphenyl group is preferable and the 2-methylphenyl group is more preferable. 5 or more and 10 or less are preferable, as for carbon atom number of the cycloalkyl group contained in a cycloalkyl alkyl group, 5 or more and 8 or less are more preferable, 5 or 6 are especially preferable. 1 or more and 8 or less are preferable, as for carbon atom number of the alkylene group contained in a cycloalkyl alkyl group, 1 or more and 4 or less are more preferable, 2 is especially preferable. Among the cycloalkyl alkyl groups, a cyclopentylethyl group is preferable. 1 or more and 8 or less are preferable, as for carbon atom number of the alkylene group contained in the phenylthioalkyl group which may have a substituent on an aromatic ring, 1 or more and 4 or less are more preferable, 2 is especially preferable. Among the phenylthioalkyl groups which may have a substituent on the aromatic ring, 2-(4-chlorophenylthio)ethyl group is preferable.

As mentioned above, ^{although Rc4} has been described, as ^Rc4 , a group represented by the following formula (Rc4-1) or (Rc4-2) is preferable.

(In formulas (Rc4-1) and (Rc4-2), R ^c11 and R ^c12 are each an organic group, p is an integer of 0 or more and 4 or less, and R ^c11 and R ^c12 are located adjacent to each other on the benzene ring. , R ^c11 and R ^c12 may combine with each other to form a ring, q is an integer of 1 or more and 8 or less, r is an integer of 1 or more and 5 or less, and s is an integer of 0 or more (r+3) or less and R ^c13 is an organic group.)

Examples of the organic group for ^{R c11} and R ^c12 in the formula (Rc4-1) are the same as those for ^{R c4 .} R ^c11 is preferably an alkyl group or a phenyl group. When R ^c11 is an alkyl group, 1 or more and 10 or less are preferable, as for the number of carbon atoms, 1 or more and 5 or less are more preferable, 1 or more and 3 or less are especially preferable, and 1 is the most preferable. That is, R ^c11 is most preferably a methyl group. When R ^c11 and R ^c12 combine to form a ring, the ring may be an aromatic ring or an aliphatic ring. Suitable examples of the group represented by the formula (Rc4-1) in which R ^c11 and R ^c12 form a ring include a naphthalen-1-yl group, a 1,2,3,4-tetrahydronaphthalen-5-yl group, and the like. can be heard In said formula (Rc4-1), p is an integer of 0 or more and 4 or less, It is preferable that it is 0 or 1, It is more preferable that it is 0.

In the formula (Rc4-2), R ^c13 is an organic group. ^Examples of the organic group include the same groups as the organic group described for R c4 . Among the organic groups, an alkyl group is preferable. The alkyl group may be linear or branched. 1 or more and 10 or less are preferable, as for carbon atom number of an alkyl group, 1 or more and 5 or less are more preferable, 1 or more and 3 or less are especially preferable. As R ^c13 , 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 (Rc4-2), r is an integer of 1 or more and 5 or less, an integer of 1 or more and 3 or less is preferable, and 1 or 2 is more preferable. In the formula (Rc4-2), s is 0 or more (r+3), preferably an integer of 0 or more and 3 or less, more preferably an integer of 0 or more and 2 or less, and particularly preferably 0. In the formula (Rc4-2), q is an integer of 1 or more and 8 or less, preferably an integer of 1 or more and 5 or less, more preferably an integer of 1 or more and 3 or less, and particularly preferably 1 or 2.

In formula (c1-1), R ^c5 is a hydrogen atom, an alkyl group having 1 to 11 carbon atoms which may have a substituent, or an aryl group which may have a substituent. When R ^c5 is an alkyl group, a phenyl group, a naphthyl group, etc. are preferably exemplified as the substituent which may be included. Moreover, ^{as a substituent which you may have when R<c5>} is an aryl group, a C1-C5 alkyl group, an alkoxy group, a halogen atom, etc. are illustrated preferably.

In formula (c1-1), R ^{c5 is preferably a} hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, phenyl group, benzyl group, methylphenyl group, naphthyl group, etc., Among these, a methyl group or a phenyl group is more preferable.

Specific examples of the compound represented by the formula (c1-1) include the following compounds.

[Fluorene-based oxime ester compound (C2)]

A fluorene-type oxime ester compound (C2) is a compound which has a fluorene ring and the bond represented by >C=N-O-CO-, and does not have a nitro group.

As a fluorene type oxime ester compound (C2), the compound represented, for example by a following formula (c2-1) is mentioned.

(In formula (c2-1), R ^c6 is a hydrogen atom or a monovalent organic group, and R ^c7 and R ^c8 are each a chain alkyl group which may have a substituent, a cyclic organic group which may have a substituent, or hydrogen atom, R ^c7 and R ^c8 may be bonded to each other to form a ring, R ^c9 is a monovalent organic ^{group, R c10} is a hydrogen atom, an alkyl group having 1 to 11 carbon atoms which may have a substituent, or It is an aryl group which may have a substituent, n2 is an integer of 0 or more and 4 or less, m2 is 0 or 1. However, the compound represented by Formula (c2-1) does not have a nitro group.)

In formula (c2-1), when R ^c6 is an organic group, R ^c6 is not particularly limited as long as the object of the present invention is not impaired, and is appropriately selected from various organic groups. Suitable examples when R ^c6 is an organic group include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, an alkoxycarbonyl group, a saturated aliphatic acyloxy group, an optionally substituted phenyl group, and an optionally substituted phenoxy group. , benzoyl group which may have a substituent, phenoxycarbonyl group which may have a substituent, benzoyloxy group which may have a substituent, phenylalkyl group which may have a substituent, naphthyl group which may have a substituent, naphthoxy which may have a substituent Group, the naphthoyl group which may have a substituent, the naphthoxycarbonyl group which may have a substituent, the naphthoyloxy group which may have a substituent, the naphthylalkyl group which may have a substituent, the heterocyclyl group which may have a substituent, a substituent The heterocyclylcarbonyl group which you may have, the amino group substituted by the organic group of 1 or 2, the morpholin-1-yl group, the piperazin-1-yl group, etc. are mentioned.

When R ^c6 is an alkyl group, 1 or more and 20 or less are preferable and, as for the number of carbon atoms of an alkyl group, 1 or more and 6 or less are more preferable. Further, when R ^c6 is an alkyl group, it may be linear or branched. Specific examples of the case where R ^c6 is an alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, and an isopentyl group. , sec-pentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, n-nonyl group, isononyl group, n- A decyl group, an isodecyl group, etc. are mentioned. In addition, when R ^c6 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 ^c6 is an alkoxy group, 1 or more and 20 or less are preferable and, as for the number of carbon atoms of an alkoxy group, 1 or more and 6 or less are more preferable. Further, when R ^c6 is an alkoxy group, it may be linear or branched. Specific examples when R ^c6 is an alkoxy group include a methoxy group, an ethoxy group, n-propyloxy group, isopropyloxy group, n-butyloxy group, isobutyloxy group, sec-butyloxy group, tert-butyloxy group, n-pentyloxy group, isopentyloxy group, sec-pentyloxy group, tert-pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, isooctyloxy group, sec-octyloxy group , tert-octyloxy group, n-nonyloxy group, isononyloxy group, n-decyloxy group, isodecyloxy group, and the like. In addition, when R ^c6 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 methoxy ethoxy group, an ethoxy ethoxy group, a methoxy ethoxy ethoxy group, an ethoxy ethoxy ethoxy group, a propyloxy ethoxy ethoxy group, and a methoxy propyloxy group. can be heard

When R ^c6 is a cycloalkyl group or a cycloalkoxy group, 3 or more and 10 or less are preferable and, as for the number of carbon atoms of a cycloalkyl group or a cycloalkoxy group, 3 or more and 6 or less are more preferable. Specific examples when R ^c1 is a cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Specific examples in the case where R ^c6 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 ^c6 is a saturated aliphatic acyl group or a saturated aliphatic acyloxy group, the number of carbon atoms in the saturated aliphatic acyl group or saturated aliphatic acyloxy group is preferably 2 or more and 21 or less, and more preferably 2 or more and 7 or less. Specific examples when R ^c6 is a saturated aliphatic acyl group include acetyl group, propanoyl group, n-butanoyl group, 2-methylpropanoyl group, n-pentanoyl group, 2,2-dimethylpropanoyl group, n-hexanoyl group, n-heptanoyl group, n-octanoyl group, n-nonanoyl group, n-decanoyl group, n-undecanoyl group, n-dodecanoyl group, n-tridecanoyl group, n-tetradecanoyl group, n- A pentadecanoyl group, n-hexadecanoyl group, etc. are mentioned. Specific examples in the case where R ^c6 is a saturated aliphatic acyloxy group include acetyloxy group, propanoyloxy group, n-butanoyloxy group, 2-methylpropanoyloxy group, n-pentanoyloxy group, and 2,2-dimethylpropanoyloxy group. Period, n-hexanoyloxy group, n-heptanoyloxy group, n-octanoyloxy group, n-nonanoyloxy group, n-decanoyloxy group, n-undecanoyloxy group, n-dodecanoyloxy group, n -tridecanoyloxy group, n-tetradecanoyloxy group, n-pentadecanoyloxy group, n-hexadecanoyloxy group, etc. are mentioned.

When R ^c6 is an alkoxycarbonyl group, 2 or more and 20 or less are preferable, and, as for the number of carbon atoms of the alkoxycarbonyl group, 2 or more and 7 or less are more preferable. Specific examples when R ^c6 is an alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, n-propyloxycarbonyl group, isopropyloxycarbonyl group, n-butyloxycarbonyl group, isobutyloxycarbonyl group, sec-butyloxycarbonyl group, tert-butyl group Oxycarbonyl group, n-pentyloxycarbonyl group, isopentyloxycarbonyl group, sec-pentyloxycarbonyl group, tert-pentyloxycarbonyl group, n-hexyloxycarbonyl group, n-heptyloxycarbonyl group, n-octyloxycarbonyl group, isooctyloxycarbonyl group, sec -octyloxycarbonyl group, tert-octyloxycarbonyl group, n-nonyloxycarbonyl group, isononyloxycarbonyl group, n-decyloxycarbonyl group, isodecyloxycarbonyl group, etc. are mentioned.

When R ^c6 is a phenylalkyl group, the number of carbon atoms in the phenylalkyl group is preferably 7 or more and 20 or less, and more preferably 7 or more and 10 or less. Moreover, when R<^c6> is a naphthylalkyl group, 11 or more and 20 or less are preferable and, as for the number of carbon atoms of a naphthylalkyl group, 11 or more and 14 or less are more preferable. Specific examples of the case where R ^c6 is a phenylalkyl group include a benzyl group, a 2-phenylethyl group, a 3-phenylpropyl group, and a 4-phenylbutyl group. Specific examples when R ^c6 is a naphthylalkyl group include an α-naphthylmethyl group, a β-naphthylmethyl group, a 2-(α-naphthyl)ethyl group, and a 2-(β-naphthyl)ethyl group. When R ^c6 is a phenylalkyl group or a naphthylalkyl group, R ^c6 may further have a substituent on the phenyl group or the naphthyl group.

When R ^c6 is a heterocyclyl group, the heterocyclyl group is a 5-membered or 6-membered monocyclic ring containing one or more N, S, O, or a heterocyclyl group obtained by condensing such monocyclic rings or such a monocyclic ring and a benzene ring. When the heterocyclyl group is a condensed ring, the number of condensed monocyclic rings is 3 or less. The heterocyclyl group may be an aromatic group (heteroaryl group) or a non-aromatic group. As a heterocycle constituting such a heterocyclyl group, furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyridine Midin, pyridazine, benzofuran, benzothiophene, indole, isoindole, indolizine, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, pr and talazine, cinnoline, quinoxarine, piperidine, piperazine, morpholine, tetrahydropyran, and tetrahydrofuran. When R ^c6 is a heterocyclyl group, the heterocyclyl group may further have a substituent.

When R ^c6 is a heterocyclylcarbonyl group, the heterocyclyl group included in the heterocyclylcarbonyl group is the ^{same as when R c6} is a heterocyclyl group.

When R ^c6 is an amino group substituted with an organic group of 1 or 2, suitable examples of the organic group include an alkyl group having 1 or more and 20 or less carbon atoms, a cycloalkyl group having 3 or more and 10 or less carbon atoms, and 2 or more and 21 or less carbon atoms. A saturated aliphatic acyl group of A naphthoyl group, a C11-C20 naphthylalkyl group which may have a substituent, a heterocyclyl group, etc. are mentioned. Specific examples of these suitable organic groups are the same as the organic group as ^{R c6 .} Specific examples of the amino group substituted with 1 or 2 organic groups include methylamino group, ethylamino group, diethylamino group, n-propylamino group, di-n-propylamino group, isopropylamino group, n-butylamino group, di-n-butyl Amino group, n-pentylamino group, n-hexylamino group, n-heptylamino group, n-octylamino group, n-nonylamino group, n-decylamino group, phenylamino group, naphthylamino group, acetylamino group, propanoylamino group, n-buta noylamino group, n-pentanoylamino group, n-hexanoylamino group, n-heptanoylamino group, n-octanoylamino group, n-decanoylamino group, benzoylamino group, α-naphthoylamino group, and β-naphthoylamino group can be heard

^Examples of the substituent in case the phenyl group, naphthyl group, and heterocyclyl group contained in R c6 further have a substituent include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and the number of carbon atoms. A monoalkylamino group having 2 or more and 7 or less saturated aliphatic acyl group, an alkoxycarbonyl group having 2 or more and 7 or less carbon atoms, a saturated aliphatic acyloxy group having 2 or more and 7 or less carbon atoms, or an alkyl group having 1 or more and 6 or less carbon atoms, and a dialkylamino group, a morpholin-1-yl group, a piperazin-1-yl group, a halogen, a nitro group, and a cyano group having an alkyl group having 1 to 6 carbon atoms. When the ^{phenyl group, naphthyl group, and heterocyclyl group contained in R c6} further have a substituent, the number of the substituents is not limited within a range that does not impair the object of the present invention, but preferably 1 or more and 4 or less. . When the ^{phenyl group, naphthyl group, and heterocyclyl group included in R c6} have a plurality of substituents, the plurality of substituents may be the same or different.

Among the groups described above, a hydrogen atom is preferable as ^{R c6} because transparency tends to be good.

R ^c7 and R ^c8 in formula (c2-1) are the same as R ^c2 and R ^c3 in formula (c1-1), respectively.

^{R c9} in formula (c2-1) is the same ^{as R c4} in formula (c1-1).

^{R c10} in formula (c2-1) is the same ^{as R c5} in formula (c1-1).

Specific examples of the compound represented by the formula (c2-1) include the following compounds.

[Compound (C3)]

A compound (C3) is at least 1 sort(s) chosen from a phosphine oxide type compound and an amino ketone type compound.

-Phosphine oxide compound-

The phosphine oxide-based compound is a pentavalent phosphorus compound having a P=O bond.

As an example of a phosphine oxide type compound, the compound which has a partial structure represented by following formula (c3-1) is mentioned.

In formula (c3-1), R ^c21 and R ^c22 are each independently an alkyl group, a cycloalkyl group, an aryl group, an aliphatic acyl group having 2 or more and 20 or less carbon atoms, or an aromatic aryl group having 7 or more and 20 or less carbon atoms. it's a mistake However, ^{both of R c21} and R ^c22 are not an aliphatic acyl group or an aromatic acyl group.

1 or more and 12 or less are preferable, as for the number of carbon atoms of the alkyl group as R ^c21 and R ^c22 , 1 or more and 8 or less are more preferable, and their 1 or more and 4 or less are still more preferable. The ^{alkyl group as R c21} and R ^c22 may be linear or branched.

Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, tert-pentyl group , n-hexyl group, n-heptyl group, n-octyl group, 2,4,4-trimethyl pentyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group, n-undecyl group, and n- A dodecyl group etc. are mentioned.

The ^{number of carbon atoms in the cycloalkyl group as R c21} and R ^c22 is preferably 5 or more and 12 or less. Specific examples of the cycloalkyl group include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, a cyclodecyl group, a cycloundecyl group, and a cyclododecyl group.

The ^{number of carbon atoms in the aryl group as R c21} and R ^c22 is preferably 6 or more and 12 or less. The aryl group may have a substituent. As an example of a substituent, a halogen atom, C1-C4 alkyl group, C1-C4 alkoxy group, etc. are mentioned. Specific examples of the aryl group include a phenyl group and a naphthyl group.

The ^{number of carbon atoms in the aliphatic acyl group as R c21} and R ^c22 is 2 or more and 20 or less, preferably 2 or more and 12 or less, more preferably 2 or more and 8 or less, and still more preferably 2 or more and 6 or less. The aliphatic acyl group may be linear or branched.

Specific examples of the aliphatic acyl group include an acetyl group, a propionyl group, a butanoyl group, a pentanoyl group, a hexanoyl group, a heptanoyl group, an octanoyl group, a nonanoyl group, a decanoyl group, an undecanoyl group, a dodecanoyl group, a tridecanoyl group, A tetradecanoyl group, a pentadecanoyl group, a hexadecanoyl group, a heptadecanoyl group, an octadecanoyl group, a nonadecanoyl group, an icosanoyl group, etc. are mentioned.

The number of carbon atoms in the aromatic acyl group as ^{R c21} and R ^{c22 is 7 or more and 20 or less.} The aromatic acyl group may have a substituent. As an example of a substituent, a halogen atom, C1-C4 alkyl group, C1-C4 alkoxy group, etc. are mentioned. Specific examples of the aromatic acyl group include benzoyl group, o-tolyl group, m-tolyl group, p-tolyl group, 2,6-dimethyl benzoyl group, 2,6-dimethoxybenzoyl group, 2,4,6-trimethylbenzoyl group diary, α-naphthoyl group, and β-naphthoyl group; and the like.

Preferred specific examples of the phosphine oxide compound containing a structural moiety represented by the formula (c3-1) include 2,4,6-trimethylbenzoyl diphenyl phosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenyl Phosphine oxide and bis(2,6-dimethoxy benzoyl)-2,4,4-trimethyl-pentyl phosphine oxide etc. are mentioned.

-Amino ketone compounds-

The amino ketone-based compound is a ketone compound having an amino group that can be used as a photopolymerization initiator. The amino ketone compound is typically an α-amino ketone compound, which is a carbonyl compound to which an optionally substituted amino group is bonded to the α position.

Examples of the amino ketone compound include 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-morph Polynopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-dimethylaminophenyl) butan-1-one, 2-(4-methylbenzyl)-2-diethylamino-1-( 4-morpholinophenyl)butan-1-one, 2-methyl-1-phenyl-2-morpholinopropan-1-one, 2-methyl-1-[4-(hexyl)phenyl]-2-morph α-amino ketone compounds such as polynopropan-1-one and 2-ethyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one; and the like.

Although the photosensitive composition may contain photopolymerizable compounds other than a fluorene type oxime ester compound (C1), a fluorene type oxime ester compound (C2), and a compound (C3), the photoinitiator (C) of a photoinitiator (C) of a photosensitive composition The total content of the fluorene-based oxime ester compound (C1), the fluorene-based oxime ester compound (C2) and the compound (C3) is preferably 80% by mass or more, more preferably 90% by mass or more, and 100% by mass % is more preferable.

Moreover, it is preferable that a photoinitiator (C) does not contain the photopolymerizable compound which has a carbazole ring.

The ratio of the mass of the fluorene-based oxime ester compound (C1) to the sum of the mass of the fluorene-based oxime ester compound (C1) and the mass of the fluorene-based oxime ester compound (C2) (mass/(C1) The mass of (C1) + the mass of (C2))) is, for example, 1 mass % or more and 40 mass % or less, and the upper limit is preferably 30 mass % or less, more preferably 25 mass % or less, 13 % by mass or less is more preferable.

In particular, when it is 3 mass % or more and 13 mass % or less, the transparent body which was more excellent in the transmittance|permeability can be obtained.

The ratio of the mass of the fluorene-based oxime ester compound (C1) to the mass of the photoinitiator (C) (mass of the fluorene-based oxime ester compound (C1)/mass of the photoinitiator (C)) is 1% by mass or more 40 mass % or less is preferable, 5 mass % or more and less than 30 mass % are more preferable, 5 mass % or more and 15 mass % or less are still more preferable.

The ratio of the mass of the fluorene-based oxime ester compound (C2) to the mass of the photoinitiator (C) (mass of the fluorene-based oxime ester compound (C2)/mass of the photoinitiator (C)) is 60% by mass or more 90 mass % or less is preferable, 70 mass % or more and 85 mass % or less are more preferable, and 75 mass % or more and 85 mass % or less are still more preferable.

The ratio of the mass of the compound (C3) to the mass of the photoinitiator (C) (the mass of the compound (C3) / the mass of the photoinitiator (C)) is preferably 5 mass % or more and 15 mass % or less, and 5 mass % % or more and 13 mass % or less are more preferable, and 5 mass % or more and 10 mass % or less are still more preferable.

As for content of a photoinitiator (C), 0.1 mass % or more and 30 mass % or less are preferable with respect to the mass of the whole solid content of the photosensitive composition, 0.5 mass % or more and 20 mass % or less are more preferable, 1 mass % or more and 10 mass % The following are more preferable.

<Solvent (S)>

As the solvent (S) to contain, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether , propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n- (poly)alkylene glycol monoalkyl ethers such as butyl ether, tripropylene glycol monomethyl ether, and tripropylene glycol monoethyl ether; (poly)alkylenes such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate glycol monoalkyl ether acetates; 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; 2-hydroxy-2-methylpropionate ethyl, 3-methoxypropionate methyl, 3-methoxypropionate ethyl, 3-ethoxypropionate methyl, 3-ethoxypropionate ethyl, ethoxypropionate ethyl, ethyl hydroxyacetate, 2 -Hydroxy-3-methylbutanoate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-acetic acid Butyl, isobutyl acetate, n-pentyl formate, isopentyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, acetoacetic acid other esters such as methyl, ethyl acetoacetate, and ethyl 2-oxobutanoate; aromatic hydrocarbons such as toluene and xylene; Amides, such as N-methylpyrrolidone, N,N- dimethylformamide, and N,N- dimethylacetamide, etc. are mentioned. These solvents may be used independently and may be used in combination of 2 or more type.

Among the above solvents, propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, 3- Methoxy butyl acetate is preferable because it can improve dispersibility of the above-mentioned (C) component while exhibiting excellent solubility in the above-mentioned (A) component and (B) component, propylene glycol monomethyl ether acetate; Particular preference is given to using 3-methoxy butyl acetate.

As for content of a solvent (S), the quantity used as solid content concentration of 1 mass % or more and 50 mass % or less of a coloring photosensitive composition is preferable, The quantity used as 5 mass % or more and 40 mass % or less is more preferable, 10 mass % or more The quantity used as 30 mass % or less is more preferable.

<Other ingredients>

The photosensitive composition which concerns on this invention may contain various additives as needed. Various additives include sensitizers, curing accelerators, photocrosslinking agents, photosensitizers, dispersing aids, fillers, adhesion promoters, antioxidants, ultraviolet absorbers, aggregation inhibitors, thermal polymerization inhibitors, defoamers, surfactants, silane coupling agents, etc. is exemplified

As a thermal polymerization inhibitor, hydroquinone, hydroquinone monoethyl ether, etc. are mentioned, for example. In addition, compounds, such as a silicone type and a fluorine type, can be illustrated as an antifoaming agent, and compounds, such as an anionic, a cationic type, and a nonionic, as surfactant, respectively.

<The preparation method of the photosensitive composition>

The said photosensitive composition can be prepared by stirring and mixing said each component, and melt|dissolving or disperse|distributing it. You may mix with stirrers, such as a roll mill, a ball mill, and a sand mill. If necessary, it can be prepared by filtration with a filter such as a 2 µm membrane filter.

«Transparent body and manufacturing method of transparent body»

By hardening the photosensitive composition demonstrated above, the transparent body as hardened|cured material can be obtained.

The manufacturing method of a transparent body includes the process of apply|coating the above-mentioned photosensitive composition to form a coating film, and the process of exposing a coating film.

In addition, the transparent body may be patterned. The manufacturing method of a patterned transparent body includes the process of apply|coating the above-mentioned photosensitive composition to form a coating film, the process of position-selectively exposing the coating film, and the process of developing the coating film after exposure.

Since the transparent body manufactured using the above-mentioned photosensitive composition has excellent adhesion to the substrate and has a tapered cross-section having an appropriate taper angle, the adhesiveness and cross-section of the insulating film or spacer to the substrate are excellent. It can use suitably for the use requested|required that it is a taper shape which has an appropriate taper angle.

Hereinafter, each process is demonstrated. The thing which apply|coats a photosensitive composition and forms a coating film is described as "coating film formation process". Exposing the coating film is described as "exposure step". Developing the coating film after exposure is described as "developing process".

<coating film forming process>

In a coating film formation process, a photosensitive composition is apply|coated on a board|substrate, and a coating film is formed.

The type of the substrate is not particularly limited, and various substrates used in optical devices such as liquid crystal display devices, organic EL display devices, and organic TFT arrays can be suitably used. As the substrate, for example, quartz, glass, optical film, ceramic material, vapor deposition film, magnetic film, reflective film, metal substrate such as Ni, Cu, Cr, Fe, SOG (Spin On Glass), polyester film, polycarbonate film , polymer substrates such as polyimide films, TFT array substrates, PDP electrode plates, glass and transparent plastic substrates, conductive substrates such as ITO and metal, insulating substrates, silicon, silicon nitride, polysilicon, silicon oxide, amorphous silicon, etc. A semiconductor substrate etc. are mentioned. Further, for example, in the case of forming a laminated structure on a substrate, any layer that becomes an underlying structure already formed on the substrate is included in the concept as a substrate to which the photosensitive composition is applied. In addition, the shape of a base material is not specifically limited, either, Plate shape may be sufficient, and roll shape may be sufficient. The substrate may have irregularities on the surface by, for example, various patterns. In addition, as said base material, a light transmissive or non-light transmissive base material can be selected.

In the coating film forming step, for example, a contact transfer type coating device such as a roll coater, a reverse coater, or a bar coater, or a non-contact type coating device such as a spinner (rotary coating device) or a curtain flow coater is used to form the photosensitive composition on the substrate. is applied, and if necessary, the solvent is removed by drying (pre-baking) to form a coating film.

The film thickness of the coating film is not particularly limited. As thickness of a coating film, 0.05 micrometer or more is preferable and 1 micrometer or more is more preferable. The thickness of the coating film may be, for example, 7 µm or more, or 10 µm or more. Although there is no upper limit in particular of the thickness of a coating film, For example, 50 micrometers or less may be sufficient and 20 micrometers or less may be sufficient. 10 micrometers or less are preferable, as for the thickness of a coating film, 5 micrometers or less are more preferable, and 2 micrometers or less are still more preferable.

The drying method is not particularly limited, for example, (1) a method of drying for 60 seconds or more and 120 seconds or less at a temperature of 80° C. or more and 120° C. or less, preferably 90° C. or more and 100° C. or less, on a hot plate, (2) a method of leaving it to stand at room temperature for several hours to several days, (3) a method of removing the solvent by putting it in a warm air heater or an infrared heater for several tens of minutes to several hours.

<Exposure process>

In an exposure process, the coating film formed in the coating film formation process is exposed. Thereby, the hardened|cured material (transparent body) of the photosensitive composition is obtained. A patterned hardened|cured material (transparent body) is obtained by exposing and developing position-selectively according to a desired pattern shape.

In an exposure process, active energy rays, such as an ultraviolet-ray and excimer laser light, are irradiated and exposed. In the case of forming a patterned cured product (transparent body), exposure to the coating film is positionally selective through, for example, a negative mask. Although an exposure amount changes also with the composition of the photosensitive composition, 10 mJ/cm<^2> or more and 100 mJ/cm<^2> or less are preferable, for example. Although the photosensitive composition of the above is due to smoking sensitivity is excellent, for example, even at a low exposure amount that 10 mJ / cm ² or more 30 mJ / cm ² or less, further to the 10 mJ / cm ² or more 20 mJ / cm ² or less, the substrate It is possible to form a cured product having excellent adhesion to the substrate and to form a pattern having a moderately tapered cross section.

You may heat with respect to the hardened|cured material hardened|cured by exposure. The temperature at the time of heating is not specifically limited, 180 degreeC or more and 280 degrees C or less are preferable, 200 degrees C or more and 260 degrees C or less are more preferable, 220 degreeC or more and 250 degrees C or less are especially preferable. The heating time is typically preferably 1 minute or more and 60 minutes or less, more preferably 10 minutes or more and 50 minutes or less, and particularly preferably 20 minutes or more and 40 minutes or less.

<Development process>

The developing process WHEREIN: The coating film exposed by the exposure process is developed with developing solutions, such as an alkali developing solution.

In a developing process, the hardened|cured material (transparent body) patterned in a desired shape is formed by developing the coating film after exposure with a developing solution. The image development method is not specifically limited, For example, an immersion method, a spray method, etc. can be used. The developer is appropriately selected according to the composition of the photosensitive composition. As a developing solution, organic developing solutions, such as monoethanolamine, diethanolamine, and triethanolamine, and aqueous solutions, such as sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, and a quaternary ammonium salt, can be used.

After image development, you may post-baking as needed, 80 degreeC or more and 250 degrees C or less are preferable and, as for the temperature of post-baking after image development, 100 degrees C or more and 230 degrees C or less are more preferable. 5 minutes or more and 60 minutes or less are preferable, and, as for the time of post-baking after image development, 10 minutes or more and 30 minutes or less are more preferable.

[Example]

EXAMPLES Hereinafter, although an Example is shown and this invention is further concretely demonstrated, the scope of the present invention is not limited to these Examples.

[Preparation of Resin A1]

In a 500 mL four-necked flask, 235 g of bisphenol fluorene type epoxy resin (epoxy equivalent 235), 110 mg of tetramethyl ammonium chloride, 100 mg of 2,6-di-tert-butyl-4-methylphenol, and 72.0 g of acrylic acid were put thereinto, 25 mL It was dissolved by heating to 90°C or higher and 100°C or lower while blowing air at a rate of /min. Next, the solution was gradually heated while still in a cloudy state, and heated to 120 DEG C for complete dissolution. At this time, although the solution gradually became transparent and viscous, stirring was continued as it was. During this time, the acid value was measured and heating and stirring was continued until it became less than 1.0 mgKOH/g. It took 12 hours for the acid value to reach the target. And it cooled to room temperature, and obtained the bisphenol fluorene type epoxy acrylate which is colorless and transparent and is represented by the following formula of solid state.

Next, 600 g of 3-methoxybutyl acetate was added to 307.0 g of the bisphenol fluorene type epoxy acrylate obtained in this way and dissolved, followed by mixing 79.4 g of biphenyl tetracarboxylic dianhydride and 1 g of tetraethyl ammonium bromide. , the temperature was gradually increased and the reaction was carried out at 110°C or higher and 115°C or lower for 4 hours. After confirming disappearance of an acid anhydride group, 41.0 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed, it was made to react at 90 degreeC for 6 hours, and resin A1 was obtained. Resin A1 is a compound represented by Formula (a-1). The disappearance of the acid anhydride group was confirmed by IR spectrum.

The mass average molecular weight of resin A1 was 4500.

[Preparation of Examples 1 to 16 and Comparative Examples 1 to 20]

<Alkali-soluble resin (A) (component A)>

As alkali-soluble resin (A), said resin A1 was used.

<Photopolymerizable monomer (B) (component B)>

As the photopolymerizable monomer (B), B1: dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.) was used.

<Photoinitiator (C) (component C)>

As the fluorene-based oxime ester compound (C1) (component C1), the following C1-a and C1-b were used.

As the fluorene-based oxime ester compound (C2) (component C2), the following C2-a and C2-b were used.

As compound (C3), C3-a to C3-c were used.

C3-a: Omnirad 　 819 (IGM 　 Resins 　 B.V. made)

C3-b: Omnirad 　369 (IGM 　Resins 　 B.V. made)

C3-c: Omnirad　907 (IGM　Resins　B.V. Manufactured)

As a fluorene-based oxime ester compound (C1), a fluorene-based oxime ester compound (C2), and a photopolymerization initiator (C') that does not correspond to the compound (C3) (hereinafter also referred to as (C') component), C': NCI -831 (made by ADEKA) was used.

In Table 1, the kind and mass parts of the base material, alkali-soluble resin (A), photopolymerizable monomer (B), photoinitiator (C), 0.2 parts by mass of surfactant (BYK310, manufactured by Bikchemi Co., Ltd.), 0.5 parts by mass A silane coupling agent (3-(phenylamino)propyl trimethoxy silane) was mixed with 3-methoxybutyl acetate (MA) and propylene glycol monomethyl ether acetate (PM) in a mixed solvent (MA/PM = 15/85 (mass ratio). )) to obtain photosensitive compositions of Examples and Comparative Examples.

[Evaluation of OD value]

After apply|coating the photosensitive composition on a 6-inch glass substrate (made by Dow Corning, 1737 glass), it dried at 90 degreeC for 60 second, and formed the coating film. Then, the coating film was irradiated with ghi rays at an exposure amount ^{of 60 mJ/cm 2 .} And post-baking was performed on a hot plate at 230 degreeC for 20 minutes. The film thickness of the formed film (cured product) was 0.8 µm, 1.0 µm, and 1.2 µm. About this film (hardened|cured material), the OD value in each film thickness was measured using D200-II (made by Macbeth), and the OD value per 1 micrometer was computed from the approximate curve. The calculated OD values were 0.1/m in both Examples 1-16 and Comparative Examples 1-20.

[Evaluation of adhesion]

It carried out similarly to evaluation of the said OD value, and formed the film|membrane (hardened|cured material) with a film thickness of 1.0 micrometer. A stud pin with an epoxy adhesive was installed vertically with respect to this film, and it was heat-dried at 220 degreeC for 5 minutes, and the said stud pin was fixed. The said stud pin was pulled perpendicularly|vertically with respect to the said film|membrane at the speed of 0.5 mm/min using Shimadzu small tabletop tester EZ test (trade name, Shimadzu Corporation make), and adhesive strength was measured as tensile strength. Adhesiveness was evaluated according to the following criteria. A result is shown in Table 2.

◎: 300N or more and 330N or less

○: 270N or more and less than 300N

×: less than 270N

[Pattern Evaluation]

The photosensitive composition of an Example and a comparative example was apply|coated using the spin coater on the glass substrate (100 mmХ100 mm), it prebaked at 70 degreeC for 120 second, and formed the coating film. Then, using a proximity exposure apparatus (product name: TME-150 RTO, manufactured by Topcon Co., Ltd.), the exposure gap was set to 50 μm, and a line-and-space pattern having a line width of 6 μm and a space width of 6 μm was formed through a negative mask formed therein. The coating film was irradiated with ultraviolet rays. Exposure dose, and a third step of ^{20mJ / cm 2, 40mJ / cm} 2, 60mJ / cm 2. After developing the coating film after exposure for 50 seconds with a 0.04 mass % KOH aqueous solution at 26°C, post-baking was performed at 230°C for 30 minutes to form a line-and-space pattern having a thickness of 3.5 µm.

(Pattern straightness evaluation)

The formed line pattern was observed with an optical microscope, and the pattern straightness was evaluated. The pattern straightness evaluated the case where there was no wobble at the edge of the line as "good", and the case where there was wobble was evaluated as "poor". In Comparative Examples 5, 7, and 8, since the pattern was peeled off from the substrate at the time of development, the straightness of the pattern could not be evaluated.

(Pattern Peel Evaluation)

The formed line and space pattern was observed with an optical microscope, and the presence or absence of pattern peeling was confirmed. A result is shown in Table 2.

(Tapered shape)

About the line-and-space pattern formed with the exposure amount of 20 mJ/cm<^{2>, the taper angle was evaluated.} About the taper angle, it measured as the bonding angle between a pattern and a board|substrate with a scanning electron microscope. This taper angle corresponds to the angle θ in FIGS. 1A and 1B . The measured taper shape was evaluated according to the following criteria. Evaluation a-e is not a taper shape which has an appropriate taper angle in all. Incidentally, evaluation e indicates that the taper angle could not be measured because the pattern was peeled off from the substrate at the time of development. A result is shown in Table 2.

◎: 75° or more and 85° or less

○: 70° or more and less than 75°

a: greater than 85° and less than 90°

b: 90° or more and 100° or less

c: >100°

d: less than 70°

e: peeled off

(transmittance)

A line and space pattern was formed in the same manner as described in [Pattern Evaluation] except that the exposure amount was 50 mJ/cm ^{2 and the post-baking was carried out at 230°C for 60 minutes.} With respect to the formed line and space pattern, the transmittance of light having a wavelength of 400 nm was measured. The transmittance was evaluated according to the following criteria. A result is shown in Table 2.

◎: 98% or more

○: 95% or more and less than 98%

△: 90% or more and less than 95%

×: less than 90%

[alien substance]

On a 680mmХ880mm glass substrate, the photosensitive compositions of Examples and Comparative Examples were applied using a spin coater (TR-45000 manufactured by Tokyo Oka Kogyo Co., Ltd.), and then dried at 90° C. for 60 seconds to form a coating film having a thickness of 1.5 μm. Then, using an ultraviolet irradiator (product name: MPA6000, manufactured by Canon Co., Ltd.), the formed coating film ^{is exposed through a mask at an exposure amount of 90 mJ/cm 2} , and then 30 with a 0.04 mass % KOH aqueous solution at 26° C. The pattern was obtained by performing image development for a second and the post-baking for 30 minutes at 230 degreeC. The shape of the pattern of the mask is a matrix shape in which vertical and horizontal lines orthogonal to 6 μm in width are formed at intervals of 150 μm in length and 50 μm in width.

The number of foreign substances having a size of 100 µm or more in the formed pattern was measured using an appearance inspection apparatus manufactured by Takano Corporation, and the following standards evaluated the foreign substances. A result is shown in Table 2.

(double-circle): The number of size foreign material of 100 micrometers or more in a pattern is 0

○: The number of foreign matter of size 100 μm or more in the pattern is 1-2 pieces

Δ: 3 to 5 foreign objects with a size of 100 μm or more in the pattern

x: 6 or more size foreign matter of 100 μm or more in the pattern

According to Tables 1 and 2, together with the alkali-soluble resin (A), the photopolymerizable monomer (B) and the solvent (S), the fluorene-based oxime ester compound (C1) having a nitro group and the fluorene-based oxime ester compound (C1) having no nitro group The photosensitive compositions of Examples 1 to 16 containing the oxime ester compound (C2) and the compound (C3) can form a cured product excellent in adhesion to a substrate, and have a tapered cross section having an appropriate taper angle. It can be seen that a patterned cured product having Moreover, from Table 1 and Table 2, by using the photosensitive composition of Examples 1-16, there is no peeling of a pattern at the time of image development, and it turns out that a pattern excellent in straightness can be formed, and a foreign material does not generate|occur|produce.

On the other hand, it can be seen that the cured products formed of the photosensitive compositions of Comparative Examples 1 to 20, which do not satisfy the above composition, do not have excellent adhesion to the substrate or have a tapered cross section having an appropriate taper angle for the pattern.

1 Cross section in the width direction in a pattern without undercut
2 Cross section in the width direction in a pattern with an undercut

Claims (8)

Alkali-soluble resin (A), a photopolymerizable monomer (B), a photoinitiator (C), and a solvent (S) are contained,
The photopolymerization initiator (C) is at least one compound (C3) selected from a fluorene-based oxime ester compound (C1), a fluorene-based oxime ester compound (C2), a phosphine oxide-based compound, and an amino ketone-based compound contains,
The fluorene-based oxime ester compound (C1) has a nitro group,
The photosensitive composition, wherein the fluorene-based oxime ester compound (C2) does not have a nitro group. The method according to claim 1,
The photosensitive composition in which a fluorene type oxime ester compound (C1) contains the compound represented by following formula (c1-1).
[Tue 1]

(R ^c1 is a nitro group, R ^c2 and R ^c3 are each a chain alkyl group which may have a substituent, a cyclic organic group which may have a substituent, or a hydrogen atom, and R ^c2 and R ^c3 are bonded to each other to form a ring may be formed, R ^c4 is a monovalent organic ^{group, R c5} 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, and n1 is 1 or more 4 It is an integer of the following, and m1 is 0 or 1.) The method according to claim 1 or 2,
The photosensitive composition in which a fluorene type oxime ester compound (C2) contains the compound represented by following formula (c2-1).
[Tue 2]

(R ^c6 is a hydrogen atom or a monovalent organic group, R ^c7 and R ^c8 are each a chain alkyl group which may have a substituent, a cyclic organic group which may have a substituent, or a hydrogen atom, R ^c7 and R ^c8 may combine with each other to form a ring, R ^c9 is a monovalent organic ^{group, R c10} 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 , n2 is an integer of 0 or more and 4 or less, and m2 is 0 or 1. However, the compound represented by the formula (c2-1) does not have a nitro group.) 4. The method according to any one of claims 1 to 3,
The ratio of the mass of the fluorene-type oxime ester compound (C1) to the sum of the mass of the fluorene-type oxime ester compound (C1) and the mass of the fluorene-type oxime ester compound (C2) is 3 mass % or more and 13 mass % or less, the photosensitive composition. 5. The method according to any one of claims 1 to 4,
The photosensitive composition whose ratio of the mass of a compound (C3) with respect to the mass of a photoinitiator (C) is 5 mass % or more and 15 mass % or less. The transparent body which consists of a hardened|cured material of the photosensitive composition of any one of Claims 1-5. A step of forming a coating film by applying the photosensitive composition of any one of claims 1 to 5;
The manufacturing method of the transparent body including the process of exposing the said coating film. A step of forming a coating film by applying the photosensitive composition of any one of claims 1 to 5;
a step of positionally selectively exposing the coating film;
The manufacturing method of the patterned transparent body including the process of developing the said coating film after exposure.

Images