JP6788971B2 - Photosensitive composition - Google Patents

Description

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 are formed so as to face each other. A color filter composed of pixel regions of each color such as red (R), green (G), and blue (B) is formed inside one of the substrates. In this color filter, a black matrix is usually formed so as to partition each pixel region such as red, green, and blue.
Further, the panel for the display device may be provided with a transparent insulating film or the like.

Color filters and transparent insulating films are often manufactured by a photolithography method using a photosensitive composition. For example, in a color filter, a black photosensitive composition is first applied onto a substrate, dried, and then exposed and developed to form a black matrix. Next, each photosensitive composition of each color such as red, green, and blue is repeatedly coated, dried, exposed, and developed to form a pixel region of each color at a specific position.

The photosensitive composition used in the manufacture of liquid crystal display and the like is required to have high sensitivity from the viewpoint of reducing the manufacturing cost of the display device and improving the productivity. In such a situation, Patent Document 1 proposes an oxime ester compound having a cycloalkyl group as a photopolymerization initiator capable of improving 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) are specifically disclosed.

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

The photosensitive composition containing the oxime ester compound described in Patent Document 1 certainly has good sensitivity.
However, the photosensitive composition containing the oxime ester compound described in Patent Document 1 does not always cure well when exposed by an LED.
LEDs are being used as light sources for exposure from the viewpoint of energy saving and reduction of environmental load.

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

In a photosensitive composition containing (A) a photopolymerizable compound and (B) a photopolymerization initiator, the present inventors have a 9,9-di-substituted fluorenyl group in (B) the photopolymerization initiator. We have found that the above problems can be solved by containing an oxime ester compound having a specific structure and blending (C) a sensitizer with a photosensitive composition, and have completed the present invention. Specifically, the present invention provides the following.

A first aspect of the present invention comprises (A) a photopolymerizable compound, (B) a photopolymerization initiator, and (C) a sensitizer.
(B) The photopolymerization initiator is the following formula (1):
(In the formula (1), R ¹ is a hydrogen atom, a nitro group or a monovalent organic group, and R ² and R ³ each have a chain alkyl group and a substituent which may have a substituent. It may be a cyclic organic group or a hydrogen atom , and R ² and R ³ may be bonded to each other to form a ring , R ⁴ is a monovalent organic group, and R ⁵ is hydrogen. An atom, an alkyl group having 1 to 11 carbon atoms which may have a substituent, or an aryl group which may have a substituent, n is an integer of 0 to 4, and m is 0 or 1. is there.)
The present invention relates to a photosensitive composition containing a compound represented by.

A second aspect of the present invention relates to a method for producing a cured product, which comprises exposing and curing the photosensitive composition according to the first aspect.

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

According to the present invention, it is possible to provide a photosensitive composition that cures well even when exposed by an LED, a method for producing a cured product of the photosensitive composition, and a cured product of the photosensitive composition. ..

≪Photosensitive composition≫
The photosensitive composition of the present invention contains (A) a photopolymerizable compound, (B) a photopolymerization initiator, and (C) a sensitizer. (B) The photopolymerization initiator contains an oxime ester compound having a specific structure having a 9,9-di-substituted fluorenyl group. The photosensitive composition may contain (D) a colorant or (E) an alkali-soluble resin. Hereinafter, the components contained in the photosensitive composition and the method for preparing the photosensitive composition will be described in order.

<(A) Photopolymerizable compound>
The photopolymerizable compound (A) contained in the photosensitive composition according to the present invention (hereinafter, also referred to as the component (A)) is not particularly limited, and conventionally known photopolymerizable compounds can be used. .. Among them, a resin or a monomer having an ethylenically unsaturated group is preferable, 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 can be improved and pattern formation can be facilitated. In the present invention, a monomer having an ethylenically unsaturated group is more preferable.

[Resin having an ethylenically unsaturated group]
Resins having an ethylenically unsaturated group include (meth) acrylic acid, fumaric acid, maleic acid, monomethyl fumarate, monoethyl fumarate, 2-hydroxyethyl (meth) acrylate, ethylene glycol monomethyl ether (meth) acrylate, and 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, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, propylene Glycoldi (meth) acrylate, trimethylolpropantri (meth) acrylate, tetramethylolpropanetetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, Oligomers obtained by polymerizing dipentaerythritol hexa (meth) acrylate, 1,6-hexanediol di (meth) acrylate, cardoepoxydiacrylate, etc .; obtained by condensing polyhydric alcohols with monobasic acid or polybasic acid. Polyester (meth) acrylate obtained by reacting the polyester prepolymer to be obtained with (meth) acrylic acid; obtained by reacting a polyol with a compound having two isocyanate groups and then reacting with (meth) acrylic acid. Polyurethane (meth) acrylate; 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, polycarboxylic acid polyglycidyl ester , Polypolyglycidyl ester, aliphatic or alicyclic epoxy resin, amine epoxy resin, dihydroxybenzene type epoxy resin, etc., and epoxy (meth) acrylate resin obtained by reacting (meth) acrylic acid, etc. Can be mentioned. Further, a resin obtained by reacting an epoxy (meth) acrylate resin with a polybasic acid anhydride can be preferably used. In addition, in this specification, "(meth) acrylic" means "acrylic or methacrylic".

Further, as the resin having an ethylenically unsaturated group, a resin obtained by further reacting a reaction product of an epoxy compound and an unsaturated group-containing carboxylic acid compound with a polybasic acid anhydride can be preferably used. ..

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

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

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

In the above general formula (a1), Y represents a residue obtained by removing the acid anhydride group (-CO-O-CO-) from the dicarboxylic acid anhydride. Examples of dicarboxylic acid anhydrides are maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, chlorendic anhydride, methyltetrahydro. Examples thereof include phthalic anhydride and glutaric anhydride.

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

The acid value of the resin having an ethylenically unsaturated group is preferably 10 to 150 mgKOH / g, more preferably 70 to 110 mgKOH / g in terms of resin solid content. It is preferable that the acid value is 10 mgKOH / g or more because sufficient solubility in a developing solution can be obtained. Further, by setting the acid value to 150 mgKOH / g or less, sufficient curability can be obtained and surface properties can be improved, which is preferable.

The mass average molecular weight of the resin having an ethylenically unsaturated group is preferably 1000 to 40,000, more preferably 2000 to 30,000. It is preferable that the mass average molecular weight is 1000 or more because good heat resistance and film strength can be obtained. Further, it is preferable to set the mass average molecular weight to 40,000 or less because good developability can be obtained.

[Monomer having an ethylenically unsaturated group]
Monomers having an ethylenically unsaturated group include monofunctional monomers and polyfunctional monomers. Hereinafter, the monofunctional monomer and the polyfunctional monomer will be described in order.

Examples of the monofunctional monomer include (meth) acrylamide, methylol (meth) acrylamide, methoxymethyl (meth) acrylamide, ethoxymethyl (meth) acrylamide, propoxymethyl (meth) acrylamide, butoxymethoxymethyl (meth) acrylamide, and N-methylol ( Meta) acrylamide, N-hydroxymethyl (meth) acrylamide, (meth) acrylic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, crotonic acid, 2-acrylamide- 2-Methylpropanesulfonic acid, tert-butylacrylamide sulfonic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-hydroxyethyl (Meta) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybuty (meth) acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2- (meth) acryloyloxy-2-hydroxypropyl phthalate, Glycerin mono (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dimethylamino (meth) acrylate, glycidyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3- Examples thereof include tetrafluoropropyl (meth) acrylate and half (meth) acrylate of a phthalic acid derivative. These monofunctional monomers may be used alone or in combination of two or more.

Examples of the polyfunctional monomer include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, and butylene glycol di ( Meta) acrylate, neopentyl glycol di (meth) acrylate, alkylene oxide-modified neopentyl glycol diacrylate having 1 to 5 carbon atoms (among others, propylene oxide-modified neopentyl glycol diacrylate) 1,6-hexane glycol di (meth) acrylate , Trimethylol propantri (meth) acrylate, glycerin di (meth) acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri. (Meta) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 2,2-bis (4- (meth) acryloxidiethoxyphenyl) propane, 2,2-Bis (4- (meth) acryloxypolyethoxyphenyl) propane, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl With ether di (meth) acrylate, diglycidyl phthalate ester di (meth) acrylate, glycerin triacrylate, glycerin polyglycidyl ether poly (meth) acrylate, urethane (meth) acrylate (ie, tolylene diisocyanate), trimethylhexamethylene diisocyanate. Polyfunctional monomers such as a reaction product of hexamethylene diisocyanate and 2-hydroxyethyl (meth) acrylate, methylenebis (meth) acrylamide, (meth) acrylamide methylene ether, and a condensate of polyhydric alcohol and N-methylol (meth) acrylamide. , Triacrylic formal and the like. These polyfunctional monomers may be used alone or in combination of two or more.

The content of the photopolymerizable compound as the component (A) is preferably 10 to 99.9 parts by mass, preferably 80 to 99.9 parts by mass, based on 100 parts by mass of the total of the components of the photosensitive composition excluding the solvent described later. It is more preferably 5.5 parts by mass, and more preferably 90 to 99 parts by mass. By setting the content of the component (A) to 10 parts by mass or more with respect to 100 parts by mass in total of the components excluding the solvent described later, heat resistance, chemical resistance, and mechanical strength can be used by using the photosensitive composition. It is easy to form an excellent film.
In the present invention, the component (A) is preferably composed of a polyfunctional monomer, and the polyfunctional monomer is more preferably a bifunctional or trifunctional monomer, and further preferably a bifunctional monomer. The proportion of the polyfunctional monomer in the component (A) is preferably 50% by mass or more, more preferably 85% by mass or more, and further preferably 90 to 100% by mass.

<(B) Photopolymerization Initiator>
The photosensitive composition contains (B) a photopolymerization initiator (hereinafter, also referred to as component (B)) containing a compound represented by the following formula (1). The photosensitive composition containing the compound represented by the following formula (1) as the photopolymerization initiator (B) is extremely sensitive. Therefore, when a photosensitive composition containing the compound represented by the formula (1) as a photopolymerization initiator is used, the photosensitive composition can be satisfactorily cured even by LED exposure.
Further, by using a photosensitive composition having excellent sensitivity, which contains a compound represented by the following formula (1), pattern peeling at the time of pattern formation is suppressed, and it occurs at the edge of the pattern at the time of forming a line pattern. The occurrence of rattling can be suppressed.

In addition, when a pattern is formed using a photosensitive composition containing no colorant, depending on the type of photopolymerization initiator, the pattern formed using the photosensitive composition may be post-baked. The transparency of the pattern may be impaired. However, when a photosensitive composition containing a compound represented by the following formula (1) is used as the (B) photopolymerization initiator, the transparency of the pattern is unlikely to decrease due to heating.

In particular, when the photosensitive composition contains a light-shielding agent as the colorant (D) described later, the bottom of the coating film of the photosensitive composition is difficult to cure due to the influence of the light-shielding agent, so that an undercut occurs in the formed pattern. There is.
When an undercut occurs in a pattern formed by using a photosensitive composition containing a light-shielding agent, for example, when a display device is created using such a pattern as a black matrix, air bubbles remaining in the undercut portion cause an undercut. There is a problem that the image quality of the display device deteriorates. However, when the photosensitive composition contains (B) a photopolymerization initiator containing a compound represented by the following formula (1) together with (D) a colorant which is a light-shielding agent, such a photosensitive composition is used. It is possible to suppress the occurrence of undercut in the pattern formed by using.

It is desired that various patterns formed by using the photosensitive composition have excellent water resistance so as not to be peeled off from the substrate due to moisture or the like. When a photosensitive composition containing a photopolymerization initiator (B) containing a compound represented by the following formula (1) is used, a pattern having excellent water resistance that is difficult to peel off from the substrate even when in contact with water is formed. Cheap.

In addition, the pattern formed by using the photosensitive composition may contain foreign substances generated due to the aggregation of the initiator and the resin during the formation of the pattern. However, when a photosensitive composition containing a (B) photopolymerization initiator containing a compound represented by the following formula (1) is used, it is easy to form a pattern in which the content of foreign substances is small.

(R ¹ is a hydrogen atom, a nitro group or a monovalent organic group, and R ² and R ³ are a chain alkyl group which may have a substituent and a cyclic organic which may have a substituent, respectively. It is a group or a hydrogen atom, and R ² and R ³ may be bonded to each other to form a ring, R ⁴ is a monovalent organic group, and R ⁵ has a hydrogen atom and a substituent. It is an alkyl group having 1 to 11 carbon atoms or an aryl group which may have a substituent, n is an integer of 0 to 4, and m is 0 or 1.)

In formula (1), R ¹ is a hydrogen atom, a nitro group or a monovalent organic group. R ¹ is attached to a 6-membered aromatic ring on the fluorene ring in the formula (1), which is different from the 6-membered aromatic ring attached to the group represented by − (CO) _m −. In the formula (1), the binding position relative to the fluorene ring of R ¹ is not particularly limited. When the compound represented by the formula (1) has 1 or more R ¹ , one of the 1 or more R ¹ is a fluorene ring because the compound represented by the formula (1) can be easily synthesized. It is preferable to bind to the 2-position of the inside. When R ¹ is plural, a plurality of R ¹ may be different even in the same.

When R ¹ is an organic group, R ¹ is not particularly limited as long as it does not interfere with the object of the present invention, and is appropriately selected from various organic groups. Preferable examples of the case where R ¹ is an organic group include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, an alkoxycarbonyl group, a saturated aliphatic acyloxy group and a substituent. A phenyl group which may have a substituent, a phenoxy group which may have a substituent, a benzoyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, and a benzoyloxy which may have a substituent. A group, a phenylalkyl group which may have a substituent, a naphthyl group which may have a substituent, a naphthoxy group which may have a substituent, a naphthoyl group which may have a substituent, and a substituent. It has a naphthoxycarbonyl group which may have a substituent, a naphthyloxy group which may have a substituent, a naphthylalkyl group which may have a substituent, a heterocyclyl group which may have a substituent, and a substituent. Examples thereof include a heterocyclylcarbonyl group, an amino group substituted with one or two organic groups, a morpholin-1-yl group, a piperazine-1-yl group and the like.

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

When R ¹ is an alkoxy group, the number of carbon atoms of the alkoxy group is preferably 1 to 20, and more preferably 1 to 6. When R ¹ is an alkoxy group, it may be a straight chain or a branched chain. Specific examples of the case where R ¹ is an alkoxy group include a methoxy group, an ethoxy group, an n-propyloxy group, an isopropyloxy group, an n-butyloxy group, an isobutyloxy group, a sec-butyloxy group, a tert-butyloxy group and n. - pentyloxy group, isopentyloxy group, sec- pentyloxy group, tert- pentyloxy group, n- hexyloxy group, n- heptyloxy group, n- octyl group, isooctyl group, sec- octyl Le Oki Examples thereof include a silicate group , a tert-octyloxy group, an n-nonyloxy group, an isononyloxy group, an n-decyloxy group, an isodecyloxy group and the like. When R ¹ is an alkoxy group, the alkoxy group may contain an ether bond (−O−) in the carbon chain. Examples of the alkoxy group having an ether bond in the carbon chain include methoxyethoxy group, ethoxyethoxy group, methoxyethoxyethoxy group, ethoxyethoxyethoxy group, propyloxyethoxyethoxy group, methoxypropyloxy group and the like.

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

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 the saturated aliphatic acyloxy group is preferably 2 to 21, more preferably 2 to 7. Specific examples of the case where R ¹ is a saturated aliphatic acyl group include an acetyl group, a propanoyl group, an n-butanoyl group, a 2-methylpropanoyl group, an n-pentanoyl group, a 2,2-dimethylpropanoyl group and n. -Hexanoyl group, n-heptanoyl group, n-octanoyl group, n-nonanoyl group, n-decanoyl group, n-undecanoyl group, n-dodecanoyl group, n-tridecanoyl group, n-tetradecanoyl group, n-pentadeca Examples thereof include a noyl group and an n-hexadecanoyl group. Specific examples of the case where R ¹ is a saturated aliphatic acyloxy group include an acetyloxy group, a propanoyloxy group, an n-butanoyloxy group, a 2-methylpropanoyloxy group, an n-pentanoyloxy group, 2, 2-Dimethylpropanoyloxy group, n-hexanoyloxy group, n-heptanoyloxy group, n-octanoyloxy group, n-nonanoyloxy group, n-decanoyloxy group, n-undecanoyloxy group, n -Dodecanoyloxy group, n-tridecanoyloxy group, n-tetradecanoyloxy group, n-pentadecanoyloxy group, n-hexadecanoyloxy group and the like can be mentioned.

When R ¹ is an alkoxycarbonyl group, the number of carbon atoms of the alkoxycarbonyl group is preferably 2 to 20, more preferably 2 to 7. Specific examples of the case where R ¹ is an alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, an n-propyloxycarbonyl group, an isopropyloxycarbonyl group, an n-butyloxycarbonyl group, an isobutyloxycarbonyl group, and sec-butyl. Oxycarbonyl group, tert-butyloxycarbonyl group, n-pentyloxycarbonyl group, isopentyloxycarbonyl group, sec-pentyloxycarbonyl group, tert-pentyloxycarbonyl group, n-hexyloxycarbonyl group, n-heptyloxycarbonyl group Group, n-octyloxycarbonyl group, isooctyloxycarbonyl group, sec-octioxylcarbonyl group, tert-octyloxycarbonyl group, n-nonyloxycarbonyl group, isononyloxycarbonyl group, n-decyloxycarbonyl group, and Examples thereof include an isodecyloxycarbonyl group.

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

When R ¹ is a heterocyclyl group, the heterocyclyl group is a 5- or 6-membered monocycle containing one or more N, S, O, or the monocycles are fused together, or the monocycle and the benzene ring are condensed. It is a heterocyclyl group. When the heterocyclyl group is a condensed ring, the number of rings is up to 3. The heterocyclyl group may be an aromatic group (heteroaryl group) or a non-aromatic group. Examples of the heterocycle constituting the heterocyclyl group include furan, thiophene, pyrrol, oxazole, isooxazole, thiazole, thiaziazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, pyridazine, benzofuran, benzothiophene, and indol. Isoindole, indridin, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalazine, cinnoline, quinoxaline, piperazine, piperazine, morpholine, piperidine, tetrahydropyrane, tetrahydrofuran and the like. Be done. When R ¹ is a heterocyclyl group, the heterocyclyl group may further have a substituent.

When R ¹ is a heterocyclyl carbonyl group, the heterocyclyl group contained in the heterocyclyl carbonyl group is the same as when R ¹ is a heterocyclyl group.

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

When the phenyl group, naphthyl group, and heterocyclyl group contained in R ¹ further have a substituent, the substituent includes an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and a carbon atom. A monoalkylamino group having a saturated aliphatic acyl group having a number of 2 to 7, an alkoxycarbonyl group having 2 to 7 carbon atoms, a saturated aliphatic acyloxy group having 2 to 7 carbon atoms, and an alkyl group having 1 to 6 carbon atoms. , Dialkylamino group having an alkyl group having 1 to 6 carbon atoms, morpholin-1-yl group, piperazin-1-yl group, halogen, nitro group, cyano group and the like. When the phenyl group, naphthyl group, and heterocyclyl group contained in R ¹ further have a substituent, the number of the substituent is not limited as long as the object of the present invention is not impaired, but 1 to 4 is preferable. When the phenyl group, the naphthyl group, and the heterocyclyl group contained in R ¹ have a plurality of substituents, the plurality of substituents may be the same or different.

Among the groups described above, it is preferable that R ¹ is a nitro group or a group represented by R ^6- CO- because the sensitivity tends to be improved. R ⁶ is not particularly limited as long as it does not interfere with the object of the present invention, and can be selected from various organic groups. Examples of a suitable group as 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 substituent. A good heterocyclyl group is mentioned. As R ^6, among these groups, a 2-methylphenyl group, thiophen-2-yl group, and α- naphthyl group are particularly preferred.
Further, when R ¹ is a hydrogen atom, the transparency tends to be good, which is preferable. If R ¹ is a hydrogen atom and R ⁴ is a group represented by the formula (R4-2) described later, the transparency tends to be better.

In the formula (1), R ² and R ³ are a chain alkyl group which may have a substituent, a cyclic organic group which may have a substituent, or a hydrogen atom, respectively. R ² and R ³ may be coupled to each other to form a ring. Among these groups, a chain alkyl group which may have a substituent is preferable as R ² and R ³ . When R ² and R ³ are chain alkyl groups which may have a substituent, the chain alkyl group may be a linear alkyl group or a branched chain alkyl group.

When R ² and R ³ are chain alkyl groups having no substituent, the number of carbon atoms of the chain alkyl group is preferably 1 to 20, more preferably 1 to 10, and particularly preferably 1 to 6. Specific examples of cases where R ² and R ³ are chain alkyl groups include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. , N-Pentyl group, Isopentyl group, sec-Pentyl group, tert-Pentyl group, n-Hexyl group, n-Heptyl group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, n-nonyl Examples thereof include a group, an isononyl group, an n-decyl group, and an isodecyl group. Further, when R ² and R ³ are alkyl groups, the alkyl group may contain an ether bond (−O−) in the carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include a methoxyethyl group, an ethoxyethyl group, a methoxyethoxyethyl group, an ethoxyethoxyethyl group, a propyloxyethoxyethyl group, a methoxypropyl group and the like.

When R ² and R ³ are chain alkyl groups having a substituent, the number of carbon atoms of the chain alkyl group is preferably 1 to 20, more preferably 1 to 10, and particularly preferably 1 to 6. In this case, the number of carbon atoms of the substituent is not included in the number of carbon atoms of the chain alkyl group. The chain alkyl group having a substituent is preferably linear.
The substituent that the alkyl group may have is not particularly limited as long as it does not impair the object of the present invention. Preferable examples of the substituent include a cyano group, a halogen atom, a cyclic organic group, and an alkoxycarbonyl group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. 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 heterocyclyl group. Specific examples of the cycloalkyl group are the same as in the preferred example when R ¹ is a cycloalkyl group. Specific examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, a biphenylyl group, an anthryl group, a phenanthryl group and the like. Specific examples of the heterocyclyl group are the same as in the preferred example when R ¹ is a heterocyclyl group. When R ¹ is an alkoxycarbonyl group, the alkoxy group contained in the alkoxycarbonyl group may be linear or branched chain, preferably linear. The number of carbon atoms of the alkoxy group contained in the alkoxycarbonyl group is preferably 1 to 10, and more preferably 1 to 6.

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

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

When R ² and R ³ are aromatic hydrocarbon groups, is the aromatic hydrocarbon group a phenyl group or a group formed by bonding a plurality of benzene rings via carbon-carbon bonds? , It is preferable that the group is formed by condensing a plurality of benzene rings. When the aromatic hydrocarbon group is a phenyl group or a group formed by bonding or condensing a plurality of benzene rings, the number of rings of the benzene ring contained in the aromatic hydrocarbon group is not particularly limited. 3 or less is preferable, 2 or less is more preferable, and 1 is particularly preferable. Preferred specific examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, a biphenylyl group, an anthryl group, a phenanthryl group and the like.

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

When R ² and R ³ are heterocyclyl groups, the heterocyclyl group is a 5- or 6-membered monocycle containing one or more N, S, O, such monocyclic rings, or such monocyclic and benzene rings. Is a heterocyclyl group condensed with. When the heterocyclyl group is a condensed ring, the number of rings is up to 3. The heterocyclyl group may be an aromatic group (heteroaryl group) or a non-aromatic group. Examples of the heterocycle constituting the heterocyclyl group include furan, thiophene, pyrrol, oxazole, isooxazole, thiazole, thiaziazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, pyridazine, benzofuran, benzothiophene, and indol. Isoindole, indridin, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalazine, cinnoline, quinoxaline, piperazine, piperazine, morpholine, piperidine, tetrahydropyrane, tetrahydrofuran and the like. Be done.

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

When the group formed by bonding R ² and R ³ is a cycloalkylidene group, the cycloalkylidene group may be condensed with one or more other rings. Examples of rings that may be fused with a cycloalkylene group include a benzene ring, a naphthalene ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a furan ring, a thiophene ring, a pyrrole ring, and a pyridine. Rings, pyrazine rings, pyrimidine rings and the like can be mentioned.

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

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

Preferable specific examples of R ² and R ³ include alkyl groups such as ethyl group, n-propyl group, n-butyl group, n-hexyl group, n-heptyl group, and n-octyl group; 2-methoxyethyl. Group, 3-methoxy-n-propyl group, 4-methoxy-n-butyl group, 5-methoxy-n-pentyl group, 6-methoxy-n-hexyl group, 7-methoxy-n-heptyl group, 8-methoxy -N-octyl group, 2-ethoxyethyl group, 3-ethoxy-n-propyl group, 4-ethoxy-n-butyl group, 5-ethoxy-n-pentyl group, 6-ethoxy-n-hexyl group, 7- Alkyl alkyl groups such as ethoxy-n-heptyl group and 8-ethoxy-n-octyl group; 2-cyanoethyl group, 3-cyano-n-propyl group, 4-cyano-n-butyl group, 5-cyano-n Cyanalkyl groups such as −pentyl group, 6-cyano-n-hexyl group, 7-cyano-n-heptyl group, and 8-cyano-n-octyl group; 2-phenylethyl group, 3-phenyl-n-propyl Phenyl such as group, 4-phenyl-n-butyl group, 5-phenyl-n-pentyl group, 6-phenyl-n-hexyl group, 7-phenyl-n-heptyl group, and 8-phenyl-n-octyl group. Alkyl group; 2-cyclohexylethyl group, 3-cyclohexyl-n-propyl group, 4-cyclohexyl-n-butyl group, 5-cyclohexyl-n-pentyl group, 6-cyclohexyl-n-hexyl group, 7-cyclohexyl-n -Heptyl group, 8-cyclohexyl-n-octyl group, 2-cyclopentylethyl group, 3-cyclopentyl-n-propyl group, 4-cyclopentyl-n-butyl group, 5-cyclopentyl-n-pentyl group, 6-cyclopentyl- Cycloalkylalkyl groups such as n-hexyl group, 7-cyclopentyl-n-heptyl group, and 8-cyclopentyl-n-octyl group; 2-methoxycarbonylethyl group, 3-methoxycarbonyl-n-propyl group, 4-methoxy carbonyl -n- butyl group, 5- methoxycarbonyl -n- pentyl group, 6-methoxy carbonylation Le -n- hexyl, 7-methoxy-carbonylation Le -n- heptyl group, 8-methoxy carbonylation Le -n- octyl group, 2-ethoxycarbonylethyl, 3-ethoxycarbonyl -n- propyl group, 4-ethoxycarbonyl -n- butyl group, 5- ethoxycarbonyl -n- pentyl group, 6-ethoxy carbonylation Le -n- hexyl Butyl, 7-ethoxyca Ruboni Le -n- heptyl, and 8-ethoxy carbonylation Le -n- alkoxycarbonylalkyl group and octyl group; 2-chloroethyl group, 3-chloro -n- propyl, 4-chloro -n- butyl group, 5-Chlor-n-pentyl group, 6-chlor-n-hexyl group, 7-chlor-n-heptyl group, 8-chlor-n-octyl group, 2-bromoethyl group, 3-bromo-n-propyl group, 4-Bromo-n-butyl group, 5-bromo-n-pentyl group, 6-bromo-n-hexyl group, 7-bromo-n-heptyl group, 8-bromo-n-octyl group, 3,3,3 Examples thereof include an alkyl halide group such as a -trifluoropropyl group and a 3,3,4,4,5,5,5-heptafluoro-n-pentyl group.

As R ² and R ³ , the most suitable groups among the above are ethyl group, n-propyl group, n-butyl group, n-pentyl group, 2-methoxyethyl group, 2-cyanoethyl group and 2-phenylethyl group. 2-Cyclohexylethyl group, 2-methoxycarbonylethyl group, 2-chloroethyl group, 2-bromoethyl group, 3,3,3-trifluoropropyl group, and 3,3,4,5,5,5-hepta It is a fluoro-n-pentyl group.

Examples of suitable organic groups for R ⁴ include alkyl groups, alkoxy groups, cycloalkyl groups, cycloalkoxy groups, saturated aliphatic acyl groups, alkoxycarbonyl groups, saturated aliphatic acyloxy groups and substituents, as in R ^1. A phenyl group which may have a substituent, a phenoxy group which may have a substituent, a benzoyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, and a substituent. A good benzoyloxy group, a phenylalkyl group which may have a substituent, a naphthyl group which may have a substituent, a naphthoxy group which may have a substituent, a naphthoyl group which may have a substituent, A naphthoxycarbonyl group which may have a substituent, a naphthyloxy group which may have a substituent, a naphthylalkyl group which may have a substituent, a heterocyclyl group which may have a substituent, and a substituent. Examples thereof include a heterocyclylcarbonyl group which may have a group, an amino group substituted with one or two organic groups, a morpholin-1-yl group, a piperazine-1-yl group and the like. Specific examples of these groups are the same as those described for R ^1. Further, as R ⁴ , 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 are also preferable. The substituents that the phenoxyalkyl group and the phenylthioalkyl group may have are the same as the substituents that the phenyl group contained in R ¹ may have.

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

Further, as R ⁴ , a group represented by −A ³ −CO—O—A ⁴ is also preferable. A ³ is a divalent organic group, preferably a divalent hydrocarbon group, and preferably an alkylene group. A ⁴ is a monovalent organic group, 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 1 to 10, more preferably 1 to 6, and particularly preferably 1 to 4.

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

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

Having described ^{R 4,} as is ^{R 4,} preferably a group represented by the following formula (R4-1) or (R4-2).
(In formulas (R4-1) and (R4-2), R ⁷ and R ⁸ are organic groups, respectively, p is an integer of 0 to 4, and R ⁷ and R ⁸ are adjacent positions on the benzene ring. When present in, R ⁷ and R ⁸ may combine with each other to form a ring, where q is an integer of 1-8, r is an integer of 1-5, and s is 0- (r + 3). ), And R ⁹ is an organic group.)

Examples of organic groups for R ⁷ and R ^{8 in} formula (R4-1) are the same as for R ¹ . As R ⁷ , an alkyl group or a phenyl group is preferable. When R ⁷ is an alkyl group, the number of carbon atoms thereof is preferably 1 to 10, more preferably 1 to 5, particularly preferably 1 to 3, and most preferably 1. That is, R ⁷ is most preferably a methyl group. When R ⁷ and R ⁸ are combined to form a ring, the ring may be an aromatic ring or an aliphatic ring. Preferable examples of the group represented by the formula (R4-1) in which R ⁷ and R ⁸ form a ring include a naphthalene-1-yl group and 1, 2, 3, 3. Examples thereof include 4-tetrahydronaphthalene-5-yl group. In the above formula (R4-1), p is an integer of 0 to 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 groups similar to the organic group described for R ¹ . Among the organic groups, an alkyl group is preferable. The alkyl group may be linear or branched. The number of carbon atoms of the alkyl group is preferably 1 to 10, more preferably 1 to 5, and particularly preferably 1 to 3. Examples of R ⁹ are preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group and the like, and among these, a methyl group is more preferable.

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

Wherein (1), R ⁵ represents a hydrogen atom, an alkyl group which may carbon atoms 1 to 11 have a substituent, or also an aryl group having a substituent. As the substituent that R ⁵ may have when it is an alkyl group, a phenyl group, a naphthyl group and the like are preferably exemplified. Further, as the substituent which may be possessed when R ¹ is an aryl group, an alkyl group having 1 to 5 carbon atoms, an alkoxy group, a halogen atom and the like are preferably exemplified.

In the formula (1), the R ^5, a hydrogen atom, a methyl group, an ethyl group, n- propyl group, an isopropyl group, n- butyl group, a phenyl group, a benzyl group, methylphenyl group, a naphthyl group and the like are preferably exemplified Of these, a methyl group or a phenyl group is more preferable.

The content of the photopolymerization initiator as the component (B) is preferably 0.001 to 30 parts by mass with respect to 100 parts by mass in total of the mass of the components other than the solvent in the photosensitive composition. 1 to 20 parts by mass is more preferable, 0.5 to 10 parts by mass is further preferable, and 1 to 5 parts by mass is particularly preferable.
The content of the photopolymerization initiator as the component (B) is preferably 0.05 to 50% by mass, preferably 0.1 to 30% by mass, based on the total of the component (A) and the component (B). It is more preferably by mass%, and even more preferably 0.5 to 20% by mass.
The content of the compound represented by the following formula (1) may be, for example, in the range of 1 to 100% by mass with respect to the entire component (B), preferably 50% by mass or more, and 70 to 100% by mass. Is more preferable.

The compound represented by the formula (1) in the component (B) may be used alone or in combination of two or more, and when two or more are used, the following (i) to (iii) are preferable.
(I) Compound combination of compounds ^{R 1} is a hydrogen atom and ^{R 1} is a compound which is a nitro group (ii) ^{R 4} is formula (R4-1) and ^{R 4} is formula (R4-2) compound compound in combination (iii) ^{R 4} is a compound with ^{R 4} is formula (R4-1) or formula (R4-2) is an alkyl group having 1 to 4 carbon atoms among them, the transmission of the sensitivity and the cured product The combination of (i) above is preferable, and the combination of (i) and (ii) or (iii) is more preferable from the viewpoint of improving characteristics such as rate.

The compounding ratio (mass ratio) of each compound based on the combination of (i) to (iii) may be appropriately adjusted according to the desired sensitivity and other characteristics. For example, 1:99 to 99: 1 is preferable. : 90 to 90:10 is more preferable, and 30:70 to 70; 30 is even more preferable.

The method for producing the compound represented by the formula (1) is not particularly limited. The compound represented by the formula (1) preferably has an oxime group (= N-OH) contained in the compound represented by the following formula (2) as an oxime ester represented by = NO-COR ^5. Manufactured by a method involving the step of converting to an ester. R ⁵ is the same as ^{R 5} in the formula (1).
(R ¹ , R ² , R ³ , R ⁴ , m, and n are the same as in equation (1). N is an integer of 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 for converting an oxime group (= N-OH) into an oxime ester group represented by = NO-COR ⁵ is not particularly limited. Typically, there is a method of reacting a hydroxyl group in an oxime group with an acylating agent that gives an acyl group represented by -COR ⁵ . The acylating ^agent, (R 5 _CO) acid anhydride represented by ₂ O ^and, R 5 COHal (Hal is a halogen atom) include acid halide represented by.

The compound represented by the general formula (1) can be synthesized, for example, according to the following scheme 1 when m is 0. In Scheme 1, a fluorene derivative represented by the following formula (1-1) is used as a raw material. When R ¹ is a nitro group or a monovalent organic group, the fluorene derivative represented by the formula (1-1) is replaced with a fluorene derivative in which the 9-position is substituted with R ² and R ³ by a well-known method. it can be obtained by introducing a substituent R ^1. The fluorene derivative in which the 9-position is substituted with R ² and R ³ is, for example, an alkali metal hydroxide as described in JP-A-06-234668 when R ² and R ³ are alkyl groups. It can be obtained by reacting fluorene with an alkylating agent in the presence of an aprotic polar organic solvent. Further, an alkylating agent such as an alkyl halide, an aqueous solution of an alkali metal hydroxide, and a phase transfer catalyst such as tetrabutylammonium iodide or potassium tert-butoxide are added to an organic solvent solution of fluorene. By carrying out the alkylation reaction, a 9,9-alkyl substituted fluorene can be obtained.

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

Next, the group represented by -CO-R ⁴ in the obtained fluorene derivative represented by the formula (1-3) is converted into the group represented by -C (= N-OH) -R ⁴ to be converted. Obtain an oxime compound represented by the formula (1-4). 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, but oxime formation with hydroxylamine is preferable. The oxime compound of the 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) can be reacted to obtain a compound represented by the following formula (1-7).

In addition, in equations (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 equation (1).

Further, in Scheme 1, R ⁴ contained in each of the formulas (1-2), formulas (1-3), and formulas (1-4) may be the same or different. That is, R ⁴ in formulas (1-2), (1-3), and formula (1-4) may undergo chemical modification in the synthetic process represented as Scheme 1. Examples of chemical modifications include esterification, etherification, acylation, amidation, halogenation, substitution of hydrogen atoms in amino groups with organic groups, and the like. Which may chemically modified R ⁴ is subjected is not limited thereto.

<Scheme 1>

When m is 1, the compound represented by the formula (1) can be synthesized, for example, according to Scheme 2 below. In Scheme 2, a fluorene derivative represented by the following formula (2-1) is used as a raw material. The fluorene derivative represented by the formula (2-1) is represented by -CO-CH _2- R ⁴ by the Friedel-Crafts reaction to the compound represented by the formula (1-1) by the same method as in Scheme 1. It is obtained by introducing the acyl group to be used. As the acylating agent, a carboxylic acid halide represented by the formula (1-8): Hal-CO-CH _2- R ⁴ is preferable. Then, in the compound represented by the formula (2-1), and oximation methylene group present between R ⁴ and the carbonyl group to obtain the ketoxime compound represented by the following formula (2-3). The method for oxime-forming the methylene group is not particularly limited, but a nitrite ester represented by the following general formula (2-2) (RONO and R are alkyl groups having 1 to 6 carbon atoms) is reacted in the presence of hydrochloric acid. The method of causing is preferable. Next, the ketooxime compound represented by the following formula (2-3) and the acid anhydride ((R ⁵ CO) ₂ O) represented by the following formula (2-4), or the following general formula (2-5). The compound represented by the following formula (2-6) can be obtained by reacting with an acid halide represented by (R ⁵ COHal, Hal is a halogen atom). In the following equations (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 substances in the pattern formed by using the photosensitive composition containing the compound represented by the formula (1) can be further reduced.

Further, in Scheme 2, R ⁴ contained in each of the formulas (1-8), formula (2-1), and formula (2-3) may be the same or different. In other words, the formula (1-8), the formula (2-1), and ^{R 4} in the formula (2-3), in a synthesis process shown as Scheme 2, may be subjected to chemical modification. Examples of chemical modifications include esterification, etherification, acylation, amidation, halogenation, substitution of hydrogen atoms in amino groups with organic groups, and the like. Which may chemically modified R ⁴ is subjected is not limited thereto.

<Scheme 2>

Preferable specific examples of the compound represented by the formula (1) include the following compounds 1 to 41.

<(C) Sensitizer>
The photosensitive composition contains (C) a sensitizer together with the above (B) photopolymerization initiator. Since the photosensitive composition contains (C) a sensitizer together with (B) a photopolymerization initiator containing the compound represented by the above formula (1), the photosensitive composition is also good even by LED exposure. Hardened to.
It is considered that this is because the compound represented by the formula (1) is particularly easily sensitized by the sensitizer.

As the (C) sensitizer, a compound conventionally used for the purpose of sensitizing a photopolymerization initiator in a photosensitive composition can be used without particular limitation.

As the (C) sensitizer, a compound having at least one selected from the group consisting of an alkoxy group, a substituted carbonyloxy group, and an oxo group (= O) as a substituent is preferable. As the compound having the substituent, a condensed polycyclic aromatic hydrocarbon compound or a condensed polycyclic aromatic heterocyclic compound is preferable.
The fused polycyclic aromatic hydrocarbon compound or the condensed polycyclic aromatic heterocyclic compound may have a substituent other than an alkoxy group, a substituted carbonyloxy group, and an oxo group (= O). Examples of substituents are an alkyl group having 1 to 20 carbon atoms, an alkyl halide group having 1 to 20 carbon atoms, an alkoxyalkyl group having 2 to 20 carbon atoms, and an aliphatic acyl having 2 to 20 carbon atoms. Examples thereof include a group, an aromatic acyl group (aloyl group) having 7 to 11 carbon atoms, a cyano group, a nitro group, a nitroso group, a halogen atom, a hydroxyl group, and a mercapto group.

The alkoxy group may be linear or branched. The number of carbon atoms of the alkoxy group is not particularly limited, but is preferably 1 to 20, more preferably 1 to 12, and particularly preferably 1 to 6.
Preferable examples of the alkoxy group are methoxy group, ethoxy group, n-propyloxy group, isopropyloxy, n-butyloxy, isobutyloxy group, tert-butyloxy group, n-pentyloxy group, n-hexyloxy group, n. -Heptyloxy group, n-octyloxy group, 2-ethylhexyl group, n-nonyloxy group, n-decyloxy group and the like can be mentioned.

The substituted carbonyloxy group is the group represented by —O—CO—A. A is not particularly limited as long as the (C) sensitizer has a desired sensitizing effect, and 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 preferable.

The aryl group or aryloxy group may have one or more substituents. The type of substituent is not particularly limited as long as the object of the present invention is not impaired. When an aryl group or an aryloxy group has a plurality of substituents, the plurality of substituents may be the same or different.
Preferable examples of the substituent are 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. , An aliphatic acyl group having 2 to 7 carbon atoms, an aromatic acyl group (aloyl group) having 7 to 11 carbon atoms, a cyano group, a nitro group, a nitroso group, a halogen atom, a hydroxyl group, a mercapto group and the like. ..

When A is an alkyl group or an alkoxy group, these groups may be linear or branched.
Preferable examples of the alkyl group are methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, n-hexyl group and n-heptyl group. , N-octyl group, 2-ethylhexyl group and the like.
Preferable examples of the aryl group include a phenyl group, an o-tolyl group, an m-tolyl group, a p-tolyl group, an α-naphthyl group, a β-naphthyl group and the like.
Preferable examples of the alkoxy group are methoxy group, ethoxy group, n-propyloxy group, isopropyloxy group, n-butyloxy group, isobutyloxy group, tert-butyloxy group, n-pentyloxy group and n-hexyloxy group. , N-Heptyloxy group, n-octyloxy group, 2-ethylhexyloxy group and the like.

In a condensed polycyclic aromatic hydrocarbon compound substituted with one or more selected from the group consisting of an alkoxy group, a substituted carbonyloxy group, and an oxo group (= O), or a condensed polycyclic aromatic heterocyclic compound. The number of rings constituting the fused ring is not particularly limited as long as the desired sensitizing action can be obtained. The number of rings is preferably 2 or more, more preferably 3 or more, particularly preferably 3 to 6, and most preferably 3 or 4.
As long as the fused polycyclic aromatic hydrocarbon compound or the condensed polycyclic aromatic heterocyclic compound has aromaticity, the monocycle forming the condensed polycycle does not necessarily have to be an aromatic ring.

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

Specific examples of the compound containing an anthracene ring and preferably used as the (C) sensitizer include 9,10-bis (acetyloxy) anthracene, 9,10-bis (propionyloxy) anthracene, and 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 (n-heptylcarbonyloxy) anthracene 2-Ethlhexanoyloxy) anthracene, 9,10-bis (n-octylcarbonyloxy) anthracene, 9,10-bis (n-nonylcarbonyloxy) anthracene, 9,10-bis (n-decylcarbonyloxy) anthracene , 9,10-bis (benzoyloxy) anthracene, 9,10-bis (4-methylbenzoyloxy) anthracene, 9,10-bis (2-naphthoyloxy) anthracene, 2-methyl-9,10-bis ( Acetyloxy) anthracene, 2-methyl-9,10-bis (propionyloxy) anthracene, 2-methyl-9,10-bis (n-propylcarbonyloxy) anthracene, 2-methyl-9,10-bis (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 (benzoyloxy) anthracene, 2-methyl-9,10-bis (4) -Methylbenzoyloxy) anthracene, 2-methyl-9,10-bis (2-naphthoyloxy) anthracene, 1-methyl-9,10-bis (acetyloxy) anthracene, 1-methyl-9,10-bis (2-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-pentylcarbonyl) Oxy) anthracene, 1-methyl-9,10-bis (n-hexylcarbonyloxy) anthracene, 1-methyl-9,10-bis (benzoyloxy) anthracene, 1-methyl-9,10-bis (4-methyl) Benzoyloxy) anthracene, 1-methyl-9,10-bis (2-naphthoyloxy) anthracene, 2-ethyl-9,10-bis (acetyloxy) anthracene, 2-ethyl-9,10-bis (propionyloxy) ) Anthracene, 2-ethyl-9,10-bis (n-propylcarbonyloxy) anthracene, 2-ethyl-9,10-bis (isobutylcarbonyloxy) anthracene, 2-ethyl-9,10-bis (n-butyl) Carbonyloxy) anthracene, 2-ethyl-9,10-bis (isobutylcarbonyloxy) anthracene, 2-ethyl-9,10-bis (n-pentylcarbonyloxy) anthracene, 2-ethyl-9,10-bis (n) -Hexylcarbonyloxy) anthracene, 2-ethyl-9,10-bis (benzoyloxy) anthracene, 2-ethyl-9,10-bis (4-ethyl-benzoyloxy) anthracene, 2-ethyl-9,10-bis (2-naphthyloxy) anthracene, 1-ethyl-9,10-bis (acetyloxy) anthracene, 1-ethyl-9,10-bis (propionyloxy) anthracene, 1-ethyl-9,10-bis (n) -Propylcarbonyloxy) anthracene, 1-ethyl-9,10-bis (isopropylcarbonyloxy) anthracene, 1-ethyl-9,10-bis (n-butylcarbonyloxy) anthracene, 1-ethyl-9,10-bis (Isobutylcarbonyloxy) anthracene, 1-ethyl-9,10-bis (n-pentylcarbonyloxy) anthracene, 1-ethyl-9,10-bis (n-hexylcarbonyloxy) anthracene, 1-ethyl-9,10 -Bis (benzoyloxy) anthracene, 1-ethyl-9,10-bis (4-ethyl-benzoyloxy) anthracene, 1-ethyl-9,10-bis (2-naphthoyloxy) anthracene, 1- (t-) Butyl) -9,10-bi Su (n-propylcarbonyloxy) anthracene, 1- (t-butyl) -9,10-bis (isopropylcarbonyloxy) anthracene, 1- (t-butyl) -9,10-bis (n-butylcarbonyloxy) Anthracene, 1- (t-butyl) -9,10-bis (isobutylcarbonyloxy) anthracene, 1- (t-butyl) -9,10-bis (n-pentylcarbonyloxy) anthracene, 1- (t-butyl) ) -9,10-Bis (n-hexylcarbonyloxy) anthracene, 1- (t-butyl) -9,10-bis (benzoyloxy) anthracene, 1- (t-butyl) -9,10-bis (4) -(T-Butyl) -benzoyloxy) anthracene, 1- (t-butyl) -9,10-bis (2-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 (benzoyloxy) anthracene, 2- (t-butyl) -9,10-bis (4- (t-t-) Butyl) -benzoyloxy) anthracene, 2- (t-butyl) -9,10-bis (2-naphthoyloxy) anthracene, 2-pentyl-9,10-bis (n-propylcarbonyloxy) anthracene, 2- Pentyl-9,10-bis (isopropylcarbonyloxy) anthracene, 2-pentyl-9,10-bis (n-butylcarbonyloxy) anthracene, 2-pentyl-9,10-bis (isobutylcarbonyloxy) anthracene, 2- Pentyl-9,10-bis (n-pentylcarbonyloxy) anthracene, 2-pentyl-9,10-bis (n-hexylcarbonyloxy) anthracene, 2-pentyl-9,10-bis (benzoyloxy) anthracene, 2 -Pentyl-9,10-bis (4- (t-butyl) -benzoyloxy) anthracene, and 2-pentyl-9,10-bis (2-na) Futoyloxy) Anthracene and the like.

An anthracene compound substituted with a halogen atom is also preferable as the (C) sensitizer. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Specific examples of the anthracene compound substituted with a halogen atom, which is preferable as the (C) sensitizer, include 2-chloro-9,10-bis (acetyloxy) anthracene and 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 (benzoyloxy) anthracene, 2-chloro-9,10-bis (4-methylbenzoyloxy) anthracene, 2-chloro-9, 10-Bis (2-naphthoyloxy) anthracene, 1-chloro-9,10-bis (acetyloxy) anthracene, 1-chloro-9,10-bis (propionyloxy) anthracene, 1-chloro-9,10- Bis (n-propylcarbonyloxy) anthracene, 1-chloro-9,10-bis (isopropylcarbonyloxy) anthracene, 1-chloro-9,10-bis (n-butylcarbonyloxy) anthracene, 1-chloro-9, 10-Bis (isobutylcarbonyloxy) anthracene, 1-chloro-9,10-bis (n-pentylcarbonyloxy) anthracene, 1-chloro-9,10-bis (n-hexylcarbonyloxy) anthracene, 1-chloro- 9,10-bis (benzoyloxy) anthracene, 1-chloro-9,10-bis (4-methylbenzoyloxy) anthracene, 1-chloro-9,10-bis (2-naphthoyloxy) anthracene, 2-fluoro -9,10-bis (acetyloxy) anthracene, 2-fluoro-9,10-bis (propionyloxy) anthracene, 2-fluoro-9,10-bis (n-propylcarbonyloxy) anthracene, 2-fluoro-9 , 10-bis (isopropylcarbonyloxy) anthracene, 2-fluoro-9,10-bis (n-butylcarbonyloxy) anthracene, 2-fluoro-9,10-bis (isobutylcarbonyloxy) anthracene , 2-Fluoro-9,10-bis (n-pentylcarbonyloxy) anthracene, 2-fluoro-9,10-bis (n-hexylcarbonyloxy) anthracene, 2-fluoro-9,10-bis (benzoyloxy) Anthracene, 2-fluoro-9,10-bis (4-methylbenzoyloxy) anthracene, 2-fluoro-9,10-bis (2-naphthoyloxy) anthracene, 1-fluoro-9,10-bis (acetyloxy) ) Anthracene, 1-fluoro-9,10-bis (propionyloxy) anthracene, 1-fluoro-9,10-bis (n-propylcarbonyloxy) anthracene, 1-fluoro-9,10-bis (isopropylcarbonyloxy) Anthracene, 1-fluoro-9,10-bis (n-butylcarbonyloxy) anthracene, 1-fluoro-9,10-bis (isobutylcarbonyloxy) anthracene, 1-fluoro-9,10-bis (n-pentylcarbonyl) Oxy) anthracene, 1-fluoro-9,10-bis (n-hexylcarbonyloxy) anthracene, 1-fluoro-9,10-bis (benzoyloxy) anthracene, 1-fluoro-9,10-bis (4-methyl) Benzoyloxy) anthracene, 1-fluoro-9,10-bis (2-naphthoyloxy) anthracene, 2-bromo-9,10-bis (acetyloxy) anthracene, 2-bromo-9,10-bis (propionyloxy) ) Anthracene, 2-bromo-9,10-bis (n-propylcarbonyloxy) anthracene, 2-bromo-9,10-bis (isopropylcarbonyloxy) anthracene, 2-bromo-9,10-bis (n-butyl) Carbonyloxy) anthracene, 2-bromo-9,10-bis (isobutylcarbonyloxy) anthracene, 2-bromo-9,10-bis (n-pentylcarbonyloxy) anthracene, 2-bromo-9,10-bis (n) -Hexylcarbonyloxy) anthracene, 2-bromo-9,10-bis (benzoyloxy) anthracene, 2-bromo-9,10-bis (4-methylbenzoyloxy) anthracene, 2-bromo-9,10-bis (benzoyloxy) 2-naphthyloxy) anthracene, 1-bromo-9,10-bis (acetyloxy) anthracene, 1-bromo-9,10-bis (propionyloxy) anthracene, 1-bromo-9,10-bi Su (n-propylcarbonyloxy) anthracene, 1-bromo-9,10-bis (isopropylcarbonyloxy) anthracene, 1-bromo-9,10-bis (n-butylcarbonyloxy) anthracene, 1-bromo-9, 10-Bis (isobutylcarbonyloxy) anthracene, 1-bromo-9,10-bis (n-pentylcarbonyloxy) anthracene, 1-bromo-9,10-bis (n-hexylcarbonyloxy) anthracene, 1-bromo- 9,10-bis (benzoyloxy) anthracene, 1-bromo-9,10-bis (4-methylbenzoyloxy) anthracene, 1-bromo-9,10-bis (2-naphthoyloxy) anthracene and the like. Be done.

Further, an anthracene compound substituted with an alkoxy group is also preferable as the (C) sensitizer.
Specific examples of the anthracene compound substituted with an alkoxy group, which is preferable as the (C) sensitizer, include 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, and 9,10-bis (n-). Propyloxy) anthracene, 9,10-bis (n-butyloxy) anthracene, 9,10-bis (n-pentyloxy) anthracene, 9,10-bis (isopentyloxyoxy) anthracene, 9,10-bis (n) -Hexyloxy) anthracene, 9,10-bis (n-heptyloxy) anthracene, 9,10-bis (n-octyloxy) anthracene, 9,10-bis (2-ethylhexyloxy) anthracene, 9-methoxyanthracene, 9-ethoxyanthracene, 9- (n-propyloxy) anthracene, 9- (n-butyloxy) anthracene, 9- (n-pentyloxy) anthracene, 9- (isopentyloxyoxy) anthracene, 9- (n-hexyl) Oxy) anthracene, 9- (n-heptyloxy) anthracene, 9- (n-octyloxy) anthracene, 9- (2-ethylhexyloxy) anthracene, 2-methyl-9,10-dimethoxyanthracene, 2-methyl-9 , 10-Diethoxyanthracene, 2-methyl-9,10-bis (n-propyloxy) anthracene, 2-methyl-9,10-bis (n-butyloxy) anthracene, 2-methyl-9,10-bis ( n-pentyloxy) anthracene, 2-methyl-9,10-bis (isopentyloxyoxy) anthracene, 2-methyl-9,10-bis (n-hexyloxy) anthracene, 2-methyl-9,10-bis (N-Heptyloxy) anthracene, 2-methyl-9,10-bis (n-octyloxy) anthracene, 2-methyl-9,10-bis (2-ethylhexyloxy) anthracene, 2-ethyl-9,10- Dimethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 2-ethyl-9,10-bis (n-propyloxy) anthracene, 2-ethyl-9,10-bis (n-butyloxy) anthracene, 2- Ethyl-9,10-bis (n-pentyloxy) anthracene, 2-ethyl-9,10-bis (isopentyloxyoxy) anthracene, 2-ethyl-9,10-bis (n-hexyloxy) anthracene, 2 -Ethrace-9,10-bis (n-he) Petiloxy) anthracene, 2-ethyl-9,10-bis (n-octyloxy) anthracene, 2-ethyl-9,10-bis (2-ethylhexyloxy) anthracene, 2-methyl-9-methoxyanthracene, 2-methyl -9-ethoxyanthracene, 2-methyl-9- (n-propyloxy) anthracene, 2-methyl-9- (n-butyloxy) anthracene, 2-methyl-9- (n-pentyloxy) anthracene, 2-methyl -9- (Isopentyloxyoxy) anthracene, 2-methyl-9- (n-hexyloxy) anthracene, 2-methyl-9- (n-heptyloxy) anthracene, 2-methyl-9- (n-octyloxy) ) Anthracene, 2-methyl-9- (2-ethylhexyloxy) anthracene, 2-ethyl-9-methoxyanthracene, 2-ethyl-9-ethoxyanthracene, 2-ethyl-9- (n-propyloxy) anthracene, 2 -Ethyl-9- (n-butyloxy) anthracene, 2-ethyl-9- (n-pentyloxy) anthracene, 2-ethyl-9- (isopentyloxyoxy) anthracene, 2-ethyl-9- (n-hexyl) Oxy) anthracene, 2-ethyl-9- (n-heptyloxy) anthracene, 2-ethyl-9- (n-octyloxy) anthracene, 2-ethyl-9- (2-ethylhexyloxy) anthracene, 2-chloro- 9,10-Dimethoxyanthracene, 2-chloro-9,10-diethoxyanthracene, 2-chloro-9,10-bis (n-propyloxy) anthracene, 2-chloro-9,10-bis (n-butyloxy) Anthracene, 2-chloro-9,10-bis (n-pentyloxy) anthracene, 2-chloro-9,10-bis (isopentyloxyoxy) anthracene, 2-chloro-9,10-bis (n-hexyloxy) ) Anthracene, 2-chloro-9,10-bis (n-heptyloxy) anthracene, 2-chloro-9,10-bis (n-octyloxy) anthracene, 2-chloro-9,10-bis (2-ethylhexyl) Oxy) 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-methoxy Anthracene, 2-chloro-9-ethoxyanthracene, 2-chloro-9- (n-propyloxy) anthracene, 2-chloro-9- (n-butyloxy) anthracene, 2-chloro-9- (n-pentyloxy) Anthracene, 2-chloro-9- (isopentyloxyoxy) anthracene, 2-chloro-9- (n-hexyloxy) anthracene, 2-chloro-9- (n-heptyloxy) anthracene, 2-chloro-9- (N-octyloxy) anthracene, 2-chloro-9- (2-ethylhexyloxy) anthracene, 2-bromo-9-methoxyanthracene, 2-bromo-9-ethoxyanthracene, 2-bromo-9- (n-propyl) Oxy) anthracene, 2-bromo-9- (n-butyloxy) anthracene, 2-bromo-9- (n-pentyloxy) anthracene, 2-ethyl-9- (isopentyloxyoxy) anthracene, 2-bromo-9 -(N-Hexyloxy) anthracene, 2-bromo-9- (n-heptyloxy) anthracene, 2-bromo-9- (n-octyloxy) anthracene, and 2-bromo-9- (2-ethylhexyloxy) Anthracene and the like can be mentioned.

Among the anthracene compounds described above, 9,10-bis (acetyloxy) anthracene, 9,10-bis (propionyloxy) anthracene, 9 from the viewpoint of ease of production and (C) performance as a sensitizer. , 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-hexanoyloxy) anthracene, 9,10-bis (n-heptanoyloxy) anthracene, 9,10-bis (n-octanoyloxy) anthracene, 9,10-bis (2) -Ethlhexanoyloxy) anthracene, 9,10-bis (n-nonanoyloxy) anthracene, 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, and 9,10-dibutoxyanthracene are preferred.

Specific examples of the compound containing a naphthacene ring and preferably used as the (C) sensitizer include
2-Methyl-5,11-dioxo-6,12-bis (acetyloxy) naphthacene, 2-methyl-5,11-dioxo-6,12-bis (propionyloxy) naphthacene, 2-methyl-5,11- Dioxo-6,12-bis (n-propylcarbonyloxy) naphthacene, 2-methyl-5,11-dioxo-6,12-bis (isopropylcarbonyloxy) naphthacene, 2-methyl-5,11-dioxo-6, 12-bis (n-butylcarbonyloxy) naphthacene, 2-methyl-5,11-dioxo-6,12-bis (isobutylcarbonyloxy) naphthacene, 2-methyl-5,11-dioxo-6,12-bis ( n-Pentylcarbonyloxy) naphthacene, 2-methyl-5,11-dioxo-6,12-bis (n-hexylcarbonyloxy) naphthacene, 2-methyl-5,11-dioxo-6,12-bis (n-) Heptylcarbonyloxy) naphthacene, 2-ethyl-5,11-dioxo-6,12-bis (acetyloxy) naphthacene, 2-ethyl-5,11-dioxo-6,12-bis (propionyloxy) naphthacene, 2- Ethyl-5,11-dioxo-6,12-bis (n-propylcarbonyloxy) naphthacene, 2-ethyl-5,11-dioxo-6,12-bis (isopropylcarbonyloxy) naphthacene, 2-ethyl-5, 11-Dioxo-6,12-bis (n-butylcarbonyloxy) naphthacene, 2-methyl-5,11-dioxo-6,12-bis (isobutylcarbonyloxy) naphthacene, 2-ethyl-5,11-dioxo- 6,12-bis (n-pentylcarbonyloxy) naphthacene, 2-ethyl-5,11-dioxo-6,12-bis (n-hexylcarbonyloxy) naphthacene, and 2-ethyl-5,11-dioxo-6 , 12-Bis (n-heptylbonyloxy) Naphthalene and other alkylcarbonyloxy group-substituted naphthacene compounds;
2-Methyl-5,11-dioxo-6,12-bis (benzoyloxy) naphthalene, 2-methyl-5,11-dioxo-6,12-bis (o-toluoleoxy) naphthacene, 2-methyl-5 , 11-Dioxo-6,12-bis (m-toluoleoxy) naphthacene, 2-methyl-5,11-dioxo-6,12-bis (p-toluoleoxy) naphthacene, 2-methyl-5,11 -Dioxo-6,12-bis (α-naphthoyloxy) naphthacene, 2-methyl-5,11-dioxo-6,12-bis (β-naphthoyloxy) naphthacene, 2-ethyl-5,11-dioxo -6,12-bis (benzoyloxy) naphthacene, 2-ethyl-5,11-dioxo-6,12-bis (o-toluoleoxy) naphthacene, 2-ethyl-5,11-dioxo-6,12- Bis (m-toluoleoxy) naphthacene, 2-ethyl-5,11-dioxo-6,12-bis (p-toluoleoxy) naphthacene, 2-ethyl-5,11-dioxo-6,12-bis ( Aloyloxy group-substituted naphthacene compounds such as α-naphthyloxy) naphthacene and 2-ethyl-5,11-dioxo-6,12-bis (β-naphthoyloxy) naphthacene;
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-pentyloxy) Carbonyloxy) naphthacene, 2-ethyl-5,11-dioxo-6,12-bis (n-hexyloxycarbonyloxy) naphthacene, 2-ethyl-5,11-dioxo-6,12-bis (n-heptyloxy) An alkoxycarbonyloxy group-substituted naphthacene compound such as carbonyloxy) naphthacene and 2-ethyl-5,11-dioxo-6,12-bis (n-octyloxycarbonyloxy) naphthacene;
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) naphthalene, 2-methyl-5,11-dioxo-6,12-bis (p-tolyloxycarbonyloxy) naphthacene, 2-methyl -5,11-dioxo-6,12-bis (α-naphthyloxycarbonyloxy) naphthacene, 2-methyl-5,11-dioxo-6,12-bis (β-naphthyloxycarbonyloxy) naphthacene, 2-ethyl -5,11-dioxo-6,12-bis (phenoxycarbonyloxy) naphthacene, 2-ethyl-5,11-dioxo-6,12-bis (o-tolyloxycarbonyloxy) naphthacene, 2-ethyl-5, 11-Dioxo-6,12-bis (m-tolyloxycarbonyloxy) naphthalene, 2-ethyl-5,11-dioxo-6,12-bis (p-tolyloxycarbonyloxy) naphthalene, 2-ethyl-5, Aloyloxycarbonyl such as 11-dioxo-6,12-bis (α-naphthyloxycarbonyloxy) naphthacene and 2-ethyl-5,11-dioxo-6,12-bis (β-naphthyloxycarbonyloxy) naphthacene Examples thereof include an oxy group-substituted naphthacene compound.

Among the above compounds containing a naphthacene ring, 5,11-dioxo-6,12-bis (methoxycarbonyloxy) naphthacene, 5,11-dioxo-6,12-bis (ethoxycarbonyloxy) naphthacene, 5,11- Dioxo-6,12-bis (isopropyloxycarbonyloxy) naphthacene, 5,11-dioxo-6,12-bis (isobutyloxycarbonyloxy) naphthacene, 5,11-dioxo-6,12-bis (n-butylcarbonyl) Oxy) naphthacene, 5,11-dioxo-6,12-bis (n-pentylcarbonyloxy) naphthacene, and 5,11-dioxo-6,12-bis (n-heptanoyloxy) naphthacene are preferred.
(A) In terms of compatibility with photopolymerizable compounds, 5,11-dioxo-6,12-bis (isopropyloxycarbonyloxy) naphthacene and 5,11-dioxo-6,12-bis (isobutyloxycarbonyloxy) ) Tetracene, 5,11-dioxo-6,12-bis (n-butyryloxy) naphthacene, 5,11-dioxo-6,12-bis (n-valeryloxy) naphthacene, 5,11-dioxo-6,12-bis (Heptanoyloxy) naphthacene is preferred.

Specific examples of the compound containing a thioxanthene ring and preferably used as a (C) sensitizer include thioxanthene-9-one, 2-methyl-9H-thioxanthene-9-one, 2-. Examples thereof include isopropyl-9H-thioxanthene-9-one, 1,4-dimethylthioxanthene-9-one, 3-methyl-9-oxo-9H-thioxanthene-2-ylacetate and the like.

The content of the sensitizer as the component (C) is preferably 0.01 to 1000 parts by mass, preferably 0.1 to 150 parts by mass, based on 100 parts by mass of the total of the component (B) in the photosensitive composition. By mass is more preferable, and 0.3 to 100 parts by mass is further preferable.
When the total amount of the component (B) is 0.01 to 3 parts by mass with respect to 100 parts by mass, coloring due to absorption of the component (C) can be reduced, so that a cured product having good transparency or brightness can be obtained. it can.

<(D) Colorant>
The photosensitive composition may further contain (D) a colorant. By containing the colorant which is the component (D), the photosensitive composition is preferably used, for example, as a color filter forming application for a liquid crystal display. Further, the photosensitive composition according to the present invention is preferably used for forming a black matrix in a color filter of a display device, for example, by containing a light-shielding agent as a colorant.

The (D) colorant contained in the photosensitive composition is not particularly limited, but is classified as Pigment in, for example, Color Index (CI; The Society of Dyers and Colorists). It is preferable to use a compound having a color index (CI) number as shown below.

Examples of preferably usable yellow pigments include C.I. I. Pigment Yellow 1 (hereinafter, "CI Pigment Yellow" is the same and only the number is described), 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 preferably usable orange pigments include C.I. I. Pigment Orange 1 (hereinafter, "CI Pigment Orange" is the same and only the number is described), 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46. , 49, 51, 55, 59, 61, 63, 64, 71, and 73.

Examples of suitably usable purple pigments include C.I. I. Pigment Violet 1 (hereinafter, "CI Pigment Violet" is the same and only the number is described), 19, 23, 29, 30, 32, 36, 37, 38, 39, 40, and 50. Can be mentioned.

Examples of preferably usable red pigments include C.I. I. Pigment Red 1 (hereinafter, "CI Pigment Red" is the same and only the number is 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 preferably usable blue pigments include C.I. I. Pigment Blue 1 (hereinafter, "CI Pigment Blue" is the same, and only the number is described.) 2, 15, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64 , And 66.

Examples of pigments of the above other hues that can be suitably used include C.I. I. Pigment Green 7, C.I. I. Pigment Green 36, C.I. I. Pigment Green 37 and other green pigments, C.I. I. Pigment Brown 23, C.I. I. Pigment Brown 25, C.I. I. Pigment Brown 26, C.I. I. Pigment Brown 28 and other brown pigments, C.I. I. Pigment Black 1, C.I. I. Examples thereof include black pigments such as Pigment Black 7.

When the colorant is a light-shielding agent, it is preferable to use a black pigment as the light-shielding agent. Examples of the black pigment include metal oxides such as carbon black, titanium black, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium and silver, composite oxides, metal sulfides, metal sulfates or metal carbonates. , Organic and inorganic substances can be mentioned. Among these, it is preferable to use carbon black having a high light-shielding property.

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

Since resin-coated carbon black has lower conductivity than carbon black without resin coating, it has low current leakage when used as a black matrix for liquid crystal display elements such as liquid crystal display, and is highly reliable. Can manufacture power consumption displays.

Further, in order to adjust the color tone of carbon black, the above organic pigment may be appropriately added as an auxiliary pigment.

Further dispersants may be used to uniformly disperse the colorants in the photosensitive composition. As such a dispersant, it is preferable to use a polyethyleneimine-based, urethane resin-based, or acrylic resin-based polymer dispersant. In particular, when carbon black is used as the colorant, it is preferable to use an acrylic resin-based dispersant as the dispersant.

Further, the inorganic pigment and the organic pigment may be used alone or in combination of two or more, but when they are used in combination, 10 to 80 parts by mass of the organic pigment is used with respect to 100 parts by mass of the total amount of the inorganic pigment and the organic pigment. It is preferable to use it in the range of 20 to 40 parts by mass, and it is more preferable to use it in the range of 20 to 40 parts by mass.

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

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

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

<(E) Alkali-soluble resin>
The photosensitive composition according to the present invention may contain (E) an alkali-soluble resin as a resin other than the resin used as the (A) photopolymerizable compound. By blending the (E) alkali-soluble resin with the photosensitive composition, alkali developability can be imparted to the photosensitive composition.

In the present specification, the alkali-soluble resin refers to KOH having a concentration of 0.05% by mass by forming a resin film having a thickness of 1 μm on a substrate with a resin solution (solvent: propylene glycol monomethyl ether acetate) having a resin concentration of 20% by mass. A solvent that dissolves in a film thickness of 0.01 μm or more when immersed in an aqueous solution for 1 minute.

(E) Among the alkali-soluble resins, a polymer of a monomer having an ethylenically unsaturated double bond because of its excellent film-forming property and the fact that the characteristics of the resin can be easily adjusted by selecting a monomer. Is preferable. Examples of the monomer having an ethylenically unsaturated double bond include (meth) allylic acid; (meth) allylic acid ester; (meth) allylic acid amide; crotonic acid; maleic acid, fumaric acid, citraconic acid, and mesaconic acid. Itaconic acid, an anhydride of these dicarboxylic acids; such as allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, allyl lactate, and allyloxyethanol. Allyl compounds; hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethyl hexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl ether, 2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether, Diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether, vinyl phenyl ether, vinyl trill ether, vinyl chlorophenyl ether, vinyl-2,4-dichlorophenyl ether, vinyl naphthyl ether, And vinyl ethers such as vinyl anthranyl ether; vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl valate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxyacetate, vinyl butoxyacetate, Binirufu E-yl acetate, vinyl acetoacetate, vinyl lactate, vinyl -β- phenylbutyrate, vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorophthalic acid, and vinyl esters such as naphthoic acid vinyl; styrene, Methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, isopropylstyrene, butylstyrene, hexylstyrene, cyclohexylstyrene, decylstyrene, benzylstyrene, chloromethylstyrene, trifluoromethylstyrene, ethoxymethylstyrene, acetoxymethylstyrene, Methoxystyrene, 4-methoxy-3-methylstyrene, dimethoxystyrene, chlorostyrene, dichlorostyle , Trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethylstyrene, and 4-fluoro-3-trifluoromethyl. Styrene or styrene derivatives such as styrene; ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4 -Methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene , 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene.

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

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

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

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

Among the polymers of one or more monomers selected from (meth) acrylic acid and (meth) acrylic acid ester, the adhesiveness of the transparent insulating film formed by using the photosensitive composition to the substrate. A resin containing a unit derived from a (meth) acrylic acid ester having a group having an epoxy group is preferable from the viewpoint of excellent mechanical strength.

The (meth) acrylic acid ester having a group having an epoxy group is a group having an alicyclic epoxy group as described later, even if it is a (meth) acrylic acid ester having a group having a chain aliphatic epoxy group. It may be a (meth) acrylic acid ester having.

The (meth) acrylic acid ester 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 (meth) acrylic acid esters having an aromatic group and a group having an epoxy group include 4-glycidyloxyphenyl (meth) acrylate, 3-glycidyloxyphenyl (meth) acrylate, and 2-glycidyloxy. Examples thereof include phenyl (meth) acrylate, 4-glycidyloxyphenylmethyl (meth) acrylate, 3-glycidyloxyphenylmethyl (meth) acrylate, and 2-glycidyloxyphenylmethyl (meth) acrylate.

When the film formed by using the photosensitive composition is required to be transparent, the (meth) acrylic acid having a group having an epoxy group is preferably one containing no aromatic group.

Examples of (meth) acrylic acid esters having a group having a chain aliphatic epoxy group include ester groups (-O-CO) such as epoxyalkyl (meth) acrylates and epoxyalkyloxyalkyl (meth) acrylates. Examples thereof include a (meth) acrylic acid ester in which a chain aliphatic epoxy group is bonded to an oxy group (−O−) in −). The chain aliphatic epoxy group contained in such a (meth) acrylic acid ester may contain one or more oxy groups (−O−) in the chain. The number of carbon atoms of the chain aliphatic epoxy group is not particularly limited, but is preferably 3 to 20, more preferably 3 to 15, and particularly preferably 3 to 10.

Specific examples of the (meth) acrylic acid ester having a group having a chain aliphatic epoxy group include glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, and 6. , Epoxyalkyl (meth) acrylates such as 7-epoxyheptyl (meth) acrylates; 2-glycidyloxyethyl (meth) acrylates, 3-glycidyloxy-n-propyl (meth) acrylates, 4-glycidyloxy-n-butyl ( Examples thereof include epoxyalkyloxyalkyl (meth) acrylates such as meth) acrylates, 5-glycidyloxy-n-hexyl (meth) acrylates, and 6-glycidyloxy-n-hexyl (meth) acrylates.

An epoxy group in a polymer of one or more monomers selected from (meth) acrylic acid and (meth) acrylic acid ester, which comprises a unit derived from a (meth) acrylic acid ester having a group having an epoxy group. The content of the unit derived from the (meth) acrylic acid ester having a group having a group is preferably 1 to 95% by mass, more preferably 40 to 80% by mass, based on the weight of the resin.

Further, among the polymers of one or more monomers selected from (meth) acrylic acid and (meth) acrylic acid ester, it is easy to form a transparent insulating film having excellent transparency by using the photosensitive composition. Therefore, a resin containing a unit derived from a (meth) acrylic acid ester having a group having an alicyclic skeleton is also preferable.

In a (meth) acrylic acid ester having a group having an alicyclic skeleton, the group having an alicyclic skeleton is a group having an alicyclic epoxy group even if it has a group having an alicyclic hydrocarbon group. You may. The alicyclic group constituting the alicyclic skeleton may be monocyclic or polycyclic. Examples of the monocyclic alicyclic group include a cyclopentyl group and a cyclohexyl group. Examples of the polycyclic alicyclic group include a norbornyl group, an isobornyl group, a tricyclononyl group, a tricyclodecyl group, a tetracyclododecyl group and the like.

Among the (meth) acrylic acid esters having a group having an alicyclic skeleton, the (meth) acrylic acid ester having a group having an alicyclic hydrocarbon group is, for example, the following formulas (d1-1) to (d1-). Examples thereof include the compounds represented by 8). Among these, the compounds represented by the following formulas (d1-3) to (d1-8) are preferable, and the compounds represented by the following formulas (d1-3) or (d1-4) are more preferable.

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

Among the (meth) acrylic acid esters having a group having an alicyclic skeleton, specific examples of the (meth) acrylic acid ester having a group having an alicyclic epoxy group include the following formulas (d2-1) to ( Examples thereof include the compounds represented by d2-16). Among these, in order to make the developability of the photosensitive composition appropriate, compounds represented by the following formulas (d2-1) to (d2-6) are preferable, and the following formulas (d2-1) to (d2-1) to The compound represented by (d2-4) is more preferable.

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 carbon atoms, and R ^d6 represents a divalent hydrocarbon having 1 to 10 carbon atoms. Indicates a group, where n represents an integer from 0 to 10. As R ^d5 , a linear or branched alkylene group, for example, a methylene group, an ethylene group, a propylene group, a tetramethylene group, an ethylethylene group, a pentamethylene group, or a hexamethylene group is preferable. Examples of R ^d6 include methylene group, ethylene group, propylene group, tetramethylene group, ethylethylene group, pentamethylene group, hexamethylene group, phenylene group, cyclohexylene group, -CH ₂ -Ph-CH _2- (Ph is (Indicating a phenylene group) is preferable.

A resin in which a polymer of one or more monomers selected from (meth) acrylic acid and (meth) acrylic acid ester contains a unit derived from (meth) acrylic acid ester having a group having an alicyclic skeleton. In the case of, the amount of the unit derived from the (meth) acrylic acid ester having a group having an alicyclic skeleton in the resin is preferably 5 to 95% by mass, more preferably 10 to 90% by mass, and 30 to 70%. Mass% is more preferred.

In addition, a polymer of one or more monomers selected from (meth) acrylic acid and (meth) acrylic acid ester, which contains a unit derived from a (meth) acrylic acid ester having a group having an alicyclic skeleton. Among them, a resin containing a unit derived from (meth) acrylic acid and a unit derived from a (meth) acrylic acid ester having a group having an alicyclic epoxy group is preferable. The film formed by using the photosensitive composition containing the alkali-soluble resin (E) has excellent adhesion to the substrate. Further, when such a resin is used, it is possible to cause a self-reaction between the carboxyl group contained in the resin and the alicyclic epoxy group. Therefore, when a photosensitive composition containing such a resin is used, a film formed by causing a self-reaction between a carboxyl group and an alicyclic epoxy group by using a method of heating the film or the like. It is possible to improve mechanical properties such as hardness of.

In a resin containing a unit derived from (meth) acrylic acid and a unit derived from (meth) acrylic acid ester having a group having an alicyclic epoxy group, a unit derived from (meth) acrylic acid in the resin. The amount of the above is preferably 1 to 95% by mass, more preferably 10 to 50% by mass. In a resin containing a unit derived from (meth) acrylic acid and a unit derived from a (meth) acrylic acid ester having a group having an alicyclic epoxy group, a group having an alicyclic epoxy group in the resin is used. The amount of the unit derived from the (meth) acrylic acid ester contained is preferably 1 to 95% by mass, more preferably 30 to 70% by mass.

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

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

(E) The mass average molecular weight of the alkali-soluble resin (Mw: measured value by gel permeation chromatography (GPC) in terms of polystyrene. The same applies in the present specification) is preferably 2000 to 200,000, preferably 2000 to 18,000. Is more preferable. Within the above range, the film-forming ability of the photosensitive composition and the developability after exposure tend 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 based on the total mass of the components other than the solvent in the photosensitive composition. It is preferably 15 to 95% by mass, more preferably 35 to 85% by mass, and particularly preferably 50 to 70% by mass.

<Other ingredients>
The photosensitive composition according to the present invention may contain various additives, if necessary. Specifically, solvents, sensitizers, curing accelerators, photocrosslinkers, dispersion aids, fillers, adhesion accelerators, antioxidants, UV absorbers, anti-aggregation agents, thermal polymerization inhibitors, defoamers. , Surfactants and the like are exemplified.

The photosensitive composition according to the present invention may be prepared by dispersing and dissolving each component in a solvent, but if the component (A) is liquid, the solvent may not be used. When a solvent is contained, examples of the solvent used in the photosensitive composition include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol-n-propyl ether, ethylene glycol mono-n-butyl ether, and diethylene glycol monomethyl ether. Diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n- Propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tri. (Poly) alkylene glycol monoalkyl ethers such as propylene glycol monoethyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol mono (Poly) alkylene glycol monoalkyl ether acetates such as ethyl ether acetate; other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone Classes; lactate alkyl esters such as methyl 2-hydroxypropionate and ethyl 2-hydroxypropionate; ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-ethoxy Methyl propionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybuty Lupropionate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl formate, isopentyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate , Methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxobutanoate and other esters; aromatic hydrocarbons such as toluene and xylene; N-methylpyrrolidone , N, N-dimethylformamide, N, N-dimethylacetamide and other amides and the like. These solvents may be used alone or in combination of two or more.

Among the above solvents, propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, and 3-methoxybutyl acetate are the above-mentioned (A). ) And the component (B) are excellently soluble, and the dispersibility of the above-mentioned component (D) can be improved, which is preferable, and propylene glycol monomethyl ether acetate and 3-methoxybutyl acetate are used. Is particularly preferred. The solvent may be appropriately determined according to the intended use of the photosensitive composition, but as an example, about 50 to 900 parts by mass is used with respect to 100 parts by mass of the total mass of the components other than the solvent in the photosensitive composition. Can be mentioned.

Examples of the thermal polymerization inhibitor used in the photosensitive composition according to the present invention include hydroquinone, hydroquinone monoethyl ether and the like. Further, examples of the defoaming agent include silicone-based and fluorine-based compounds, and examples of the surfactant include anionic, cationic and nonionic compounds.

[Method for preparing photosensitive composition]
The photosensitive composition according to the present invention is prepared by mixing all the above components with a stirrer. When the prepared photosensitive composition does not contain an insoluble component such as a pigment, the photosensitive composition may be filtered using a filter so as to be uniform.

≪Manufacturing method of cured product≫
The photosensitive composition described above is cured by being exposed to a desired light source.
Hereinafter, a method of forming a film used as an insulating film or a color filter using a photosensitive composition will be described. The film formed using the photosensitive composition may be patterned, if necessary.

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

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

Next, the coating film is exposed. The light source is not particularly limited, and examples thereof include a high-pressure mercury lamp and an LED, and an LED is preferable from the viewpoint of energy saving and reduction of environmental load. Examples of the wavelength used in the exposure by the LED include those in the UV region such as 365 to 405 nm, more specifically 385 nm, 395 nm, and 405 nm. In general, the energy dose emitted by the LED tends to be small. However, since the photosensitive composition described above contains the above-mentioned (B) photopolymerization initiator and (C) sensitizer and has excellent sensitivity, it is sufficient to perform exposure using an LED as a light source. It is possible to effectively obtain a cured product having good properties. As a result, the productivity of a display device such as a liquid crystal display display panel can be improved.

When the coating film is regioselectively exposed, the exposed film is patterned with a developing solution to form a desired shape. The developing method is not particularly limited, and for example, a dipping method, a spraying method, or the like can be used. The developer is appropriately selected according to the composition of the photosensitive composition. When the photosensitive composition contains an alkali-soluble component such as an alkali-soluble resin, the developer may be an organic developer such as monoethanolamine, diethanolamine or triethanolamine, sodium hydroxide or potassium hydroxide. , Sodium carbonate, ammonia, quaternary ammonium salt and the like can be used.

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

The pattern formed in this way can be suitably used for applications such as an insulating film, pixels constituting a color filter, and a black matrix used in a display device such as a liquid crystal display. Such an insulating film, a color filter, and a display device in which the color filter is used are also one of the present inventions.

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

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

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

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

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

In Examples and Comparative Examples, the following (C) -1 to (C) -4 were used as the (C) sensitizer.
(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-propylfluorene)
6.64 g (40 mmol) of fluorene was dissolved in 27 mL of THF. To the obtained solution, 0.12 g (1.1 mmol) of potassium tert-butoxide, 12.30 g (100 mmol) of 1-bromopropane, and 27 mL of a sodium hydroxide aqueous solution having a concentration of 50% by mass were gradually added under a nitrogen atmosphere. did. The resulting mixture was stirred at 80 ° C. for 3 hours for reaction. After adding 33 g of ethyl acetate and 33 g of water to the mixture after the reaction, the mixture was separated into an organic layer and an aqueous layer. After dehydrating the obtained organic layer with anhydrous sodium sulfate, the solvent was removed from the organic layer using a rotary evaporator to obtain 8.32 g (yield 83%) of 9,9-di-n-propylfluorene. ..

[Synthesis Example 2]
(Synthesis of Compound 1)
4.10 g (16.37 mmol) of 9,9-di-n-propylfluorene and 3.04 g (18.00 mmol) of (2-methylphenyl) acetate chloride in the presence of 2.62 g of aluminum chloride. The reaction was carried out in 50 ml of a dichloromethane solvent under ice-cooling for 1 hour. The reaction mixture was poured into ice water and the organic layer was separated. The recovered organic layer was dried over anhydrous magnesium sulfate and then evaporated. The residue was purified on a silica gel column with an eluent of ethyl acetate / hexane = 1/2 to obtain 5.95 g (15.55 mmol) of 2- (2-methylphenyl) acetyl-9,9-di-n-propylfluorene. It was. 2.95 g (15.55 mmol) of 2- (2-methylphenyl) acetyl-9,9-di-n-propylfluorene and 1.60 g (15.55 mmol) of concentrated hydrochloric acid were added to 2.42 g (2.55 mmol) of isobutyl nitrite. The reaction was carried out in 25 ml of a dimethylformamide solvent in the presence of 23.33 mmol) under ice-cooling for 3 hours. The reaction mixture was evaporated, ethyl acetate was added to the residue, washed with saturated brine, dried over anhydrous magnesium sulfate, and evaporated to 2- [2-methylphenyl (hydroxyimino) acetyl] -9, having the following structure. 4.80 g (11.67 mmol) of 9-di-n-propylfluorene was obtained.

The ¹ H-NMR measurement results of 2- [2-methylphenyl (hydroxyimino) acetyl] -9,9-di-n-propylfluorene were as follows.
^{1 1} H-NMR (600 MHz, CDCl ₃ , ppm): 8.60 (bs, 1H), 8.15 (d, 1H), 8.14 (s, 1H), 7.76-8.00 (m, 2H), 7.26-7.53 (m, 7H), 2.35 (s, 3H), 1.98-2.01 (m, 4H), 0.63-0.67 (m, 10H)

2- [2-Methylphenyl (hydroxyimino) acetyl] -9,9-di-n-propylfluorene 4.80 g (11.67 mmol), acetic anhydride 1.43 g (13.42 mmol), and triethylamine 1.36 g (13.42 mmol) and 45.00 ml of a dimethylformamide solvent were mixed and stirred at 35 ° C. for 3 hours. After cooling to room temperature, ethyl acetate was added to the reaction solution, the mixture was washed with water, dried over anhydrous magnesium sulfate, and evaporated. The residue was purified by silica gel column purification with an eluent of ethyl acetate / hexane = 2/1 to obtain 4.76 g (10.50 mmol, yield 72%) of compound 1. The measurement results of ¹ H-NMR of Compound 1 were as follows.
^{1 1} H-NMR (600 MHz, CDCl ₃ , ppm): 8.25 (d, 1H), 8.22 (s, 1H), 7.83 (d, 1H), 7.81 (dd, 1H), 7 .33-7.40 (m, 3H), 7.26-7.33 (m, 4H), 2.35 (s, 3H), 2.14 (s, 3H), 1.95-2.07 (M, 4H), 0.63-0.66 (m, 10H).

[Synthesis Example 3]
(Synthesis of compound 2)
Intermediate in the same manner as in Synthesis Example 2, except that 3.04 g (18.00 mmol) of (2-methylphenyl) acetate chloride was changed to 3.14 g (18.00 mmol) of 3-cyclohexylpropionate. 2- [Cyclohexylmethyl (hydroxyimino) acetyl] -9,9-di-n-propylfluorene having the following structure and compound 2, 4.96 g (10.80 mmol, yield 75%) were obtained. ..

The ¹ H-NMR measurement results of 2- [cyclohexylmethyl (hydroxyimino) acetyl] -9,9-di-n-propylfluorene were as follows.
^{1 1} H-NMR (600 MHz, CDCl ₃ , ppm): 8.80 (bs, 1H), 7.90-7.98 (m, 2H), 7.70-7.80 (m, 2H), 7. 30-7.40 (m, 3H), 2.72 (d, 2H), 1.88-2.02 (m, 4H), 1.54-1.80 (m, 6H), 0.95- 1.28 (m, 5H), 0.67-0.77 (m, 10H)

The measurement results of ¹ H-NMR of Compound 2 were as follows.
^{1 1} H-NMR (600 MHz, CDCl ₃ , ppm): 8.08-8.14 (m, 2H), 7.70-7.79 (m, 2H), 7.32-7.40 (m, 3H) ), 2.78 (d, 2H), 2.28 (s, 3H), 1.88-2.10 (m, 4H), 1.53-1.78 (m, 6H), 1.00- 1.30 (m, 5H), 0.60-0.77 (m, 10H).

[Examples 1 to 7 and Comparative Examples 1 to 2]
The components (A), (B), and (C) of the types and amounts shown in Table 1 below were uniformly mixed to obtain photosensitive compositions of Examples and Comparative Examples, respectively. ..
The obtained photosensitive composition was dropped onto the substrate with a dropper, and then the droplets of the photosensitive composition were exposed to a commercially available LED light for 15 seconds. With respect to the exposed droplets, it was confirmed whether or not the inside of the droplets was cured, and the curability of each photosensitive composition by LED exposure was evaluated.
The case where the inside of the droplet was cured was judged as ◯, and the case where the droplet was not cured was judged as ×.
Table 1 shows the evaluation results of curability by LED exposure.

From the examples in Table 1, a photosensitive composition containing (A) a photopolymerizable compound, (B) a photopolymerization initiator containing a compound represented by the formula (1), and (C) a sensitizer. Can be seen to be well cured by LED exposure. Further, regarding Examples 1 to 3, coloring was confirmed in Examples 1 and 2, but coloring was not confirmed in Example 3. It was confirmed that even if the amount of the component (C) added was reduced in order to prevent coloring, good curability by LED exposure could be maintained.
On the other hand, according to the comparative example, when the (B) photopolymerizable compound contained in the photosensitive composition does not contain the compound represented by the formula (1), or when the photosensitive composition is represented by the formula (1). It can be seen that even if the compound to be (B) is contained as a photopolymerizable compound, the photosensitive composition is not well cured by LED exposure when (C) a sensitizer is not contained.

Claims (9)

It contains (A) a photopolymerizable compound, (B) a photopolymerization initiator, and (C) a sensitizer.
The photopolymerization initiator according to the following formula (1):
(In the formula (1), R ¹ is a hydrogen atom, a nitro group or a monovalent organic group, and R ² and R ³ have a methyl group, an ethyl group, an n-propyl group, an isopropyl group and a substituent, respectively. It may have a cyclic organic group or a hydrogen atom, and R ² and R ³ may be bonded to each other to form a ring, and R ⁴ is represented by the following formula (R4-1) or (R4-2). ), R ⁵ is a hydrogen atom, an alkyl group having 1 to 11 carbon atoms which may have a substituent, or an aryl group which may have a substituent, and n is an aryl group. It is an integer from 0 to 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 organic groups, respectively, p is 0, and R ⁷ and R ⁸ are present at adjacent positions on the benzene ring. , R ⁷ and R ⁸ may be coupled to each other to form a ring, where q is an integer of 1 to 8, r is an integer of 1 to 5, and s is an integer of 0 to (r + 3). Yes, R ⁹ is an organic group.)
A photosensitive composition comprising a compound represented by. It contains (A) a photopolymerizable compound, (B) a photopolymerization initiator, and (C) a sensitizer.
The photopolymerization initiator according to the following formula (1):
(In the formula (1), R ¹ may have 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, and a substituent. A good phenyl group, a phenoxy group which may have a substituent, a benzoyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, a benzoyloxy group which may have a substituent, It has a phenylalkyl group which may have a substituent, a naphthyl group which may have a substituent, a naphthoxy group which may have a substituent, a naphthoyl group which may have a substituent, and a substituent. A naphthoxycarbonyl group which may have a substituent, a naphthyloxy group which may have a substituent, a naphthylalkyl group which may have a substituent, a heterocyclyl group which may have a substituent, or an organic group of 1 or 2. Amino group, morpholin-1-yl group, or piperazine-1-yl group substituted with, and R ² and R ³ each have a chain alkyl group and a substituent which may have a substituent. It may be a cyclic organic group or a hydrogen atom, and R ² and R ³ may be bonded to each other to form a ring, and R ⁴ is a group represented by the following formula (R4-2). There, ^{R 5} is a methyl group or a phenyl group, n is an integer of 0 to 4, m is than zero or 1 der, provided that when m is 1, ^{R 1} is not a nitro group.)
(In the 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 comprising a compound represented by. It contains (A) a photopolymerizable compound, (B) a photopolymerization initiator, and (C) a sensitizer.
A photosensitive composition, wherein the photopolymerization initiator (B) contains one or more compounds selected from the following compounds 6 to 15, compounds 17 to 22, and compounds 24 to 41.
It contains (A) a photopolymerizable compound, (B) a photopolymerization initiator, and (C) a sensitizer.
A photosensitive composition in which the (B) photopolymerization initiator contains one or more compounds selected from the following compounds 4, compound 5, and compound 23.
In the above formula (1), R ² and R ³ are a chain alkyl group which may have a substituent or a cyclic organic group which may have a substituent, respectively, and R ² and R ³ The photosensitive composition according to claim 2, wherein may be bonded to each other to form a ring. (C) A condensed polycyclic aromatic hydrocarbon ring compound or a condensed polycyclic aromatic having one or more selected from the group consisting of an alkoxy group, a substituted carbonyloxy group, and an oxo group as a substituent. The photosensitive composition according to any one of claims 1 to 5, which is a group heterocyclic compound. A method for producing a cured product, which comprises exposing and curing the photosensitive composition according to any one of claims 1 to 6. The method for producing a cured product according to claim 7, wherein the exposure is performed by an LED. The cured product of the photosensitive composition according to any one of claims 1 to 6.