TWI722088B - Photosensitive composition, method for producing cured product formed therefrom, and cured product - Google Patents

Abstract

The present invention is to provide a photosensitive composition that can be cured well even when exposed to light by an LED, a method for producing a cured product of the photosensitive composition, and a cured product of the photosensitive composition.

The solution is that for a photosensitive composition containing (A) a photopolymerizable compound and (B) a photopolymerization initiator, the (B) photopolymerization initiator contains a compound represented by the following formula (1), and (C) The sensitizer is added to the photosensitive composition. 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 combine to form a ring, R ⁴ is a monovalent organic group, R ⁵ is a hydrogen atom, an optionally substituted alkyl group with 1 to 11 carbon atoms or an optionally substituted aryl group, n is An integer from 0 to 4, and m is 0 or 1.

Description

Photosensitive composition, method for producing cured product formed therefrom, and cured product

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.

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 a pair of electrodes in opposing directions are formed. On the inner side of one substrate, a color filter formed by pixel regions of red (R), green (G), blue (B), etc. is formed. For this color filter, it is usually divided into pixel areas such as red, green, and blue to form a black matrix.

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

Color filters or transparent insulating films use photosensitive compositions, and many are manufactured by photolithography. For example, in the color filter, a black photosensitive composition is first coated and dried on a substrate, and then exposed and developed to form a black matrix. This is produced by repeating coating, drying, exposure, and development on the photosensitive composition of each color such as red, green, and blue, and forming pixel regions of each color in specific positions.

And for the sensitivity used in the manufacture of liquid crystal displays, etc. The composition is required to be highly sensitive from the viewpoints of reducing the manufacturing cost of the display device and improving the productivity. Under such circumstances, Patent Document 1 proposes an oxime ester compound having a cycloalkyl group as a photopolymerization initiator that can change the sensitivity of the photosensitive composition. In the examples described in Patent Document 1, the compounds represented by the following chemical formulas (a) and (b) have been specifically disclosed.

[Advanced Technical Literature] [Patent Literature]

[Patent Document 1] People's Republic of China Patent Publication No. 101508744

The sensitivity of the photosensitive composition containing the oxime ester compound described in Patent Document 1 is indeed good.

However, when a photosensitive composition containing the oxime ester compound described in Patent Document 1 is exposed by LED, it may not be cured well.

From the viewpoint of energy saving or environmental load reduction, LED can be used as a light source for exposure.

The present invention was made in view of the above problems to provide a photosensitive composition that can be cured well even if exposed by LED, a method for producing a cured product of the photosensitive composition, and curing of the photosensitive composition Things for the purpose.

The inventors of the present invention have found that the photosensitive composition containing (A) photopolymerizable compound and (B) photopolymerization initiator has a 9,9-disubstituted fluorenyl group The oxime ester compound having a specific structure and the (C) sensitizer can be added to the photosensitive composition to solve the above-mentioned problems, and the present invention has been completed. Specifically, the present invention provides the following.

(式(1)中，R¹為氫原子、硝基或1價有機基，R²及R³各為可具有取代基的鏈狀烷基、可具有取代基的環狀有機 基或氫原子，R²與R³彼此結合可形成環，R⁴為1價有機基，R⁵為氫原子、可具有取代基之碳原子數1~11的烷基或可具有取代基之芳基，n為0~4的整數，m為0或1)。 The first aspect of the present invention is a photosensitive composition which contains (A) a photopolymerizable compound, (B) a photopolymerization initiator and (C) a sensitizer, and (B) a photopolymerization initiator contains The compound represented by the following formula (1);

(In formula (1), R ¹ is a hydrogen atom, a nitro group or a monovalent organic group, and 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 combine to form a ring, R ⁴ is a monovalent organic group, R ⁵ is a hydrogen atom, an optionally substituted alkyl group with 1 to 11 carbon atoms or an optionally substituted aryl group, n It is an integer from 0 to 4, and m is 0 or 1).

The second aspect of the present invention relates to a method of manufacturing a cured product obtained by exposing and curing the photosensitive composition of the first aspect.

The third aspect of the present invention relates to the cured product of the photosensitive composition of the first aspect.

According to the present invention, there are provided a photosensitive composition that can be cured satisfactorily even when exposed to an LED, a method for producing a cured product of the photosensitive composition, and a cured product of the photosensitive composition.

[The form of implementing the invention] ≪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 is an oxime ester compound containing a specific structure having a 9,9-disubstituted fluorenyl group. The photosensitive composition also contains (D) a coloring agent, and (E) an alkali-soluble resin may also be contained. The following describes the ingredients and the photosensitive composition in order Preparation method of photosensitive composition.

<(A) Photopolymerizable compound>

The (A) photopolymerizable compound (hereinafter also referred to as (A) component) contained in the photosensitive composition of the present invention is not particularly limited, and conventionally known photopolymerizable compounds can be used. Among them, resins or monomers having ethylenically unsaturated groups are also preferred, and these may be combined. By combining a resin having an ethylenically unsaturated group and a monomer having an ethylenically unsaturated group, the curability of the photosensitive composition is improved, and the pattern can be easily formed. According to the present invention, a monomer having an ethylenically unsaturated group is preferred.

[Resin with ethylenic unsaturated group]

Examples of resins having ethylenically unsaturated groups include (meth)acrylic acid, fumaric acid, maleic acid, monomethyl fumarate, monoethyl fumarate, and 2-hydroxyethyl (methyl) Acrylate, ethylene glycol monomethyl ether (meth)acrylate, ethylene glycol monoethyl ether (meth)acrylate, glycerol (meth)acrylate, (meth)acrylamide, acrylonitrile, Methacrylonitrile, methyl (meth) acrylate, ethyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, benzyl (meth) acrylate Base) acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylic acid Ester, butanediol di(meth)acrylate, propylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, tetramethylolpropane tetra(meth)acrylate, Pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 1,6-hexanediol bis(meth) Acrylate, Cardo type epoxy diacrylate and other polymerized oligomers; the polyester prepolymer obtained by condensation of polyhydric alcohols with a basic acid or a polybasic acid is obtained by reacting with (meth)acrylic acid Polyurethane (meth)acrylate; Polyurethane (meth)acrylate obtained by reacting (meth)acrylic acid after the reaction of polyol with a compound having two isocyanate groups; 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, triphenol methane type epoxy resin, polycarboxylate Acid polyglycidyl ester, polyol polyglycidyl ester, aliphatic or alicyclic epoxy resin, amine epoxy resin, dihydroxybenzene type epoxy resin and other epoxy resins react with (meth)acrylic acid Obtained epoxy (meth)acrylate resin and so on. In addition, it is preferable to use epoxy (meth)acrylate resin and polybasic acid anhydride to react. In addition, in this specification, "(meth)acrylic acid" means "acrylic acid or methacrylic acid".

In addition, as the resin having an ethylenically unsaturated group, a resin obtained by further reacting a reactant of an epoxy compound and an unsaturated group-containing carboxylic acid compound with a polybasic acid anhydride is preferably used.

Among them, the compound represented by the following general formula (a1) is preferred. The compound represented by the general formula (a1) is preferable because of its high photohardenability.

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

In the above general formula (a2), R ^1a each independently represents a hydrogen atom, a hydrocarbon group with 1 to 6 carbon atoms or a halogen atom, R ^2a each independently represents a hydrogen atom or a methyl group, and W represents a single bond or the following structural formula (a3 ) Shown in the base. In addition, in general formula (a2) and structural formula (a3), "*" represents the end of the divalent group bonding hand.

In the above general formula (a1), Y represents a residue obtained by excluding an acid anhydride group (-CO-O-CO-) from a dicarboxylic anhydride. Examples of dicarboxylic anhydrides include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, Tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl endormethylene (Methyl endormethylene) tetrahydrophthalic anhydride, chlorbacteric acid anhydride, methyl tetrahydrophthalic anhydride, glutaric acid Acid anhydride and so on.

In addition, in the above general formula (a1), Z represents a residue obtained by excluding two acid anhydride groups from tetracarboxylic dianhydride. Examples of tetracarboxylic dianhydride include pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, biphenyl ether tetracarboxylic dianhydride, and the like. In addition, in the above general formula (a1), a represents an integer of 0-20.

The acid value of the resin with ethylenic unsaturated group is preferably 10~150mgKOH/g, preferably 70~110mgKOH/g in the case of resin solid content. By setting the acid value to 10 mgKOH/g or more, sufficient solubility for the developing solution can be obtained, which is preferable. Moreover, by setting the acid value to 150 mgKOH/g or less, sufficient curability can be obtained, and the surface properties can also be improved, which is preferable.

In addition, the mass average molecular weight of the resin having an ethylenically unsaturated group is preferably 1,000 to 40,000, and more preferably 2,000 to 30,000. When the mass average molecular weight is set to 1000 or more, good heat resistance and film strength can be obtained, which is preferable. In addition, it is preferable to set the mass average molecular weight to 40,000 or less because good developability can be obtained.

[Monomers with ethylenically unsaturated groups]

For monomers with ethylenically unsaturated groups, they are monofunctional monomers and polyfunctional monomers. The following describes the monofunctional monomer and the multifunctional monomer in order.

As a monofunctional monomer, (meth)acrylic acid Amine, hydroxymethyl(meth)acrylamide, methoxymethyl(meth)acrylamide, ethoxymethyl(meth)acrylamide, propoxymethyl(meth)acrylamide Amine, butoxymethoxymethyl(meth)acrylamide, N-hydroxymethyl(meth)acrylamide, N-hydroxymethyl(meth)acrylamide, (meth)acrylic acid, Fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, crotonic acid, 2-propenamide-2-methylpropane sulfonic acid, tert-butyl propylene Amidosulfonic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) Acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-phenoxy-2-hydroxypropyl (Meth)acrylate, 2-(meth)acryloyloxy-2-hydroxypropyl phthalate, glycerol mono(meth)acrylate, tetrahydrofurfuryl (meth)acrylate, Dimethylamino (meth)acrylate, glycidyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3-tetrafluoropropane Alkyl (meth)acrylate, half (meth)acrylate of phthalic acid derivatives, etc. These monofunctional monomers may be used alone or in combination of two or more kinds.

Examples of multifunctional monomers include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, and propylene glycol di(meth)acrylate. Acrylate, polypropylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, epoxide-modified neopentyl glycol with 1 to 5 carbons Diacrylate (in which neopentyl glycol dipropylene is denatured with propylene oxide Acid ester is better) 1,6-hexaneglycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, glycerol di(meth)acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate Acrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylic acid Esters, dipentaerythritol hexa(meth)acrylate, 2,2-bis(4-(meth)propenyloxydiethoxyphenyl)propane, 2,2-bis(4-(meth)propene) Glyoxylic (polyethoxyphenyl) propane, 2-hydroxy-3-(meth)acryloxypropyl (meth)acrylate, ethylene glycol diglycidyl ether di(meth)acrylate , Diethylene glycol diglycidyl ether di(meth)acrylate, diglycidyl phthalate di(meth)acrylate, glycerol triacrylate, glycerol polyglycidyl ether poly(methyl) )Acrylate, urethane (meth)acrylate (i.e. toluene diisocyanate), trimethylhexamethylene diisocyanate and hexamethylene diisocyanate and 2-hydroxyethyl (meth)acrylate The reactants, methyl bis (meth) acrylamide, (meth) acrylamide methyl ether, polyol and N-methylol (meth) acrylamide condensation products and other multifunctional mono Body or triacrylic acid formaldehyde and so on. These polyfunctional monomers may be used alone or in combination of two or more kinds.

(A) The content of the photopolymerizable compound of the component is preferably 10 to 99.9 parts by mass, and more preferably 80 to 99.5 parts by mass, based on a total of 100 parts by mass of the components other than the solvent described below of the photosensitive composition Good, preferably with a mass of 90 to 99 parts by mass. By converting (A) into The content of the components is set to 10 parts by mass or more in total excluding 100 parts by mass of the components other than the solvent described below. Using the photosensitive composition, it is easy to form a film with excellent heat resistance, chemical resistance, and mechanical strength.

For the present invention, it is preferable that the component (A) is composed of a multifunctional monomer, and the multifunctional monomer is preferably a bifunctional or trifunctional monomer, and more preferably a bifunctional monomer. The ratio of the polyfunctional monomer in the component (A) is preferably 50% by mass or more, more preferably 85% by mass or more, and more preferably 90-100% by mass.

<(B) Photopolymerization initiator>

The photosensitive composition contains a (B) photopolymerization initiator (hereinafter also referred to as (B) component) containing a compound represented by the following formula (1). The photosensitive composition containing the compound represented by the following formula (1) as the (B) photopolymerization initiator has very excellent sensitivity. Therefore, when a photosensitive composition containing the compound represented by the formula (1) as a photopolymerization initiator is used, the photosensitive composition can be cured well even by LED exposure.

In addition, by using a photosensitive composition containing a compound represented by the following formula (1) with excellent sensitivity, pattern peeling during pattern formation can be suppressed. Although it occurs at the edge of the pattern when the line pattern is formed, it can Suppress deviations.

In addition, when forming a pattern using a photosensitive composition that does not contain a colorant, depending on the type of the photopolymerization initiator, by applying post-baking to the pattern formed using the photosensitive composition, there is a possibility of not damaging the pattern The situation of transparency. However, when a photosensitive composition containing a compound represented by the following formula (1) is used as the photopolymerization initiator (B), it is difficult to produce by adding The transparency of the heat pattern is reduced.

In particular, when the photosensitive composition contains a light-shielding agent as the colorant (D) described later, it is difficult to harden the bottom of the coating film of the photosensitive composition due to the influence of the light-shielding agent, so the formed pattern may be undercut. produce.

If an undercut is produced in a pattern formed by using a photosensitive composition containing a light-shielding agent, for example, when such a pattern is made into a display device that is used as a black matrix, the display device is caused by bubbles remaining in the undercut part. The problem of reduced picture quality. However, when the photosensitive composition contains both the (D) colorant containing a light-shielding agent and the (B) photopolymerization initiator containing the compound represented by the following formula (1), the pattern formed by using such a photosensitive composition The undercut production can be suppressed.

For the various patterns formed using the photosensitive composition, it is expected to have excellent water resistance such as not being peeled off the substrate by moisture or the like. When using the photosensitive composition containing the (B) photopolymerization initiator containing the compound represented by the following formula (1), it is not easy to peel off from the substrate even when it comes into contact with water, and it is easy to form a pattern with excellent water resistance .

In addition, in the pattern formed using the photosensitive composition, foreign matter generated by the aggregation of the initiator or resin may be included in the pattern formation. However, when a 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 with a small amount of foreign matter.

(R¹為氫原子、硝基或1價有機基，R²及R³各為可具有取代基之鏈狀烷基、可具有取代基之環狀有機基或氫原子，R²與R³彼此結合可形成環，R⁴為1價有機基，R⁵為氫原子、可具有取代基之碳原子數1~11的烷基或可具有取代基之芳基，n為0~4的整數，m為0或1)

(R ¹ is a hydrogen atom, a nitro group or a monovalent organic group, R ² and R ^{3 are} each an optionally substituted chain alkyl group, an optionally substituted cyclic organic group or a hydrogen atom, R ² and R ³ Combine each other to form a ring, R ⁴ is a monovalent organic group, R ⁵ is a hydrogen atom, an optionally substituted alkyl group with 1 to 11 carbon atoms or an optionally substituted aryl group, n is an integer of 0 to 4 , M is 0 or 1)

In the formula (1), R ¹ is a hydrogen atom, a nitro group, or a monovalent organic group. R ^{1 is} on the fluorene ring in the formula (1), and is bonded to the 6-membered aromatic ring bonded to the group represented _{by -(CO) m -, which is a different 6-membered aromatic ring.} In the formula (1), R ¹ is not particularly limited to the bonding position of the fluorene ring. When the compound represented by formula (1) has more than one R ¹ , because the synthesis of the compound represented by formula (1) is easy, one of the more than one R ¹ is bonded to the second position in the fluorene ring good. When R ¹ is a plural number, the plural R ¹ may be the same or different.

When R ¹ is an organic group, R ¹ is not particularly limited as long as it does not hinder the purpose of the present invention, and various organic groups can be appropriately selected. Preferable examples when R ¹ is an organic group include alkyl groups, alkoxy groups, cycloalkyl groups, cycloalkoxy groups, saturated aliphatic acyl groups, alkoxycarbonyl groups, saturated aliphatic acyloxy groups, A phenyl group that may have a substituent, a phenoxy group that may have a substituent, a benzyloxy group that may have a substituent, a phenoxycarbonyl group that may have a substituent, a benzyloxy group that may have a substituent, A substituted phenylalkyl group, a substituted naphthyl group, a substituted naphthyloxy group, a substituted naphthyloxy group, a substituted naphthyloxycarbonyl group, a substituted naphthyl group The naphthyloxy group, the naphthyl group which may have a substituent, the heterocyclic group which may have a substituent, the heterocyclic carbonyl group which may have a substituent, the amino group which may be substituted by 1 or 2 organic groups, Lin-1-yl, piperazin-1-yl and the like.

When R ¹ is an alkyl group, the number of carbon atoms of the alkyl group is preferably 1-20, and more preferably 1-6. In addition, when R ¹ is an alkyl group, it may be a straight chain or a 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, tert-pentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, sec-octyl, tert-octyl, n-nonyl, Isononyl, n-decyl and isodecyl, etc. In addition, when R ¹ is an alkyl group, the carbon chain of the alkyl group may contain an ether bond (-O-). Examples of alkyl groups having ether bonds in the carbon chain include methoxyethyl, ethoxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl, propyloxy Ethoxyethyl and methoxypropyl, etc.

When R ¹ is an alkoxy group, the number of carbon atoms of the alkoxy group is preferably 1-20, and more preferably 1-6. In addition, when R ¹ is an alkoxy group, it may be a straight chain or a branched chain. Specific examples when R ¹ is an alkoxy group include methoxy group, ethoxy group, n-propyloxy group, isopropyloxy group, n-butyloxy group, isobutyloxy group, sec -Butyloxy, tert-butyloxy, n-pentyloxy, isopentyloxy, sec-pentyloxy, tert-pentyloxy, n-hexyloxy, n-heptyl Oxy, n-octyloxy, isooctyloxy, sec-octyloxy, tert-octyloxy, n-nonyloxy, isononyloxy, n-decyloxy, and Isodecyloxy and so on. In addition, when R ¹ is an alkoxy group, the carbon chain of the alkoxy group may contain an ether bond (-O-). Examples of alkoxy groups having ether bonds in the carbon chain include methoxyethoxy, ethoxyethoxy, methoxyethoxyethoxy, and ethoxyethoxyethoxy. Group, propyloxyethoxyethoxy, and methoxypropyloxy, etc.

When R ¹ is a cycloalkyl group or a cycloalkoxy group, the number of carbon atoms of the cycloalkyl group or a cycloalkoxy group is preferably 3-10, more preferably 3-6. Specific examples when R ¹ is a cycloalkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. Specific examples when R ¹ is a cycloalkoxy group include cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, cycloheptyloxy, and cyclooctyloxy Wait.

When R ¹ is a saturated aliphatic acyl group or a saturated aliphatic acyloxy group, the number of carbon atoms of the saturated aliphatic acyl group or saturated aliphatic acyloxy group is preferably 2-21, more preferably 2-7. As ^{specific examples when R 1} is a saturated aliphatic acyl group, acetyl group, propionyl group, n-butyryl group, 2-methylpropionyl group, n-pentanyl group, 2,2-dimethyl group can be mentioned. Propyl, n-hexyl, n-heptanyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-thirteen醯基, n-fourteen 醯基, n-fifteen 醯基, and n-17 醯基, etc. Specific examples when R ¹ is a saturated aliphatic oxy group include acetoxy group, propoxy group, n-butoxy group, 2-methylpropoxy group, and n-pentoxy group. Baseoxy, 2,2-Dimethylpropanyloxy, n-hexyloxy, n-heptanyloxy, n-octanyloxy, n-nonanyloxy, n-decyloxy N-decanoyloxy, n-undecanoyloxy, n-dodecanoyloxy, n-tridecanoyloxy, n-tetradecanoyloxy, n-pentadecanoyloxy, And n-heptadecyloxy and so on.

When R ¹ is an alkoxycarbonyl group, the number of carbon atoms of the alkoxycarbonyl group is preferably 2-20, more preferably 2-7. Specific examples when R ¹ is an alkoxycarbonyl group include methoxycarbonyl, ethoxycarbonyl, n-propyloxycarbonyl, isopropyloxycarbonyl, n-butyloxycarbonyl, isobutyloxy Carbonyl, sec-butyloxycarbonyl, tert-butyloxycarbonyl, n-pentyloxycarbonyl, isopentyloxycarbonyl, sec-pentyloxycarbonyl, tert-pentyloxycarbonyl, n-hexyloxycarbonyl, n -Heptyloxycarbonyl, n-octyloxycarbonyl, isooctyloxycarbonyl, sec-octyloxycarbonyl, tert-octyloxycarbonyl, n-nonyloxycarbonyl, isononyloxycarbonyl, n-decyl Oxycarbonyl and isodecyloxycarbonyl, etc.

When R ¹ is a phenylalkyl group, the number of carbon atoms of the phenylalkyl group is preferably 7-20, more preferably 7-10. In addition, when R ¹ is a naphthyl group, the number of carbon atoms of the naphthyl group is preferably 11-20, more preferably 11-14. Specific examples when R ¹ is a phenylalkyl group include benzyl group, 2-phenylethyl group, 3-phenylpropyl group, and 4-phenylbutyl group. Specific examples when R ¹ is a naphthyl group include α-naphthylmethyl, β-naphthylmethyl, 2-(α-naphthalene)ethyl, and 2-(β-naphthalene)ethyl. When R ¹ is a phenylalkyl group or a naphthyl group, R ¹ may further have a substituent on the phenyl group or the naphthyl group.

When R ¹ is a heterocyclic group, the heterocyclic group is a 5-membered or 6-membered monocyclic ring containing at least one N, S, O, or a heterocyclic group in which the monocyclic rings are condensed with each other or the monocyclic ring and a benzene ring. When the heterocyclic group is a condensed ring, it has a ring number of three. The heterocyclic group may be an aromatic group (heteroaryl group) or a non-aromatic group. Examples of the heterocyclic ring constituting the heterocyclic group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, Pyridazine, benzofuran, benzothiophene, indole, isoindole, indazine, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline , Quinazoline, phthalazine, cinnoline, quinoxaline, piperidine, piperazine, morpholine, piperidine, tetrahydropyran and tetrahydrofuran, etc. When R ¹ is a heterocyclic group, the heterocyclic group may further have a substituent.

When R ¹ is a heterocyclic carbonyl group, the heterocyclic group contained in the heterocyclic carbonyl group is the same as when ^{R 1 is a heterocyclic group.}

When R ¹ is an amino group substituted with 1 or 2 organic groups, preferable examples of the organic group include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, and 2 to 21 saturated aliphatic acyl groups, optionally substituted phenyl groups, optionally substituted benzyl groups, optionally substituted C7-20 phenylalkyl groups, optionally substituted Naphthyl, optionally substituted naphthoyl, optionally substituted naphthyl with 11 to 20 carbon atoms, heterocyclic group, and the like. Specific examples of these preferred organic groups are the same as ^{R 1.} Specific examples of amino groups substituted with 1 or 2 organic groups include methylamino, ethylamino, diethylamino, n-propylamino, and di-n-propylamine Base, isopropylamino, n-butylamino, di-n-butylamino, n-pentylamino, n-hexylamino, n-heptylamino, n-octylamino , N-nonylamino, n-decylamino, phenylamino, naphthylamino, acetamido, acrylamido, n-butyrylamino, n-pentylamino, n -Hexylamino, n-heptanylamino, n-octylamino, n-decylamino, benzylamino, α-naphthylamino and β-naphthylamino Amino groups and so on.

Examples of the substituent when the phenyl group, naphthyl group, and heterocyclic group contained 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, Saturated aliphatic acyl group with 2 to 7 carbon atoms, alkoxycarbonyl group with 2 to 7 carbon atoms, saturated aliphatic acyloxy group with 2 to 7 carbon atoms, and alkyl group with 1 to 6 carbon atoms The monoalkylamino group, the dialkylamino group having an alkyl group of 1 to 6 carbon atoms, morpholin-1-yl, piperazin-1-yl, halogen, nitro and cyano, etc. When the phenyl group, naphthyl group, and heterocyclic group contained in R ¹ further have a substituent, the number of the substituent is not limited as long as it does not hinder the purpose of the present invention, and 1 to 4 are preferred. When the phenyl group, naphthyl group, and heterocyclic group contained in R ¹ have plural substituents, the plural substituents may be the same or different.

Among the groups described above, when R ¹ is a nitro group or a group represented by R ⁶ -CO-, the sensitivity tends to be improved, so it is preferable. R ⁶ is not particularly limited as long as it does not hinder the purpose of the present invention, and it can be selected from various organic groups. Examples of preferable groups 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 heterocyclic group which may have a substituent. Among these groups as R ⁶ , 2-methylphenyl, thiophen-2-yl and α-naphthyl are particularly preferred.

In addition, when R ¹ is a hydrogen atom, it is preferable to have good transparency. In addition, when R ¹ is a hydrogen atom and R ⁴ is a group represented by the formula (R4-2) described later, there is a tendency for better transparency.

In the 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 be bonded to each other to form a ring. Among these groups, as R ² and R ³ , a chain alkyl group which may have a substituent is preferred. When R ² and R ³ are a chain alkyl group which may have a substituent, the chain alkyl group may be a straight chain alkyl group or a branched chain alkyl group.

When R ² and R ³ are chain alkyl groups without substituents, the number of carbon atoms of the chain alkyl group is preferably 1-20, preferably 1-10, and particularly preferably 1-6. Specific examples of the chain alkyl group of R ² and R ³ include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert- Butyl, n-pentyl, isopentyl, sec-pentyl, tert-pentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, sec-octyl, tert-octyl, n-nonyl, isononyl, n-decyl, and isodecyl, etc. In addition, when R ² and R ³ are alkyl groups, the carbon chain of the alkyl group may contain an ether bond (-O-). Examples of alkyl groups having ether bonds in the carbon chain include methoxyethyl, ethoxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl, propyloxy Ethoxyethyl and methoxypropyl, etc.

When R ² and R ³ are chain alkyl groups having substituents, the number of carbon atoms of the chain alkyl group is preferably 1-20, preferably 1-10, and particularly preferably 1-6. In this case, the number of carbon atoms of the substituent is not included in the number of carbon atoms of the chain alkyl group. The chain alkyl group having a substituent is preferably a linear one.

The substituent which may have an alkyl group is not specifically limited in the range which does not hinder the objective of this invention. Preferable examples of the substituent include a cyano group, a halogen atom, a cyclic organic group, and an alkoxycarbonyl group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among these, a fluorine atom, a chlorine atom, and a bromine atom are preferable. Examples of the cyclic organic group include a cycloalkyl group, an aromatic hydrocarbon group, and a heterocyclic group. Specific examples of the cycloalkyl group are the same as the preferred examples when ^{R 1 is a cycloalkyl group.} Specific examples of aromatic hydrocarbon groups include phenyl, naphthyl, biphenyl, anthracenyl, and phenanthryl. Specific examples of the heterocyclic group are the same as the preferred examples when ^{R 1 is a heterocyclic group.} When R ¹ is an alkoxycarbonyl group, the alkoxy group contained in the alkoxycarbonyl group may be linear or branched, preferably linear. The number of carbon atoms of the alkoxy group contained in the alkoxycarbonyl group is preferably 1-10, more preferably 1-6.

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

When R ² and R ³ are a cyclic organic group, the cyclic organic group may be an alicyclic group or an aromatic group. Examples of the cyclic organic group include aliphatic cyclic hydrocarbon groups, aromatic hydrocarbon groups, and heterocyclic groups. When R ² and R ³ are cyclic organic groups, the substituents that may have a cyclic organic group are the same as when R ² and R ³ are chain alkyl groups.

R ² and R ³ are preferably groups formed by bonding via a carbon-carbon bond, or groups formed by condensation of plural benzene rings. When the aromatic hydrocarbon group is a phenyl group, or a group formed by bonding or condensing a plurality of benzene rings, the number of benzene rings contained in the aromatic hydrocarbon group is not particularly limited. 3 or less is preferable, and 2 or less is more preferable. Good, with 1 being particularly good. Preferable specific examples of the aromatic hydrocarbon group include phenyl, naphthyl, biphenyl, anthracenyl, and phenanthryl.

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 of the aliphatic cyclic hydrocarbon group is not particularly limited, and is preferably 3-20, and more preferably 3-10. Examples of monocyclic cyclic hydrocarbon groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, norbornyl, isobornyl, tricyclononyl, Tricyclodecyl, tetracyclododecyl, adamantyl, etc.

When R ² and R ³ are heterocyclic groups, the heterocyclic group is a 5-membered or 6-membered monocyclic ring containing more than one N, S, O, or a heterocyclic ring in which the monocyclic rings are condensed with each other or the monocyclic ring and a benzene ring base. When the heterocyclic group is a condensed ring, the number of rings is up to 3. The heterocyclic group may be an aromatic group (heteroaryl group) or a non-aromatic group. Examples of the heterocyclic ring constituting the heterocyclic group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, Pyridazine, benzofuran, benzothiophene, indole, isoindole, indazine, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline , Quinazoline, phthalazine, cinnoline, quinoxaline, piperidine, piperazine, morpholine, piperidine, tetrahydropyran and tetrahydrofuran, etc.

R ² and R ³ may be bonded to each other to form a ring. The group formed by the ring formed by R ² and R ^{3 is preferably a cycloalkylene group.} When R ² and R ³ are bonded to form a cycloalkylene group, the ring constituting the cycloalkylene group is preferably a 5-membered to 6-membered ring, and more preferably a 5-membered ring.

When ^{the group formed by bonding R 2} and R ³ is a cycloalkylene group, the cycloalkylene group may be condensed with one or more other rings. Examples of the ring that can be condensed with the cycloalkylene ring include a benzene ring, a naphthalene ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, and a furan ring. , Thiophene ring, pyrrole ring, pyridine ring, pyrazine ring and pyrimidine ring, etc.

As an example of a group that is also preferable among ^{R 2} and R ^{3 described above, a group represented by the formula -A 1} -A ² can be given. In the formula, A ¹ is a linear alkylene group, and A ² is an alkoxy group, a cyano group, a halogen atom, a halogenated alkyl group, a cyclic organic group, or an alkoxycarbonyl group.

The number of carbon atoms of the straight-chain alkyl extension of ^{A 1 is preferably 1-10, and more preferably 1-6.} When A ² is an alkoxy group, the alkoxy group may be linear or branched, preferably linear. The number of carbon atoms of the alkoxy group is preferably 1-10, more preferably 1-6. When A ² is a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are preferable, and a fluorine atom, a chlorine atom, and a bromine atom are preferable. When A ² is a halogenated alkyl group, the halogen atom contained in the halogenated alkyl group is preferably a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom, a chlorine atom, and a bromine atom are preferred. The halogenated alkyl group may be linear or branched, preferably linear. When A ² is a cyclic organic group, examples of the cyclic organic group are the same as the cyclic organic group possessed as a substituent in ^{R 2} and R ^3. When A ² is an alkoxycarbonyl group, examples of the alkoxycarbonyl group are the same as the alkoxycarbonyl group that ^{R 2} and R ^{3 have as a substituent.}

Preferred specific examples of R ² and R ³ include alkyl groups such as ethyl, n-propyl, n-butyl, n-hexyl, n-heptyl, and n-octyl; 2-methyl Oxyethyl, 3-methoxy-n-propyl, 4-methoxy-n-butyl, 5-methoxy-n-pentyl, 6-methoxy-n-hexyl, 7- Methoxy-n-heptyl, 8-methoxy-n-octyl, 2-ethoxyethyl, 3-ethoxy-n-propyl, 4-ethoxy-n-butyl, Alkoxyalkyl groups such as 5-ethoxy-n-pentyl, 6-ethoxy-n-hexyl, 7-ethoxy-n-heptyl and 8-ethoxy-n-octyl; 2-cyanoethyl, 3-cyano-n-propyl, 4-cyano-n-butyl, 5-cyano-n-pentyl, 6-cyano-n-hexyl, 7-cyano -n-heptyl, and 8-cyano-n-octyl and other cyanoalkyl groups; 2-phenylethyl, 3-phenyl-n-propyl, 4-phenyl-n-butyl, 5 -Phenyl alkyl such as phenyl-n-pentyl, 6-phenyl-n-hexyl, 7-phenyl-n-heptyl, and 8-phenyl-n-octyl; 2-cyclohexylethyl , 3-cyclohexyl-n-propyl, 4-cyclohexyl-n-butyl, 5-cyclohexyl-n-pentyl, 6-cyclohexyl-n-hexyl, 7-cyclohexyl-n-heptyl, 8-cyclohexyl-n-octyl, 2-cyclopentylethyl, 3-cyclopentyl-n-propyl, 4-cyclopentyl-n-butyl, 5-cyclopentyl-n-pentyl , 6-cyclopentyl-n-hexyl, 7-cyclopentyl-n-heptyl, and 8-cyclopentyl-n-octyl and other cycloalkylalkyl groups; 2-methoxycarbonylethyl, 3 -Methoxycarbonyl-n-propyl, 4-methoxycarbonyl-n-butyl, 5-methoxycarbonyl-n-pentyl, 6-methoxycarbonyl-n-hexyl, 7-methoxycarbonyl Carbonyl-n-heptyl, 8-methoxycarbonyl-n-octyl, 2-ethoxycarbonylethyl, 3-ethoxycarbonyl-n-propyl, 4-ethoxycarbonyl-n- Butyl, 5-ethoxycarbonyl-n-pentyl, 6-ethoxycarbonyl-n-hexyl, 7-ethoxycarbonyl-n-heptyl and 8-ethoxycarbonyl-n-octyl, etc. The alkoxycarbonyl alkyl group; 2-chloroethyl, 3-chloro-n-propyl, 4-chloro-n-butyl, 5-chloro-n-pentyl, 6-chloro-n-hexyl, 7 -Chloro-n-heptyl, 8-chloro-n-octyl, 2-bromoethyl, 3-bromo-n-propyl, 4-bromo-n-butyl, 5-bromo-n-pentyl, 6-bromo-n-hexyl, 7-bromo-n-heptyl, 8-bromo-n-octyl, 3,3,3-trifluoropropyl and 3,3,4,4,5,5,5 -Halogenated alkyl groups such as pentafluoro-n-pentyl.

As R ² and R ³ , among the above-mentioned preferred groups are ethyl, n-propyl, n-butyl, n-pentyl, 2-methoxyethyl, 2-cyanoethyl, 2-phenylethyl, 2-cyclohexylethyl, 2-methoxycarbonylethyl, 2-chloroethyl, 2-bromoethyl, 3,3,3-trifluoropropyl, and 3,3 ,4,4,5,5,5-Pentafluoro-n-pentyl.

Examples of preferable organic groups for R ⁴ include alkyl groups, alkoxy groups, cycloalkyl groups, cycloalkoxy groups, saturated aliphatic acyl groups, alkoxycarbonyl groups, and saturated aliphatic acyl groups, which are the same as ^{those of R 1.} Group oxy, phenyl which may have substituents, phenoxy which may have substituents, benzyl which may have substituents, phenoxycarbonyl which may have substituents, and benzyl which may have substituents An oxy group, a phenylalkyl group which may have a substituent, a naphthyl group which may have a substituent, a naphthoxy group which may have a substituent, a naphthyloxy group which may have a substituent, a naphthyloxycarbonyl group which may have a substituent, Substitutable naphthyloxy group, substitutable naphthyl group, substitutable heterocyclic group, substitutable heterocyclic carbonyl group, substituted by 1 or 2 organic groups Amino, morpholin-1-yl, piperazin-1-yl, etc. Specific examples of these groups are the same as those described ^{for R 1.} Moreover, as R ⁴ , it is also preferable to use a cycloalkylalkyl group, a phenoxyalkyl group which may have a substituent on the aromatic ring, and a phenylthioalkyl group which may have a substituent on the aromatic ring. A phenoxy group may have an alkyl group, a phenyl group and the alkyl substituents contained in R ¹ may be a phenyl substituent of the same group.

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

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. When A ³ is an alkylene group, the number of carbon atoms of the alkylene group is preferably from 1 to 10, preferably from 1 to 6, and particularly preferably from 1 to 4.

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

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

The above ^{description is about R 4} , but R ⁴ is preferably a group represented by the following formula (R4-1) or (R4-2).

(式(R4-1)及(R4-2)中，R⁷及R⁸各為有機基，p為0~4的整數，R⁷及R⁸存在於苯環上的磷接位置時，R⁷與R⁸彼此鍵結可形成環，q為1~8的整數，r為1~5的整數，s為0~(r+3)的整數，R⁹為有機基)

(In formulas (R4-1) and (R4-2), R ⁷ and R ^{8 are} each an organic group, p is an integer from 0 to 4, when R ⁷ and R ⁸ are present in the phosphorus attachment position on the benzene ring, R ⁷ and R ⁸ can bond to 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), and R ⁹ is an organic group)

The examples of the organic groups of ^{R 7} and R ⁸ in the formula (R4-1) are the same as those of ^{R 1.} As R ⁷ , an alkyl group or a phenyl group is preferred. When R ⁷ is an alkyl group, the number of carbon atoms is preferably from 1 to 10, preferably from 1 to 5, particularly preferably from 1 to 3, and 1 is the most preferred. In other words, the ^{best R 7} is methyl. When R ⁷ and R ⁸ are bonded to form a ring, the ring may be an aromatic ring or an aliphatic ring. Among the groups represented by the formula (R4-1) ^{, examples of preferred groups for forming a ring between R 7} and R ⁸ include primaphthalene-1-yl or 1,2,3,4-tetrahydronaphthalene-5-yl Wait. In the above formula (R4-1), p is an integer of 0-4, preferably 0 or 1, and more preferably 0.

In the above formula (R4-2), R ⁹ is an organic group. Examples of the organic group include the same organic groups described for R ¹ for the group. Among the organic groups, an alkyl group is preferred. The alkyl group may be linear or branched. The number of carbon atoms of the alkyl group is preferably from 1 to 10, preferably from 1 to 5, and particularly preferably from 1 to 3. As R ⁹ , a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, etc. are preferable, and among them, a methyl group is preferable.

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

In the formula (1), R ⁵ is a hydrogen atom, an optionally substituted alkyl group having 1 to 11 carbon atoms, or an optionally substituted aryl group. Examples of substituents that may be possessed when R ⁵ is an alkyl group include a phenyl group, a naphthyl group, and the like. In addition, ^{examples of substituents that may be possessed when R 1} is an aryl group include an alkyl group having 1 to 5 carbon atoms, an alkoxy group, a halogen atom, and the like.

In the formula (1), as R ⁵ , a hydrogen atom, methyl, ethyl, n-propyl, isopropyl, n-butyl, phenyl, benzyl, methylphenyl, naphthyl can be exemplified Etc. are preferred, and among each other, methyl or phenyl is also preferred.

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

In addition, the content of the photopolymerization initiator of component (B) is preferably 0.05-50% by mass, preferably 0.1-30% by mass, based on the total of component (A) and component (B). 0.5-20% by mass is more preferable.

The content of the compound represented by the following formula (1), for example, for the entire component (B), if it is in the range of 1-100% by mass, it is preferably 50% by mass or more, and 70-100% by mass is more preferred. good.

(B) The compound represented by formula (1) in component can be used alone Two or more types can also be used. When two or more types are used, the following (i) to (iii) are preferred.

(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) R ⁴ is a combination of a compound of formula (R4-1) and R ⁴ is a compound of formula (R4-2)

Compound (III) R ⁴ is of formula (R4-1) or Formula (R4-2) and R ⁴ of the carbon atoms of an alkyl group of 1 to 4

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

The mixing ratio (mass ratio) of each compound after the combination of (i) to (iii) above can be adjusted appropriately to match the characteristics of the purpose such as sensitivity, for example, 1:99~99:1 is better, and 10:90 ~90:10 is better, and 30:70~70; 30 is more preferred.

The method for producing the compound represented by formula (1) is not particularly limited. The compound represented by the formula (1) is preferably produced by a method containing a step of converting the oxime group (=N-OH) contained in the compound represented by the following formula (2) into an ^{oxime ester group represented by =NO-COR 5.} . Same as R (1) and ⁵ R ⁵ in the formula.

(R¹、R²、R³、R⁴、m、及n與式(1)相同。n為0~4的 整數，m為0或1)

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

Therefore, the compound represented by the above formula (2) is useful as an intermediate for the synthesis of the compound represented by the formula (1).

The method of converting the oxime group (=N-OH) into the ^{oxime ester group represented by =NO-COR 5} is not particularly limited. Typically, a method of imparting an acylating agent for the 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 or acid halides represented by R 5} COHal (Hal is a halogen atom).

When m is 0 in the compound represented by general formula (1), it can be synthesized according to the following scheme 1, for example. In Scheme 1, the 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 ^{substituted with R 2} and R ³ at the 9th position, which can be substituted by a known method Derived from base R ^1. The ninth bit by R ² and R ³ substituted fluorene derivatives, for example, R ² and R ³ is an alkyl group, such as Laid Open Publication No. 06-234668 described, it may be in the presence of an alkali metal hydroxide, It is obtained by reacting fluorene with an alkylating agent in an aprotic polar organic solvent. In addition, in the organic solvent solution of fluorene, add an alkylating agent such as alkyl halide, an aqueous solution of alkali metal hydroxide, and an interphase moving catalyst such as potassium tert-butoxide and tetrabutylammonium iodide or potassium tert-butoxide. After the alkylation reaction, 9,9-alkyl substituted fluorene can be obtained.

For the fluorene derivative represented by the formula (1-1), the fluorene derivative represented by the formula (1-3) is obtained by ^{introducing the fluorene group represented by -CO-R 4 through the Friedel-Crafts acylation reaction.} The acylating agent to be introduced into the ^{acyl group represented by -CO-R 4} may be a halogenated carbonyl compound or an acid anhydride. As the acylating agent, a halocarbonyl compound represented by formula (1-2) is preferred. In formula (1-2), Hal is a halogen atom. The position where the fluorene ring is introduced can be selected by appropriately changing the conditions of the Friedel-Crafts reaction, or by applying protection and deprotection to positions other than the fused position.

^{Next, the group represented by -CO-R 4} in the obtained fluorene derivative represented by formula (1-3) is transformed into a group represented by -C(=N-OH)-R ^{4 to} obtain formula (1-4 ) The oxime compound shown. The method for ^{converting the group represented by -CO-R 4 to the} group represented by -C(=N-OH)-R ⁴ is not particularly limited, and oximation by hydroxylamine is preferred. Make the oxime compound of formula (1-4) and the acid anhydride ((R ⁵ CO) ₂ O) represented by the following formula (1-5) or the acid halide represented by the following general formula (1-6) (R ⁵ COHal , Hal is a halogen atom.) By reacting, a compound represented by the following formula (1-7) can be obtained.

And, 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 the} same as the formula (1).

^{In addition, with respect to Scheme 1, R 4} contained in each of formula (1-2), formula (1-3), and formula (1-4) may be the same or different. ^{In other words, R 4 in} formula (1-2), formula (1-3), and formula (1-4) can be chemically modified during the synthesis process shown in Scheme 1. Examples of chemical modification include esterification, etherification, acylation, amination, halogenation, and substitution of organic groups with hydrogen atoms in amino groups. The ^{acceptable chemical modification of R 4} is not limited to these.

<Process 1>

When m is 1 in the compound represented by formula (1), it can be synthesized according to the following scheme 2, for example. In Scheme 2, the fluorene derivative represented by the following formula (2-1) is used as a raw material. The fluorene derivative represented by formula (2-1) is introduced into the compound represented by formula (1-1) by Friedel-Crafts reaction by the same method as in Scheme 1. -CO-CH ₂ -R ⁴ Derived from the shown 醯基. As the acylating agent, a carboxylic acid halide represented by the formula (1-8): Hal-CO-CH ₂ -R ^{4 is preferred. Next, the methylidene group existing between R 4} and the carbonyl group in the compound represented by the formula (2-1) is oximated to obtain the ketoxime compound represented by the following formula (2-3). The method of oximating methylidene is not particularly limited, but nitrite represented by the following general formula (2-2) (RONO, R is an alkyl group having 1 to 6 carbons) is carried out in the presence of hydrochloric acid. The method of reaction is better. Next, combine the ketoxime compound represented by the following formula (2-3) with the acid anhydride ((R ⁵ CO) ₂ O) represented by the following formula (2-4), or with the following general formula (2-5) An acid halide (R ⁵ COHal and Hal are halogen atoms.) is reacted to obtain a compound represented by the following formula (2-6). And, for 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 is a tendency that the generation of foreign matter in the pattern formed by using the photosensitive composition containing the compound represented by the formula (1) can be further reduced.

^{In addition, with respect to Scheme 2, R 4} contained in each of formula (1-8), formula (2-1), and formula (2-3) may be the same or different. ^{In other words, R 4 in} formula (1-8), formula (2-1), and formula (2-3) can also be chemically modified during the synthesis process shown in Scheme 2. Examples of chemical modification include esterification, etherification, acylation, amination, halogenation, and organic substitution of hydrogen atoms in the amine group. The ^{acceptable chemical modification of R 4 is} not limited to these.

As a preferable specific example of the compound represented by formula (1), the following compound 1 to compound 41 can be mentioned.

<(C) Sensitizer>

The photosensitive composition contains the above-mentioned (B) photopolymerization initiator and (C) sensitizer at the same time. The photosensitive composition contains a compound represented by the above formula (1) The (B) photopolymerization initiator of the product also contains the (C) sensitizer, so the photosensitive composition can also be cured well by LED exposure.

This may be because the compound represented by formula (1) is particularly sensitized by the sensitizer.

(C) As a sensitizer, the compound used for the sensitization purpose of the photosensitive composition from the past as a photopolymerization initiator can be used especially without limitation.

As the (C) sensitizer, it is preferable to have one or more compounds selected from the group consisting of an alkoxy group as a substituent, a substituted carbonyloxy group, and an oxo group (=O). As the compound having this substituent, a condensed polycyclic aromatic hydrocarbon compound or a condensed polycyclic aromatic heterocyclic compound is preferred.

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). As an example of the substituent, Examples include alkyl groups with 1 to 20 carbon atoms, halogenated alkyl groups with 1 to 20 carbon atoms, alkoxyalkyl groups with 2 to 20 carbon atoms, aliphatic acyl groups with 2 to 20 carbon atoms, and carbon atoms. Aromatic acyl groups (aryl acyl groups), cyano groups, nitro groups, nitroso groups, halogen atoms, hydroxyl groups, and mercapto groups with 7 to 11 atoms.

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

Preferred examples of alkoxy groups include methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, tert- Butyloxy, n-pentyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, 2-ethylhexyl, n-nonyloxy, and n-decyl Oxy etc.

The substituted carbonyloxy group is the group represented by -O-CO-A. A is not particularly limited as long as it has the sensitization expected by the (C) sensitizer, and it may be various organic groups. As A, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and an aryloxy group having 6 to 10 carbon atoms are preferred.

The aryl group or aryloxy group may have 1 or more substituents. The type of the substituent is not particularly limited as long as it does not hinder the purpose of the present invention. When the aryl group or the aryloxy group has plural substituents, the plural substituents may be the same or different.

Preferred examples of the substituent include an alkoxy group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, and an aryloxy group having 6 to 10 carbon atoms. 10 aryloxy groups, aliphatic acyl groups with 2 to 7 carbon atoms, aromatic acyl groups with 7 to 11 carbon atoms (aryl acyl groups), cyano groups, nitro groups, nitroso groups, halogen atoms, hydroxyl groups , And sulfhydryl, etc.

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, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n -Heptyl, n-octyl, and 2-ethylhexyl, etc.

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

As preferred examples of alkoxy groups, methoxy, ethoxy, n- Propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, tert-butyloxy, n-pentyloxy, n-hexyloxy, n-heptyloxy , N-octyloxy, and 2-ethylhexyloxy, etc.

Condensed polycyclic aromatic hydrocarbon compounds or condensed polycyclic aromatic heterocyclic compounds substituted by one or more selected from the group consisting of alkoxy, substituted carbonyloxy, and oxo (=O) The number of rings constituting the condensed ring is not particularly limited as long as the desired sensitization effect can be obtained. The number of rings is preferably 2 or more, 3 or more is more preferable, 3-6 is particularly preferable, and 3 or 4 is most preferable.

In addition, the condensed polycyclic aromatic hydrocarbon compound or the condensed polycyclic aromatic heterocyclic compound has only aromaticity, and the monocyclic ring forming the condensed polycyclic ring does not necessarily need to be an aromatic ring.

Preferable examples of the condensed polycyclic ring contained 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, and a condensed polycyclic aromatic heterocyclic compound. Ton ring, and sulphur ton ring. Among these rings, anthracene ring, naphthacene ring, and thioxanthene ring are preferred.

Among the anthracycline-containing compounds, as specific examples of preferred compounds used as (C) sensitizers, 9,10-bis(acetoxy)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-ethylhexyloxy)anthracene, 9,10-bis(n-octylcarbonyloxy)anthracene, 9,10 - Bis(n-nonylcarbonyloxy)anthracene, 9,10-bis(n-decylcarbonyloxy)anthracene, 9,10-bis(benzyloxy)anthracene, 9,10-bis(4- Methylbenzyloxy)anthracene, 9,10-bis(2-naphthyloxy)anthracene, 2-methyl-9,10-bis(acetoxy)anthracene, 2-methyl- 9,10-bis(propionyloxy)anthracene, 2-methyl-9,10-bis(n-propylcarbonyloxy)anthracene, 2-methyl-9,10-bis(isopropylcarbonyl) Oxy)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(benzyl (A-oxy)anthracene, 2-methyl-9,10-bis(4-methylbenzyloxy)anthracene, 2-methyl-9,10-bis(2-naphthyloxy)anthracene , 1-methyl-9,10-bis(acetoxy)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(benzyloxy)anthracene, 1-methyl-9,10-bis(4-methylbenzyloxy) )Anthracene, 1-methyl-9,10-bis(2-naphthyloxy)anthracene, 2-ethyl-9,10-bis(acetoxy)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(benzyloxy) base) Anthracene, 2-ethyl-9,10-bis(4-ethyl-benzyloxy)anthracene, 2-ethyl-9,10-bis(2-naphthyloxy)anthracene, 1- Ethyl-9,10-bis(acetoxy)anthracene, 1-ethyl-9,10-bis(propionyloxy)anthracene, 1-ethyl-9,10-bis(n-propyl) Carbonyloxy)anthracene, 1-ethyl-9,10-bis(isopropylcarbonyloxy)anthracene, 1-ethyl-9,10-bis(n-butylcarbonyloxy)anthracene, 1-ethyl Base-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(benzyloxy)anthracene, 1-ethyl-9,10-bis(4-ethyl-benzyloxy)anthracene , 1-Ethyl-9,10-bis(2-naphthyloxy)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(benzyloxy)anthracene, 1-(t-butyl) )-9,10-bis(4-(t-butyl)-benzyloxy)anthracene, 1-(t-butyl)-9,10-bis(2-naphthyloxy)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(benzyloxy)anthracene, 2-(t-butyl)-9,10-bis(4-(t-butyl)-benzyloxy )Anthracene, 2-(t-butyl)-9,10-bis(2-naphthyloxy)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(isobutylcarbonyloxy)anthracene, 2-pentyl-9,10-bis(n-pentylcarbonyloxy)anthracene, 2 -Pentyl-9,10-bis(n-hexylcarbonyloxy)anthracene, 2-pentyl-9,10-bis(benzyloxy)anthracene, 2-pentyl-9,10-bis(4 -(t-butyl)-benzyloxy)anthracene, 2-pentyl-9,10-bis(2-naphthyloxy)anthracene, and the like.

In addition, anthracene compounds substituted with halogen atoms may also be used as (C) sensitizers. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.

Anthracene compounds substituted by halogen atoms, as specific examples of preferred compounds used as sensitizers (C), include 2-chloro-9,10-bis(acetoxy)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-butylcarbonyloxy)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(benzyloxy)anthracene, 2 -Chloro-9,10-bis(4-methylbenzyloxy)anthracene, 2-chloro-9,10-bis(2-naphthyloxy)anthracene, 1-chloro-9,10- Bis(acetoxy)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(isobutylcarbonyl) Oxy)anthracene, 1-chloro-9,10-bis(n-pentylcarbonyloxy)anthracene, 1-chloro-9,10-bis(n-hexylcarbonyl) Oxy)anthracene, 1-chloro-9,10-bis(benzyloxy)anthracene, 1-chloro-9,10-bis(4-methylbenzyloxy)anthracene, 1-chloro- 9,10-bis(2-naphthyloxy)anthracene, 2-fluoro-9,10-bis(acetoxy)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-hexyl oxy)anthracene, 2-fluoro-9,10-bis(benzyloxy)anthracene, 2-fluoro-9,10-bis(4- Methylbenzyloxy)anthracene, 2-fluoro-9,10-bis(2-naphthyloxy)anthracene, 1-fluoro-9,10-bis(acetoxy)anthracene, 1- Fluoro-9,10-bis(propionyloxy)anthracene, 1-fluoro-9,10-bis(n-propylcarbonyloxy)anthracene, 1-fluoro-9,10-bis(isopropylcarbonyl) Oxy)anthracene, 1-fluoro-9,10-bis(n-butylcarbonyloxy)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(benzyloxy)anthracene , 1-fluoro-9,10-bis(4-methylbenzyloxy)anthracene, 1-fluoro-9,10-bis(2-naphthyloxy)anthracene, 2-bromo-9, 10-bis(acetoxy)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(isobutyl Carbonyloxy)anthracene, 2-bromo-9,10-bis(n-pentylcarbonyloxy)anthracene, 2-bromo-9,10-bis(n-hexylcarbonyloxy)anthracene, 2-bromo- 9,10-bis(benzyloxy)anthracene, 2-bromo-9,10-bis(4-methylbenzyloxy)anthracene, 2-bromo-9,10-bis(2-naphthylmethyl) Acetyloxy)anthracene, 1-bromo-9,10-bis(acetoxy)anthracene, 1-bromo-9,10-bis(propyl (Alkyloxy)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-pentylcarbonyl) (Oxy)anthracene, 1-bromo-9,10-bis(n-hexylcarbonyloxy)anthracene, 1-bromo-9,10-bis(benzyloxy)anthracene, 1-bromo-9,10- Bis(4-methylbenzyloxy)anthracene, 1-bromo-9,10-bis(2-naphthyloxy)anthracene, and the like.

In addition, anthracene compounds substituted with alkoxy groups can also be used as (C) sensitizers.

The anthracene compound substituted by the alkoxy group, as specific examples of the preferred compound of the (C) 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(iso Pentyloxyoxy)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, 9-(n-heptyl) Oxy)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-dimethoxy Anthracene, 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-ethoxy Anthracene, 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)anthracene, 2-methyl-9-(n-heptyloxy)anthracene Yl)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 Base-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(isopentyloxy) Oxy)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-hexyl) Oxy)anthracene, 2-chloro-9-(n-heptyloxy)anthracene, 2-chloro-9-(n-octyloxy)anthracene, 2-chloro-9-(2-ethylhexyloxy) 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-ethyl Hexyloxy) anthracene and the like.

Among the anthracene compounds described above, from the viewpoint of ease of manufacture and performance as a sensitizer (C), 9,10-bis(acetoxy)anthracene, 9,10-bis(propionyl) Oxy)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-hexyloxy)anthracene, 9,10-bis(n-heptanyloxy)anthracene, 9,10-bis(n-octanyloxy)anthracene, 9,10-bis(2-ethylhexyloxy)anthracene, 9,10-bis(n-nonanoyloxy)anthracene, 9,10 10-diethoxyanthracene, 9,10-dipropoxyanthracene, and 9,10-dibutoxyanthracene are preferred.

The compound containing naphthacene ring, as a specific example of the preferred compound used as the sensitizer (C), there can be mentioned 2-methyl-5,11-dioxo-6,12-bis(acetoxy )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) Yl)naphthacene, 2-methyl-5,11-dioxo-6,12-bis(n-pentylcarbonyloxy)naphthacene, 2-methyl-5,11-dioxo- 6,12-bis(n-hexylcarbonyloxy)naphthacene, 2-methyl-5,11-dioxo-6,12-bis(n-heptylcarbonyloxy)naphthacene, 2- Ethyl-5,11-dioxo-6,12-bis(acetoxy)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-pentyl Carbonyloxy) naphthacene, 2-ethyl-5,11-dioxo-6,12-bis(n-hexylcarbonyloxy) naphthacene, and 2-ethyl-5,11-diox Alkylcarbonyloxy substituted naphthacene compounds such as -6,12-bis(n-heptylcarbonyloxy)naphthacene; 2-methyl-5,11-dioxo-6,12-bis (Benzoyloxy) naphthacene, 2-methyl-5,11-dioxo-6,12-bis(o-tolyloxy) naphthacene, 2-methyl-5,11 -Dioxo-6,12-bis(m-tolyloxy) naphthacene, 2-methyl-5,11-dioxo-6,12-bis(p-tolyloxy) Naphthacene, 2-Methyl-5,11-dioxo-6,12-bis(α-naphthyloxy)naphthacene, 2-methyl-5,11-dioxo-6,12-bis (β-Naphthyloxy) naphthacene, 2-ethyl-5,11-dioxo-6,12-bis(benzyloxy) naphthacene, 2-ethyl-5, 11-dioxo-6,12-bis(o-tolyloxy)naphthacene, 2-ethyl-5,11-dioxo-6,12-bis(m-tolyloxy) ) Naphthacene, 2-ethyl-5,11-dioxo-6,12-bis(p-tolyloxy) naphthacene, 2-ethyl-5,11-dioxo-6 ,12-bis(α-naphthyloxy)naphthacene, and 2-ethyl-5,11-dioxo-6,12-bis(β-naphthyloxy)naphthacene Aryloxy substituted naphthacene compounds; 2-methyl-5,11-dioxo-6,12-bis(methoxycarbonyloxy)naphthacene, 2-methyl-5,11 -Dioxo-6,12-bis(ethoxycarbonyloxy)naphthacene, 2-methyl-5,11-dioxo-6,12-bis(n-propyloxycarbonyloxy) Naphthacene, 2-methyl-5,11-dioxo-6,12-bis(isopropyloxycarbonyloxy) 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-propyloxycarbonyloxy)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-hexyl Oxycarbonyloxy) naphthacene, 2-ethyl-5,11-dioxo-6,12-bis(n-heptyloxycarbonyloxy) naphthacene, and 2-ethyl-5,11 -Alkoxycarbonyloxy substituted naphthacene compounds such as dioxo-6,12-bis(n-octyloxycarbonyloxy)naphthacene; 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-naphthoxycarbonyloxy)naphthacene, 2-ethyl-5,11-dioxo-6,12-bis(phenoxycarbonyloxy) Base) 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)naphtho Naphthalene, 2-ethyl-5,11-dioxo-6,12-bis(α-naphthoxycarbonyloxy)naphthalene, and 2-ethyl-5,11-dioxo-6,12 -Aryloxycarbonyloxy substituted naphthacene compounds such as bis(β-naphthoxycarbonyloxy) naphthacene.

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- Double (different Butyloxycarbonyloxy) 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-heptanyloxy)naphthacene are preferred.

From the viewpoint of compatibility with the (A) photopolymerizable compound, 5,11-dioxo-6,12-bis(isopropyloxycarbonyloxy)naphthacene, 5,11-diox -6,12-bis(isobutyloxycarbonyloxy)naphthacene, 5,11-dioxo-6,12-bis(n-butyryloxy)naphthacene, 5,11-diox Substituted-6,12-bis(n-vanillyloxy)naphthacene and 5,11-dioxo-6,12-bis(heptanyloxy)naphthacene are preferred.

For compounds containing thioxanthene ring, specific examples of preferred compounds used as (C) sensitizers include thioxanthene-9-one, 2-methyl-9H-thioxanthene-9-one, 2-isopropyl-9H-thioxanthene-9-one, 1,4-dimethylthioxanthene-9-one, and 3-methyl-9-oxo-9H-thioxanthene-2 -Glycoacetate etc.

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

Moreover, when it is 0.01-3 mass parts with respect to the total of 100 mass parts of (B) component, the good cured|curing material used for the transparency or brightness of the coloring by absorption of (C) component can be obtained.

<(D) Colorant>

The photosensitive composition may further contain (D) a colorant. Since the photosensitive composition contains the coloring agent of the component (D), it is preferably used as a color filter for liquid crystal display. In addition, when the photosensitive composition of the present invention contains a light-shielding agent as a colorant, it can be used, for example, as a black matrix forming application in a color filter of a display device.

The (D) coloring agent contained in the photosensitive composition is not particularly limited. For example, the color rendering index (CI; issued by The Society of Dyers and Colourists) can be classified as a pigment (Pigment) compound, specifically using The following color rendering index (CI) number is preferred.

Examples of yellow pigments that can be used preferably include CI Pigment Yellow 1 (hereinafter "CI Pigment Yellow" is the same, and only the numbers are listed), 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.

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

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

Examples of suitable red pigments that can be used include CI Pigment Red 1 (hereinafter, "CI Pigment Red" is the same, and only the numbers are described) 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, 217, 220, 223, 224, 226, 227, 228, 240, 242, 243, 245, 254, 255, 264, and 265.

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

As examples of pigments of the above-mentioned other hues that can be preferably used, C.I. Pigment Green 7, C.I. Pigment Green 36, and C.I. Pigment Green 37 Green pigments, C.I. Pigment Brown 23, C.I. Pigment Brown 25, C.I. Pigment Brown 26, C.I. Pigment Brown 28 and other brown pigments, C.I. Pigment Black 1, C.I. Pigment Black 7 and other black pigments.

In addition, when a colorant is used as a light-shielding agent, it is preferable to use a black pigment as the light-shielding agent. Examples of black pigments include carbon black, titanium black, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, silver and other metal oxides, composite oxides, metal sulfides, metal sulfates, or metal carbonates. The various pigments can be organic or inorganic. Among these, it is preferable to use carbon black with high light-shielding properties.

As the carbon black, well-known carbon blacks such as tunnel black, furnace black, thermal black, lamp black, etc. can be used, but it is preferable to use tunnel black with excellent light-shielding properties. In addition, resin-coated carbon black can also be used.

Resin-coated carbon black has lower conductivity than carbon black without resin coating. Therefore, when used as a black matrix of liquid crystal display elements such as liquid crystal display displays, it can produce less current leakage and high reliability. A display that consumes electricity.

Moreover, in order to adjust the hue of carbon black, the above-mentioned organic pigments can be suitably added as auxiliary pigments.

In order to uniformly disperse the above-mentioned colorant in the photosensitive composition, a dispersant can be further used. As such a dispersing agent, polyethyleneimine-based, urethane resin-based, or acrylic resin-based polymer dispersing agents are preferably used. Especially when carbon black is used as a coloring agent, it is preferable to use an acrylic resin-based dispersing agent as a dispersing agent.

In addition, inorganic pigments and organic pigments can be used alone or in combination 2 More than one species, but when used in combination, for the total amount of 100 parts by mass of inorganic pigments and organic pigments, it is better to use organic pigments in the range of 10 to 80 parts by mass, and preferably in the range of 20 to 40 parts by mass .

The amount of the coloring agent used in the photosensitive composition can be appropriately determined only according to the use of the photosensitive composition, but as an example, for the total mass of 100 parts by mass of the components other than the solvent in the photosensitive composition, 5~ 70 parts by mass is preferred, and 25-60 parts by mass is preferred. By setting it in the above range, it is preferable to form a black matrix or each colored layer of the desired pattern.

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

The colorant is preferably added to the photosensitive composition after being dispersed into a dispersion liquid at an appropriate concentration using a dispersant.

<(E) Alkali-soluble resin>

The photosensitive composition related to the present invention may contain (E) an alkali-soluble resin as a resin other than the resin used for the (A) photopolymerizable compound. After (E) alkali-soluble resin is added to the photosensitive composition, alkali developability can be imparted to the photosensitive composition.

The alkali-soluble resin in this specification refers to a resin solution with a resin concentration of 20% by mass (solvent: propylene glycol monomethyl ether Acetate), a resin film with a film thickness of 1 μm is formed on a substrate, and when it is immersed in a KOH aqueous solution with a concentration of 0.05% by mass for 1 minute, it can be dissolved with a film thickness of 0.01 μm or more.

Among (E) alkali-soluble resins, the polymerization of homopolymers with ethylenically unsaturated double bonds is based on the viewpoint of excellent film-forming properties, or easy adjustment of the characteristics of the resin by the selection of homopolymers, etc. Good things. Examples of homopolymers having ethylenically unsaturated double bonds include (meth)acrylic acid; (meth)acrylate; (meth)acrylamide; crotonic acid; maleic acid, fumaric acid, and citracan Acid, mesaconic acid, itaconic acid, the anhydrate of these dicarboxylic acids; such as allyl acetate, allyl hexanoate, allyl octanoate, allyl laurate, allyl palmitate, stearic acid Allyl compounds of allyl ester, allyl benzoate, allyl acetate, allyl lactate, and allyloxyethanol; such as hexyl vinyl ether, octyl vinyl ether, decyl ethylene Base ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2-dimethylpropyl ethylene Base ether, 2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, Butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether, vinyl phenyl ether, vinyl tolyl ether, vinyl chlorophenyl ether, vinyl-2,4 -Dichlorophenyl ether, vinyl naphthalene ether, and vinyl ethers such as vinyl anthracenyl ether; vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl Acetate, vinyl pivalate, vinyl hexanoate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxy acetate, vinyl butoxy ethyl Ester, vinyl phenyl acetate, vinyl acetyl acetate, vinyl lactate, vinyl-β-phenyl butyrate, vinyl benzoate, vinyl salicylate, chlorobenzoic acid Vinyl esters, vinyl tetrachlorobenzoate, and vinyl esters such as vinyl naphthoate; styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl benzene Ethylene, isopropyl styrene, butyl styrene, hexyl styrene, cyclohexyl styrene, decyl styrene, benzyl styrene, chloromethyl styrene, trifluoromethyl styrene, ethoxymethane Styrene, acetoxymethylstyrene, methoxystyrene, 4-methoxy-3-methylstyrene, dimethoxystyrene, chlorostyrene, dichlorostyrene, trichloro Styrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethylstyrene, and 4 -Styrene or styrene derivatives of fluoro-3-trifluoromethylstyrene; such as vinyl, propenyl, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene Ene, 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, 1- Alkenes of dodecene, 1-tetradecene, 1-heptadecene, 1-octadecene, and 1-eicosene.

(E) Alkali-soluble resins, which are polymers of homopolymers with ethylenically unsaturated double bonds, usually contain units derived from unsaturated carboxylic acids. Examples of unsaturated carboxylic acids include (meth)acrylic acid; Meth)acrylamide; crotonic acid; maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, anhydrous of these dicarboxylic acids. Contained in polymers of homopolymers with ethylenically unsaturated double bonds used as alkali-soluble resins The unit amount derived from the unsaturated carboxylic acid is not particularly limited as long as it has the alkali solubility desired by the resin. The unit amount derived from the unsaturated carboxylic acid in the resin used as the alkali-soluble resin is preferably 5-25% by mass, and more preferably 8-16% by mass relative to the mass of the resin.

One or more homopolymers selected from the above-exemplified homopolymers, among polymers of homopolymers having ethylenically unsaturated double bonds, selected from (meth)acrylic acid and (meth)acrylates One or more homopolymers are preferred. Hereinafter, the polymer of one or more homopolymers selected from (meth)acrylic acid and (meth)acrylic acid ester will be described.

The (meth)acrylate used in the preparation of a polymer of one or more homopolymers selected from (meth)acrylic acid and (meth)acrylate is not particularly limited as long as it does not hinder the purpose of the present invention It is limited and can be suitably selected from well-known (meth)acrylates.

As a preferable example of (meth)acrylate, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, pentyl (meth)acrylate can be mentioned , T-octyl (meth)acrylate and other linear or branched 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; A (meth)acrylate having a group with an epoxy group; a (meth)acrylate having a group with an alicyclic skeleton. The details of the (meth)acrylate having a group having an epoxy group and the (meth)acrylate having a group having an alicyclic skeleton will be described later.

Among the polymers of one or more homopolymers selected from (meth)acrylic acid and (meth)acrylic acid esters, the adhesiveness or mechanical properties of the substrate to the transparent insulating film formed using the photosensitive composition From the viewpoint of excellent strength, a resin derived from a unit of (meth)acrylate having an epoxy group is preferred.

The (meth)acrylate having a group having an epoxy group, even if it is a (meth)acrylate having a group having a chain aliphatic epoxy group, may have an alicyclic epoxy group as described later The base-based (meth)acrylate.

The (meth)acrylate having a group having an epoxy group may contain an aromatic group. Examples of the aromatic ring constituting the aromatic group include a benzene ring and a naphthalene ring. Examples of the (meth)acrylate having an aromatic group and a group having an epoxy group include 4-glycidyloxyphenyl (meth)acrylate and 3-glycidyloxy Phenyl (meth)acrylate, 2-glycidyloxyphenyl (meth)acrylate, 4-glycidyloxyphenylmethyl (meth)acrylate, 3-glycidyloxy Phenylmethyl (meth)acrylate, 2-glycidyloxyphenylmethyl (meth)acrylate, etc.

When transparency is required for a film formed using a photosensitive composition, the (meth)acrylic acid having an epoxy group-containing group is preferably one that does not contain an aromatic group.

Examples of (meth)acrylates having a chain aliphatic epoxy group-containing group include epoxyalkyl (meth)acrylate, and epoxyalkoxyalkyl (meth) Base) acrylate, etc., in the ester group (-O-CO-) A (meth)acrylate in which a chain aliphatic epoxy group is bonded to the oxygen group (-O-). The chain aliphatic epoxy group having such a (meth)acrylate may contain 1 or plural oxy groups (-O-) in the chain. The number of carbon atoms of the chain aliphatic epoxy group is not particularly limited, and is preferably 3-20, preferably 3-15, and particularly preferably 3-10.

Specific examples of the (meth)acrylate having a group having a chain aliphatic epoxy group include glycidyl (meth)acrylate and 2-methylglycidyl (meth)acrylate , 3,4-epoxybutyl (meth)acrylate, 6,7-epoxyheptyl (meth)acrylate and other epoxy alkyl (meth)acrylates; 2-glycidyl Oxyethyl (meth)acrylate, 3-glycidyloxy-n-propyl (meth)acrylate, 4-glycidyloxy-n-butyl (meth)acrylate, 5 -Epoxy alkoxyalkyl (meth)acrylates such as glycidyloxy-n-hexyl (meth)acrylate and 6-glycidyloxy-n-hexyl (meth)acrylate.

Contains a unit derived from a (meth)acrylate having an epoxy group, selected from (meth)acrylic acid and (meth)acrylate The unit content of the (meth)acrylate of the epoxy group is preferably 1 to 95% by mass, and more preferably 40 to 80% by mass relative to the weight of the resin.

In addition, in the polymer of one or more homopolymers selected from (meth)acrylic acid and (meth)acrylate, since the photosensitive composition can be used to easily form a transparent insulating film with excellent transparency, it contains self-sustaining Resins with units of (meth)acrylate having an alicyclic skeleton are also good.

For (meth)acrylates having a group having an alicyclic skeleton, the group having an alicyclic skeleton may be a group having an alicyclic hydrocarbon group or a group having an alicyclic epoxy group. The alicyclic group constituting the alicyclic skeleton may be monocyclic or polycyclic. As a monocyclic alicyclic group, a cyclopentyl group, a cyclohexyl group, etc. are mentioned. In addition, examples of the polycyclic alicyclic group include norbornyl, isobornyl, tricyclononyl, tricyclodecyl, tetracyclododecyl, and the like.

Among (meth)acrylates having a group having an alicyclic skeleton, examples of (meth)acrylates having a group having an alicyclic hydrocarbon group include the following formula (d1-1)~ The compound represented by (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 preferred.

In the above formulas, R ^d1 represents a hydrogen atom or a methyl group, R ^d2 represents a single bond or 2 carbon atoms, divalent aliphatic saturated hydrocarbon group having 1 to 6, R ^d3 represents a hydrogen atom or an alkyl group of 1 to 5. As R ^d2 , a single bond, linear or branched alkylene group, such as ethylene group, ethylene group, propyl group, tetraethylene group, ethyl ethylene group, pentamethylene group, and hexaethylene group Methyl is preferred. As R ^d3, methyl and ethyl are preferred.

Among (meth)acrylates having a group having an alicyclic skeleton, specific examples of (meth)acrylates having a group having an alicyclic epoxy group include, for example, the following formula ( Compounds shown in d2-1)~(d2-16). Among them, because the developability of the photosensitive composition can be moderate, the compounds represented by the following formulas (d2-1)~(d2-6) are preferred, and the following formulas (d2-1)~( The compound shown in d2-4) is preferred.

In the above formula, R ^d4 represents a hydrogen atom or a methyl group, R ^d5 represents a divalent aliphatic saturated hydrocarbon group having 1 to 6 ^{carbons, R d6} represents a divalent hydrocarbon group having 1 to 10 carbons, and n represents an integer of 0-10. As R ^d5 , a straight-chain or branched-chain alkylene group, for example, ethylene group, ethylene group, propyl group, tetraethylene group, ethyl ethylene group, pentamethylene group, and hexaethylene group Base is better. As R ^d6 , for example, ethylene group, ethylene group, propyl group, tetraethylene group, ethyl ethylene group, pentamethyl group, hexamethyl group, phenyl group, cyclopentyl group, -CH ₂ -Ph-CH _2- (Ph represents phenylene) is preferred.

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

In addition, a polymer containing one or more homopolymers of (meth)acrylic acid and (meth)acrylic acid esters containing units derived from (meth)acrylate having a group having an alicyclic skeleton, containing The resin derived from the unit derived from (meth)acrylic acid and the unit derived from the (meth)acrylate which has an alicyclic epoxy group is preferable. The film formed using the photosensitive composition containing (E) the alkali-soluble resin in this way has excellent adhesion to the substrate. In addition, when such resins are used, self-reaction of the carboxyl groups contained in the resin and the alicyclic epoxy groups may occur. Therefore, when a photosensitive composition containing such a resin is used, a method of heating the film or the like is used. By generating self-reaction of the carboxyl group and the alicyclic epoxy group, the mechanical properties such as the hardness of the formed film can be improved.

For units containing (meth)acrylic acid, from A resin with a unit of (meth)acrylate having an alicyclic epoxy group. The amount of the unit derived from (meth)acrylic acid in the resin is preferably 1-95% by mass, and 10-50% by mass Better. For resins containing units derived from (meth)acrylic acid and units derived from (meth)acrylate having alicyclic epoxy groups, the resin is derived from those having alicyclic epoxy groups The unit amount of (meth)acrylate is preferably 1 to 95% by mass, and more preferably 30 to 70% by mass.

Containing a unit derived from (meth)acrylic acid and a unit derived from (meth)acrylate having an alicyclic epoxy group, one or more selected from the group consisting of (meth)acrylic acid and (meth)acrylate In the polymer of the homopolymer, a unit derived from (meth)acrylic acid, a unit derived from (meth)acrylate having an alicyclic hydrocarbon group, and (former) derived from a group having an alicyclic epoxy group are used. The resin of the acrylate unit is preferred.

For resins containing units derived from (meth)acrylic acid, units derived from (meth)acrylates with alicyclic hydrocarbon groups, and units derived from (meth)acrylates with alicyclic epoxy groups The unit amount derived from (meth)acrylic acid in the resin is preferably 1-95% by mass, preferably 10-50% by mass. For resins containing units derived from (meth)acrylic acid, units derived from (meth)acrylates with alicyclic hydrocarbon groups, and units derived from (meth)acrylates with alicyclic epoxy groups , The unit amount derived from the (meth)acrylate having an alicyclic hydrocarbon group in the resin is preferably 1 to 95% by mass, preferably 10 to 70% by mass. For units derived from (meth)acrylic acid, units derived from (meth)acrylate esters with alicyclic hydrocarbon groups, and units derived from alicyclic hydrocarbon groups The epoxy-based (meth)acrylate unit of the resin, the amount of the unit derived from the (meth)acrylate having an alicyclic epoxy group in the resin is preferably 1 to 95% by mass, It is preferably 30 to 80% by mass.

(E) The mass average molecular weight of the alkali-soluble resin (Mw: the measured value of gel permeation chromatograph (GPC) polystyrene conversion. Same as this manual) 2000~200000 is better, 2000~18000 For better. By setting it in the above range, there is a tendency that the balance of the film forming ability of the photosensitive composition and the developability after exposure tends to be easily balanced.

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

<Other ingredients>

The photosensitive composition of the present invention may contain various additives as necessary. Specific examples include solvents, sensitizers, hardening accelerators, photocrosslinkers, dispersion aids, fillers, adhesion promoters, antioxidants, ultraviolet absorbers, aggregation inhibitors, thermal polymerization inhibitors, and defoamers , Surfactant, etc.

With regard to the photosensitive composition of the present invention, the components can be dispersed in a solvent. It is prepared after dissolution, but if the aforementioned (A) component is in a liquid form, it is not necessary to use a solvent. When a solvent is contained, it is used as a photosensitive composition The solvent of the substance, for example, 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, two Propylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether and other (poly)alkylene glycol monoalkyl ethers; ethylene glycol monomethyl Base ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, Propylene glycol monoethyl ether acetate and other (poly)alkylene glycol monoalkyl ether acetates; diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether , Tetrahydrofuran and other ethers; methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone and other ketones; 2-hydroxypropionic acid methyl ester, 2-hydroxypropionic acid ethyl ester and other alkyl lactate Class; Ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxy Ethyl propionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methyl-3-methoxybutyl acetate, 3-methyl 3-methoxybutyl propionate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl formate, isoamyl acetate, N-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, ethyl Other esters such as methyl acetate, ethyl acetate, ethyl 2-oxobutanoate; toluene, xylene Aromatic hydrocarbons such as N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, etc. These solvents may be used alone or in combination of two or more kinds.

Among the above solvents, propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and diethylene glycol dimethyl ether , Diethylene Glycol Methyl Ethyl Ether, Cyclohexanone, 3-Methoxybutyl Acetate shows excellent solubility for the above (A) component and (B) component, and at the same time can make the above (D) component It is preferable because of good dispersibility, and it is particularly preferable to use propylene glycol monomethyl ether acetate and 3-methoxybutyl acetate. The solvent can be appropriately determined according to the use of the photosensitive composition. As an example, the total mass of components other than the solvent in the photosensitive composition may be about 50 to 900 parts by mass for a total of 100 parts by mass.

Examples of the thermal polymerization inhibitor used in the photosensitive composition of the present invention include hydroquinone, hydroquinone monoethyl ether, and the like. In addition, as the defoaming agent, compounds such as silicone-based and fluorine-based compounds can be exemplified, and as the surfactant, compounds such as anionic, cationic, and nonionic can be exemplified.

[Preparation method of photosensitive composition]

The photosensitive composition according to the present invention can be prepared by mixing the above-mentioned components with a blender. In addition, when the prepared photosensitive composition does not contain insoluble components such as pigments, the photosensitive composition can be filtered using a filter if it is desired to make the photosensitive composition uniform.

≪Method of manufacturing hardened material≫

The photosensitive composition described above is cured after exposure by using a desired light source.

The method of forming a film used as an insulating film or a color filter using the photosensitive composition will be described below. The film formed using the photosensitive composition can be patterned as necessary.

When using the photosensitive composition of the present invention to form a film, first use a roll coater, reverse coater, bar coater, etc. to contact transfer type coating device or spinner (rotary coating device), curtain coating A non-contact coating device such as a cloth machine coats the photosensitive composition on the substrate.

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

Next, the coating film is exposed to light. The light source is not particularly limited, and examples include high-pressure mercury lamps, LEDs, and the like. From the viewpoint of energy saving and environmental load reduction, LEDs are preferred. Regarding the exposure by the LED, the used wavelengths include, for example, 365 to 405 nm, and more specifically, those in the UV region such as 385 nm, 395 nm, and 405 nm. Generally, the amount of energy rays irradiated by the LED tends to decrease. However, the photosensitive composition described above contains the aforementioned (B) photopolymerization initiator and (C) sensitizer, and has excellent sensitivity. Therefore, the LED can be used as a light source for exposure. Fully hardened, can effectively obtain a hardened product with good characteristics. Thereby, as a result, the productivity of a display device such as a liquid crystal display panel can be improved.

When the coated film is exposed at a selective position, the exposed film is developed with a developer to obtain a drawing of the desired shape. The imaging method is not particularly limited, and for example, a dipping method, a spray method, etc. can be used. The developer can be appropriately selected according to the composition of the photosensitive composition. When the photosensitive composition contains alkali-soluble components such as alkali-soluble resins, as the developing solution, organic ones such as monoethanolamine, diethanolamine, and triethanolamine can be used, or sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, etc. can be used. Aqueous solutions such as grade 4 ammonium salt.

Secondly, it is better to bake the pattern after development at about 200~250℃.

The pattern formed in this way can be used, for example, in display devices such as a liquid crystal display, and can be used as an insulating film or as a pixel constituting a color filter, a black matrix, and the like. Such a display device used in an insulating film, a color filter, or the color filter is also one of the present invention.

The following examples describe the present invention in further detail, and the scope of the present invention is not limited to these examples.

[Example]

The following examples describe the present invention in further detail, and the scope of the present invention is not limited to these examples.

For the examples and comparative examples, as (A) photopolymerization The compound uses propylene oxide denatured neopentyl glycol diacrylate.

In the examples, as the (B) photopolymerization initiator, the compound 1 obtained in the following Synthesis Example 2 was used as (B)-1, and the compound 2 obtained in the following Synthesis Example 3 was used as (B)-2 .

The structures of compound 1 and compound 2 are shown below.

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

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

(C)-1: 2-isopropyl-9H-thioxanthene-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-propyl fluorene)

Dissolve 6.64 g (40 mmol) of fluorene in 27 mL of THF. From To the solution, 0.12 g (1.1 mmol) of potassium tert-butoxide, 12.30 g (100 mmol) of 1-bromopropane, and 27 mL of a sodium hydroxide aqueous solution with a concentration of 50% by mass were gradually added in a nitrogen environment. The resulting mixture was stirred and reacted at 80°C for 3 hours. After adding 33 g of ethyl acetate and 33 g of water to the reaction mixture, the organic layer and the water layer were separated. 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 (83% yield).

[Synthesis Example 2] (Synthesis of compound 1)

Combine 4.10g (16.37mmol) of 9,9-di-n-propylfluorene and 3.04g (18.00mmol) of (2-methylphenyl) acetate in the presence of 2.62g of aluminum chloride in dichloromethane In 50 ml of solvent, the reaction was carried out for 1 hour under ice cooling. The reaction mixture was put into ice water, and the organic layer was separated. The recovered organic layer was dried with anhydrous magnesium sulfate and evaporated. The residue was purified by silica gel column with ethyl acetate/hexane=1/2 eluent to obtain 2-(2-methylphenyl)acet-9,9-di-n-propylfluorene 5.95g ( 15.55mmol). Combine 5.95g (15.55mmol) of 2-(2-methylphenyl)acetamide-9,9-di-n-propylfluorene and 1.60g (15.55mmol) of concentrated hydrochloric acid in 2.42g (23.33) of isobutyl nitrite. In the presence of mmol), the reaction was carried out for 3 hours in 25 ml of dimethylformamide solvent under ice cooling. After the reaction solution was evaporated, ethyl acetate was added to the residue, washed with saturated brine, dried with anhydrous magnesium sulfate, and evaporated to obtain 2-[2-methylphenyl (hydroxyimine) with the following structure Acetyl)-9,9-di-n-propylfluorene 4.80g (11.67 mmol).

^{The 1} H-NMR measurement results of 2-[2-methylphenyl(hydroxyimine)acetate]-9,9-di-n-propylfluorene are shown below. ¹ H-NMR (600MHz, 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).

Mix 2.80g (11.67mmol) of 2-[2-methylphenyl(hydroxyimine)acetate]-9,9-di-n-propylfluorene, 1.43g (13.42mmol) of acetic anhydride, and triethylamine 1.36g (13.42mmol) and 45.00ml of dimethylformamide solvent were stirred at 35°C for 3 hours. After cooling to room temperature, ethyl acetate was added to the reaction solution, washed with water, dried with anhydrous magnesium sulfate, and evaporated. The residue was purified by silica gel column with ethyl acetate/hexane=2/1 eluent to obtain compound 1, 4.76 g (10.50 mmol, yield 72%). ^{The 1} H-NMR measurement results of Compound 1 are shown below. ¹ H-NMR (600MHz, 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)

Except that 3.04 g (18.00 mmol) of (2-methylphenyl) acetate hydrochloride was changed to 3.14 g (18.00 mmol) of 3-cyclohexyl propionate hydrochloride, the following structure of the intermediate was obtained in the same manner as in Synthesis Example 2 2-[cyclohexylmethyl(hydroxyimine)acetyl]-9,9-di-n-propylfluorene and 4.96g of compound 2 (10.80mmol, yield 75%).

^{The 1} H-NMR measurement results of 2-[cyclohexylmethyl(hydroxyimine)acetate]-9,9-di-n-propylfluorene are shown below. ¹ H-NMR (600MHz, 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 1} H-NMR measurement results of Compound 2 are shown below. ¹ H-NMR (600MHz, 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 types and amounts of (A) component, (B) component, and (C) component as described in Table 1 below were uniformly uniformed to obtain photosensitive compositions of the respective Examples and Comparative Examples.

After the obtained photosensitive composition was dropped on the substrate with a syringe, the droplets of the photosensitive composition were exposed with a commercially available LED lamp for 15 seconds. For the exposed droplets, it is confirmed whether the inside of the droplets has hardened, and the curability is evaluated by LED exposure of each photosensitive composition.

When the inside of the droplet was hardened, it was evaluated as ○, and when the inside of the droplet was not hardened, it was evaluated as ×.

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

From the examples in Table 1, it is known that (A) a photopolymerizable compound, (B) a photopolymerization initiator containing a compound represented by formula (1), and (C) The photosensitive composition of the sensitizer can be cured well by LED exposure. In addition, in Examples 1 to 3, although coloring was confirmed in Examples 1 and 2, coloring was not confirmed in Example 3. It was also confirmed that to prevent coloring, even if the amount of component (C) added is reduced, good curability by LED exposure can be maintained.

In addition, according to the comparative example, even when the (B) photopolymerizable compound contained in the photosensitive composition does not contain the compound represented by the formula (1), or the photosensitive composition contains the compound represented by the formula (1) as (B) When the photopolymerizable compound is contained, when the (C) sensitizer is not contained, the photosensitive composition is not cured well by LED exposure.

Claims (9)

A photosensitive composition characterized by containing (A) a photopolymerizable compound, (B) a photopolymerization initiator, and (C) a sensitizer, and the aforementioned (B) photopolymerization initiator contains the following formula (1) Shown compound;

(In formula (1), R ¹ is a hydrogen atom, a nitro group, or a monovalent organic group, and R ² and R ^{3 are} each a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a cyclic group which may have a substituent An organic group or a hydrogen atom, R ² and R ³ are bonded to each other to form a ring, R ⁴ is a group represented by the following formula (R4-1) or (R4-2), R ⁵ is a hydrogen atom, which may have a substituent C 1-11 alkyl group or optionally substituted aryl group, n is an integer of 0-4, m is 0 or 1, but when m is 0, R ¹ is a hydrogen atom);

(In formulas (R4-1) and (R4-2), R ⁷ and R ^{8 are} each an organic group, p is 0, and when R ⁷ and R ⁸ are present at adjacent positions on the benzene ring, R ⁷ and R ⁸ are each other Combination can 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), and R ⁹ is an organic group). A photosensitive composition containing (A) a photopolymerizable compound, (B) a photopolymerization initiator, and (C) a sensitizer; the aforementioned (B) photopolymerization initiator contains a compound represented by the following formula (1) ；

(In formula (1), R ¹ is a nitro group, 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, which may have Substituent phenyl group, optionally substituted phenoxy group, optionally substituted benzyl group, optionally substituted phenoxycarbonyl group, optionally substituted benzyloxy group, optionally substituted The phenylalkyl group of the group, the naphthyl group which may have a substituent, the naphthyl group which may have a substituent, the naphthyl group which may have a substituent, the naphthyloxycarbonyl group which may have a substituent, the naphthyloxy group which may have a substituent , Naphthyl which may have substituents, heterocyclic groups which may have substituents, amino groups which may be substituted by 1 or 2 organic groups, morpholin-1-yl, or piperazin-1-yl, R ² and Each of R ³ is a chain alkyl group that may have a substituent, a cyclic organic group that may have a substituent, or a hydrogen atom. R ² and R ³ are bonded to each other to form a ring, and R ⁴ is the following formula (R4-2 ), R ⁵ is methyl or phenyl, n is an integer from 0 to 4, m is 0 or 1, but when m is 1, R ^{1 is} not a nitro group)

(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). A photosensitive composition containing (A) a photopolymerizable compound, (B) a photopolymerization initiator, and (C) a sensitizer; the aforementioned (B) photopolymerization initiator contains a compound selected from the following 6~ 15. Compounds 17-22, and more than one compound of compounds 24-41;

A photosensitive composition containing (A) a photopolymerizable compound, and (C) a sensitizer; the aforementioned (B) photopolymerization initiator contains 1 selected from the following compound 4, compound 5, and compound 23 More than one compound

The photosensitive composition of claim 2, wherein in the aforementioned formula (1), R ² and R ^{3 are} each a linear alkyl group which may have a substituent, or a cyclic organic group which may have a substituent, and R ² and R ³ means that they can form a ring when combined with each other. The photosensitive composition according to any one of claims 1 to 5, wherein (C) the sensitizer is one or more selected from the group consisting of alkoxy, substituted carbonyloxy, and oxo as a substituent Condensed polycyclic aromatic hydrocarbon ring compound or condensed polycyclic aromatic heterocyclic compound. A method for manufacturing a hardened product, which is characterized by exposing and hardening the photosensitive composition according to any one of claims 1 to 6. The method for manufacturing a hardened object according to claim 7, wherein the aforementioned exposure is performed by LED. A cured product characterized by the photosensitive composition according to any one of claims 1 to 6.