JP6847580B2 - A photosensitive resin composition for a black column spacer, a black column spacer, a display device, and a method for forming the black column spacer. - Google Patents

Description

The present invention relates to a photosensitive resin composition for a black column spacer, a black column spacer formed using the composition, a display device including the black column spacer, and a method for forming a black column spacer using the composition. ..

In display devices such as liquid crystal display devices and organic EL display devices, spacers are used to keep the distance (cell gap) between two substrates constant.

Conventionally, in order to form a spacer, a method of spraying bead particles serving as a spacer on the entire surface of a substrate has been adopted. However, with this method, it is difficult to form the spacer with high position accuracy, and beads adhere to the pixel display portion, so that there is a problem that the contrast of the image and the display image quality are deteriorated.

Therefore, in order to solve these problems, various methods for forming the spacer with the photosensitive resin composition have been proposed. In this method, a photosensitive resin composition is applied onto a substrate, exposed through a predetermined mask, and then developed to form a column-shaped spacer, which is a predetermined portion other than a pixel display portion. Spacers can only be formed in. Further, in recent years, a so-called black column spacer in which a spacer is provided with a light-shielding property by a light-shielding agent such as carbon black has also been proposed (Patent Document 1 and the like).

Japanese Unexamined Patent Publication No. 2011-170075

However, when the black column spacer is formed by using the photosensitive resin composition described in Patent Document 1 or the like, the film formed by using the photosensitive resin composition is wrinkled or a smooth film is formed. It can be difficult.
If the surface of the black column spacer that is in close contact with the substrate is wrinkled or not smooth, the height of the black column spacer may become uneven and the image quality of the display device may deteriorate.

The present invention has been made in view of the above problems, and is formed by using a photosensitive resin composition for forming a black column spacer, which can form a smooth film without causing wrinkles. It is an object of the present invention to provide a black column spacer, a display device including the black column spacer, and a method for forming a black column spacer using the composition.

The present inventors have conducted extensive research to achieve the above object. As a result, in the photosensitive resin composition containing (A) alkali-soluble resin, (B) photopolymerizable monomer, (C) photopolymerization initiator, and (D) light-shielding agent, (B1) polyfunctional or higher We have found that the above problems can be solved by using a (B) photopolymerizable monomer containing a functional monomer and a (B2) bifunctional monomer and / or a trifunctional monomer, and have completed the present invention. Specifically, the present invention provides the following.

The first aspect of the present invention contains (A) an alkali-soluble resin, (B) a photopolymerizable monomer, (C) a photopolymerization initiator, and (D) a light-shielding agent.
(B) A photosensitive resin composition for a black column spacer, wherein the photopolymerizable monomer contains (B1) a polyfunctional monomer having four or more functionalities and (B2) a bifunctional monomer and / or a trifunctional monomer.

A second aspect of the present invention is a black column spacer made of a cured product of the photosensitive resin composition for a black column spacer according to the first aspect.

A third aspect of the present invention is a display device including a black column spacer according to the second aspect.

A fourth aspect of the present invention comprises forming a photosensitive resin layer by applying the photosensitive resin composition for a black column spacer according to the first aspect onto a substrate.
Exposure of the photosensitive resin layer according to a predetermined spacer pattern,
It is a method of forming a black column spacer including forming a spacer pattern by developing a photosensitive resin layer after exposure.

According to the present invention, a photosensitive resin composition for forming a black column spacer, a black column spacer formed by using the composition, and a display including the black column spacer, which can form a smooth film without causing wrinkles. An apparatus and a method for forming a black column spacer using the composition can be provided.

<< Photosensitive resin composition for black column spacer >>
The photosensitive resin composition for a black column spacer (hereinafter, simply referred to as “photosensitive resin composition”) includes (A) an alkali-soluble resin, (B) a photopolymerizable monomer, (C) a photopolymerization initiator, and ( D) Contains a light-shielding agent.
The (B) photopolymerizable monomer includes (B1) a polyfunctional monomer having four or more functionalities, and (B2) a bifunctional monomer and / or a trifunctional monomer.
When the photosensitive resin composition has the above-mentioned structure, a smooth film can be formed without causing wrinkles, and then a black column spacer can be formed.

By the way, in a display device such as a liquid crystal display device, a substrate such as a TFT substrate in which an element is formed on the substrate is often used. When such a substrate is used, it may be necessary to form a black column spacer on the element formed on the substrate or at a position facing the element of the substrate paired with the substrate on which the element is formed. In such a case, it is necessary to change the height of the black column spacer between the place where the element is formed and the other place in consideration of the height of the element.

When a black column spacer is formed using a photosensitive resin composition having the above structure, a photosensitive resin layer made of the photosensitive resin composition is exposed through a halftone mask to obtain blacks having different heights. Easy to form column spacers.
In this case, the photosensitive resin layer made of the photosensitive resin composition is exposed with a ghi line at a predetermined exposure amount, developed with a 0.05 mass% KOH aqueous solution at 25 ° C. for 70 seconds, and then at 230 ° C. 20 minutes, the black column spacer above thickness 2.5μm obtained by performing post-baking, the predetermined exposure dose, and the film thickness _{H FT} when a 70 mJ / cm ^2, is 6.3mJ / cm ² the difference ΔH between the film thickness _{H HT} when ₍₌ H FT _{-H HT)} is preferably a 2500～6000Å.

Hereinafter, essential or arbitrary components and the like contained in the photosensitive resin composition will be described.

<(A) Alkali-soluble resin>
The photosensitive resin composition according to the present invention contains (A) an alkali-soluble resin.
The alkali-soluble resin is a resin solution having a resin concentration of 20% by mass (solvent: propylene glycol monomethyl ether acetate) to form a resin film having a thickness of 1 μm on a substrate, and a KOH aqueous solution having a concentration of 0.05% by mass for 1 minute. A solvent that dissolves in a film thickness of 0.01 μm or more when immersed.

The alkali-soluble resin (A) is not particularly limited as long as it satisfies the above requirements. Preferable examples of the alkali-soluble resin include (A1) a resin having a cardo structure and (A2) an acrylic resin.

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

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

In the above formula (a-2), R ^a1 independently represents a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a halogen atom, and Ra ² independently represents a hydrogen atom or a methyl group, respectively. , ^{W a} represents a group represented by a single bond or the following formula (a-3).

Further, in the above formula ^{(a-1), Y} a represents the residue obtained by removing dicarboxylic acid anhydride from the acid anhydride group (-CO-O-CO-). 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 formula ^(a-1), Z a represents a residue obtained by removing two acid anhydride groups from a tetracarboxylic acid dianhydride. Examples of the tetracarboxylic dianhydride include pyromellitic dianhydride, benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, biphenyl ether tetracarboxylic dianhydride and the like.
Further, in the above formula (a-1), m represents an integer of 0 to 20.

The mass average molecular weight of the resin having the (A1) cardo structure is preferably 1000 to 40,000, more preferably 2000 to 30,000. Within the above range, sufficient heat resistance and film strength can be obtained while obtaining good developability.

As the (A2) acrylic resin, a resin containing a structural unit derived from (meth) acrylic acid and / or a structural unit derived from (meth) acrylic acid ester is used. The (meth) acrylic acid is acrylic acid or methacrylic acid. The (meth) acrylic acid ester is represented by the following formula (a-4), and is not particularly limited as long as the object of the present invention is not impaired.

In the above formula (a-4), Ra ³ is a hydrogen atom or a methyl group, and Ra ⁴ is a monovalent organic group containing no ethylenic or acetylene unsaturated bond. This organic group may contain a bond or a substituent other than the hydrocarbon group such as a hetero atom in the organic group. Further, the organic group may be linear, branched or cyclic.

The substituent other than a hydrocarbon group in the organic group R ^a4, the effect is not particularly limited as long as they do not impair the present invention, a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a cyano group, an isocyano group, a cyanato group , Isocyanato group, thiocyanato group, isothiocyanato group, silyl group, silanol group, alkoxy group, alkoxycarbonyl group, carbamoyl group, thiocarbamoyl group, nitro group, nitroso group, carboxyl group, carboxylate group, acyl group, acyloxy group, sulfino Group, sulfo group, sulfonate group, phosphino group, phosphinyl group, phosphono group, phosphonato group, hydroxyimino group, alkyl ether group, alkyl thioether group, aryl ether group, aryl thioether group, amino group (-NH ₂ , -NHR, -NRR': R and R'independently indicate a hydrocarbon group) and the like. The hydrogen atom contained in the above substituent may be substituted with a hydrocarbon group. The hydrocarbon group contained in the substituent may be linear, branched or cyclic.

R ^a4 is preferably an alkyl group, an aryl group, an aralkyl group, or a heterocyclic group, and these groups may be substituted with a halogen atom, a hydroxyl group, an alkyl group, or a heterocyclic group. When these groups contain an alkylene moiety, the alkylene moiety may be interrupted by an ether bond, a thioether bond, or an ester bond.

When the alkyl group is linear or branched, the number of carbon atoms thereof is preferably 1 to 20, more preferably 1 to 15, and particularly preferably 1 to 10. Examples of suitable alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, sec. -Pentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, n-nonyl group, isononyl group, n-decyl group, Examples thereof include an isodecyl group.

When the alkyl group is an alicyclic group or a group containing an alicyclic group, suitable alicyclic groups contained in the alkyl group include a cyclopentyl group and a monocyclic alicyclic group such as a cyclohexyl group. Examples thereof include a polycyclic alicyclic group such as an adamantyl group, a norbornyl group, an isobornyl group, a tricyclononyl group, a tricyclodecyl group, and a tetracyclododecyl group.

Preferable examples of the (meth) acrylic acid ester in which the alkyl group is an alicyclic group or an alicyclic group include compounds represented by the following formulas (a4-1) to (a4-7). Can be mentioned. Among these, compounds represented by the following formulas (a4-3) to (a4-8) are preferable because it is easy to obtain a photosensitive resin composition having excellent developability, and the following formula (a4-3) or The compound represented by (a4-4) is more preferable.

In the formula ^{(a4-1) ~ (a4-8),} R a3 represents a hydrogen atom or a methyl ^{group, R a5} represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms , ^Ra6 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. As R ^a5 , a single bond, linear or branched alkylene group, for example, a methylene group, an ethylene group, a propylene group, a tetramethylene group, an ethylethylene group, a pentamethylene group, or a hexamethylene group is preferable. As R ^a6 , for example, a methyl group and an ethyl group are preferable.

The aryl group in R ^a4, preferably those having 6 to 20 carbon atoms, more preferably from 6 to 10 carbon atoms. Specific examples of a suitable aryl group include a phenyl group, a tolyl group, a xsilyl group, an ethylphenyl group, a naphthyl group, an anthryl group, a phenanthryl group and the like.

The aralkyl group in R ^a4, preferably having a carbon number of 7 to 20, more preferably having a carbon number of 7 to 12. Examples of the aralkyl group include a benzyl group, an α-methylbenzyl group, an α, α-dimethylbenzyl group, a phenylethyl group, a phenylethenyl group and the like.

^Examples of the heterocyclic group in Ra4 include a heterocyclic group having a 5-membered ring or more, preferably a 5- to 7-membered ring containing at least one atom of a nitrogen atom, a sulfur atom, and an oxygen atom. This heterocyclic group may contain a fused ring. Examples of the heterocyclic group include a pyrrolyl group, a pyridyl group, a pyrimidyl group, a frill group, a thienyl group and the like.

Further, the (A2) acrylic resin may be obtained by further polymerizing a compound other than (meth) acrylic acid and (meth) acrylic acid ester. Examples of such other compounds include (meth) acrylamides, unsaturated carboxylic acids, allyl compounds, vinyl ethers, vinyl esters, styrenes and the like. These compounds can be used alone or in combination of two or more.

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

Examples of unsaturated carboxylic acids include monocarboxylic acids such as crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, and itaconic acid; and anhydrides of these dicarboxylic acids.

Examples of the allyl compound include allyl esters such as allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, and allyl lactate; allyloxyethanol; and the like. Can be mentioned.

Examples of vinyl ethers include 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 and hydroxyethyl vinyl ether. , Diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether and other alkyl vinyl ethers; vinyl phenyl ether, vinyl trill ether, vinyl chlorophenyl ether, vinyl-2,4-dichlorophenyl ether. , Vinyl aryl ethers such as vinyl naphthyl ethers and vinyl anthranyl ethers; and the like.

Examples of vinyl esters include vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl ballerate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxyacetate, vinyl butoxyacetate, and vinyl fluoride. Examples thereof include enyl acetate, vinyl acetoacetate, vinyl lactate, vinyl-β-phenylbutyrate, vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, vinyl naphthoate and the like.

Examples of styrenes include styrene; methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, isopropylstyrene, butylstyrene, hexylstyrene, cyclohexylstyrene, decylstyrene, benzylstyrene, chloromethylstyrene, trifluoromethylstyrene, ethoxy. Alkylstyrene such as methylstyrene and acetoxymethylstyrene; alkoxystyrene such as methoxystyrene, 4-methoxy-3-methylstyrene and dimethoxystyrene; chlorostyrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, Examples thereof include halostyrene such as dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethylstyrene, and 4-fluoro-3-trifluoromethylstyrene.

The amount of the structural unit derived from (meth) acrylic acid and the amount of the structural unit derived from (meth) acrylic acid ester in the (A2) acrylic resin are not particularly limited as long as the object of the present invention is not impaired. .. The amount of the structural unit derived from (meth) acrylic acid in the (A2) acrylic resin is preferably 5 to 50% by mass, more preferably 10 to 30% by mass, based on the mass of the acrylic resin. The amount of the structural unit derived from the (meth) acrylic acid ester in the (A2) acrylic resin is preferably 10 to 95% by mass, more preferably 30 to 90% by mass, based on the mass of the acrylic resin. ..

The total of the amount of the structural unit derived from (meth) acrylic acid and the amount of the structural unit derived from (meth) acrylic acid ester in the (A2) acrylic resin is particularly large as long as the object of the present invention is not impaired. Although not limited, it is preferably 5 to 100% by mass, more preferably 10 to 50% by mass, based on the mass of the (A2) acrylic resin. The (A2) acrylic resin contains a structural unit derived from (meth) acrylic acid and a structural unit derived from (meth) acrylic acid in such an amount, so that the photosensitive resin has excellent halftone characteristics. It is easy to obtain a sex resin composition. When the photosensitive resin composition is excellent in halftone characteristics, it is easy to form a black calm spacer having a sufficiently different height depending on the light transmittance by exposing through a halftone mask.

As the (A2) acrylic resin, one having an unsaturated bond can also be used. The method for preparing an acrylic resin having an unsaturated bond is not particularly limited, and for example, a resin containing a structural unit derived from (meth) acrylic acid and a structural unit derived from (meth) acrylic acid ester, etc. Examples thereof include a method of reacting at least a part of the carboxyl groups of an acrylic resin containing a carboxyl group with an epoxy group-containing unsaturated compound.

The epoxy group-containing unsaturated compound is not particularly limited as long as it is a compound containing an unsaturated bond and an epoxy group, but is an (a-5) epoxy group-containing unsaturated compound having no alicyclic group, or ( a-6) An alicyclic epoxy group-containing unsaturated compound is preferable.

Examples of the (a-6) epoxy group-containing unsaturated compound having no alicyclic group include glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, 6, (Meta) acrylic acid epoxyalkyl esters such as 7-epoxyheptyl (meth) acrylate; glycidyl α-ethylacrylic acid, glycidyl α-n-propylacrylic acid, glycidyl α-n-butylacrylic acid, α-ethylacrylic acid Α-alkylacrylic acid epoxyalkyl esters such as 6,7-epoxyheptyl; and the like. Among these, glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, and 6,7-epoxyheptyl (meth) acrylate are preferable. These (a-6) epoxy group-containing unsaturated compounds can be used alone or in combination of two or more.

(A-6) In the alicyclic epoxy group-containing unsaturated compound, the alicyclic group constituting the alicyclic epoxy group may be monocyclic or polycyclic. Examples of the monocyclic alicyclic group include a cyclopentyl group and a cyclohexyl group. Examples of the polycyclic alicyclic group include a norbornyl group, an isobornyl group, a tricyclononyl group, a tricyclodecyl group, a tetracyclododecyl group and the like. These (a-6) alicyclic epoxy group-containing unsaturated compounds can be used alone or in combination of two or more.

Specifically, examples of the (a-6) alicyclic epoxy group-containing unsaturated compound include compounds represented by the following formulas (a-6-1) to (a-6-16). Among these, in order to moderately develop the photosensitive resin composition, the compounds represented by the following formulas (a-6-1) to (a-6-6) are preferable, and the following formula (a) is preferable. The compounds represented by −6-1) to (a-6-4) are more preferable.

In the above ^{formulas, R a3} represents a hydrogen atom or a methyl ^{group, R a8} represents a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon ^{atoms, R a9} represents a hydrogen atom or a methyl ^{group, R a10} Indicates a divalent hydrocarbon group having 1 to 10 carbon atoms, and n represents an integer of 0 to 10. As R ^a8 , 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 ¹³ include a methylene group, an ethylene group, a propylene group, a tetramethylene group, an ethylethylene group, a pentamethylene group, a hexamethylene group, a phenylene group, a cyclohexylene group, and -CH ₂ -Ph-CH _2- (Ph is (Indicating a phenylene group) is preferable.

When the (A2) acrylic resin has an unsaturated bond, the amount of the structural unit having an unsaturated bond in the acrylic resin is 1 to 20% by mass with respect to the mass of the (A2) acrylic resin. Is preferable, and 1 to 10% by mass is more preferable. When an acrylic resin containing a structural unit having an unsaturated bond in such an amount is used as the (A2) acrylic resin, it is easy to obtain a photosensitive resin composition having excellent halftone characteristics.

The mass average molecular weight of the acrylic resin (A2) is preferably 2000 to 20000, more preferably 5000 to 30000. Within the above range, the film-forming ability of the photosensitive resin composition and the developability after exposure tend to be easily balanced.

The alkali-soluble resin (A) may contain other conventionally known alkali-soluble resins other than the resin having the cardo structure (A1) and the acrylic resin (A2).
However, the total ratio of the resin having the (A1) cardo structure and the (A2) acrylic resin to the (A) alkali-soluble resin is preferably 80% by mass or more, more preferably 90% by mass or more, and 100. Most preferably by mass.

The ratio of the resin having the cardo structure (A1) to 100 parts by mass of the alkali-soluble resin (A) is preferably 10 to 100 parts by mass, and more preferably 20 to 100 parts by mass.

The content of the alkali-soluble resin (A) is preferably 20 to 85% by mass, more preferably 30 to 75% by mass, based on the solid content of the photosensitive resin composition. Within the above range, it tends to be easy to balance the developability.

<(B) Photopolymerizable monomer>
The photosensitive resin composition contains (B) a photopolymerizable monomer. The (B) photopolymerizable monomer contains (B1) a polyfunctional monomer having four or more functionalities and (B2) a bifunctional monomer and / or a trifunctional monomer in combination.
Hereinafter, the (B) photopolymerizable monomer is also referred to as "(B) component", (B1) a polyfunctional monomer having four or more functionalities is also referred to as "(B1) component", and (B2) a bifunctional monomer and / or a trifunctional monomer. The monomer is also referred to as "(B3) component".
This makes it easy to form a smooth film with a high elastic recovery rate using the photosensitive resin composition. Further, when forming a black column spacer using a photosensitive resin composition, it is easy to form a black column spacer having a sufficiently different height by exposing the photosensitive resin layer with a halftone mask. .. In this case, black column spacers having different heights can be formed by one exposure.

The component (B1) is not particularly limited as long as it contains 4 or more unsaturated double bonds and can be polymerized by exposure in the presence of the (C) photopolymerization initiator. Further, the component (B2) is not particularly limited as long as it is a compound containing two or more unsaturated double bonds and can be polymerized by exposure in the presence of the (C) photopolymerization initiator.

Preferable examples of the component (B1) include ditrimethylolpropane tetra (meth) acrylate, diglycerin tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and pentaerythritol tetra (b1). Examples thereof include meta) acrylates and condensates of polyhydric alcohols and N-methylol (meth) acrylamide.

Suitable examples of the bifunctional monomer among the components (B2) include, for example, (B2-1) di (meth) acrylate of alkanediol having 2 to 6 carbon atoms, (B2-2) -O (-R ^b1). Examples thereof include di (meth) acrylate in which a (meth) acryloyl group is bonded to both ends of a divalent group represented by −O) p−.
R ^b1 is an alkylene group having 2 to 6 carbon atoms, and p is an integer of 2 or more. The ^{number of carbon atoms of R b1} is preferably 2 or 3. The p is preferably 2 or more and 20 or less. When p is an integer of 2 or more, the plurality of R ^b1s may be the same or different.

(B2-1) Examples of the di (meth) acrylate of alcandiol having 2 to 6 carbon atoms include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, and 1,3-propanediol di (meth) acrylate. , 1,4-Butanediol (di (meth) acrylate, 1,3-butanediol di (meth) acrylate (butylene glycol di (meth) acrylate), 1,5-pentanediol di (meth) acrylate, 2,2 Examples thereof include -dimethyl-1,3-propanediol di (meth) acrylate (neopentyl glycol di (meth) acrylate) and 1,6-hexanediol (meth) acrylate.

Examples of the di (meth) acrylate in which a (meth) acryloyl group is bonded to both ends of a divalent group represented by (B2-2) -O (-R ^{b1-O) p- include diethylene glycol di (meth) acrylate and tri.} Ethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate having 5 or more repetitions of ethylene oxy group, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) ) Acrylate, tetrapropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate having 5 or more repetitions of propylene lenoxy group, di (meth) acrylate of ethoxylated polypropylene glycol and the like can be mentioned.
As the di (meth) acrylate of ethoxylated polypropylene glycol, for example, one containing a propyleneoxy unit 12 and an ethyleneoxy unit 6 is available as 1206PE (manufactured by Kowa Company, Ltd.).

In addition to the above, bifunctional monomers that can be suitably used as the component (B2) include glycerindi (meth) acrylate, pentaerythritol di (meth) acrylate, and 2,2-bis (4- (meth) acryloxidiethoxyphenyl). Propane, 2,2-bis (4- (meth) acryloxipolyethoxyphenyl) propane, xylylene glycol di (meth) acrylate, cyclohexane-1,4-dimethanol di (meth) acrylate, cyclohexane-1,3-dimethanoldi ( Meta) acrylate, tricyclodecanedimethanol di (meth) acrylate, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) ) Acrylate, diglycidyl phthalate di (meth) acrylate, reaction product of trimethylhexamethylene diisocyanate, hexamethylene diisocyanate and 2-hydroxyethyl (meth) acrylate, methylenebis (meth) acrylamide, (meth) acrylamide methylene ether, and Examples thereof include 1,3,5- (2'-hydroxyethyl) isocyanurate di (meth) acrylate.

Preferable examples of the trifunctional monomer among the components (B2) are trimethylolpropane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, glycerin tri (meth) acrylate, and di Examples thereof include glycerin tri (meth) acrylate, polyglycerin tri (meth) acrylate, glycerin triglycidyl ether tri (meth) acrylate, and triacrylic formal.

The component (B) may contain, in addition to the components (B1) and (B2), a (B3) monofunctional monomer (hereinafter, also referred to as a component (B3)) as long as the desired effect is not impaired.
The components (B3) 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-hydroxy Ethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 3-phenoxy-2-hydroxypropyl (meth) acrylate, 2- (Meta) acryloyloxy-2-hydroxypropylphthalate, glycerin mono (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dimethylaminoethyl (meth) acrylate, glycidyl (meth) acrylate, 2,2,2-tri Fluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, half (meth) acrylate of phthalic acid derivative and the like can be mentioned. These monofunctional monomers can be used alone or in combination of two or more.

The following alicyclic monofunctional monomers are also preferably used.

In the (B) photopolymerizable monomer, the content of the component (B2) is preferably 80% by mass or less, more preferably 50% by mass or less, based on the total of the mass of the component (B1) and the mass of the component (B2). preferable.
The content of the component (B2) is preferably 1% by mass or more, more preferably 5% by mass or more, based on the total of the mass of the component (B1) and the mass of the component (B2).
The total ratio of the mass of the component (B1) and the mass of the component (B2) to the mass of the (B) photopolymerizable monomer is preferably 70% by mass or more, more preferably 80% by mass or more, and 90% by mass or more. Is particularly preferable, and 100% by mass is most preferable.

The content of the photopolymerizable monomer (B) is preferably 1 to 30% by mass, more preferably 5 to 20% by mass, based on the solid content of the photosensitive resin composition. Within the above range, it tends to be easy to balance sensitivity, developability, and resolution.

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

Specifically, as the photopolymerization initiator, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2- Hydroxy-2-methyl-1-propane-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4-dodecylphenyl) -2-hydroxy-2 -Methylpropan-1-one, bis (4-dimethylaminophenyl) ketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 4-benzoyl-4'-methyldimethylsulfide, 4-dimethylaminobenzoic acid, 4- Methyl dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, butyl 4-dimethylaminobenzoate, 4-dimethylamino-2-ethylhexyl benzoic acid, 4-dimethylamino-2-isoamylbenzoic acid, benzyl-β-methoxyethyl Acetal, benzyldimethylketal, 1-phenyl-1,2-propandion-2- (o-ethoxycarbonyl) oxime, methyl o-benzoyl benzoate, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4- Dimethylthioxanthone, 1-chloro-4-propoxythioxanthone, thioxanthene, 2-chlorothioxanthene, 2,4-diethylthioxanthene, 2-methylthioxanthene, 2-isopropylthioxanthene, 2-ethylanthraquinone, octamethylanthraquinone, 1 , 2-Benz anthraquinone, 2,3-diphenylanthraquinone, azobisisobutyronitrile, benzoylperoxide, cumenehydroperoxide, 2-mercaptobenzoimidal, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2-( o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di (methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5- Diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer, 2,4,5- Triarylimidazole dimer, benzophenone, 2-chlorobenzophenone, 4,4'-bisdimethylaminobenzophenone (ie, Michler's ketone) ), 4,4'-Bisdiethylaminobenzophenone (ie, ethylmichler's ketone), 4,4'-dichlorobenzophenone, 3,3-dimethyl-4-methoxybenzophenone, benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, Benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, benzoin butyl ether, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p-tert- Butylacetophenone, p-dimethylaminoacetophenone, p-tert-butyltrichloroacetophenone, p-tert-butyldichloroacetophenone, α, α-dichloro-4-phenoxyacetophenone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, dibenzos Beron, Pentyl-4-dimethylaminobenzoate, 9-phenylaclydin, 1,7-bis- (9-acridinyl) heptane, 1,5-bis- (9-acridinyl) pentane, 1,3-bis- (9-) Acridinyl) propane, p-methoxytriazine, 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2- [2- (5) -Methylfuran-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (fran-2-yl) ethenyl] -4,6-bis (trichloromethyl)- s-triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4-dimethoxyphenyl) ethenyl ] -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxystyryl) -4, 6-bis (trichloromethyl) -s-triazine, 2- (4-n-butoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-bis-trichloromethyl-6- (3) -Bromo-4-methoxy) phenyl-s-triazine, 2,4-bis-trichloromethyl-6- (2-bromo-4-methoxy) phenyl-s-triazine, 2, 4-Bis-trichloromethyl-6- (3-bromo-4-methoxy) styrylphenyl-s-triazine, 2,4-bis-trichloromethyl-6- (2-bromo-4-methoxy) styrylphenyl-s- Examples thereof include triazine, "IRGACURE OXE02", "IRGACURE OXE01", "IRGACURE 369", "IRGACURE 651", "IRGACURE 907" (trade name: manufactured by BASF), "NCI-831" (trade name: manufactured by ADEKA), and the like. .. These photopolymerization initiators can be used alone or in combination of two or more.

Among these, it is particularly preferable to use an oxime-based photopolymerization initiator in terms of sensitivity, and it is particularly preferable to use an oxime-based photopolymerization initiator having a carbazole skeleton.

A preferred example of the oxime-based photopolymerization initiator is a photopolymerization initiator represented by the following formula (c-1).

In the above formula (c-1), R ^c1 represents a heterocyclic group, a condensed cyclic aromatic group, or an aromatic group which may have a substituent. R ^{c2 to} R ^c4 each independently represent a monovalent organic group.

^Examples of the heterocyclic group in R c1 include a 5-membered ring or more, preferably a 5-membered ring or a 6-membered ring heterocyclic group containing at least one atom of a nitrogen atom, a sulfur atom, and an oxygen atom. Examples of heterocyclic groups include nitrogen-containing 5-membered ring groups such as pyrrolyl group, imidazolyl group and pyrazolyl group; nitrogen-containing 6-membered ring groups such as pyridyl group, pyrazinyl group, pyrimidyl group and pyridadinyl group; Such as nitrogen-containing sulfur-containing groups; nitrogen-containing oxygen-containing groups such as oxazolyl group and isooxazolyl group; sulfur-containing groups such as thienyl group and thiopyranyl group; oxygen-containing groups such as furyl group and pyranyl group; and the like. Among these, those containing one nitrogen atom or one sulfur atom are preferable. This heterocycle may contain a fused ring. Examples of the heterocyclic group containing a fused ring include a benzothienyl group and the like.

^Examples of the fused cyclic aromatic group in R c1 include a naphthyl group, an anthryl group, a phenanthryl group and the like. Moreover, ^{as an aromatic group in R c1} , a phenyl group can be mentioned.

The heterocyclic group, condensed cyclic aromatic group, or aromatic group may have a substituent. In particular, when R ^c1 is an aromatic group, it preferably has a substituent. Examples of such substituents include -NO ₂ , -CN, -SO ₂ R ^c5 , -COR ^c5 , -NR ^c6 R ^c7 , -R ^c8 , -OR ^c8 , ^{-OR c9 -OR c10,} etc. Can be mentioned.

Each of R ^c5 independently represents an alkyl group, which may be substituted with a halogen atom, or may be interrupted by an ether bond, a thioether bond, or an ester bond. The alkyl group in R ^c5 preferably has 1 to 5 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and an isobutyl group.

R ^c6 and R ^c7 each independently represent a hydrogen atom, an alkyl group, or an alkoxy group, and these may be substituted with a halogen atom, in which the alkyl group and the alkylene portion of the alkoxy group are ether-bonded. It may be interrupted by a thioether bond or an ester bond. Further, R ^c6 and R ^c7 may be bonded to form a ring structure. The alkyl group or alkoxy group in R ^c6 and R ^c7 preferably has 1 to 5 carbon atoms, and for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a methoxy group, and an ethoxy group. , Propyl group and the like.

As a ring structure that can be formed by combining ^{R c6} and R ^{c7, a heterocycle can be mentioned.} Examples of this heterocycle include a 5-membered ring containing at least a nitrogen atom, preferably a 5- to 7-membered heterocycle. This heterocycle may contain a fused ring. Examples of the heterocycle include a piperidine ring, a morpholine ring, a thiomorpholine ring and the like. Of these, the morpholine ring is preferred.

R ^c8 represents an alkyl group in which some or all of the hydrogen atoms may be substituted with halogen atoms. The alkyl group in R ^c8 preferably has 1 to 6 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and an isobutyl group.

R ^c9 and R ^c10 each independently represent an alkyl group, which may be substituted with a halogen atom or interrupted by an ether bond, a thioether bond, or an ester bond. The preferred number of carbon atoms and specific examples thereof are the same as those described in R ^c1 above.

Among these, ^{as R c1} , a phenyl group having a pyrrolyl group, a pyridyl group, a thienyl group, a thiopyralyl group, a benzothienyl group, a naphthyl group and a substituent can be mentioned as a preferable example.

In the above formula (c-1), R ^c2 represents a monovalent organic group. As the organic group, groups represented by -R ^c11 , -OR ^c11 , -COR ^c11 , -SR ^c11 , and -NR ^c11 R ^c12 are preferable. R ^c11 and R ^c12 independently represent an alkyl group, an alkenyl group, an aryl group, an aralkyl group, or a heterocyclic group, which may be substituted with a halogen atom, an alkyl group, or a heterocyclic group, and these may be substituted. Of these, the alkylene moiety of the alkyl group and the aralkyl group may be interrupted by an unsaturated bond, an ether bond, a thioether bond or an ester bond. Further, R ^c11 and R ^c12 may be bonded to form a ring structure together with a nitrogen atom.

As the ^{alkyl group in R c11} and R ^c12 , those having 1 to 20 carbon atoms are preferable, and those having 1 to 5 carbon atoms are more preferable. Examples of alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, sec-pentyl group. Group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, n-nonyl group, isononyl group, n-decyl group, isodecyl group. Such as linear or branched group. Moreover, this alkyl group may have a substituent. Examples of those having a substituent include a methoxyethoxyethyl group, an ethoxyethoxyethyl group, a propyroxyethoxyethyl group, a methoxypropyl group and the like.

As the ^{alkenyl group in R c11} and R ^c12 , those having 1 to 20 carbon atoms are preferable, and those having 1 to 5 carbon atoms are more preferable. Examples of the alkenyl group include a linear or branched chain group such as a vinyl group, an allyl group, a butenyl group, an ethenyl group and a propynyl group. Moreover, this alkenyl group may have a substituent. Examples of those having a substituent include a 2- (benzoxazole-2-yl) ethenyl group and the like.

As the ^{aryl group in R c11} and R ^c12 , those having 6 to 20 carbon atoms are preferable, and those having 6 to 10 carbon atoms are more preferable. Examples of the aryl group include a phenyl group, a tolyl group, a xsilyl group, an ethylphenyl group, a naphthyl group, an anthryl group, a phenanthryl group and the like.

As the ^{aralkyl group in R c11} and R ^c12 , those having 7 to 20 carbon atoms are preferable, and those having 7 to 12 carbon atoms are more preferable. Examples of the aralkyl group include a benzyl group, an α-methylbenzyl group, an α, α-dimethylbenzyl group, a phenylethyl group, a phenylethenyl group and the like.

^Examples of the heterocyclic group in R ^c11 and R c12 include a 5-membered ring or more, preferably a 5- to 7-membered heterocyclic group containing at least one atom of a nitrogen atom, a sulfur atom, and an oxygen atom. This heterocyclic group may contain a fused ring. Examples of the heterocyclic group include a pyrrolyl group, a pyridyl group, a pyrimidyl group, a frill group, a thienyl group and the like.

Of these R ^c11 and R ^c12 , the alkylene moiety of the alkyl group and the aralkyl group may be interrupted by an unsaturated bond, an ether bond, a thioether bond or an ester bond.

Further, as a ring structure that can be formed by combining ^{R c11} and R ^{c12, a heterocycle can be mentioned.} Examples of this heterocycle include a 5-membered ring containing at least a nitrogen atom, preferably a 5- to 7-membered heterocycle. This heterocycle may contain a fused ring. Examples of the heterocycle include a piperidine ring, a morpholine ring, a thiomorpholine ring and the like.

Of these, R ^c2 is most preferably a methyl group, an ethyl group, a propyl group, or a phenyl group.

In the above formula (c-1), R ^c3 represents a monovalent organic group. The organic group includes an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms which may have a substituent, a group represented by the following formula (c-2), or a substituent. A heterocyclic group which may have a group is preferable. Examples of the substituent include the same groups as in the case of ^{R c1 described above.} Examples of the aryl group having 6 to 12 carbon atoms include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group and the like.

In the above formula (c-2), R ^c13 represents an alkylene group having 1 to 5 carbon atoms which may be interrupted by an oxygen atom. Examples of such an alkylene group include a methylene group, an ethylene group, an n-propylene group, an isopropylene group, an n-butylene group, an isobutylene group, a sec-butylene group, an n-pentylene group, an isopentylene group and a sec-pentylene group. Examples include linear or branched groups. Of these, R ^c13 is most preferably an isopropylene group.

In the above formula (c-2), R ^c14 represents a monovalent organic group represented by −NR ^c15 R ^{c16 (R c15} and R ^c16 each independently represent a monovalent organic group). Among such organic groups, if ^{the structure of R c14} is represented by the following formula (c-3), it is preferable in that the solubility of the photopolymerization initiator can be improved.

In the above formula (c-3), R ^c17 and R ^c18 each independently represent an alkyl group having 1 to 5 carbon atoms. Examples of such an alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, and sec-. Examples thereof include a pentyl group and a tert-pentyl group. Of these, R ^c17 and R ^c18 are most preferably methyl groups.

^Examples of the heterocyclic group in R c3 include a 5-membered ring or more, preferably a 5-membered ring or a 6-membered ring heterocyclic group containing at least one atom of a nitrogen atom, a sulfur atom, and an oxygen atom. Examples of heterocyclic groups include nitrogen-containing 5-membered ring groups such as pyrrolyl group, imidazolyl group and pyrazolyl group; nitrogen-containing 6-membered ring groups such as pyridyl group, pyrazinyl group, pyrimidyl group and pyridadinyl group; Such as nitrogen-containing sulfur-containing groups; nitrogen-containing oxygen-containing groups such as oxazolyl group and isooxazolyl group; sulfur-containing groups such as thienyl group and thiopyranyl group; oxygen-containing groups such as furyl group and pyranyl group; and the like. Among these, those containing one nitrogen atom or one sulfur atom are preferable. This heterocycle may contain a fused ring. Examples of the heterocyclic group containing a fused ring include a benzothienyl group and the like.

Moreover, the heterocyclic group may have a substituent. Examples of the substituent include the same groups as in the case of ^{R c1 described above.}

In the above formula (c-1), R ^c4 represents a monovalent organic group. Among these, an alkyl group having 1 to 5 carbon atoms is preferable. Examples of such an alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, and sec-. Examples thereof include a pentyl group and a tert-pentyl group. Of these, R ^c4 is most preferably a methyl group.

Further, as another preferable example of the oxime-based photopolymerization initiator, there is a photopolymerization initiator represented by the following formula (c-4) proposed in JP-A-2010-15025.

In the above formula (c-4), R ^c21 and R ^c22 independently represent R ^c31 , OR ^c31 , COR ^c31 , SR ^c31 , CONR ^c32 R ^c33 , or CN, respectively.

R ^c31 , R ^c32 , and R ^c33 independently have a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or carbon. It shows a heterocyclic group having 2 to 20 atoms. Alkyl group, aryl group, arylalkyl group, and a hydrogen atom of the heterocyclic group, further ^{OR c41, COR c41, SR c41} , NR c42 R c43, CONR c42 R c43, -NR c42 -OR c43, -NCOR c42 - ^{OCOR c43, -C (= N-} OR c41) -R c42, -C (= N-OCOR c41) -R c42, CN, halogen ^{atom, -CR c41 = CR c42 R c43} , -CO-CR c41 = CR ^{It may be substituted with c42} R c43, a carboxyl group, or an epoxy group. R ^{c41, R c 42,} and ^{R c43} are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or carbon It shows a heterocyclic group having 2 to 20 atoms.

Methylene groups in the alkylene moiety of the substituents on the ^{R c31, R c32, R c33} , R c41, R c42, and ^{R c43} are unsaturated bond, an ether bond, a thioether bond, an ester bond, a thioester bond, an amide bond, or It may be interrupted 1 to 5 times by a urethane bond, the alkyl moiety of the substituent may have a branched chain, it may be a cyclic alkyl, and the alkyl end of the substituent is an unsaturated bond. At best, ^{also, R c32} and ^{R c33,} and ^{R c 42} and ^{R c43} may form a ring structure, respectively.

In the above formula (c-4), R ^c23 and R ^c24 are independently R ^c31 , OR ^c31 , COR ^c31 , SR ^c31 , CONR ^c32 R ^c33 , NR ^c31 COR ^c32 , OCOR ^c31 , COOR ^c31 , SCOR ^c31. , OCSR ^c31 , COSR ^c31 , CSOR ^c31 , CN, halogen atom, or hydroxyl group. a and b each independently represent an integer of 0 to 4.
R ^c23 is, -X c2 ^- may form a one bonded to the ring structure of the carbon atom of the adjacent benzene ring via, to form a ring structure by bonding with R ^c23 and R ^c24 You may.

In the above formula (c-4), X ^c1 represents a single bond or CO.

In the above formula (c-4), X ^c2 represents an oxygen atom, a sulfur atom, a selenium atom, CR ^c51 R ^c52 , CO, NR ^c53 , or PR ^c54 . R ^c51 , R ^c52 , R ^c53 , and R ^c54 independently represent R ^c31 , OR ^c31 , COR ^c31 , SR ^c31 , CONR ^c32 R ^c33 , or CN, respectively. R ^c51 , R ^c53 , and R ^c54 may independently form a ring structure together with either adjacent benzene ring.

In the formula ^(c-4), as the alkyl group in ^{R c31, R c32, R c33} , R c41, R c42, and ^{R c43,} methyl group, ethyl group, n- propyl group, an isopropyl group, n- butyl Examples include groups, isobutyl groups, sec-butyl groups, tert-butyl groups, n-pentyl groups, isopentyl groups, sec-pentyl groups, tert-pentyl groups and the like.

In the formula ^(c-4), the aryl group in ^{R c31, R c32, R c33} , R c41, R c42, and ^{R c43,} a phenyl group, a tolyl group, xylyl group, ethylphenyl group, a chlorophenyl group, a naphthyl Examples include a group, an anthryl group, a phenylslenyl group and the like.

In the formula ^(c-4), the aryl group in ^{R c31, R c32, R c33} , R c41, R c42, and ^{R c43,} benzyl group, chlorobenzyl group, alpha-methylbenzyl, alpha, alpha -Includes dimethylbenzyl group, phenylethyl group, phenylethenyl group and the like.

In the formula ^(c-4), as the heterocyclic group in ^{R c31, R c32, R c33} , R c41, R c42, and ^{R c43,} pyridyl group, pyrimidyl group, furyl group, a thienyl group, a tetrahydrofuryl group, Dioxoranyl group, benzoxazole-2-yl group, tetrahydropyranyl group, pyrrolidyl group, imidazolidyl group, pyrazolydyl group, thiazolidyl group, isothiazolydyl group, oxazolidyl group, isooxazoledyl group, piperidyl group, piperazyl group, morpholinyl group, etc. A 5- to 7-membered ring is preferably mentioned.

In the formula ^(c-4), the ring and ^{R c32} and ^{R c33} may be ^formed by combining the ring and the ^{R c 42} and ^{R c43} may be formed by bonding, and together with the benzene ring ^{to which R c23} is adjacent Examples of the ring that can be formed include a 5- to 7-membered ring such as a cyclopentane ring, a cyclohexane ring, a cyclopentene ring, a benzene ring, a piperidine ring, a morpholine ring, a lactone ring, and a lactam ring.
When X ^c2 is NR ^c53 and R ^c23 is bonded to one of the carbon atoms of the adjacent benzene ring to form a 5-membered ring structure together with ^{X c2, the photopolymerization initiator has a carbazole skeleton.} Become.

In the formula ^(c-4), as the halogen atom in ^{R c31, R c32, R c33} , R c41, R c42, and ^{R c43} which may be substituted halogen atoms, and ^{R c24, R c25,} fluorine atom , Chlorine atom, bromine atom, iodine atom.

The methylene group of the alkylene moiety of the substituent may be interrupted 1 to 5 times by an unsaturated bond, an ether bond, a thioether bond, an ester bond, a thioester bond, an amide bond, or a urethane bond. In this case, the interfering binding group may be one kind or two or more kinds of groups, and in the case of a group that can be interrupted continuously, two or more kinds may be interrupted continuously. Further, the alkyl moiety of the substituent may have a branched chain, may be a cyclic alkyl, and the alkyl terminal of the substituent may be an unsaturated bond.

A compound represented by the following formula (c-5) is also preferable as the photopolymerization initiator (C).

（Ｒ^１は水素原子、ニトロ基又は１価の有機基であり、Ｒ^２及びＲ^３は、それぞれ、置換基を有してもよい鎖状アルキル基、置換基を有してもよい環状有機基、又は水素原子であり、Ｒ^２とＲ^３とは相互に結合して環を形成してもよく、Ｒ^４は１価の有機基であり、Ｒ^５は、水素原子、置換基を有してもよい炭素原子数１〜１１のアルキル基、又は置換基を有してもよいアリール基であり、ｎは０〜４の整数であり、ｍは０又は１である。）

(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 (c-5), 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 (c-5), which is different from the 6-membered aromatic ring attached to the group represented by _{− (CO) m −.} Wherein (c-5), the binding position relative to the fluorene ring of R ¹ is not particularly limited. When the compound represented by the formula (c-5) has one or more of R ^1, from such that the synthesis of compounds of formula (c-5) is easy, of one or more of R ¹ One is preferably attached to the 2-position in the fluorene ring. 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, 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. 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, 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-octyloxy group, isooctyloxy group, sec-octyloxyl group , Trt-octyloxy group, n-nonyloxy group, isononyloxy group, n-decyloxy group, 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 a methoxyethoxy group, an ethoxyethoxy group, a methoxyethoxyethoxy group, an ethoxyethoxyethoxy group, a propyloxyethoxyethoxy group, a 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, and 2, 2-Dimethylpropanoyloxy group, n-hexanoyloxy group, n-heptanoyloxy group, n-octanoyloxy group, n-nonanoyloxy group, n-decanoyloxy group, n-undecanoyloxy group, n -Dodecanoyloxy group, n-tridecanoyloxy group, n-tetradecanoyloxy group, n-pentadecanoyloxy group, n-hexadecanoyloxy group 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-octyloxylcarbonyl 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, 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. Heterocyclyl group. When the heterocyclyl group is a fused 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 such a heterocyclyl group include furan, thiophene, pyrrol, oxazole, isooxazole, thiazole, thiadiazol, 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 has 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, the naphthyl group, and the 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 are 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, R ¹ is preferably 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 (c-5), 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, 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 number of preferred 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 a carbon-carbon bond? , 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 fused 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 such a heterocyclyl group include furan, thiophene, pyrrol, oxazole, isooxazole, thiazole, thiadiazol, 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 benzene ring, naphthalene ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, furan ring, thiophene ring, pyrrole ring, and 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, 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, 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 alkoxycarbonyl groups are similar to the alkoxycarbonyl groups that ^{R 2} and R ^{3 have as substituents.}

Preferable specific examples of R ² and R ³ include alkyl groups such as ethyl group, n-propyl group, n-butyl group, n-hexyl group, n-heptyl group, and n-octyl group; 2-methoxyethyl. Group, 3-methoxy-n-propyl group, 4-methoxy-n-butyl group, 5-methoxy-n-pentyl group, 6-methoxy-n-hexyl group, 7-methoxy-n-heptyl group, 8-methoxy -N-octyl group, 2-ethoxyethyl group, 3-ethoxy-n-propyl group, 4-ethoxy-n-butyl group, 5-ethoxy-n-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-methoxycarbonyl-n-hexyl group, 7-methoxycarbonyl-n-heptyl group, 8-methoxycarbonyl-n-octyl group, 2-ethoxy Carbonyl ethyl group, 3-ethoxycarbonyl-n-propyl group, 4-ethoxycarbonyl-n-butyl group, 5-ethoxycarbonyl-n-pentyl group, 6-ethoxycarbonyl-n-hexyl group, 7-ethoxyka Alkoxycarbonylalkyl groups such as rubonyl-n-heptyl group and 8-ethoxycarbonyl-n-octyl group; 2-chloroethyl group, 3-chloro-n-propyl group, 4-chloro-n-butyl group, 5-chloro -N-pentyl group, 6-chloro-n-hexyl group, 7-chloro-n-heptyl group, 8-chloro-n-octyl group, 2-bromoethyl group, 3-bromo-n-propyl group, 4-bromo -N-butyl group, 5-bromo-n-pentyl group, 6-bromo-n-hexyl group, 7-bromo-n-heptyl group, 8-bromo-n-octyl group, 3,3,3-trifluoro Examples thereof include a propyl group and an alkyl halide group such as a 3,3,4,4,5,5,5-heptafluoro-n-pentyl group.

Among the above-mentioned suitable groups as R ² and R ³ , the preferred groups 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, a β-naphthylmethyl group and the like.

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.

（式（Ｒ４−１）及び（Ｒ４−２）中、Ｒ^７及びＲ^８はそれぞれ有機基であり、ｐは０〜４の整数であり、Ｒ^７及びＲ^８がベンゼン環上の隣接する位置に存在する場合、Ｒ^７とＲ^８とが互いに結合して環を形成してもよく、ｑは１〜８の整数であり、ｒは１〜５の整数であり、ｓは０〜（ｒ＋３）の整数であり、Ｒ^９は有機基である。） 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. 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. As R ⁹ , a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group and the like are preferably exemplified, and among these, a methyl group is more preferable.

In the 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.

In formula (c-5), R ⁵ is a hydrogen atom, an alkyl group having 1 to 11 carbon atoms which may have a substituent, or an aryl group which may have a substituent. As 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.

Wherein (c-5), as is 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 preferable Illustrated, among these, a methyl group or a phenyl group is more preferable.

The compound represented by the formula (c-5) 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 From the viewpoint of improving characteristics such as rate, the combination of (i) above is preferable, and the combination satisfying (i) and (ii) or (iii) is more preferable.

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.

（Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、ｍ、及びｎは、式（ｃ−５）と同様である。ｎは０〜４の整数であり、ｍは０又は１である。） The method for producing the compound represented by the formula (c-5) is not particularly limited. The compound represented by the formula (c-5) preferably represents the oxime group (= N-OH) contained in the compound represented by the following formula (c-6) by = NO-COR ⁵ . It is produced by a method including a step of converting to an oxime ester group to be produced. R ⁵ is the same as ^{R 5} in the formula (c-5).

(R ¹ , R ² , R ³ , R ⁴ , m, and n are the same as in equation (c-5). N is an integer from 0 to 4, and m is 0 or 1.)

Therefore, the compound represented by the above formula (c-6) is useful as an intermediate for the synthesis of the compound represented by the formula (c-5).

The method for converting an oxime group (= N-OH) into an oxime ester group represented by ^{= NO-COR 5 is not particularly limited.} Typically, a method of reacting a hydroxyl group in an oxime group with an acylating agent that gives an acyl group represented by ^{−COR 5 can be mentioned.} 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 (c-5) 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 at which the acyl group is introduced on the fluorene ring can be selected by appropriately changing the conditions of the Friedel-Crafts reaction or by protecting and deprotecting other positions at 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.} The oxime compound represented by the formula (1-4) is obtained. 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 the formulas (1-1), (1-2), (1-3), (1-4), (1-5), (1-6), and (1-7), R ¹ , ^{R 2, R 3, R 4} , and ^{R 5} are the same as the formula (c-5).

^{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 the formulas (1-2), (1-3), and (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>

The compound represented by the formula (c-5) can be synthesized, for example, according to the following scheme 2 when m is 1. 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. The acylating agent of the formula (1-8): carboxylic acid halide is preferably represented by ^{_{Hal-CO-CH 2 -R 4}} . 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), the acid anhydride represented by the following formula (2-4) ((R ⁵ CO) ₂ O), or the following general formula (2-5). By reacting with an acid halide represented by (R ⁵ COHal, Hal is a halogen atom), a compound represented by the following formula (2-6) can be obtained. In the following formulas (2-1), (2-3), (2-4), (2-5), and (2-6), R ¹ , R ² , R ³ , R ⁴ , and R ⁵ is the same as in the formula (c-5).
When m is 1, there is a tendency that the generation of foreign substances in the pattern formed by using the photosensitive resin composition containing the compound represented by the formula (c-5) can be further reduced.

Further, in Scheme 2, Formula (1-8), the formula (2-1), and ^{R 4} included in each formula (2-3) may have be the same or different. ^{That is, R 4} in formulas (1-8), formula (2-1), and formula (2-3) may undergo chemical modification in the synthetic process represented as Scheme 2. 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 (c-5) include the following compounds 1 to 41.

The content of the photopolymerization initiator (C) is preferably 0.5 to 20 parts by mass with respect to 100 parts by mass of the solid content of the photosensitive resin composition. Within the above range, sufficient heat resistance and chemical resistance can be obtained, the coating film forming ability can be improved, and curing defects can be suppressed.

<(D) Shading agent>
The photosensitive resin composition according to the present invention contains a light-shielding agent. It is preferable to use a black pigment as the light-shielding agent. Black pigments used as light-shielding agents include carbon black, perylene pigments, silver-tin alloys, titanium black, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, silver and other metal oxides, and composite oxidation. Various pigments can be mentioned regardless of organic or inorganic substances such as substances, metal sulfides, metal sulfates or metal carbonates. Two or more of these black pigments can be used in combination.

The light-shielding agent (D) preferably contains a perylene-based pigment because it is easy to improve the adhesion of the black column spacer formed by using the photosensitive resin composition to the substrate. The content of the perylene pigment in the (D) light-shielding agent is preferably 85% by mass or more, preferably 90% by mass or more, particularly preferably 100% by mass or more, based on the total mass of the (D) light-shielding agent. ..

Specific examples of the perylene-based pigment include a perylene-based pigment represented by the following general formula (d-1) and a perylene-based pigment represented by the following general formula (d-2). As commercially available products, product names K0084 and K0083 manufactured by BASF, Pigment Black 21, 30, 31, 32, 33, 34, and the like can be preferably used.

（式（ｄ−１）中、Ｒ^ｄ１、Ｒ^ｄ２は、それぞれ独立して炭素原子数１〜３のアルキレン基を表し、Ｒ^ｄ３、Ｒ^ｄ４は、それぞれ独立に水素原子、水酸基、メトキシ基又はアセチル基を表す。）

(In the formula (d-1), R ^d1 and R ^d2 independently represent an alkylene group having 1 to 3 carbon atoms, and R ^d3 and R ^d4 independently represent a hydrogen atom, a hydroxyl group, a methoxy group or a group. Represents an acetyl group.)

（式（ｄ−２）中、Ｒ^ｄ５、Ｒ^ｄ６は、それぞれ独立して炭素原子数１〜７のアルキレン基を表す。）

(In the formula (d-2), R ^d5 and R ^d6 each independently represent an alkylene group having 1 to 7 carbon atoms.)

The compound represented by the general formula (d-1) and the compound represented by the general formula (d-2) are described in, for example, Japanese Patent Application Laid-Open No. 62-1753 and Japanese Patent Application Laid-Open No. 63-26784. Can be synthesized using. That is, a heating reaction is carried out in water or an organic solvent using perylene-3,5,9,10-tetracarboxylic acid or its dianhydride or amines as raw materials. Then, the desired product can be obtained by reprecipitating the obtained crude product in sulfuric acid or recrystallizing it in water, an organic solvent or a mixed solvent thereof.

Further, in order to satisfactorily disperse the perylene-based pigment in the photosensitive resin composition, the average particle size of the perylene-based pigment is preferably 10 to 1000 nm.

Further, as the (D) light-shielding agent, a black pigment and a pigment having a hue such as red, blue, green, yellow, or purple can be used in combination for the purpose of adjusting the color tone or the like. A dye having a hue other than the black pigment can be appropriately selected from known dyes and used. As for the pigments having hues other than the black pigment, the amount of the other pigments used is preferably 15% by mass or less, more preferably 10% by mass or less, based on the total mass of the (D) light-shielding agent.

The content of the light-shielding agent (D) in the photosensitive resin composition can be appropriately selected within a range that does not impair the object of the present invention, and is typically 5 to 50% by mass with respect to the solid content of the photosensitive resin composition. % Is preferable. By using an amount of the light-shielding agent in such a range, the light-shielding property of the black column spacer obtained by using the photosensitive resin composition is improved, and the exposure failure and curing failure when the photosensitive resin composition is exposed are improved. Is easy to suppress.

<(E) Light absorber>
The photosensitive resin composition according to the present invention preferably contains a light absorber.
The light absorber is not particularly limited, and an agent capable of absorbing exposure light can be used, but an agent capable of absorbing light in a wavelength region of 200 to 450 nm is particularly preferable. For example, naphthalene compounds, dinaphthalene compounds, anthracene compounds, phenanthroline compounds, dyes and the like can be mentioned.

Specifically, lauric acid derivatives such as 2-ethylhexyl silicate, 2-ethylhexyl paramethoxysilicate, isopropyl methoxycinnamate, and isoamyl methoxycinnamate; α-naphthal, β-naphthol, α-naphtholmethyl ether, α −naphtholethyl ether, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8 Naphthalene derivatives such as −dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene; anthracenes such as anthracene and 9,10-dihydroxyanthracene and their derivatives; azo dyes, benzophenone-based Dyes, aminoketone dyes, quinoline dyes, anthraquinone dyes, diphenylcyanoacrylate dyes, triazine dyes, p-aminobenzoic acid dyes and the like; and the like can be mentioned. Among these, it is preferable to use a cinnamic acid derivative and a naphthalene derivative, and it is particularly preferable to use a cinnamic acid derivative. These light absorbers can be used alone or in combination of two or more.

The content of the light absorber (E) is preferably 0.5 to 20 parts by mass with respect to 100 parts by mass of the solid content of the photosensitive resin composition. Within the above range, the rate of change in film thickness when the exposure amount is changed can be increased while maintaining good fracture strength after curing.

<(S) Organic solvent>
The photosensitive resin composition according to the present invention preferably contains an organic solvent for dilution. Examples of the organic solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and 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, di (Poly) alkylene glycols such as propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, and tripropylene glycol monoethyl ether. Monoalkyl ethers; (poly) alkylene glycol monoalkyl such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, etc. Ether acetates; 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; methyl 2-hydroxypropionate, 2-hydroxy Lactate alkyl esters such as ethyl propionate; ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethoxy Ethyl acetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate, n acetate -Propyl, 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, pyruvate Other esters such as ethyl, n-propyl pyruvate, methyl acetoacetamide, ethyl acetoacetate, ethyl 2-oxobutanoate; aromatic hydrocarbons such as toluene and xylene; N-methyl-2-pyrrolidone, N, N -Dimethylformamide, N, N-dimethylacetamide, N, N-dimethylisobutylamide, N, N-diethylacetamide, N, N-diethylformamide, N-methylcaprolactam, 1,3-dimethyl-2-imidazolidinone, Examples thereof include pyridine and nitrogen-containing polar organic solvents such as N, N, N', N'-tetramethylurea.

Among these, alkylene glycol monoalkyl ethers, alkylene glycol monoalkyl ether acetates, the above-mentioned other ethers, lactic acid alkyl esters, and the above-mentioned other esters are preferable, and alkylene glycol monoalkyl ether acetates, the above-mentioned. Other ethers and other esters described above are more preferred. Further, it is also preferable that the (S) organic solvent contains a nitrogen-containing polar organic solvent in terms of the solubility of each component and the dispersibility of the (D) light-shielding agent. As the nitrogen-containing polar organic solvent, N, N, N', N'-tetramethylurea are preferable.
These solvents can be used alone or in combination of two or more.

The content of the organic solvent (S) is preferably such that the solid content concentration of the photosensitive resin composition is 1 to 50% by mass, and more preferably 5 to 30% by mass.

<Other ingredients>
The photosensitive resin composition according to the present invention may contain various additives, if necessary. Examples of the additive include a sensitizer, a curing accelerator, a filler, an adhesion accelerator, an antioxidant, an antioxidant, a thermal polymerization inhibitor, a defoaming agent, a surfactant and the like.

<Method of preparing photosensitive resin composition>
The photosensitive resin composition according to the present invention is prepared by mixing each of the above components with a stirrer. In addition, you may filter using a membrane filter or the like so that the prepared photosensitive resin composition becomes uniform.

≪Formation method of spacer, display device, black column spacer≫
The black column spacer according to the present invention is the same as the conventional black column spacer except that it is formed from the photosensitive resin composition according to the present invention. Further, the display device according to the present invention is the same as the conventional display device except that it includes a spacer formed from the photosensitive resin composition according to the present invention. In the following, only the method of forming the black column spacer will be described.

A suitable method for forming the black column spacer is
The formation of a photosensitive resin layer (coating step) by applying the photosensitive resin composition according to the present invention onto a substrate, and
Exposure of the photosensitive resin layer according to a predetermined spacer pattern (exposure process),
It includes forming a spacer pattern (development step) by developing the photosensitive resin layer after exposure.

First, in the coating process, a contact transfer type coating device such as a roll coater, a reverse coater, or a bar coater, a spinner (rotary coating device), or a non-contact type such as a curtain flow coater is placed on a substrate on which a black column spacer should be formed. The photosensitive resin composition according to the present invention is applied using a coating device, and if necessary, the solvent is removed by drying to form a photosensitive resin layer.

Next, in the exposure step, the photosensitive resin layer is irradiated with active energy rays such as ultraviolet rays and excimer laser light via a negative mask, and the photosensitive resin layer is partially exposed according to the pattern of the black column spacer. To do. For the exposure, a light source that emits ultraviolet rays such as a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a xenon lamp, and a carbon arc lamp can be used. The amount of exposure varies depending on the composition of the photosensitive resin composition, but is preferably about 10 to ^{600 mJ / cm 2, for example.}

When the substrate is a TFT substrate or the like in which an element is formed on the substrate, a black column spacer is formed on the element or at a position facing the element of the substrate paired with the substrate on which the element is formed. It may be necessary. In such a case, it is necessary to change the height of the black column spacer between the place where the element is formed and the other place in consideration of the height of the element. Therefore, in such a case, it is preferable to perform exposure through a halftone mask. By using the photosensitive resin composition according to the present invention, black column spacers having different heights can be easily formed by performing exposure through a halftone mask.

Next, in the developing step, a black column spacer is formed by developing the photosensitive resin layer after exposure with a developing solution. The developing method is not particularly limited, and a dipping method, a spraying method, or the like can be used. Specific examples of the developing solution include organic ones such as monoethanolamine, diethanolamine and triethanolamine, and aqueous solutions such as sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia and quaternary ammonium salts.

Then, the developed black column spacer is post-baked and heat-cured. Post-baking is preferably at 150-250 ° C. for 15-60 minutes.

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

<Examples 1 to 5 and Comparative Examples 1 to 4>
(A) 5 parts by mass of alkali-soluble resin, 2 parts by mass of (B1) component, 0.8 parts by mass of (B2) component or (B3) component, and 2.5 parts by mass of (C) photopolymerization initiator. A photosensitive resin in which a pigment dispersion (pigment: perylene black 4.64 parts by mass) and 0.05 parts by mass of α-naphthol are dispersed and dissolved in a solvent so that the solid content is 20% by mass. The composition was prepared.

The composition of the solvent in the photosensitive composition is such that methoxybutyl acetate is 10% by mass, N, N, N', N'-tetramethiurea is 10% by mass, and propylene glycol monomethyl ether acetate is 80% by mass. Adjusted to.
The following components were used as the components of the photosensitive resin composition.

((A) Alkali-soluble resin)
The following resin A-1 was used as the alkali-soluble resin (A).
A-1: Resin obtained by the following production method (solid content 55%, solvent: 3-methoxybutyl acetate)

((B) Photopolymerizable Monomer)
As the component (B1), dipentaerythritol hexaacrylate was used.
As the component (B2), the compounds shown in Table 1 were used. The compounds listed in Table 1 are as follows.
B2-1: Tetraethylene glycol dimethacrylate B2-2: Dimethacrylate of ethoxylated polypropylene glycol (including propyleneoxy unit 12 and ethyleneoxy unit 6; 1206PE (manufactured by Kowa Co., Ltd.))
B2-3: Diacrylate compound having the following structure B2-4: 1,3,5- (2'-hydroxyethyl) isocyanuric acid Diacrylate B2-5: 1,3,5- (2'-hydroxyethyl) isocyanuric acid Triacrylate

As the component (B3), the compounds shown in Table 1 were used. The components (B3) shown in Table 1, B3-1, B3-2, B3-3, and B3-4 are shown below.

((C) Photopolymerization Initiator)
(C) The following C1 and C2 were used as the photopolymerization initiator. The amount of C1 used was 1.5 parts by mass, and the amount of C2 used was 1 part by mass.

The method for synthesizing the resin (A-1) is as follows.
First, in a 500 ml four-necked flask, 235 g of bisphenol fluoride type epoxy resin (epoxy equivalent 235), 110 mg of tetramethylammonium chloride, 100 mg of 2,6-di-tert-butyl-4-methylphenol, and 72.0 g of acrylic acid. Was charged, and the mixture was heated and dissolved at 90 to 100 ° C. while blowing air at a rate of 25 ml / min. Next, the temperature of the solution was gradually raised while the solution was cloudy, and the solution was heated to 120 ° C. to completely dissolve the solution. At this time, the solution gradually became transparent and viscous, but stirring was continued as it was. During this period, the acid value was measured, and heating and stirring were continued until the acid value became less than 1.0 mgKOH / g. It took 12 hours for the acid value to reach the target value. Then, it was cooled to room temperature to obtain a colorless and transparent solid bisphenol fluorene type epoxy acrylate represented by the following formula (a-7).

Next, 600 g of 3-methoxybutyl acetate was added to 307.0 g of the above-mentioned bisphenol fluorene type epoxy acrylate thus obtained to dissolve it, and then 80.5 g of benzophenone tetracarboxylic dianhydride and 1 g of tetraethylammonium bromide were added. The mixture was mixed, gradually heated, and reacted at 110 to 115 ° C. for 4 hours. After confirming the disappearance of the acid anhydride group, 38.0 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed and reacted at 90 ° C. for 6 hours to obtain a resin (A-1). The disappearance of the acid anhydride group was confirmed by the IR spectrum.
The resin (A-1) corresponds to the resin represented by the above formula (a-1).

Using the obtained photosensitive resin composition, the halftone characteristic (ΔH) and the pattern adhesion were evaluated according to the following method. The evaluation results are shown in Table 1.

<Surface roughness Ra evaluation method>
An atomic force microscope (“AFM (device name)”, manufactured by SII Nanotechnology) was used for a cured film cured at ^{an exposure rate of 70 mJ / cm 2} by the method described in the halftone characterization method described later. Surface roughness (Ra) was evaluated. The results are shown in Table 1.

<Elastic recovery rate evaluation method>
^{The elastic recovery rate of the cured film cured at an exposure of 70 mJ / cm 2} was measured with a hardness tester FISCHERSCOPE HM2000 (manufactured by Fisher Instruments) by the method described in the halftone characteristic evaluation method described later. The results are shown in Table 1.

<Halftone characterization method>
After applying the photosensitive resin composition on a glass substrate of 10 cm × 10 cm, it was dried at 100 ° C. for 120 seconds to form a photosensitive resin layer having a film thickness of 3.5 μm. In the same manner, a total of two photosensitive resin layers formed on the glass substrate were prepared.
^{Next, this photosensitive resin layer is exposed to one photosensitive layer resin layer at an exposure amount of 70 mJ / cm 2} by using an exposure machine using a high-pressure mercury lamp via a negative mask having a mask size of 30 μm. The sex resin layer was selectively exposed at an exposure amount of 6.3 mJ / cm ^2.
The exposed photosensitive resin layer was spray-developed at 25 ° C. for 70 seconds using a KOH aqueous solution having a concentration of 0.04% by mass to obtain a black column spacer.
The obtained black column spacer was post-baked at 230 ° C. for 20 minutes.
Exposure 70 mJ / cm ² of black column spacer formed in a thickness _{(height, H FT)} and the exposure dose 6.3mJ / cm ² the thickness of the black column spacer formed in (a _{height, H HT)} Was measured, and the value of ΔH was determined according to the following equation.
ΔH (Å) = H _FT- H _HT
When the value of ΔH is 2500 Å or more, it is judged that the halftone characteristic is good.

From the examples in Table 1, when the photosensitive resin composition contains (B1) a polyfunctional monomer having four or more functionalities and (B2) a bifunctional monomer and / or a trifunctional monomer, the elastic restoration rate is high and wrinkles are formed. It can be seen that a black column spacer that is unlikely to occur can be formed.
In addition, the photosensitive resin composition of Examples is also excellent in halftone characteristics.

On the other hand, from the comparative example, the photosensitive resin composition contains (B1) a polyfunctional monomer having a tetrafunctionality or higher and (B3) a monofunctional monomer in combination, or contains only a polyfunctional monomer having a (B1) tetrafunctionality or higher. When it is contained, it can be seen that the elastic recovery rate of the photosensitive resin composition is low and the halftone characteristics are also inferior.

Claims (7)

Contains (A) alkali-soluble resin, (B) photopolymerizable monomer, (C) photopolymerization initiator, and (D) light-shielding agent.
(B) the photopolymerizable monomer is, (B1) and dipentaerythritol hexa (meth) acrylate, (B2) 2-functional monomer and / or 3-functional monomer and a free body (provided that the following formula (I) and (V ), The photosensitive resin composition for a black column spacer , wherein the light-shielding agent (D) contains a perylene-based black pigment.

(In the formula (I), R ¹ is an alkylene group having 2 to 4 carbon atoms, and X is the following formula (II):

It is a group represented by or a hydrogen atom, R ² is an alkylene group having 2 to 4 carbon atoms, and R ³ is the following formula (III):

P is an integer of 0 to 4, q is an integer of 0 to 5, r is 1, and the formula (II) out of the six Xs in the formula (I). The number of groups represented by is an integer of 4 to 6, and the groups represented by a plurality of formulas (II) in formula (I) may be the same or different, and formula (I) may be used. ) represented by the compounds of - (R 1 ^-O) - number of divalent and represented by - (R 2 ^-O) - the sum of the divalent numbers represented by one or more There, in the formula (III), ^{R 4} represents a hydrogen atom or a methyl group. )

(In formula (V), R independently represents -H, -F, or -CH ₃ , X represents a substituent having an acrylic group, a methacrylic group, or a vinyl group, and Y independently represents -H, -F, -OH, -CH ₃ , -CH ₂ OH, or -X.) The photosensitive resin composition for a black column spacer according to claim 1, further comprising (E) a light absorber. The photosensitive resin layer composed of the photosensitive resin composition for a black column spacer is exposed with a ghi line at a predetermined exposure amount, developed with a 0.05 mass% KOH aqueous solution at 25 ° C. for 70 seconds, and then 230. ℃ for 20 minutes, the black column spacer above thickness 2.5μm obtained by performing post-baking, the predetermined exposure amount, and the film thickness _{H FT} when a 70mJ / cm ^2, 6.3mJ / cm the difference between the film thickness _{H HT} when a ^{_{2 ΔH (= H FT -H HT}} ) black column spacer photosensitive resin composition according to claim 1 or 2 is 2500～6000Å. A black column spacer comprising a cured product of the photosensitive resin composition for a black column spacer according to any one of claims 1 to 3. A display device including the black column spacer according to claim 4. The formation of a photosensitive resin layer by applying the photosensitive resin composition for a black column spacer according to any one of claims 1 to 3 onto a substrate.
Exposure of the photosensitive resin layer according to a predetermined spacer pattern and
A method for forming a black column spacer, which comprises forming a spacer pattern by developing the photosensitive resin layer after exposure. The method for forming a black column spacer according to claim 6 , wherein the exposure is an exposure through a halftone mask.