KR102557630B1 - Photosensitive Composition - Google Patents

Abstract

It is to provide a photosensitive composition that can be satisfactorily cured even when exposed to light by an LED, a method for producing a cured product of the photosensitive composition, and providing a cured product of the photosensitive composition.
In a photosensitive composition containing (A) a photopolymerizable compound and (B) a photopolymerization initiator, (B) a compound represented by the following formula (1) is contained as the photopolymerization initiator, and (C) a sensitizer is incorporated into the photosensitive composition. do. In formula (1), R ¹ is a hydrogen atom, a nitro group or a monovalent organic group, R ² and R ³ 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 ² and R ³ may be bonded to each other to form a ring, R ⁴ is a monovalent organic group, R ⁵ is a hydrogen atom, an alkyl group having 1 to 11 carbon atoms which may have a substituent, or a substituent which may have a substituent It is an aryl group, n is an integer from 0 to 4, and m is 0 or 1.

Description

Photosensitive composition

The present invention relates to a photosensitive composition, a method for producing a cured product of the photosensitive composition, and a cured product of the photosensitive composition.

BACKGROUND OF THE INVENTION [0002] A display device such as a liquid crystal display has a structure in which a liquid crystal layer is sandwiched between two substrates on which electrodes that face each other and form a pair are formed. On the inside of one substrate, a color filter composed of pixel areas of each color such as red (R), green (G), and blue (B) is formed. In this color filter, a black matrix is usually formed so as to partition each pixel area of red, green, blue, etc.

In addition, a panel for a display device may be provided with a transparent insulating film or the like.

A color filter or a transparent insulating film is often manufactured by a photolithography method using a photosensitive composition. For example, a color filter is first coated with a black photosensitive composition on a substrate, dried, exposed, and developed to form a black matrix. Next, for each color photosensitive composition such as red, green, and blue, coating, drying, exposure, and development are repeated to form a pixel area of each color at a specific position, and it is manufactured.

And about the photosensitive composition used for manufacture, such as a liquid crystal display, high sensitivity is requested|required from viewpoints, such as reduction of manufacturing cost of a display device, productivity improvement, etc. In such a situation, the oxime ester compound which has a cycloalkyl group is proposed by patent document 1 as a photoinitiator which can improve the sensitivity of a photosensitive composition. In the examples described in Patent Literature 1, compounds represented by the following formulas (a) and (b) are specifically disclosed.

[Tue 1]

Publication of the People's Republic of China Patent Publication No. 101508744

The photosensitive composition containing the oxime ester compound described in patent document 1 certainly has a favorable sensitivity.

However, the photosensitive composition containing the oxime ester compound described in Patent Literature 1 is not necessarily cured satisfactorily when exposed to light with an LED.

LEDs are being used as light sources for exposure from the viewpoints of energy saving and environmental load reduction.

The present invention has been made in view of the above problems, and an object of the present invention is to provide a photosensitive composition that can be satisfactorily cured even when exposed to light with an LED, a method for producing a cured product of the photosensitive composition, and a cured product of the photosensitive composition.

In the photosensitive composition containing (A) a photopolymerizable compound and (B) a photopolymerization initiator, the inventors of the present invention contain an oxime ester compound having a specific structure having a 9,9-disubstituted fluorenyl group as a photopolymerization initiator (B), Furthermore, (C) By mix|blending a sensitizer with a photosensitive composition, it discovered that said subject was solvable, and came to complete this invention. Specifically, the present invention provides the following.

The first aspect of the present invention comprises (A) a photopolymerizable compound, (B) a photopolymerization initiator, and (C) a sensitizer,

(B) the photopolymerization initiator has the following formula (1):

[Tue 2]

(R ¹ is a hydrogen atom, a nitro group or a monovalent organic group, R ² and R ³ 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 ² and R ³ may combine with each other to form a ring, R ⁴ is a monovalent organic group, R ⁵ 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, n is an integer from 0 to 4, and m is 0 or 1.)

It relates to a photosensitive composition comprising a compound represented by

A second aspect of the present invention relates to a method for producing a cured product in which the photosensitive composition related to the first aspect is cured by exposure to light.

A third aspect of the present invention relates to a cured product of the photosensitive composition related to the first aspect.

ADVANTAGE OF THE INVENTION According to this invention, the photosensitive composition which hardens satisfactorily even when exposed by LED, the manufacturing method of the hardened|cured material of the said photosensitive composition, and the hardened|cured material of the said photosensitive composition can be provided.

<<Photosensitive composition>>

The photosensitive composition of the present invention contains (A) a photopolymerizable compound, (B) a photopolymerization initiator, and (C) a sensitizer. (B) The photopolymerization initiator contains an oxime ester compound having a specific structure having a 9,9-disubstituted fluorenyl group. The photosensitive composition may contain (D) a coloring agent, and may contain (E) alkali-soluble resin. Hereinafter, the components contained in the photosensitive composition and the method for preparing the photosensitive composition are described in order.

<(A) photopolymerizable compound>

The (A) photopolymerizable compound (hereinafter also referred to as component (A)) contained in the photosensitive composition of the present invention is not particularly limited, and conventionally known photopolymerizable compounds can be used. Especially, resin or monomer which has an ethylenically unsaturated group is preferable, and you may combine these. By combining a resin having an ethylenically unsaturated group and a monomer having an ethylenically unsaturated group, the curability of the photosensitive composition can be improved to facilitate pattern formation. In the present invention, a monomer having an ethylenically unsaturated group is more preferred.

[Resin having an ethylenically unsaturated group]

As the resin having an ethylenically unsaturated group, (meth)acrylic acid, fumaric acid, maleic acid, monomethyl fumarate, monoethyl fumarate, 2-hydroxyethyl (meth)acrylate, ethylene glycol monomethyl ether (meth)acrylate, ethylene glycol mono Ethyl ether (meth)acrylate, glycerol (meth)acrylate, (meth)acrylamide, acrylonitrile, methacrylonitrile, methyl (meth)acrylate, ethyl (meth)acrylate, isobutyl (meth)acryl Rate, 2-ethylhexyl (meth)acrylate, benzyl (meth)acrylate, ethylene glycol di (meth)acrylate, diethylene glycol di (meth)acrylate, triethylene glycol di (meth)acrylate, tetraethylene Glycol di(meth)acrylate, butylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, tetramethylolpropanetetra(meth)acrylate, pentaeryth Litol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 1,6-hexanedioldi(meth) Oligomers polymerized with acrylate, cardoepoxydiacrylate and the like; Polyester (meth)acrylate obtained by making (meth)acrylic acid react with the polyester prepolymer obtained by condensing polyhydric alcohol and monobasic acid or polybasic acid; Polyurethane (meth)acrylate obtained by making (meth)acrylic acid react after making a polyol and the compound which has two isocyanate groups react; Bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol or cresol novolac type epoxy resin, resol type epoxy resin, triphenolmethane type epoxy resin, polycarboxylic acid polyglycidyl ester, polyol polyglyc and epoxy (meth)acrylate resins obtained by reacting (meth)acrylic acid with epoxy resins such as cydyl esters, aliphatic or alicyclic epoxy resins, amine epoxy resins, and dihydroxybenzene type epoxy resins. Additionally, a resin obtained by reacting a polybasic acid anhydride with an epoxy (meth)acrylate resin can be suitably used. In addition, in this specification, "(meth)acryl" means "acryl or methacryl."

Moreover, as resin which has an ethylenically unsaturated group, resin obtained by making the reactant of an epoxy compound and an unsaturated group containing carboxylic acid compound further react with a polybasic acid anhydride can be used suitably.

Especially, the compound represented by the following general formula (a1) is preferable. The compound represented by this general formula (a1) is preferable in that it itself has high photocurability.

[Tue 3]

In the general formula (a1), X represents a group represented by the following general formula (a2).

[Tuesday 4]

In the general formula (a2), R ^1a each independently represents a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a halogen atom, and R ^2a each independently represents a hydrogen atom or a methyl group, and W is A bond or a group represented by the following structural formula (a3) is shown. In general formula (a2) and structural formula (a3), "*" means the end of a bond of a divalent group.

[Tuesday 5]

In the general formula (a1), Y represents a residue obtained by removing an acid anhydride group (-CO-O-CO-) from a dicarboxylic acid anhydride. Examples of dicarboxylic acid anhydrides include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl-endo-methylenetetrahydrophthalic anhydride, chlorendic anhydride, methyltetrahydrophthalic anhydride, Anhydrous glutaric acid etc. are mentioned.

Moreover, in the said general formula (a1), Z represents the residue obtained by removing two acid anhydride groups from tetracarboxylic dianhydride. Examples of tetracarboxylic dianhydride include pyromellitic anhydride, benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, and biphenyl ether tetracarboxylic dianhydride. Furthermore, in the said general formula (a1), a represents the integer of 0-20.

The acid value of the resin having an ethylenically unsaturated group is preferably 10 to 150 mgKOH/g, and more preferably 70 to 110 mgKOH/g, in terms of resin solid content. When the acid value is 10 mgKOH/g or more, sufficient solubility in the developing solution can be obtained, which is preferable. Moreover, since sufficient hardenability can be obtained and surface property can be made favorable by making an acid value into 150 mgKOH/g or less, it is preferable.

Moreover, it is preferable that it is 1000-40000, and, as for the mass average molecular weight of resin which has an ethylenically unsaturated group, it is more preferable that it is 2000-30000. By setting the mass average molecular weight to 1000 or more, it is preferable because good heat resistance and film strength can be obtained. Moreover, since favorable developability can be acquired by making mass mean molecular weight into 40000 or less, it is preferable.

[Monomer having an ethylenically unsaturated group]

The monomer having an ethylenically unsaturated group includes a monofunctional monomer and a polyfunctional monomer. Hereinafter, a monofunctional monomer and a polyfunctional monomer are explained in order.

Monofunctional monomers include (meth)acrylamide, methylol (meth)acrylamide, methoxymethyl (meth)acrylamide, ethoxymethyl (meth)acrylamide, propoxymethyl (meth)acrylamide, and butoxymethoxymethyl. (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-acrylamide-2-methylpropanesulfonic acid, tert-butylacrylamidesulfonic acid, methyl(meth)acrylate, ethyl(meth)acrylate, butyl(meth)acrylate , 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate Late, 2-phenoxy-2-hydroxypropyl (meth)acrylate, 2-(meth)acryloyloxy-2-hydroxypropyl phthalate, glycerin mono(meth)acrylate, tetrahydrofurfuryl (meth) Acrylate, dimethylamino (meth) acrylate, glycidyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) ) acrylates, half (meth)acrylates of phthalic acid derivatives, and the like. These monofunctional monomers may be used alone or in combination of two or more.

As the polyfunctional monomer, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate rate, butylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, alkylene oxide-modified neopentyl glycol diacrylate having 1 to 5 carbon atoms (especially propylene oxide-modified neopentyl glycol diacrylate) ) 1,6-hexane glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, glycerin di(meth)acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol Pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate Acrylate, dipentaerythritol hexa(meth)acrylate, 2,2-bis(4-(meth)acryloxydiethoxyphenyl)propane, 2,2-bis(4-(meth)acryloxypolyethoxyphenyl ) Propane, 2-hydroxy-3-(meth)acryloyloxypropyl (meth)acrylate, ethylene glycol diglycidyl ether di(meth)acrylate, diethylene glycol diglycidyl ether di(meth) Acrylate, phthalic acid diglycidyl ester di(meth)acrylate, glycerin triacrylate, glycerin polyglycidyl ether poly(meth)acrylate, urethane (meth)acrylate (i.e., tolylene diisocyanate), trimethylhexa The reaction product of methylene diisocyanate, hexamethylene diisocyanate and 2-hydroxyethyl (meth)acrylate, methylenebis(meth)acrylamide, (meth)acrylamidemethylene ether, polyhydric alcohol and N-methylol(meth)acrylamide Polyfunctional monomers, such as condensates of , triacryl formal, etc. are mentioned. These polyfunctional monomers may be used alone or in combination of two or more.

(A) The content of the photopolymerizable compound as component is preferably 10 to 99.9 parts by mass, more preferably 80 to 99.5 parts by mass, and 90 to 99 by mass with respect to 100 parts by mass in total of the components excluding the solvent described later in the photosensitive composition. It is more preferable that it is a mass part. When the content of component (A) is 10 parts by mass or more based on 100 parts by mass in total of the components excluding the solvent described later, it is easy to form a film excellent in heat resistance, chemical resistance, and mechanical strength using the photosensitive composition.

In the present invention, component (A) is preferably composed of a polyfunctional monomer, and the polyfunctional monomer is more preferably a bifunctional or trifunctional monomer, and still more preferably a bifunctional monomer. The ratio of the polyfunctional monomer in component (A) is preferably 50% by mass or more, more preferably 85% by mass or more, and still more preferably 90 to 100% by mass.

<(B) photopolymerization initiator>

The photosensitive composition contains a (B) photopolymerization initiator (hereinafter, also referred to as component (B)) containing a compound represented by the following formula (1). The photosensitive composition containing the compound represented by following formula (1) as (B) photoinitiator is very excellent in sensitivity. For this reason, when using the photosensitive composition containing the compound represented by Formula (1) as a photoinitiator, the photosensitive composition can be hardened favorably also by LED exposure.

In addition, by using a photosensitive composition with excellent sensitivity containing a compound represented by the following formula (1), it is possible to suppress pattern peeling at the time of pattern formation and to suppress the occurrence of blurring at the edge of the pattern when forming a line pattern. can

Moreover, when forming a pattern using the photosensitive composition containing no coloring agent, the transparency of a pattern may be impaired by performing post-baking with respect to the pattern formed using the photosensitive composition depending on the kind of photoinitiator. However, (B) When using the photosensitive composition containing the compound represented by following formula (1) as a photoinitiator, the fall of the transparency of a pattern by heating is hard to occur.

In particular, when the photosensitive composition contains a light-shielding agent as the colorant (D) described later, under the influence of the light-shielding agent, it is difficult to cure the bottom of the coating film of the photosensitive composition, so undercutting may occur in the formed pattern.

When an undercut occurs in a pattern formed using a photosensitive composition containing a light-shielding agent, for example, when creating a display device using such a pattern as a black matrix, air bubbles remaining in the undercut portion degrade the image quality of the display device. there is However, when the photosensitive composition contains (B) a photopolymerization initiator containing a compound represented by the following formula (1) together with a colorant (D) as a light-shielding agent, occurrence of undercut in a pattern formed using such a photosensitive composition is prevented. can be suppressed

For various patterns formed using the photosensitive composition, excellent water resistance that does not peel off from the substrate due to moisture or the like is desirable. When the photosensitive composition containing the (B) photopolymerization initiator containing the compound represented by the following formula (1) is used, it is easy to form a pattern having excellent water resistance that is difficult to peel from the substrate even when in contact with water.

In addition, in patterns formed using the photosensitive composition, there are cases in which foreign matter generated due to aggregation of an initiator or resin during pattern formation is included. However, if the photosensitive composition containing the (B) photoinitiator containing the compound represented by following formula (1) is used, it will be easy to form a pattern with little content of a foreign material.

[Tue 6]

(R ¹ is a hydrogen atom, a nitro group or a monovalent organic group, R ² and R ³ 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 ² and R ³ may combine with each other to form a ring, R ⁴ is a monovalent organic group, R ⁵ 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, n is an integer from 0 to 4, and m is 0 or 1.)

In formula (1), R ¹ is a hydrogen atom, a nitro group or a monovalent organic group. R ¹ bonds to a 6-membered aromatic ring different from the 6-membered aromatic ring bonded to the group represented by -(CO) _m - on the fluorene ring in Formula (1). In formula (1), the bonding position of R ¹ to the fluorene ring is not particularly limited. When the compound represented by formula (1) has one or more R ¹ , one of the one or more R ¹ is preferably bonded to the 2-position of the fluorene ring from the viewpoint of easy synthesis of the compound represented by formula (1). . When there are a plurality of R ^{1 '} s, the plurality of R ^{1 '} s may be the same or different.

When R ¹ is an organic group, R ¹ is not particularly limited as long as the object of the present invention is not impaired, and is appropriately selected from various organic groups. Preferred examples in the case where R ¹ 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, a phenyl group which may have a substituent, a phenoxy group which may have a substituent, 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 group which may have a substituent , naphthoyl group which may have a substituent, naphthoxycarbonyl group which may have a substituent, naphthoyloxy group which may have a substituent, naphthylalkyl group which may have a substituent, heterocyclyl group which may have a substituent, substituent The heterocyclylcarbonyl group which may have, the amino group substituted with 1 or 2 organic groups, the morpholin-1-yl group, the piperazin-1-yl group, etc. are mentioned.

As for the number of carbon atoms of an alkyl group, when R ^<1> is an alkyl group, 1-20 are preferable and 1-6 are more preferable. Moreover, when R ^<1> is an alkyl group, it may be straight-chain or branched-chain. Specific examples when R ¹ is an alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, n-nonyl group, isononyl group, n-decyl group A real group, an isodecyl group, etc. are mentioned. Moreover, when R ^<1> is an alkyl group, the alkyl group may contain the ether bond (-O-) in a carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include methoxyethyl group, ethoxyethyl group, methoxyethoxyethyl group, ethoxyethoxyethyl group, propyloxyethoxyethyl group, and methoxypropyl group.

As for the number of carbon atoms of an alkoxy group, when R ^<1> is an alkoxy group, 1-20 are preferable and 1-6 are more preferable. Moreover, when R ^<1> is an alkoxy group, it may be straight chain or branched chain. Specific examples in case R ¹ is an alkoxy group include methoxy group, ethoxy group, n-propyloxy group, isopropyloxy group, n-butyloxy group, isobutyloxy group, sec-butyloxy group, tert-butyloxy group, n -Pentyloxy group, isopentyloxy group, sec-pentyloxy group, tert-pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, isooctyloxy group, sec-octyloxy group, tert-octyloxy group, n-nonyloxy group, isononyloxy group, n-decyloxy group, isodecyloxy group, etc. are mentioned. Moreover, when R ^<1> is an alkoxy group, the alkoxy group may contain the ether bond (-O-) in a carbon chain. Examples of the alkoxy group having an ether bond in the carbon chain include a methoxyethoxy group, an ethoxyethoxy group, a methoxyethoxyethoxy group, an ethoxyethoxyethoxy group, a propyloxyethoxyethoxy group, and a methoxy group. A propyloxy group etc. are mentioned.

As for the carbon atom number of a cycloalkyl group or a cycloalkoxy group, when R ^<1> is a cycloalkyl group or a cycloalkoxy group, 3-10 are preferable and 3-6 are more preferable. A cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group etc. are mentioned as a specific example in case R ^<1> is a cycloalkyl group. Specific examples in case R ¹ is a cycloalkoxy group include cyclopropyloxy group, cyclobutyloxy group, cyclopentyloxy group, cyclohexyloxy group, cycloheptyloxy group, and cyclooctyloxy group.

As for the carbon atom number of a saturated aliphatic acyl group or a saturated aliphatic acyloxy group, when R ^<1> is a saturated aliphatic acyl group or a saturated aliphatic acyloxy group, 2-21 are preferable and 2-7 are more preferable. Specific examples of when R ¹ 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-pentanoyl group A decanoyl group, and an n-hexadecanoyl group, etc. are mentioned. Specific examples in case R ¹ 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. , 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.

As for the carbon atom number of an alkoxycarbonyl group, when R ^<1> is an alkoxycarbonyl group, 2-20 are preferable and 2-7 are more preferable. Specific examples in case R ¹ is an alkoxycarbonyl group include methoxycarbonyl group, ethoxycarbonyl group, n-propyloxycarbonyl group, isopropyloxycarbonyl group, n-butyloxycarbonyl group, isobutyloxycarbonyl group, sec-butyloxycarbonyl group, tert-butyloxy group. carbonyl 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 ¹ is a phenylalkyl group, the number of carbon atoms in the phenylalkyl group is preferably 7 to 20, and more preferably 7 to 10. Moreover, as for the number of carbon atoms of a naphthylalkyl group, when R ^<1> is a naphthylalkyl group, 11-20 are preferable and 11-14 are more preferable. Specific examples in case R ¹ is a phenylalkyl group include a benzyl group, a 2-phenylethyl group, a 3-phenylpropyl group, and a 4-phenylbutyl group. Specific examples in the case where R ¹ 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 ¹ is a phenylalkyl group or a naphthylalkyl group, R ¹ may further have a substituent on the phenyl group or naphthyl group.

When R ¹ is a heterocyclyl group, the heterocyclyl group is a 5-membered or 6-membered monocyclic ring containing at least one of N, S, and O, or a heterocyclyl group formed by condensation of such monocyclic rings or a benzene ring. When the heterocyclyl group is a condensed ring, it is assumed that the ring number is up to 3. The heterocyclyl group may be an aromatic group (heteroaryl group) or a non-aromatic group. Examples of the heterocycle constituting the heterocyclyl group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, and pyrimidine. , pyridazine, benzofuran, benzothiophene, indole, isoindole, indolizine, benzoimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthala gin, chinoline, quinoxaline, piperidine, piperazine, morpholine, piperidine, tetrahydropyran, and tetrahydrofuran; and the like. When R ¹ is a heterocyclyl group, the heterocyclyl group may further have a substituent.

When R ¹ is a heterocyclylcarbonyl group, the heterocyclyl groups included in the heterocyclylcarbonyl group are the same as those in the case where R ¹ is a heterocyclyl group.

When R ¹ is an amino group substituted with an organic group of 1 or 2, suitable examples of the organic group include an alkyl group of 1 to 20 carbon atoms, a cycloalkyl group of 3 to 10 carbon atoms, and a saturated aliphatic group of 2 to 21 carbon atoms. A phenyl group which may have a real group, a substituent, a benzoyl group which may have a substituent, a phenylalkyl group having 7 to 20 carbon atoms which may have a substituent, a naphthyl group which may have a substituent, a naphthoyl group which may have a substituent, a substituent A naphthylalkyl group having 11 to 20 carbon atoms which may have, and a heterocyclyl group. Specific examples of these suitable organic groups are the same as for R ¹ . 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, and di-n-butylamino group. , n-pentylamino group, n-hexylamino group, n-heptylamino group, n-octylamino group, n-nonylamino group, n-decylamino group, phenylamino group, naphthylamino group, acetylamino group, propanoylamino group, n-butanoyl amino 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

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

Among the groups described above, a nitro group or a group represented by R ⁶ -CO- as R ¹ is preferable because the sensitivity tends to improve. R ⁶ is not particularly limited as long as the object of the present invention is not impaired, and can be selected from various organic groups. Examples of groups suitable for R ⁶ include an alkyl group having 1 to 20 carbon atoms, a phenyl group which may have a substituent, a naphthyl group which may have a substituent, and a heterocyclyl group which may have a substituent. Among these groups as R ⁶ , a 2-methylphenyl group, a thiophen-2-yl group, and an α-naphthyl group are particularly preferred.

In addition, when R ¹ is a hydrogen atom, transparency tends to be improved and is preferable. Transparency tends to be better when R ¹ is a hydrogen atom and R ⁴ is a group represented by the formula (R4-2) described later.

In formula (1), each of R ² and R ³ is a chain alkyl group which may have a substituent, a cyclic organic group which may have a substituent, or a hydrogen atom. R ² and R ³ may combine with each other to form a ring. Among these groups, chain-like alkyl groups which may have substituents as R ² and R ³ are preferable. When R ² and R ³ are chain alkyl groups which may have a substituent, the chain alkyl group may be either a straight chain alkyl group or a branched chain alkyl group.

When R ² and R ³ are chain alkyl groups having no substituent, the number of carbon atoms in the chain alkyl group is preferably 1 to 20, more preferably 1 to 10, and particularly preferably 1 to 6. Specific examples when R ² and R ³ are chain alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, Isopentyl group, sec-pentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, n-nonyl group, isononyl group , n-decyl group, and isodecyl group. Moreover, when ^R2 and ^R3 are an alkyl group, the alkyl group may contain the ether bond (-O-) in the carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include methoxyethyl group, ethoxyethyl group, methoxyethoxyethyl group, ethoxyethoxyethyl group, propyloxyethoxyethyl group, and methoxypropyl group.

When R ² and R ³ are chain alkyl groups having a substituent, the number of carbon atoms in the chain alkyl group is preferably 1 to 20, more preferably 1 to 10, and particularly preferably 1 to 6. In this case, the number of carbon atoms in the substituent is not included in the number of carbon atoms in the chain alkyl group. It is preferable that the chain|chain alkyl group which has a substituent is linear.

Substituents that the alkyl group may have are not particularly limited as long as the object of the present invention is not impaired. Preferable examples of the substituent include a cyano group, a halogen atom, a cyclic organic group, and an alkoxycarbonyl group. As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned. Among these, a fluorine atom, a chlorine atom, and a bromine atom are preferable. As a cyclic organic group, a cycloalkyl group, an aromatic hydrocarbon group, and a heterocyclyl group are mentioned. As a specific example of a cycloalkyl group, it is the same as the suitable example in case R ^<1> is a cycloalkyl group. Specific examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, a biphenylyl group, an anthryl group, and a phenanthryl group. Specific examples of the heterocyclyl group are the same as those in the case where R ¹ is a heterocyclyl group. When R ¹ is an alkoxycarbonyl group, the alkoxy group contained in the alkoxycarbonyl group may be linear or branched, preferably linear. 1-10 are preferable and, as for the number of carbon atoms of the alkoxy group contained in an alkoxycarbonyl group, 1-6 are more preferable.

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

When R ² and R ³ are cyclic organic groups, the cyclic organic groups may be either alicyclic groups or aromatic groups. As a cyclic organic group, an aliphatic cyclic hydrocarbon group, an aromatic hydrocarbon group, and a heterocyclyl group are mentioned. When R ² and R ³ are cyclic organic groups, the substituents that the cyclic organic groups may have are the same as those in the case where R ² and R ³ are chain alkyl groups.

When R ² and R ³ are aromatic hydrocarbon groups, the aromatic hydrocarbon group is preferably a phenyl group, a group formed by bonding of a plurality of benzene rings via 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 condensation of a plurality of benzene rings, the number of rings of the benzene rings contained in the aromatic hydrocarbon group is not particularly limited, preferably 3 or less, more preferably 2 or less, and particularly 1 desirable. Preferable specific examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, a biphenylyl group, an anthryl group, and a phenanthryl group.

When R ² and R ³ are an aliphatic cyclic hydrocarbon group, the aliphatic cyclic hydrocarbon group may be monocyclic or polycyclic. The number of carbon atoms in the aliphatic cyclic hydrocarbon group is not particularly limited, but is preferably 3 to 20 and more preferably 3 to 10. Examples of the monocyclic cyclic hydrocarbon group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a norbornyl group, an isobornyl group, a tricyclononyl group, a tricyclodecyl group, A tetracyclododecyl group, an adamantyl group, etc. are mentioned.

When R ² and R ³ are heterocyclyl groups, the heterocyclyl group is a 5-membered or 6-membered monocyclic ring containing at least one N, S, and O, or a heterocyclyl condensed between these monocycles or such monocycles and a benzene ring. It is Ki. When the heterocyclyl group is a condensed ring, it is assumed that the ring number is up to 3. The heterocyclyl group may be an aromatic group (heteroaryl group) or a non-aromatic group. Examples of the heterocycle constituting the heterocyclyl group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, and pyrimidine. , pyridazine, benzofuran, benzothiophene, indole, isoindole, indolizine, benzoimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthala gin, chinoline, quinoxaline, piperidine, piperazine, morpholine, piperidine, tetrahydropyran, and tetrahydrofuran; and the like.

R ² and R ³ may combine with each other to form a ring. The group consisting of a ring formed by R ² and R ³ is preferably a cycloalkylidene group. When R ² and R ³ combine to form a cycloalkylidene group, the ring constituting the cycloalkylidene group is preferably a 5-membered to 6-membered ring, more preferably a 5-membered ring.

When the group formed by combining R ² and R ³ is a cycloalkylidene group, the cycloalkylidene group may be condensed with one or more other rings. Examples of rings that may be condensed with a cycloalkylidene group include a benzene ring, a naphthalene ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a furan ring, a thiophene ring, a pyrrole ring, a pyridine ring, and a pyraline ring. A true ring, and a pyrimidine ring, etc. are mentioned.

Examples of suitable groups among R ² and R ³ described above include groups represented by the formula -A ¹ -A ² . In the formula, A ¹ is a straight-chain alkylene group, and A ² is an alkoxy group, a cyano group, a halogen atom, a halogenated alkyl group, a cyclic organic group, or an alkoxycarbonyl group.

1-10 are preferable and, as for carbon atoms of the linear alkylene group of A ^<1> , 1-6 are more preferable. When A ² is an alkoxy group, the alkoxy group may be linear or branched, preferably linear. 1-10 are preferable and, as for the number of carbon atoms of an alkoxy group, 1-6 are more preferable. When A ² is a halogen atom, a fluorine atom, a chlorine atom, a bromine atom and an iodine atom are preferable, and a fluorine atom, a chlorine atom and a bromine atom are more preferable. When A ² is a halogenated alkyl group, the halogen atom contained in the halogenated alkyl group is preferably a fluorine atom, chlorine atom, bromine atom or iodine atom, and more preferably a fluorine atom, chlorine atom or bromine atom. The halogenated alkyl group may be linear or branched, and is preferably linear. When A ² is a cyclic organic group, examples of the cyclic organic group are the same as the cyclic organic groups that R ² and R ³ have as substituents. When A ² is an alkoxycarbonyl group, examples of the alkoxycarbonyl group are the same as the alkoxycarbonyl groups that R ² and R ³ have as substituents.

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

Suitable groups among the above as R ² and R ³ are ethyl group, n-propyl group, n-butyl group, n-pentyl group, 2-methoxyethyl group, 2-cyanoethyl group, 2-phenylethyl group, 2-cyclohexylethyl group, 2-methoxycarbonylethyl group, 2-chloroethyl group, 2-bromoethyl group, 3,3,3-trifluoropropyl group, and 3,3,4,4,5,5,5-heptafluoro- It is an n-pentyl group.

Examples of suitable organic groups for R ⁴ include, as in R ¹ , an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, an alkoxycarbonyl group, a saturated aliphatic acyloxy group, a phenyl group which may have a substituent, or a substituent; A phenoxy group which may have a substituent, a benzoyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, a benzoyloxy group which may have a substituent, a phenylalkyl group which may have a substituent, a naphthyl group which may have a substituent, a substituent naphthoxy group which may have a substituent, naphthoyl group which may have a substituent, naphthoxycarbonyl group which may have a substituent, naphthoyloxy group which may have a substituent, naphthylalkyl group which may have a substituent, hetero group which may have a substituent A krill group, a heterocyclylcarbonyl group which may have a substituent, an amino group substituted with 1 or 2 organic groups, a morpholin-1-yl group, and a piperazin-1-yl group. Specific examples of these groups are as described for R ¹ . Moreover, as R ^<4> , a cycloalkylalkyl group, the phenoxyalkyl 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 substituents that the phenoxyalkyl group and the phenylthioalkyl group may have are the same as the substituents that the phenyl group contained in R ¹ may have.

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

Moreover, as R ⁴ , a group represented by -A ³ -CO-OA ⁴ is also preferable. A ³ is a divalent organic group, preferably a divalent hydrocarbon group, and preferably an alkylene group. A ⁴ is a monovalent organic group, preferably a monovalent hydrocarbon group.

When A ³ is an alkylene group, the alkylene group may be linear or branched, preferably linear. As for the number of carbon atoms of an alkylene group, when A ^<3> is an alkylene group, 1-10 are preferable, 1-6 are more preferable, and 1-4 are especially preferable.

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

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

As mentioned above, although R ^<4> was demonstrated, as R ^<4> , the group represented by the following formula (R4-1) or (R4-2) is preferable.

[Tue 7]

(In formulas (R4-1) and (R4-2), R ⁷ and R ⁸ are each an organic group, p is an integer of 0 to 4, and R ⁷ and R ⁸ are present at adjacent positions on the benzene ring. In this case, R ⁷ and R ⁸ may combine with each other to form a ring, q is an integer from 1 to 8, r is an integer from 1 to 5, s is an integer from 0 to (r + 3), R ⁹ is an integer device.)

Examples of organic groups for R ⁷ and R ⁸ in formula (R4-1) are the same as for R ¹ . As R ⁷ , an alkyl group or a phenyl group is preferable. As for the number of carbon atoms, when R ^<7> is an alkyl group, 1-10 are preferable, 1-5 are more preferable, 1-3 are especially preferable, and 1 is the most preferable. That is, R ⁷ is most preferably a methyl group. When R ⁷ and R ⁸ combine to form a ring, the ring may be an aromatic ring or an aliphatic ring. As a group represented by formula (R4-1), suitable examples of the group in which R ⁷ and R ⁸ 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 the formula (R4-1), p is an integer of 0 to 4, preferably 0 or 1, and more preferably 0.

In the formula (R4-2), R ⁹ is an organic group. Examples of the organic group include the same groups as those described for R ¹ . Among the organic groups, an alkyl group is preferable. The alkyl group may be linear or branched. 1-10 are preferable, as for the number of carbon atoms of an alkyl group, 1-5 are more preferable, and 1-3 are especially preferable. As R ⁹ , a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group and the like are exemplified preferably, and among these, a methyl group is more preferred.

In the formula (R4-2), r is an integer of 1 to 5, preferably an integer of 1 to 3, and more preferably 1 or 2. In the formula (R4-2), s is 0 to (r+3), preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and particularly preferably 0. In the formula (R4-2), q is an integer of 1 to 8, preferably an integer of 1 to 5, more preferably an integer of 1 to 3, and particularly preferably 1 or 2.

In formula (1), R ⁵ is a hydrogen atom, an alkyl group having 1 to 11 carbon atoms which may have a substituent, or an aryl group which may have a substituent. As a substituent which may have when R ^<5> is an alkyl group, a phenyl group, a naphthyl group, etc. are illustrated preferably. Moreover, as a substituent which may have when R ^<1> is an aryl group, a C1-C5 alkyl group, an alkoxy group, a halogen atom, etc. are illustrated preferably.

In Formula (1), preferred examples of R ⁵ include a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a phenyl group, a benzyl group, a methylphenyl group, a naphthyl group, and the like, and among these, a methyl group Or a phenyl group is more preferable.

(B) The content of the photopolymerization initiator as component is preferably 0.001 to 30 parts by mass, more preferably 0.1 to 20 parts by mass, and still more preferably 0.5 to 10 parts by mass, based on 100 parts by mass in total of the components other than the solvent in the photosensitive composition. It is preferred, and 1 to 5 parts by mass is particularly preferred.

In addition, the content of the photopolymerization initiator as component (B) is preferably 0.05 to 50% by mass, more preferably 0.1 to 30% by mass, and 0.5 to 20% by mass relative to the total of component (A) and component (B). It is more preferable that it is mass %.

The content of the compound represented by the following formula (1) should just be in the range of, for example, 1 to 100 mass% with respect to the entire component (B), preferably 50 mass% or more, and more preferably 70 to 100 mass%. .

(B) The compound represented by Formula (1) in component may be used independently or may be used 2 or more types, and when using 2 or more types, the following (i) - (iii) are preferable.

(i) Combination of a compound in which R ¹ is a hydrogen atom and a compound in which R ¹ is a nitro group

(ii) a combination of a compound in which R ⁴ is of formula (R4-1) and a compound in which R ⁴ is of formula (R4-2);

(iii) A compound in which R ⁴ is formula (R4-1) or (R4-2) and a compound in which R ⁴ is an alkyl group having 1 to 4 carbon atoms

Among them, a combination of the above (i) is preferable, and a combination satisfying the above (i), (ii) or (iii) is more preferable from the viewpoint of improving characteristics such as sensitivity and transmittance of the cured product.

The compounding ratio (mass ratio) of each compound by the combination of the above (i) to (iii) may be appropriately adjusted according to the characteristics such as the target sensitivity, for example, 1:99 to 99:1 is preferable, and 10:90 -90:10 is more preferred, and 30:70 - 70:30 is still more preferred.

The manufacturing method of the compound represented by Formula (1) is not specifically limited. The compound represented by Formula (1) is preferably a method including a step of converting an oxime group (=N-OH) contained in a compound represented by Formula (2) below into an oxime ester group represented by =NO-COR ⁵ . is manufactured by R ⁵ is the same as R ⁵ in Formula (1).

[Tue 8]

(R ¹ , R ² , R ³ , R ⁴ , m, and n are as in Formula (1). n is an integer from 0 to 4, and m is 0 or 1.)

For this reason, the compound represented by the formula (2) is useful as an intermediate for synthesis of the compound represented by the formula (1).

The method of converting an oxime group (=N-OH) into an oxime ester group represented by =NO-COR ⁵ is not particularly limited. Typically, a method of reacting an acylating agent that imparts an acyl group represented by -COR ⁵ to the hydroxyl group in the oxime group is exemplified. Examples of the acylating agent include acid anhydrides represented by (R ⁵ CO) ₂ O and acid halides represented by R ⁵ COHal (Hal is a halogen atom).

When m is 0, the compound represented by general formula (1) can be synthesize|combined according to the following scheme 1, for example. In Scheme 1, a fluorene derivative represented by the following formula (1-1) is used as a raw material. When R ¹ is a nitro group or a monovalent organic group, the fluorene derivative represented by formula (1-1) is a fluorene derivative in which the 9th position is substituted with R ² and R ³ , and the substituent R ¹ is substituted by a known method. can be obtained by introducing A fluorene derivative in which the 9-position is substituted with R ² and R ³ , for example, when R ² and R ³ are alkyl groups, as described in Japanese Patent Laid-Open No. 06-234668, in the presence of an alkali metal hydroxide, It can be obtained by reacting fluorene with an alkylating agent in a protic polar organic solvent. In addition, an alkylating agent such as an alkyl halide, an aqueous solution of an alkali metal hydroxide, and a phase transfer catalyst such as tetrabutylammonium iodide or potassium tert-butoxide are added to an organic solvent solution of fluorene to carry out an alkylation reaction, 9-alkyl substituted fluorene can be obtained.

An acyl group represented by -CO-R ⁴ is introduced into the fluorene derivative represented by formula (1-1) by a Friedel Crafts acylation reaction to obtain a fluorene derivative represented by formula (1-3). The acylating agent for introducing an acyl group represented by -CO-R ⁴ may be a halocarbonyl compound or an acid anhydride. As the acylating agent, a halocarbonyl compound represented by formula (1-2) is preferable. In Formula (1-2), Hal is a halogen atom. The position at which the acyl group is introduced into the fluorene ring can be selected by appropriately changing the conditions of the Friedel Crafts reaction or by performing protection and deprotection at a position other than the position to be acylated.

Next, the group represented by -CO-R ⁴ in the obtained fluorene derivative represented by formula (1-3) is converted into a group represented by -C(=N-OH)-R ⁴ to obtain formula (1-4) The oxime compound shown is obtained. Although the method of converting the group represented by -CO-R ⁴ into the group represented by -C(=N-OH)-R ⁴ is not particularly limited, oximation by hydroxylamine is preferred. An oxime compound of formula (1-4), an acid anhydride ((R ⁵ CO) ₂ O) represented by formula (1-5) below, or an acid halide (R ⁵ COHal represented by formula (1-6) below, Hal is a halogen atom) to react to obtain a compound represented by the following formula (1-7).

Also in formulas (1-1), (1-2), (1-3), (1-4), (1-5), (1-6), and (1-7), R ¹ , R ² , R ³ , R ⁴ , and R ⁵ are as in Formula (1).

Moreover, in Scheme 1, R ⁴ contained in each of Formulas (1-2), Formulas (1-3), and Formulas (1-4) may be the same or different. That is, R ⁴ in Formulas (1-2), Formulas (1-3), and Formulas (1-4) may be chemically modified in the synthetic process represented by Scheme 1. Examples of the chemical modification include esterification, etherification, acylation, amidation, halogenation, substitution of a hydrogen atom in an amino group with an organic group, and the like. The chemical formulas R ⁴ may accept are not limited thereto.

<Scheme 1>

[Tue 9]

When m is 1, the compound represented by Formula (1) can be synthesize|combined, for example according to the following scheme 2. In Scheme 2, a fluorene derivative represented by the following formula (2-1) is used as a raw material. The fluorene derivative represented by Formula (2-1) is obtained by introducing an acyl group represented by -CO-CH ₂ -R ⁴ into a compound represented by Formula (1-1) by a Friedel Craft reaction in the same manner as in Scheme 1. year is obtained As the acylating agent, a carboxylic acid halide represented by Formula (1-8): Hal-CO-CH ₂ -R ⁴ is preferable. Next, the methylene group present between R ⁴ and the carbonyl group in the compound represented by formula (2-1) is oximated to obtain a ketoxime compound represented by formula (2-3) below. The method of oximating the methylene group is not particularly limited, but a method of reacting a nitrite ester (RONO, where R is an alkyl group having 1 to 6 carbon atoms) represented by the following general formula (2-2) in the presence of hydrochloric acid is preferable. Next, a ketoxime compound represented by the following formula (2-3) and an acid anhydride ((R ⁵ CO) ₂ O) represented by the following formula (2-4) or the following general formula (2-5) A compound represented by the following formula (2-6) can be obtained by reacting an acid halide (R ⁵ COHal, Hal is a halogen atom). Further, in the following formulas (2-1), (2-3), (2-4), (2-5), and (2-6), R ¹ , R ² , R ³ , R ⁴ , and R ⁵ Is the same as the general formula (1).

When m is 1, there exists a tendency that the generation|occurrence|production of a foreign material in the pattern formed using the photosensitive composition containing the compound represented by Formula (1) can be reduced more.

Moreover, in scheme 2, R ^<4> contained in each of formula (1-8), formula (2-1), and formula (2-3) may be same or different. That is, R ⁴ in Formulas (1-8), Formulas (2-1), and Formulas (2-3) may be chemically modified in the synthetic process represented by Scheme 2. Examples of the chemical modification include esterification, etherification, acylation, amidation, halogenation, substitution of a hydrogen atom in an amino group with an organic group, and the like. The chemical formulas R ⁴ may accept are not limited thereto.

<Scheme 2>

[Tue 10]

As a suitable specific example of the compound represented by Formula (1), the following compound 1 - compound 41 are mentioned.

[Tue 11]

[Tue 12]

<(C) Sensitizer>

The photosensitive composition contains (C) a sensitizer together with the above (B) photopolymerization initiator. When the photosensitive composition contains the (C) sensitizer with the (B) photopolymerization initiator containing the compound represented by the above-mentioned formula (1), the photosensitive composition is cured satisfactorily also by LED exposure.

It is considered that this is because the compound represented by Formula (1) is particularly easily sensitized by a sensitizer.

(C) As the sensitizer, compounds conventionally used for the purpose of sensitizing photopolymerization initiators in photosensitive compositions can be used without particular limitation.

(C) As a sensitizer, the compound which has at least 1 sort(s) selected from the group which consists of an alkoxy group, a substituted carbonyloxy group, and an oxo group (=O) as a substituent is preferable. As the compound having the above substituent, a condensed polycyclic aromatic hydrocarbon compound or a condensed polycyclic aromatic heterocyclic compound is preferable.

The condensed polycyclic aromatic hydrocarbon compound or the condensed polycyclic aromatic heterocyclic compound may have a substituent other than an alkoxy group, a substituted carbonyloxy group, and an oxo group (=O). Examples of such a substituent having 1 to 20 carbon atoms Alkyl group, halogenated alkyl group of 1 to 20 carbon atoms, alkoxyalkyl group of 2 to 20 carbon atoms, aliphatic acyl group of 2 to 20 carbon atoms, aromatic acyl group (aroyl group) of 7 to 11 carbon atoms, cyano group , a nitro group, a nitroso group, a halogen atom, a hydroxyl group, and a mercapto group.

The alkoxy group may be linear or branched. The number of carbon atoms in the alkoxy group is not particularly limited, but is preferably 1 to 20, more preferably 1 to 12, and particularly preferably 1 to 6.

Suitable examples of the alkoxy group include methoxy group, ethoxy group, n-propyloxy group, isopropyloxy group, n-butyloxy group, isobutyloxy group, tert-butyloxy group, n-pentyloxy group, n-hexyloxy group, n - Heptyloxy group, n-octyloxy group, 2-ethylhexyl group, n-nonyloxy group, and n-decyloxy group, etc. are mentioned.

A substituted carbonyloxy group is a group represented by -O-CO-A. A is not particularly limited as long as the sensitizer (C) has a desired sensitizing effect, and may be various organic groups. As A, an alkyl group of 1 to 20 carbon atoms, an aryl group of 6 to 10 carbon atoms, an alkoxy group of 1 to 20 carbon atoms, and an aryloxy group of 6 to 10 carbon atoms are preferable.

The aryl group or aryloxy group may have one or more substituents. The type of substituent is not particularly limited as long as the object of the present invention is not impaired. When an aryl group or an aryloxy group has a plurality of substituents, the plurality of substituents may be the same or different.

Suitable examples of the substituent include an alkoxy group of 1 to 6 carbon atoms, an alkoxy group of 1 to 6 carbon atoms, an aryloxy group of 6 to 10 carbon atoms, an aryloxy group of 6 to 10 carbon atoms, and a carbon atom 2 An aliphatic acyl group of 7 to 7, an aromatic acyl group (aroyl group) of 7 to 11 carbon atoms, a cyano group, a nitro group, a nitroso group, a halogen atom, a hydroxyl group, and a mercapto group.

When A is an alkyl group or an alkoxy group, these groups may be linear or branched.

Preferable examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, and n-octyl group. , and 2-ethylhexyl group, etc. are mentioned.

Preferable examples of the aryl group include a phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, α-naphthyl group, and β-naphthyl group.

Suitable examples of the alkoxy group include methoxy group, ethoxy group, n-propyloxy group, isopropyloxy group, n-butyloxy group, isobutyloxy group, tert-butyloxy group, n-pentyloxy group, and n-hexyloxy group. , n-heptyloxy group, n-octyloxy group, and 2-ethylhexyloxy group.

A condensed polycyclic aromatic hydrocarbon compound or a condensed polycyclic aromatic heterocyclic compound substituted with at least one selected from the group consisting of an alkoxy group, a substituted carbonyloxy group, and an oxo group (=O) constitutes a condensed ring. The water change to be performed is not particularly limited as long as a desired sensitizing action is obtained. The number of rings is preferably 2 or more, more preferably 3 or more, particularly preferably 3 to 6, and most preferably 3 or 4.

Further, as long as the condensed polycyclic aromatic hydrocarbon compound or the condensed polycyclic aromatic heterocyclic compound has aromaticity, the monocycle forming the condensed polycyclic ring may not necessarily be an aromatic ring.

Preferable examples of the condensed polycyclic ring included in the condensed polycyclic aromatic hydrocarbon compound or the condensed polycyclic aromatic heterocyclic compound include an acenaphthylene ring, a phenanthrene ring, an anthracene ring, a naphthacene ring, a xanthene ring, and a thioxanthene ring. Among these rings, an anthracene ring, a naphthacene ring, and a thioxanthene ring are preferable.

As a compound containing an anthracene ring, (C) specific examples of the compound suitably used as a sensitizer include 9,10-bis(acetyloxy)anthracene, 9,10-bis(propionyloxy)anthracene, 9,10-bis( n-propylcarbonyloxy)anthracene, 9,10-bis(isopropylcarbonyloxy)anthracene, 9,10-bis(n-butylcarbonyloxy)anthracene, 9,10-bis(isobutylcarbonyloxy) Anthracene, 9,10-bis(n-pentylcarbonyloxy)anthracene, 9,10-bis(n-hexylcarbonyloxy)anthracene, 9,10-bis(n-heptylcarbonyloxy)anthracene, 9,10 -bis(2-ethylhexanoyloxy)anthracene, 9,10-bis(n-octylcarbonyloxy)anthracene, 9,10-bis(n-nonylcarbonyloxy)anthracene, 9,10-bis(n- Decylcarbonyloxy)anthracene, 9,10-bis(benzoyloxy)anthracene, 9,10-bis(4-methylbenzoyloxy)anthracene, 9,10-bis(2-naphthoyloxy)anthracene, 2-methyl- 9,10-bis(acetyloxy)anthracene, 2-methyl-9,10-bis(propionyloxy)anthracene, 2-methyl-9,10-bis(n-propylcarbonyloxy)anthracene, 2-methyl- 9,10-bis(isopropylcarbonyloxy)anthracene, 2-methyl-9,10-bis(n-butylcarbonyloxy)anthracene, 2-methyl-9,10-bis(isobutylcarbonyloxy)anthracene , 2-methyl-9,10-bis (n-pentylcarbonyloxy) anthracene, 2-methyl-9,10-bis (n-hexylcarbonyloxy) anthracene, 2-methyl-9,10-bis (benzoyl Oxy) anthracene, 2-methyl-9,10-bis (4-methylbenzoyloxy) anthracene, 2-methyl-9,10-bis (2-naphthoyloxy) anthracene, 1-methyl-9,10-bis ( Acetyloxy)anthracene, 1-methyl-9,10-bis(propionyloxy)anthracene, 1-methyl-9,10-bis(n-propylcarbonyloxy)anthracene, 1-methyl-9,10-bis( Isopropylcarbonyloxy)anthracene, 1-methyl-9,10-bis(n-butylcarbonyloxy)anthracene, 1-methyl-9,10-bis(isobutylcarbonyloxy)anthracene, 1-methyl-9 ,10-bis(n-pentylcarbonyloxy)anthracene, 1-methyl-9,10-bis(n-hexylcarbonyloxy)anthracene, 1-methyl-9,10-bis(benzoyloxy)anthracene, 1- Methyl-9,10-bis(4-methylbenzoyloxy)anthracene, 1-methyl-9,10-bis(2-naphthoyloxy)anthracene, 2-ethyl-9,10-bis(acetyloxy)anthracene, 2 -Ethyl-9,10-bis(propionyloxy)anthracene, 2-ethyl-9,10-bis(n-propylcarbonyloxy)anthracene, 2-ethyl-9,10-bis(isobutylcarbonyloxy) Anthracene, 2-ethyl-9,10-bis(n-butylcarbonyloxy)anthracene, 2-ethyl-9,10-bis(isobutylcarbonyloxy)anthracene, 2-ethyl-9,10-bis(n -Pentylcarbonyloxy)anthracene, 2-ethyl-9,10-bis(n-hexylcarbonyloxy)anthracene, 2-ethyl-9,10-bis(benzoyloxy)anthracene, 2-ethyl-9,10- Bis(4-ethyl-benzoyloxy)anthracene, 2-ethyl-9,10-bis(2-naphthoyloxy)anthracene, 1-ethyl-9,10-bis(acetyloxy)anthracene, 1-ethyl-9, 10-bis(propionyloxy)anthracene, 1-ethyl-9,10-bis(n-propylcarbonyloxy)anthracene, 1-ethyl-9,10-bis(isopropylcarbonyloxy)anthracene, 1-ethyl -9,10-bis(n-butylcarbonyloxy)anthracene, 1-ethyl-9,10-bis(isobutylcarbonyloxy)anthracene, 1-ethyl-9,10-bis(n-pentylcarbonyloxy) )Anthracene, 1-ethyl-9,10-bis(n-hexylcarbonyloxy)anthracene, 1-ethyl-9,10-bis(benzoyloxy)anthracene, 1-ethyl-9,10-bis(4-ethyl -Benzoyloxy)anthracene, 1-ethyl-9,10-bis(2-naphthoyloxy)anthracene, 1-(t-butyl)-9,10-bis(n-propylcarbonyloxy)anthracene, 1-( t-butyl)-9,10-bis(isopropylcarbonyloxy)anthracene, 1-(t-butyl)-9,10-bis(n-butylcarbonyloxy)anthracene, 1-(t-butyl)- 9,10-bis(isobutylcarbonyloxy)anthracene, 1-(t-butyl)-9,10-bis(n-pentylcarbonyloxy)anthracene, 1-(t-butyl)-9,10-bis (n-hexylcarbonyloxy)anthracene, 1-(t-butyl)-9,10-bis(benzoyloxy)anthracene, 1-(t-butyl)-9,10-bis(4-(t-butyl) -Benzoyloxy)anthracene, 1-(t-butyl)-9,10-bis(2-naphthoyloxy)anthracene, 2-(t-butyl)-9,10-bis(n-propylcarbonyloxy)anthracene , 2-(t-butyl)-9,10-bis(isopropylcarbonyloxy)anthracene, 2-(t-butyl)-9,10-bis(n-butylcarbonyloxy)anthracene, 2-(t -Butyl)-9,10-bis(isobutylcarbonyloxy)anthracene, 2-(t-butyl)-9,10-bis(n-pentylcarbonyloxy)anthracene, 2-(t-butyl)-9 ,10-bis(n-hexylcarbonyloxy)anthracene, 2-(t-butyl)-9,10-bis(benzoyloxy)anthracene, 2-(t-butyl)-9,10-bis(4-( t-butyl)-benzoyloxy)anthracene, 2-(t-butyl)-9,10-bis(2-naphthoyloxy)anthracene, 2-pentyl-9,10-bis(n-propylcarbonyloxy)anthracene , 2-pentyl-9,10-bis(isopropylcarbonyloxy)anthracene, 2-pentyl-9,10-bis(n-butylcarbonyloxy)anthracene, 2-pentyl-9,10-bis(isobutyl Carbonyloxy)anthracene, 2-pentyl-9,10-bis(n-pentylcarbonyloxy)anthracene, 2-pentyl-9,10-bis(n-hexylcarbonyloxy)anthracene, 2-pentyl-9, 10-bis(benzoyloxy)anthracene, 2-pentyl-9,10-bis(4-(t-butyl)-benzoyloxy)anthracene, and 2-pentyl-9,10-bis(2-naphthoyloxy)anthracene etc. can be mentioned.

Moreover, the anthracene compound substituted by the halogen atom is also preferable as a sensitizer (C). As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom is mentioned.

As an anthracene compound substituted with a halogen atom, (C) specific examples of compounds suitable as a sensitizer include 2-chloro-9,10-bis(acetyloxy)anthracene, 2-chloro-9,10-bis(propionyloxy)anthracene, 2-chloro-9,10-bis(n-propylcarbonyloxy)anthracene, 2-chloro-9,10-bis(isopropylcarbonyloxy)anthracene, 2-chloro-9,10-bis(n-butyl Carbonyloxy)anthracene, 2-chloro-9,10-bis(isobutylcarbonyloxy)anthracene, 2-chloro-9,10-bis(n-pentylcarbonyloxy)anthracene, 2-chloro-9,10 -bis(n-hexylcarbonyloxy)anthracene, 2-chloro-9,10-bis(benzoyloxy)anthracene, 2-chloro-9,10-bis(4-methylbenzoyloxy)anthracene, 2-chloro-9 , 10-bis (2-naphthoyloxy) anthracene, 1-chloro-9,10-bis (acetyloxy) anthracene, 1-chloro-9,10-bis (propionyloxy) anthracene, 1-chloro-9, 10-bis(n-propylcarbonyloxy)anthracene, 1-chloro-9,10-bis(isopropylcarbonyloxy)anthracene, 1-chloro-9,10-bis(n-butylcarbonyloxy)anthracene, 1-chloro-9,10-bis(isobutylcarbonyloxy)anthracene, 1-chloro-9,10-bis(n-pentylcarbonyloxy)anthracene, 1-chloro-9,10-bis(n-hexyl Carbonyloxy)anthracene, 1-chloro-9,10-bis(benzoyloxy)anthracene, 1-chloro-9,10-bis(4-methylbenzoyloxy)anthracene, 1-chloro-9,10-bis(2 -Naphthoyloxy)anthracene, 2-fluoro-9,10-bis(acetyloxy)anthracene, 2-fluoro-9,10-bis(propionyloxy)anthracene, 2-fluoro-9,10-bis (n-propylcarbonyloxy)anthracene, 2-fluoro-9,10-bis(isopropylcarbonyloxy)anthracene, 2-fluoro-9,10-bis(n-butylcarbonyloxy)anthracene, 2 -Fluoro-9,10-bis(isobutylcarbonyloxy)anthracene, 2-fluoro-9,10-bis(n-pentylcarbonyloxy)anthracene, 2-fluoro-9,10-bis(n -Hexylcarbonyloxy)anthracene, 2-fluoro-9,10-bis(benzoyloxy)anthracene, 2-fluoro-9,10-bis(4-methylbenzoyloxy)anthracene, 2-fluoro-9, 10-bis(2-naphthoyloxy)anthracene, 1-fluoro-9,10-bis(acetyloxy)anthracene, 1-fluoro-9,10-bis(propionyloxy)anthracene, 1-fluoro- 9,10-bis(n-propylcarbonyloxy)anthracene, 1-fluoro-9,10-bis(isopropylcarbonyloxy)anthracene, 1-fluoro-9,10-bis(n-butylcarbonyl Oxy) anthracene, 1-fluoro-9,10-bis (isobutylcarbonyloxy) anthracene, 1-fluoro-9,10-bis (n-pentylcarbonyloxy) anthracene, 1-fluoro-9, 10-bis(n-hexylcarbonyloxy)anthracene, 1-fluoro-9,10-bis(benzoyloxy)anthracene, 1-fluoro-9,10-bis(4-methylbenzoyloxy)anthracene, 1- Fluoro-9,10-bis(2-naphthoyloxy)anthracene, 2-bromo-9,10-bis(acetyloxy)anthracene, 2-bromo-9,10-bis(propionyloxy)anthracene, 2-Bromo-9,10-bis(n-propylcarbonyloxy)anthracene, 2-bromo-9,10-bis(isopropylcarbonyloxy)anthracene, 2-bromo-9,10-bis( n-butylcarbonyloxy)anthracene, 2-bromo-9,10-bis(isobutylcarbonyloxy)anthracene, 2-bromo-9,10-bis(n-pentylcarbonyloxy)anthracene, 2- Bromo-9,10-bis(n-hexylcarbonyloxy)anthracene, 2-bromo-9,10-bis(benzoyloxy)anthracene, 2-bromo-9,10-bis(4-methylbenzoyloxy ) Anthracene, 2-bromo-9,10-bis (2-naphthoyloxy) anthracene, 1-bromo-9,10-bis (acetyloxy) anthracene, 1-bromo-9,10-bis (propy Oneyloxy)anthracene, 1-bromo-9,10-bis(n-propylcarbonyloxy)anthracene, 1-bromo-9,10-bis(isopropylcarbonyloxy)anthracene, 1-bromo-9 ,10-bis(n-butylcarbonyloxy)anthracene, 1-bromo-9,10-bis(isobutylcarbonyloxy)anthracene, 1-bromo-9,10-bis(n-pentylcarbonyloxy ) Anthracene, 1-bromo-9,10-bis (n-hexylcarbonyloxy) anthracene, 1-bromo-9,10-bis (benzoyloxy) anthracene, 1-bromo-9,10-bis ( 4-methylbenzoyloxy)anthracene, 1-bromo-9,10-bis(2-naphthoyloxy)anthracene, and the like.

Furthermore, an anthracene compound substituted with an alkoxy group is also preferable as a sensitizer (C).

As an anthracene compound substituted with an alkoxy group, specific examples of compounds suitable as (C) a sensitizer include 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 9,10-bis(n-propyloxy)anthracene, 9, 10-bis(n-butyloxy)anthracene, 9,10-bis(n-pentyloxy)anthracene, 9,10-bis(isopentyloxyoxy)anthracene, 9,10-bis(n-hexyloxy)anthracene , 9,10-bis (n-heptyloxy) anthracene, 9,10-bis (n-octyloxy) anthracene, 9,10-bis (2-ethylhexyloxy) anthracene, 9-methoxyanthracene, 9- Ethoxyanthracene, 9-(n-propyloxy)anthracene, 9-(n-butyloxy)anthracene, 9-(n-pentyloxy)anthracene, 9-(isopentyloxyoxy)anthracene, 9-(n-hexyloxy)anthracene Siloxy)anthracene, 9-(n-heptyloxy)anthracene, 9-(n-octyloxy)anthracene, 9-(2-ethylhexyloxy)anthracene, 2-methyl-9,10-dimethoxyanthracene, 2 -Methyl-9,10-diethoxyanthracene, 2-methyl-9,10-bis(n-propyloxy)anthracene, 2-methyl-9,10-bis(n-butyloxy)anthracene, 2-methyl-9 ,10-bis(n-pentyloxy)anthracene, 2-methyl-9,10-bis(isopentyloxyoxy)anthracene, 2-methyl-9,10-bis(n-hexyloxy)anthracene, 2-methyl -9,10-bis(n-heptyloxy)anthracene, 2-methyl-9,10-bis(n-octyloxy)anthracene, 2-methyl-9,10-bis(2-ethylhexyloxy)anthracene, 2-ethyl-9,10-dimethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 2-ethyl-9,10-bis(n-propyloxy)anthracene, 2-ethyl-9,10-bis (n-butyloxy)anthracene, 2-ethyl-9,10-bis(n-pentyloxy)anthracene, 2-ethyl-9,10-bis(isopentyloxyoxy)anthracene, 2-ethyl-9,10- Bis (n-hexyloxy) anthracene, 2-ethyl-9,10-bis (n-heptyloxy) anthracene, 2-ethyl-9,10-bis (n-octyloxy) anthracene, 2-ethyl-9, 10-bis(2-ethylhexyloxy)anthracene, 2-methyl-9-methoxyanthracene, 2-methyl-9-ethoxyanthracene, 2-methyl-9-(n-propyloxy)anthracene, 2-methyl -9-(n-butyloxy)anthracene, 2-methyl-9-(n-pentyloxy)anthracene, 2-methyl-9-(isopentyloxyoxy)anthracene, 2-methyl-9-(n-hexyloxy) cy)anthracene, 2-methyl-9-(n-heptyloxy)anthracene, 2-methyl-9-(n-octyloxy)anthracene, 2-methyl-9-(2-ethylhexyloxy)anthracene, 2- Ethyl-9-methoxyanthracene, 2-ethyl-9-ethoxyanthracene, 2-ethyl-9-(n-propyloxy)anthracene, 2-ethyl-9-(n-butyloxy)anthracene, 2-ethyl- 9-(n-pentyloxy)anthracene, 2-ethyl-9-(isopentyloxyoxy)anthracene, 2-ethyl-9-(n-hexyloxy)anthracene, 2-ethyl-9-(n-heptyloxy ) Anthracene, 2-ethyl-9- (n-octyloxy) anthracene, 2-ethyl-9- (2-ethylhexyloxy) anthracene, 2-chloro-9,10-dimethoxyanthracene, 2-chloro-9 ,10-diethoxyanthracene, 2-chloro-9,10-bis(n-propyloxy)anthracene, 2-chloro-9,10-bis(n-butyloxy)anthracene, 2-chloro-9,10-bis (n-pentyloxy)anthracene, 2-chloro-9,10-bis(isopentyloxyoxy)anthracene, 2-chloro-9,10-bis(n-hexyloxy)anthracene, 2-chloro-9,10 -bis(n-heptyloxy)anthracene, 2-chloro-9,10-bis(n-octyloxy)anthracene, 2-chloro-9,10-bis(2-ethylhexyloxy)anthracene, 2-bromo -9,10-dimethoxyanthracene, 2-bromo-9,10-diethoxyanthracene, 2-bromo-9,10-bis(n-propyloxy)anthracene, 2-bromo-9,10-bis (n-butyloxy)anthracene, 2-bromo-9,10-bis(n-pentyloxy)anthracene, 2-bromo-9,10-bis(isopentyloxyoxy)anthracene, 2-bromo-9 ,10-bis(n-hexyloxy)anthracene, 2-bromo-9,10-bis(n-heptyloxy)anthracene, 2-bromo-9,10-bis(n-octyloxy)anthracene, 2 -Bromo-9,10-bis(2-ethylhexyloxy)anthracene, 2-chloro-9-methoxyanthracene, 2-chloro-9-ethoxyanthracene, 2-chloro-9-(n-propyloxy )Anthracene, 2-chloro-9-(n-butyloxy)anthracene, 2-chloro-9-(n-pentyloxy)anthracene, 2-chloro-9-(isopentyloxyoxy)anthracene, 2-chloro-9 -(n-hexyloxy)anthracene, 2-chloro-9-(n-heptyloxy)anthracene, 2-chloro-9-(n-octyloxy)anthracene, 2-chloro-9-(2-ethylhexyloxy) cy) anthracene, 2-bromo-9-methoxyanthracene, 2-bromo-9-ethoxyanthracene, 2-bromo-9-(n-propyloxy)anthracene, 2-bromo-9-(n -Butyloxy)anthracene, 2-bromo-9-(n-pentyloxy)anthracene, 2-ethyl-9-(isopentyloxyoxy)anthracene, 2-bromo-9-(n-hexyloxy)anthracene , 2-bromo-9-(n-heptyloxy)anthracene, 2-bromo-9-(n-octyloxy)anthracene, and 2-bromo-9-(2-ethylhexyloxy)anthracene, etc. can be heard

Among the anthracene compounds described above, 9,10-bis(acetyloxy)anthracene, 9,10-bis(propionyloxy)anthracene, and 9,10-bis are selected from the viewpoint of ease of production and (C) performance as a sensitizer. (n-propylcarbonyloxy)anthracene, 9,10-bis(isopropylcarbonyloxy)anthracene, 9,10-bis(n-butylcarbonyloxy)anthracene, 9,10-bis(isobutylcarbonyloxy) )Anthracene, 9,10-bis(n-hexanoyloxy)anthracene, 9,10-bis(n-heptanoyloxy)anthracene, 9,10-bis(n-octanoyloxy)anthracene, 9,10-bis (2-ethylhexanoyloxy)anthracene, 9,10-bis(n-nonanoyloxy)anthracene, 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, and 9,10-dibutoxyanthracene this is preferable

As a compound containing a naphthacene ring, as a specific example of a compound suitably used as a sensitizer (C),

2-methyl-5,11-dioxo-6,12-bis(acetyloxy)naphthacene, 2-methyl-5,11-dioxo-6,12-bis(propionyloxy)naphthacene, 2-methyl -5,11-dioxo-6,12-bis(n-propylcarbonyloxy)naphthacene, 2-methyl-5,11-dioxo-6,12-bis(isopropylcarbonyloxy)naphthacene, 2-methyl-5,11-dioxo-6,12-bis(n-butylcarbonyloxy)naphthacene, 2-methyl-5,11-dioxo-6,12-bis(isobutylcarbonyloxy) Naphthacene, 2-methyl-5,11-dioxo-6,12-bis(n-pentylcarbonyloxy)naphthacene, 2-methyl-5,11-dioxo-6,12-bis(n-hexyl Carbonyloxy) naphthacene, 2-methyl-5,11-dioxo-6,12-bis (n-heptylcarbonyloxy) naphthacene, 2-ethyl-5,11-dioxo-6,12-bis (acetyloxy)naphthacene, 2-ethyl-5,11-dioxo-6,12-bis(propionyloxy)naphthacene, 2-ethyl-5,11-dioxo-6,12-bis(n- Propylcarbonyloxy)naphthacene, 2-ethyl-5,11-dioxo-6,12-bis(isopropylcarbonyloxy)naphthacene, 2-ethyl-5,11-dioxo-6,12-bis (n-butylcarbonyloxy)naphthacene, 2-methyl-5,11-dioxo-6,12-bis(isobutylcarbonyloxy)naphthacene, 2-ethyl-5,11-dioxo-6, 12-bis(n-pentylcarbonyloxy)naphthacene, 2-ethyl-5,11-dioxo-6,12-bis(n-hexylcarbonyloxy)naphthacene, and 2-ethyl-5,11- alkylcarbonyloxy group-substituted naphthacene compounds such as dioxo-6,12-bis(n-heptylbonyloxy)naphthacene;

2-Methyl-5,11-dioxo-6,12-bis(benzoyloxy)naphthacene, 2-methyl-5,11-dioxo-6,12-bis(o-toluoyloxy)naphthacene, 2 -Methyl-5,11-dioxo-6,12-bis(m-toluoyloxy)naphthacene, 2-methyl-5,11-dioxo-6,12-bis(p-toluoyloxy)naphthacene , 2-methyl-5,11-dioxo-6,12-bis(α-naphthoyloxy)naphthacene, 2-methyl-5,11-dioxo-6,12-bis(β-naphthoyloxy) Naphthacene, 2-ethyl-5,11-dioxo-6,12-bis(benzoyloxy)naphthacene, 2-ethyl-5,11-dioxo-6,12-bis(o-toluoyloxy)naphtha Sen, 2-ethyl-5,11-dioxo-6,12-bis(m-toluoyloxy)naphthacene, 2-ethyl-5,11-dioxo-6,12-bis(p-toluoyloxy) ) naphthacene, 2-ethyl-5,11-dioxo-6,12-bis(α-naphthoyloxy)naphthacene, and 2-ethyl-5,11-dioxo-6,12-bis(β- aroyloxy group-substituted naphthacene compounds such as naphthoyloxy)naphthacene;

2-Methyl-5,11-dioxo-6,12-bis(methoxycarbonyloxy)naphthacene, 2-methyl-5,11-dioxo-6,12-bis(ethoxycarbonyloxy)naphtha Cene, 2-methyl-5,11-dioxo-6,12-bis(n-propyloxycarbonyloxy)naphthacene, 2-methyl-5,11-dioxo-6,12-bis(isopropyloxy Carbonyloxy)naphthacene, 2-methyl-5,11-dioxo-6,12-bis(n-butyloxycarbonyloxy)naphthacene, 2-methyl-5,11-dioxo-6,12- Bis(isobutyloxycarbonyloxy)naphthacene, 2-methyl-5,11-dioxo-6,12-bis(n-pentyloxycarbonyloxy)naphthacene, 2-methyl-5,11-dioxo -6,12-bis(n-hexyloxycarbonyloxy)naphthacene, 2-methyl-5,11-dioxo-6,12-bis(n-heptyloxycarbonyloxy)naphthacene, 2-methyl -5,11-dioxo-6,12-bis(n-octyloxycarbonyloxy)naphthacene, 2-ethyl-5,11-dioxo-6,12-bis(methoxycarbonyloxy)naphthacene , 2-ethyl-5,11-dioxo-6,12-bis(ethoxycarbonyloxy)naphthacene, 2-ethyl-5,11-dioxo-6,12-bis(n-propyloxycarbonyl Oxy) naphthacene, 2-ethyl-5,11-dioxo-6,12-bis (isopropyloxycarbonyloxy) naphthacene, 2-ethyl-5,11-dioxo-6,12-bis (n -Butyloxycarbonyloxy)naphthacene, 2-ethyl-5,11-dioxo-6,12-bis(isobutyloxycarbonyloxy)naphthacene, 2-ethyl-5,11-dioxo-6, 12-bis(n-pentyloxycarbonyloxy)naphthacene, 2-ethyl-5,11-dioxo-6,12-bis(n-hexyloxycarbonyloxy)naphthacene, 2-ethyl-5, 11-dioxo-6,12-bis(n-heptyloxycarbonyloxy)naphthacene, and 2-ethyl-5,11-dioxo-6,12-bis(n-octyloxycarbonyloxy)naphthacene alkoxycarbonyloxy group-substituted naphthacene compounds such as the like; and,

2-methyl-5,11-dioxo-6,12-bis(phenoxycarbonyloxy)naphthacene, 2-methyl-5,11-dioxo-6,12-bis(o-tolyloxycarbonyloxy) ) naphthacene, 2-methyl-5,11-dioxo-6,12-bis (m-tolyloxycarbonyloxy) naphthacene, 2-methyl-5,11-dioxo-6,12-bis (p -Tolyloxycarbonyloxy)naphthacene, 2-methyl-5,11-dioxo-6,12-bis(α-naphthyloxycarbonyloxy)naphthacene, 2-methyl-5,11-dioxo- 6,12-bis(β-naphthyloxycarbonyloxy)naphthacene, 2-ethyl-5,11-dioxo-6,12-bis(phenoxycarbonyloxy)naphthacene, 2-ethyl-5, 11-dioxo-6,12-bis(o-tolyloxycarbonyloxy)naphthacene, 2-ethyl-5,11-dioxo-6,12-bis(m-tolyloxycarbonyloxy)naphthacene, 2-ethyl-5,11-dioxo-6,12-bis(p-tolyloxycarbonyloxy)naphthacene, 2-ethyl-5,11-dioxo-6,12-bis(α-naphthyloxy aroyloxycarbonyloxy group-substituted naphthacene compounds such as carbonyloxy)naphthacene, and 2-ethyl-5,11-dioxo-6,12-bis(β-naphthyloxycarbonyloxy)naphthacene; can

Among the compounds containing the above naphthacene ring, 5,11-dioxo-6,12-bis(methoxycarbonyloxy)naphthacene, 5,11-dioxo-6,12-bis(ethoxycarbonyloxy) ) naphthacene, 5,11-dioxo-6,12-bis (isopropyloxycarbonyloxy) naphthacene, 5,11-dioxo-6,12-bis (isobutyloxycarbonyloxy) naphthacene, 5,11-dioxo-6,12-bis(n-butylcarbonyloxy)naphthacene, 5,11-dioxo-6,12-bis(n-pentylcarbonyloxy)naphthacene, 5,11- Dioxo-6,12-bis(n-heptanoyloxy)naphthacene is preferred.

(A) In terms of compatibility with photopolymerizable compounds, 5,11-dioxo-6,12-bis(isopropyloxycarbonyloxy)naphthacene, 5,11-dioxo-6,12-bis(isobutyl Oxycarbonyloxy)naphthacene, 5,11-dioxo-6,12-bis(n-butyryloxy)naphthacene, 5,11-dioxo-6,12-bis(n-valeryloxy)naphtha Cene, 5,11-dioxo-6,12-bis(heptanoyloxy)naphthacene is preferred.

As a compound containing a thioxanthene ring, (C) specific examples of compounds suitably used as a sensitizer include thioxanthen-9-one, 2-methyl-9H-thioxanthen-9-one, 2-isopropyl-9H - Thioxanthen-9-one, 1,4-dimethylthioxanthen-9-one, 3-methyl-9-oxo-9H-thioxanthen-2-yl acetate, etc. are mentioned.

The content of the sensitizer as component (C) is preferably 0.01 to 1000 parts by mass, more preferably 0.1 to 150 parts by mass, and even more preferably 0.3 to 100 parts by mass with respect to 100 parts by mass of the total of component (B) in the photosensitive composition. .

In addition, when 0.01 to 3 parts by mass relative to 100 parts by mass of the component (B) in total, coloration due to absorption of the component (C) can be reduced, so that a cured product having good transparency or brightness can be obtained.

<(D) colorant>

The photosensitive composition may further contain (D) a coloring agent. The photosensitive composition is preferably used as a color filter forming application for, for example, a liquid crystal display by including a colorant as component (D). Moreover, the photosensitive composition concerning this invention contains a light-shielding agent as a coloring agent, and is suitably used for black-matrix formation use in the color filter of a display apparatus, for example.

Although it does not specifically limit as a coloring agent (D) contained in the photosensitive composition, For example, the compound classified as a pigment in the color index (C.I.; published by The Society of Dyers and Colourists), specifically the following It is preferable to use one with the same color index (C.I.) number attached.

Examples of yellow pigments that can be suitably used include C.I. Pigment Yellow 1 (hereinafter, "C.I. Pigment Yellow" is the same, only numbers are written), 3, 11, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 55, 60 , 61, 65, 71, 73, 74, 81, 83, 86, 93, 95, 97, 98, 99, 100, 101, 104, 106, 108, 109, 110, 113, 114, 116, 117, 119 , 120, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 166, 167, 168, 175, 180, and 185 to can be heard

Examples of orange pigments that can be suitably used include C.I. Pigment Orange 1 (hereinafter, "C.I. Pigment Orange" is the same, only numbers are written), 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51 , 55, 59, 61, 63, 64, 71, and 73.

Examples of purple pigments that can be suitably used include C.I. Pigment Violet 1 (hereinafter "C.I. Pigment Violet" is the same, only numbers are described), 19, 23, 29, 30, 32, 36, 37, 38, 39, 40, and 50.

Examples of red pigments that can be suitably used include C.I. Pigment Red 1 (hereinafter, "C.I. Pigment Red" is the same, only numbers are written) 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 40, 41, 42, 48:1, 48:2, 48:3, 48:4, 49:1, 49: 2, 50:1, 52:1, 53:1, 57, 57:1, 57:2, 58:2, 58:4, 60:1, 63:1, 63:2, 64:1, 81: 1, 83, 88, 90:1, 97, 101, 102, 104, 105, 106, 108, 112, 113, 114, 122, 123, 144, 146, 149, 150, 151, 155, 166, 168, 170, 171, 172, 174, 175, 176, 177, 178, 179, 180, 185, 187, 188, 190, 192, 193, 194, 202, 206, 207, 208, 209, 215, 216, 2 17, 220, 223, 224, 226, 227, 228, 240, 242, 243, 245, 254, 255, 264, and 265.

Examples of blue pigments that can be suitably used include C.I. Pigment Blue 1 (hereinafter, "C.I. Pigment Blue" is the same, only numbers are written), 2, 15, 15:3, 15:4, 15:6, 16, 22, 60, 64, and 66 can be heard

Examples of pigments of other colors that can be suitably used include C.I. Pigment Green 7, C.I. Pigment Green 36, C.I. Green pigments such as Pigment Green 37, C.I. Pigment Brown 23, C.I. Pigment Brown 25, C.I. Pigment Brown 26, C.I. Brown pigments such as Pigment Brown 28, C.I. Pigment Black 1, C.I. Black pigments, such as Pigment Black 7, are mentioned.

Moreover, when using a colorant as a light-shielding agent, it is preferable to use a black pigment as a light-shielding agent. As the black pigment, carbon black, titanium black, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, metal oxides, composite oxides, metal sulfides, metal sulfates, or metal carbonates such as silver, organic substances and inorganic substances, etc. Various pigments are mentioned. Among these, it is preferable to use carbon black having high light-shielding properties.

As the carbon black, known carbon black such as channel black, furnace black, thermal black, and lamp black can be used, but it is preferable to use a channel black having excellent light-shielding properties. Moreover, you may use resin-coated carbon black.

Since resin-coated carbon black has lower conductivity than carbon black without resin coating, when it is used as a black matrix for a liquid crystal display device such as a liquid crystal display, it can produce a display with low current leakage and high reliability and low power consumption. can

Moreover, in order to adjust the color tone of carbon black, you may add the said organic pigment suitably as an auxiliary pigment.

In order to uniformly disperse the said colorant in the photosensitive composition, you may use a dispersing agent further. As such a dispersing agent, it is preferable to use a polyethyleneimine-based, urethane resin-based, or acrylic resin-based polymer dispersing agent. In particular, when using carbon black as a colorant, it is preferable to use an acrylic resin-type dispersant as a dispersant.

In addition, the inorganic pigment and the organic pigment may be used individually or in combination of two or more, but when used in combination, the organic pigment is preferably used in the range of 10 to 80 parts by mass based on 100 parts by mass of the total amount of the inorganic pigment and the organic pigment. It is more preferable to use it in the range of 20-40 mass parts.

The amount of the colorant used in the photosensitive composition may be appropriately determined according to the use of the photosensitive composition, but as an example, 5 to 70 parts by mass is preferable, and 25 to 60 parts by mass is preferably 25 to 60 parts by mass with respect to 100 parts by mass in total of the components other than the solvent in the photosensitive composition. Addition is more preferable. By setting it as said range, a black matrix and each colored layer can be formed in the target pattern, and it is preferable.

In particular, when forming a black matrix using the photosensitive composition, it is preferable to adjust the amount of the light-shielding agent in the photosensitive composition so that the OD value per 1 μm of the film of the black matrix is 4 or more. If the OD value per 1 μm of the film in the black matrix is 4 or more, sufficient display contrast can be obtained when used for a black matrix of a liquid crystal display.

It is preferable to add the colorant to the photosensitive composition after dispersing the colorant at an appropriate concentration using a dispersing agent to form a dispersion.

<(E) alkali-soluble resin>

The photosensitive composition concerning this invention may contain (E) alkali-soluble resin as resin other than resin used as (A) photopolymerizable compound. By mix|blending (E) alkali-soluble resin with a photosensitive composition, alkali developability can be provided to a photosensitive composition.

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

(E) Among the alkali-soluble resins, polymers of monomers having ethylenically unsaturated double bonds are preferred in terms of excellent film forming properties and ease of adjusting the properties of the resin by selecting monomers. 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, anhydrides of these dicarboxylic acids; allyl compounds such as allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, allyl lactate, and allyloxyethanol; 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, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether, vinylphenyl 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 Methoxyacetate, Vinyl Butoxyacetate, Vinylphenyl Acetate, Vinyl Aceto vinyl esters such as acetate, vinyl lactate, vinyl-β-phenylbutyrate, vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, and vinyl naphthoate; Styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, isopropylstyrene, butylstyrene, hexylstyrene, cyclohexylstyrene, decylstyrene, benzylstyrene, chloromethylstyrene, trifluoromethylstyrene, ethoxy Methyl styrene, acetoxymethyl styrene, methoxy styrene, 4-methoxy-3-methyl styrene, dimethoxy styrene, chloro styrene, dichloro styrene, trichloro styrene, tetrachloro styrene, pentachloro styrene, bromo styrene, dibro styrene or styrene derivatives such as moststyrene, 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.

The alkali-soluble resin (E), which is a polymer of monomers having ethylenically unsaturated double bonds, usually contains units derived from unsaturated carboxylic acids. Examples of unsaturated carboxylic acids include (meth)acrylic acid; (meth)acrylic acid amide; crotonic acid; maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, and anhydrides of these dicarboxylic acids. The amount of units derived from an unsaturated carboxylic acid contained in the polymer of monomers having ethylenically unsaturated double bonds used as the alkali-soluble resin is not particularly limited as long as the resin has desired alkali-solubility. 5-25 mass % is 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, 8-16 mass % is more preferable.

Among the polymers of monomers having ethylenically unsaturated double bonds, which are polymers of one or more monomers selected from the above-exemplified monomers, polymers of one or more monomers selected from (meth)acrylic acid and (meth)acrylic acid esters are preferable. Hereinafter, the polymer of one or more types of monomers selected from (meth)acrylic acid and (meth)acrylic acid ester will be described.

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

Suitable examples of (meth)acrylic acid esters include linear or branched esters such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, amyl (meth)acrylate, and t-octyl (meth)acrylate. chain alkyl (meth)acrylates; Chloroethyl (meth)acrylate, 2,2-dimethylhydroxypropyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, trimethylolpropane mono(meth)acrylate, benzyl (meth)acrylate, furfuryl (meth)acrylate; (meth)acrylic acid ester having a group having an epoxy group; and (meth)acrylic acid esters having a group having an alicyclic skeleton. Details of the (meth)acrylic acid ester having a group having an epoxy group and the (meth)acrylic acid ester having a group having an alicyclic skeleton will be described later.

Among the polymers of at least one type of monomer selected from (meth)acrylic acid and (meth)acrylic acid ester, (meth) having an epoxy group-containing group in terms of excellent adhesion to a substrate and mechanical strength of a transparent insulating film formed using a photosensitive composition A resin containing a unit derived from an acrylic acid ester is preferred.

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 a (meth)acrylic acid ester having a group having an alicyclic epoxy group described later.

The (meth)acrylic acid ester having a group having an epoxy group may contain an aromatic group. A benzene ring and a naphthalene ring are mentioned as an example of the aromatic ring which comprises an aromatic group. Examples of the (meth)acrylic acid ester having an aromatic group and a group having an epoxy group include 4-glycidyloxyphenyl (meth)acrylate, 3-glycidyloxyphenyl (meth)acrylate, and 2-glycidyloxyphenyl. (meth)acrylate, 4-glycidyloxyphenylmethyl (meth)acrylate, 3-glycidyloxyphenylmethyl (meth)acrylate, and 2-glycidyloxyphenylmethyl (meth)acrylate, etc. can be heard

When transparency is required for a film formed using the photosensitive composition, (meth)acrylic acid having an epoxy group preferably 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- ) to which a chain aliphatic epoxy group binds (meth)acrylic acid ester. The chain aliphatic epoxy group of such (meth)acrylic acid ester may contain one or more oxy groups (-O-) in the chain. The number of carbon atoms in the chain aliphatic epoxy group is not particularly limited, but is preferably 3 to 20, more preferably 3 to 15, and particularly preferably 3 to 10.

Specific examples of the (meth)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, epoxyalkyl (meth)acrylates such as 7-epoxyheptyl (meth)acrylate; 2-glycidyloxyethyl (meth)acrylate, 3-glycidyloxy-n-propyl (meth)acrylate, 4-glycidyloxy-n-butyl (meth)acrylate, 5-glycidyl Epoxyalkyl oxyalkyl (meth)acrylates, such as oxy-n-hexyl (meth)acrylate and 6-glycidyloxy-n-hexyl (meth)acrylate, are mentioned.

(meth)acrylic acid ester having a group having an epoxy group in a polymer of at least one type of monomer selected from (meth)acrylic acid and (meth)acrylic acid ester containing units derived from (meth)acrylic acid ester having a group having an epoxy group 1-95 mass % is preferable with respect to the weight of resin, and, as for content of the derived unit, 40-80 mass % is more preferable.

In addition, among the polymers of at least one monomer selected from (meth)acrylic acid and (meth)acrylic acid esters, (meth)acrylic acid having a group having an alicyclic backbone is preferred because it is easy to form a transparent insulating film having excellent transparency using a photosensitive composition. Resins containing units derived from esters are also preferred.

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 backbone may be monocyclic or polycyclic. A cyclopentyl group, a cyclohexyl group, etc. are mentioned as a monocyclic alicyclic group. Moreover, as a polycyclic alicyclic group, a norbornyl group, an isobornyl group, a tricyclononyl group, a tricyclodecyl group, a tetracyclododecyl group, etc. are mentioned.

Among the (meth)acrylic acid esters having a group having an alicyclic backbone, examples of the (meth)acrylic acid ester having a group having an alicyclic hydrocarbon group include compounds represented by the following formulas (d1-1) to (d1-8) . Among these, compounds represented by the following formulas (d1-3) to (d1-8) are preferred, and compounds represented by the following formulas (d1-3) or (d1-4) are more preferred.

[Tue 13]

In the above formula, R ^d1 represents a hydrogen atom or a methyl group, R ^d2 represents a single bond or a divalent saturated aliphatic hydrocarbon group having 1 to 6 carbon atoms, and R ^d3 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. indicate As R ^d2 , a single bond, linear or branched alkylene group such as a methylene group, an ethylene group, a propylene group, a tetramethylene group, an ethylethylene group, a pentamethylene group, or a hexamethylene group is preferable. As R ^d3 , a methyl group or an ethyl group is preferable.

Among (meth)acrylic acid esters having a group having an alicyclic backbone, specific examples of the (meth)acrylic acid ester having a group having an alicyclic epoxy group include compounds represented by the following formulas (d2-1) to (d2-16) can Among these, in order to make the developability of the photosensitive composition suitable, the compounds represented by the following formulas (d2-1) to (d2-6) are preferred, and the compounds represented by the following formulas (d2-1) to (d2-4) more preferable

[Tue 14]

In the above formula, R ^d4 represents a hydrogen atom or a methyl group, R ^d5 represents a divalent saturated aliphatic hydrocarbon group having 1 to 6 carbon atoms, R ^d6 represents a divalent hydrocarbon group having 1 to 10 carbon atoms, and n is 0 to 10 represents an integer. As R ^d5 , a straight-chain or branched-chain alkylene group such as a methylene group, ethylene group, propylene group, tetramethylene group, ethylethylene group, pentamethylene group, or hexamethylene group is preferable. Examples of R ^d6 include a methylene group, an ethylene group, a propylene group, a tetramethylene group, an ethylethylene group, a pentamethylene group, a hexamethylene group, a phenylene group, a cyclohexylene group, -CH ₂ -Ph-CH ₂ -(Ph represents a phenylene group) is preferred.

When the polymer of at least one monomer selected from (meth)acrylic acid and (meth)acrylic acid ester is a resin containing a unit derived from a (meth)acrylic acid ester having a group having an alicyclic backbone, the alicyclic backbone in the resin is The amount of units derived from (meth)acrylic acid ester having a group is preferably 5 to 95% by mass, more preferably 10 to 90% by mass, and still more preferably 30 to 70% by mass.

In addition, among polymers of at least one monomer selected from (meth)acrylic acid and (meth)acrylic acid esters containing units derived from (meth)acrylic acid esters having a group having an alicyclic backbone, units derived from (meth)acrylic acid And a resin containing a unit derived from (meth)acrylic acid ester having a group having an alicyclic epoxy group is preferable. A film formed using the photosensitive composition containing such an alkali-soluble resin (E) has excellent adhesion to a substrate. Moreover, in the case of using such a resin, it is possible to cause a self-reaction between the carboxyl group and the alicyclic epoxy group contained in the resin. For this reason, when a photosensitive composition containing such a resin is used, mechanical properties such as hardness of a formed film can be improved by causing a self-reaction between the carboxyl group and the alicyclic epoxy group by using a method such as heating the film.

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

Among the polymers of one or more monomers selected from (meth)acrylic acid and (meth)acrylic acid esters containing units derived from (meth)acrylic acid and units derived from (meth)acrylic acid esters having groups having alicyclic epoxy groups, A resin containing a unit derived from (meth)acrylic acid, a unit derived from a (meth)acrylic acid ester having an alicyclic hydrocarbon group, and a unit derived from a (meth)acrylic acid ester having a group having an alicyclic epoxy group is preferred.

In a resin comprising a unit derived from (meth)acrylic acid, a unit derived from a (meth)acrylic acid ester having an alicyclic hydrocarbon group, and a unit derived from a (meth)acrylic acid ester having a group having an alicyclic epoxy group, , 1 to 95% by mass is preferable, and, as for the quantity of the unit derived from (meth)acrylic acid, 10 to 50 mass% is more preferable. In a resin comprising a unit derived from (meth)acrylic acid, a unit derived from a (meth)acrylic acid ester having an alicyclic hydrocarbon group, and a unit derived from a (meth)acrylic acid ester having a group having an alicyclic epoxy group, , The amount of units derived from (meth)acrylic acid ester having an alicyclic hydrocarbon group is preferably 1 to 95% by mass, and more preferably 10 to 70% by mass. In a resin comprising a unit derived from (meth)acrylic acid, a unit derived from a (meth)acrylic acid ester having an alicyclic hydrocarbon group, and a unit derived from a (meth)acrylic acid ester having a group having an alicyclic epoxy group, , The amount of units derived from (meth)acrylic acid ester having a group having an alicyclic epoxy group is preferably 1 to 95% by mass, and more preferably 30 to 80% by mass.

(E) The mass average molecular weight of the alkali-soluble resin (Mw: measured value in terms of polystyrene by gel permeation chromatography (GPC). The same applies herein) is preferably 2000 to 200000, more preferably 2000 to 18000 do. By setting it as said range, there exists a tendency for the film-forming ability of a photosensitive composition and the developability after exposure to balance easily.

When the photosensitive composition contains (E) alkali-soluble resin, the content of (E) alkali-soluble resin in the photosensitive composition is preferably 15 to 95 mass% with respect to the total mass of components other than the solvent in the photosensitive composition, 35 ~ 85% by mass is more preferred, and 50 - 70% by mass is particularly preferred.

＜Other ingredients＞

The photosensitive composition according to the present invention may contain various additives as needed. Specifically, solvents, sensitizers, curing accelerators, photocrosslinking agents, dispersing aids, fillers, adhesion promoters, antioxidants, ultraviolet absorbers, aggregation inhibitors, thermal polymerization inhibitors, antifoaming agents, surfactants and the like are exemplified.

The photosensitive composition according to the present invention may be prepared by dispersing and dissolving each component in a solvent, but as long as the component (A) is liquid, it is not necessary to use a solvent. When a solvent is included, examples of the solvent used in the photosensitive composition include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol mono Methyl 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 (poly)alkylene glycol monoalkyl ethers such as glycol mono-n-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; lactate alkyl esters such as methyl 2-hydroxypropionate and ethyl 2-hydroxypropionate; 2-Hydroxy-2-methylethylpropionate, 3-methoxymethylpropionate, 3-methoxyethylpropionate, 3-ethoxymethylpropionate, 3-ethoxyethylpropionate, ethoxyacetate ethyl, hydroxyacetate ethyl, 2 -Hydroxy-3-methylbutanoate, 3-methyl-3-methoxybutylacetate, 3-methyl-3-methoxybutylpropionate, 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; and amides such as N-methylpyrrolidone, N,N-dimethylformamide, and N,N-dimethylacetamide. These solvents may be used alone or in combination of two or more.

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- Methoxybutyl acetate is preferable because it can improve the dispersibility of the above-mentioned component (D) while exhibiting excellent solubility with respect to the above-mentioned component (A) and component (b), and propylene glycol monomethyl ether acetate, 3 - It is particularly preferred to use methoxybutyl acetate. Although what is necessary is just to determine the solvent suitably according to the use of a photosensitive composition, as an example, about 50-900 mass parts can be mentioned with respect to 100 mass parts of the total mass of components other than the solvent in a photosensitive composition.

As a thermal polymerization inhibitor used for the photosensitive composition concerning this invention, hydroquinone, hydroquinone monoethyl ether, etc. are mentioned, for example. Moreover, compounds, such as silicone type and a fluorine type, can be illustrated as an antifoamer, and compounds, such as anionic type, cationic type, and nonionic type, respectively, as surfactant, respectively.

[Preparation method of photosensitive composition]

The photosensitive composition according to the present invention is prepared by mixing all of the above components with a stirrer. Moreover, when the prepared photosensitive composition does not contain insoluble components, such as a pigment, you may filter using a filter so that a photosensitive composition may become uniform.

≪Method for producing cured material≫

The photosensitive composition described above is cured by being exposed to light using a desired light source.

Hereinafter, a method of forming a film to be used as an insulating film or a color filter using a photosensitive composition will be described. The film formed using the photosensitive composition may be patterned as needed.

In order to form a film using the photosensitive composition of the present invention, first, the photosensitive composition is coated on a substrate using a contact transfer type coating device such as a roll coater, reverse coater, or bar coater, or a non-contact type coating device such as a spinner (rotary coating device) or a curtain flow coater. to spread

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

Then, exposure is performed with respect to this coating film. A light source is not specifically limited, For example, a high pressure mercury lamp, LED, etc. are mentioned, From a viewpoint of energy saving or environmental load reduction, LED is preferable. In exposure by LED, the wavelength used is, for example, 365 to 405 nm, more specifically, those in the UV region such as 385 nm, 395 nm, and 405 nm. In general, the energy dose irradiated by the LED tends to be small. However, since the photosensitive composition described above contains the above-mentioned (B) photopolymerization initiator and (C) sensitizer, and has excellent sensitivity, it is sufficiently cured even when exposed to light using an LED as a light source, resulting in a cured product having good characteristics. can be obtained effectively. By this, as a result, productivity of display devices such as liquid crystal display panels can be improved.

When the coated film is positionally selectively exposed, the film after exposure is developed with a developing solution to be patterned into a desired shape. The developing method is not particularly limited, and for example, an immersion method, a spray method, or the like can be used. A developer is appropriately selected depending on the composition of the photosensitive composition. When the photosensitive composition contains an alkali-soluble component such as an alkali-soluble resin, the developing solution is an organic developer such as monoethanolamine, diethanolamine, triethanolamine, etc., sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, quaternary ammonium salt, etc. Aqueous solutions can be used.

Next, it is preferable to post-bake the pattern after development at about 200 to 250°C.

The pattern formed in this way can be suitably used for applications such as an insulating film used in a display device such as a liquid crystal display, a pixel constituting a color filter, and a black matrix, for example. Such an insulating film, a color filter, and a display device using the color filter are also examples of the present invention.

[ Example ]

Hereinafter, the present invention will be described in further detail by showing examples, but the scope of the present invention is not limited to these examples.

In Examples and Comparative Examples, (A) propylene oxide-modified neopentyl glycol diacrylate was used as the photopolymerizable compound.

In Examples, as the (B) photopolymerization initiator, Compound 1 obtained in Synthesis Example 2 below was used as (B)-1, and Compound 2 obtained in Synthesis Example 3 below was used as (B)-2. The structures of Compound 1 and Compound 2 are shown below.

[Tuesday 15]

In Comparative Example 2, 1-hydroxycyclohexan-1-ylphenyl ketone was used as the photopolymerization initiator (B')-1, which does not correspond to the compound represented by formula (1).

In Examples and Comparative Examples, (C) the following (C)-1 to (C)-4 were used as sensitizers.

(C) -1: 2-isopropyl-9H-thioxanthen-9-one

(C)-2: 9,10-bis(n-heptylcarbonyloxy)anthracene

(C)-3: 9,10-bis(n-butyloxy)anthracene

(C)-4: 5,11-dioxo-6,12-bis(methoxycarbonyloxy)naphthacene

[Synthesis Example 1]

(Synthesis of 9,9-di-n-propylfluorene)

6.64 g (40 mmol) of fluorene was dissolved in 27 mL of THF. To the obtained solution, 0.12 g (1.1 mmol) of potassium tert-butoxide, 12.30 g (100 mmol) of 1-bromopropane, and 27 mL of an aqueous sodium hydroxide solution having a concentration of 50% by mass were gradually added under a nitrogen atmosphere. The obtained mixture was stirred at 80°C for 3 hours to react. After adding 33 g of ethyl acetate and 33 g of water to the mixture after reaction, it separated into an organic layer and an aqueous layer. After the obtained organic layer was dehydrated with anhydrous sodium sulfate, the solvent was removed from the organic layer using a rotary evaporator to obtain 8.32 g of 9,9-di-n-propylfluorene (yield: 83%).

[Synthesis Example 2]

(Synthesis of Compound 1)

4.10 g (16.37 mmol) of 9,9-di-n-propylfluorene and 3.04 g (18.00 mmol) of (2-methylphenyl)acetic acid chloride were mixed with 2.62 g of aluminum chloride in a dichloromethane solvent, 50 ml, and ice-cooled. It was reacted for 1 hour under The reaction mixture was poured into ice water and the organic layer was separated. The recovered organic layer was dried over anhydrous magnesium sulfate and then evaporated. The residue was purified on a silica gel column with ethyl acetate/hexane = 1/2 as the eluent to obtain 5.95 g (15.55 mmol) of 2-(2-methylphenyl)acetyl-9,9-di-n-propylfluorene. 5.95 g (15.55 mmol) of 2-(2-methylphenyl)acetyl-9,9-di-n-propylfluorene and 1.60 g (15.55 mmol) of concentrated hydrochloric acid, in the presence of 2.42 g (23.33 mmol) of isobutyl nitrite, In 25 ml of dimethylformamide solvent, it was made to react under ice-cooling for 3 hours. The reaction solution was evaporated, ethyl acetate was added to the residue, washed with saturated brine, dried over anhydrous magnesium sulfate, and then evaporated to obtain 2-[2-methylphenyl(hydroxyimino)acetyl]-9,9-di- 4.80 g (11.67 mmol) of n-propylfluorene was obtained.

[Tue 16]

The measurement results of ¹ H-NMR of 2-[2-methylphenyl(hydroxyimino)acetyl]-9,9-di-n-propylfluorene were as follows.

¹ H-NMR (600 MHz, CDCl ₃ , ppm): 8.60 (bs, 1H), 8.15 (d, 1H), 8.14 (s, 1H), 7.76-8.00 (m, 2H), 7.26-7.53 (m, 7H) ), 2.35(s, 3H), 1.98-2.01(m, 4H), 0.63-0.67(m, 10H)

4.80 g (11.67 mmol) of 2-[2-methylphenyl (hydroxyimino)acetyl] -9,9-di-n-propylfluorene, 1.43 g (13.42 mmol) of acetic anhydride, and 1.36 g (13.42 mmol) of triethylamine mmol) and 45.00 ml of a dimethylformamide solvent were mixed and stirred at 35°C for 3 hours. After cooling to room temperature, ethyl acetate was added to the reaction solution, washed with water, dried over anhydrous magnesium sulfate, and then evaporated. The residue was purified on a silica gel column with ethyl acetate/hexane = 2/1 as the eluent to obtain 4.76 g (10.50 mmol, yield 72%) of Compound 1. The measurement results of ¹ H-NMR of Compound 1 were as follows.

¹ H-NMR (600 MHz, CDCl ₃ , ppm): 8.25 (d, 1H), 8.22 (s, 1H), 7.83 (d, 1H), 7.81 (dd, 1H), 7.33-7.40 (m, 3H), 7.26-7.33 (m, 4H), 2.35 (s, 3H), 2.14 (s, 3H), 1.95-2.07 (m, 4H), 0.63-0.66 (m, 10H).

[Synthesis Example 3]

(Synthesis of Compound 2)

3.04 g (18.00 mmol) of (2-methylphenyl) acetate chloride was replaced with 3.14 g (18.00 mmol) of 3-cyclohexyl propionic acid chloride, but in the same manner as in Synthesis Example 2, 2-[cyclohexylmethyl of the intermediate structure (Hydroxyimino)acetyl] -9,9-di-n-propylfluorene and compound 2, 4.96 g (10.80 mmol, yield 75%) were obtained.

[Tue 17]

The measurement results of ¹ H-NMR of 2-[cyclohexylmethyl(hydroxyimino)acetyl]-9,9-di-n-propylfluorene were as follows.

¹ H-NMR (600 MHz, CDCl ₃ , ppm): 8.80 (bs, 1H), 7.90-7.98 (m, 2H), 7.70-7.80 (m, 2H), 7.30-7.40 (m, 3H), 2.72 (d , 2H), 1.88-2.02 (m, 4H), 1.54-1.80 (m, 6H), 0.95-1.28 (m, 5H), 0.67-0.77 (m, 10H)

The measurement results of ¹ H-NMR of Compound 2 were as follows.

¹ H-NMR (600 MHz, CDCl ₃ , ppm): 8.08-8.14 (m, 2H), 7.70-7.79 (m, 2H), 7.32-7.40 (m, 3H), 2.78 (d, 2H), 2.28 (s) , 3H), 1.88-2.10 (m, 4H), 1.53-1.78 (m, 6H), 1.00-1.30 (m, 5H), 0.60-0.77 (m, 10H).

[Examples 1 to 7, and Comparative Examples 1 to 2]

The photosensitive compositions of Examples and Comparative Examples were obtained by uniformly mixing the types and amounts of component (A), component (B), and component (C), respectively, as shown in Table 1 below.

After the obtained photosensitive composition was dropped onto the substrate with a pipette, droplets of the photosensitive composition were exposed to light with a commercially available LED light for 15 seconds. Regarding the droplets after exposure, whether or not the inside of the droplets was cured was evaluated, and the curability of each photosensitive composition by LED exposure was evaluated.

A case where the inside of the droplet was cured was judged as ○, and a case where the droplet was not cured was judged as ×.

The evaluation results of curability by LED exposure are listed in Table 1.

From the examples in Table 1, the photosensitive composition containing (A) a photopolymerizable compound, (B) a photopolymerization initiator containing a compound represented by Formula (1), and (C) a sensitizer is well cured by LED exposure. can be known to be In Examples 1 to 3, coloration was observed in Examples 1 and 2, but no coloration was observed in Example 3. Even if the addition amount of component (C) was lowered in order to prevent coloring, it was confirmed that good curability by LED exposure could be maintained.

On the other hand, according to the comparative example, when the (B) photopolymerizable compound contained in the photosensitive composition does not contain the compound represented by formula (1), or the photosensitive composition contains the compound represented by formula (1) (B) photopolymerizable Even if it contains as a compound, it turns out that the photosensitive composition does not harden favorably by LED exposure, when (C) a sensitizer is not included.

Claims (6)

(A) a photopolymerizable compound, (B) a photopolymerization initiator, and (C) a sensitizer,
The (B) photopolymerization initiator has the following formula (1):

(R ¹ is a hydrogen atom, an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, an alkoxycarbonyl group, a saturated aliphatic acyloxy group, a phenyl group which may have a substituent, a phenoxy group which may have a substituent, or a substituent A benzoyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, a benzoyloxy group which may have a substituent, a phenylalkyl group which may have a substituent, a naphthyl group which may have a substituent, a naphthoxy group which may have a substituent, a 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, even if it has a substituent a heterocyclylcarbonyl group, an amino group substituted with 1 or 2 organic groups, a morpholin-1-yl group, or a piperazin-1-yl group, and R ² and R ³ are each a chain alkyl group which may have a substituent or a substituent An optional cyclic organic group or a hydrogen atom, R ² and R ³ may be bonded to each other to form a ring, R ⁴ is a group represented by the following formula (R4-1), R ⁵ is a hydrogen atom or a substituent It is an alkyl group having 1 to 11 carbon atoms which may have, or an aryl group which may have a substituent, n is an integer of 0 to 4, and m is 0 or 1.)
A photosensitive composition comprising a compound represented by

(In formula (R4-1), R ⁷ and R ⁸ are each an organic group, p is an integer of 0 to 4, and when R ⁷ and R ⁸ are present at adjacent positions on the benzene ring, R ⁷ and R ⁸ may combine with each other to form a ring.) (A) a photopolymerizable compound, (B) a photopolymerization initiator, and (C) a sensitizer,
The (B) photopolymerization initiator has the following formula (1):

(R ¹ is a hydrogen atom, a nitro group or a monovalent organic group, R ² and R ³ 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 ² and R ³ may combine with each other to form a ring, R ⁴ is a group represented by the following formula (R4-2), R ⁵ is a hydrogen atom, an alkyl group having 1 to 11 carbon atoms which may have a substituent, or a substituent. It is an aryl group, n is an integer from 0 to 4, and m is 0 or 1.)
A photosensitive composition comprising a compound represented by

(In formula (R4-2), q is an integer of 1 to 8, r is an integer of 1 to 5, s is an integer of 0 to (r+3), and R ⁹ is an organic group.) According to claim 1 or claim 2,
(C) A photosensitive composition in which the sensitizer is a condensed polycyclic aromatic hydrocarbon ring compound or a condensed polycyclic aromatic heterocyclic compound having at least one selected from the group consisting of an alkoxy group, a substituted carbonyloxy group, and an oxo group as a substituent. A method for producing a cured product in which the photosensitive composition of claim 1 or claim 2 is cured by exposure. The method of claim 4,
A method for producing a cured product in which the exposure is performed by an LED. A cured product of the photosensitive composition of claim 1 or claim 2.