TW201740188A - Photosensitive resin composition for black column spacer, black column spacer, display device, and method for forming black column spacer characterized in that the photosensitive resin composition comprises an alkali-soluble resin, a photopolymerizable monomer, a photopolymerization initiator, and a light blocking agent - Google Patents

Abstract

The present invention provides a photosensitive resin composition for forming a black column spacer which can form a smooth film without causing wrinkles, a black column spacer formed by using the composition, a display device comprising the black column spacer, and a method for forming a black column spacer by using the composition. A photosensitive resin composition comprises (A) an alkali-soluble resin, (B) a photopolymerizable monomer, (C) a photopolymerization initiator, and (D) a light blocking agent, in which the (B) photopolymerizable monomer comprises (B1) a polyfunctional monomer having 4 or more functional groups, and (B2) a bifunctional monomer and/or trifunctional monomer.

Description

Photosensitive resin composition for black column spacer, black column spacer, display device, and method for forming black column spacer

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 of forming a black column spacer using the same .

A display device such as a liquid crystal display device or an organic EL display device uses a spacer in order to keep the interval between the two substrates (cell gap/cell gap) constant.

Conventionally, in order to form a spacer, a method of dispersing bead particles as a spacer on the entire surface of a substrate is employed. However, in this method, it is difficult to form the spacer with high positional accuracy, and since the pixel display portion also adheres to the beads, there is a problem that the contrast of the image or the display image quality is lowered.

Here, in order to solve such problems, various proposals have been made for a method of forming a spacer by a photosensitive resin composition. In this method, a photosensitive resin composition is applied onto a substrate, and after exposure and development through a predetermined mask, a spacer such as a columnar shape is formed, and only a pixel display can be formed. The specified part other than the part is a spacer. In addition, in recent years, a so-called black column spacer having a light shielding property by a light shielding agent such as carbon black has been proposed (Patent Document 1 and the like).

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2011-170075

However, when the black column spacer is formed using the photosensitive resin composition described in Patent Document 1 or the like, the film formed using the photosensitive resin composition may wrinkle or form a smooth film.

When wrinkles or non-smoothness occurs on the surface of the black column spacer and the substrate, the height of the black column spacer becomes uneven, and the image quality of the display device is lowered.

The present invention has been made in view of the above-described problems, and an object of the invention is to provide a photosensitive resin composition for forming a black column spacer which does not generate wrinkles and which can form a smooth film, and a black column spacer formed using the composition, and A display device for a black column spacer and a method of forming a black column spacer using the composition.

The inventors of the present invention have conducted intensive studies in order to achieve the above object. As a result, it was found that by containing (A) alkali-soluble resin, (B) light The (B1) tetrafunctional or higher polyfunctional monomer and (B2) 2-functional monomer are used as the photosensitive resin composition of the polymerizable monomer, (C) photopolymerization initiator, and (D) opacifier. The (B) photopolymerizable monomer of the trifunctional monomer and/or the trifunctional monomer can solve the above problems, and thus the present invention has been completed. In particular, the present invention provides the following.

The first aspect of the present invention is a photosensitive resin composition for a black column spacer, which comprises (A) an alkali-soluble resin, (B) a photopolymerizable monomer, (C) a photopolymerization initiator, and D) The opacifier, the (B) photopolymerizable single system comprising (B1) a tetrafunctional or higher polyfunctional monomer, and (B2) a bifunctional monomer and/or a trifunctional monomer.

A second aspect of the present invention is a black column spacer formed of a cured product of a photosensitive resin composition of a black column spacer associated with the first state.

A third aspect of the invention is a display device having a black column spacer associated with a second aspect.

A fourth aspect of the present invention provides a method for forming a black column spacer, comprising: applying a photosensitive resin composition to a substrate by applying a photosensitive resin composition related to the first state to form a photosensitive property; The resin layer is formed by exposing the photosensitive resin layer in accordance with a pattern of a predetermined spacer; and developing the exposed photosensitive resin layer to form a spacer.

According to the present invention, it is possible to provide a photosensitive resin composition for forming a black column spacer which does not generate wrinkles and form a smooth film, a black column spacer formed using the composition, a display device including the black column spacer, And a method of forming a black column spacer using the composition.

[Best Mode for Carrying Out the Invention] Photosensitive resin composition for black column spacers≫

The photosensitive resin composition for a black column spacer (hereinafter, abbreviated as "photosensitive resin composition") contains (A) alkali-soluble resin, (B) photopolymerizable monomer, (C) photopolymerization initiator, And (D) sunscreen.

Then, the (B) photopolymerizable monomer is a (B1) tetrafunctional or higher polyfunctional monomer, and (B2) a bifunctional monomer and/or a trifunctional monomer.

In the photosensitive resin composition, by providing the above-described configuration, a film which is free from wrinkles and smooth can be formed, and a black column spacer can be formed.

However, a display device such as a liquid crystal display device often uses a substrate such as a TFT substrate on which a device is formed. When the substrate is used, it is necessary to form a black pillar spacer on the element formed on the substrate or on the portion of the substrate that is paired with the substrate on which the element is formed. In this case, it is necessary to change the height of the black column spacer depending on the position of the element and the other parts depending on the height of the element.

Using a photosensitive resin composition having the above configuration to form In the case of forming a black pillar spacer, the photosensitive resin layer formed of the photosensitive resin composition is exposed through a halftone mask, whereby a black pillar spacer having a different height can be easily formed.

In this case, it is preferred that the photosensitive resin layer formed of the photosensitive resin composition is exposed by a ghi line and a specified exposure amount, and developed at 25° C. for 70 seconds using a 0.05% by mass aqueous KOH solution, and then 230 After post-baking at ° C for 20 minutes, a black column spacer having a film thickness of 2.5 μm or more was obtained. With respect to the black column spacer, the film thickness H _FT when the above-mentioned specified exposure amount was 70 mJ/cm ² , and The difference ΔH (=H _FT -H _HT ) between the film thickness H _HT when the specified exposure amount is 6.3 mJ/cm ² is 2500 to 6000 Å.

Hereinafter, necessary or optional components and the like included 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" refers to a resin film having a film thickness of 1 μm formed on a substrate by a resin solution (solvent: propylene glycol monomethyl ether acetate) having a resin concentration of 20% by mass, and immersed in a concentration of 0.05 mass. In the case of 1 minute of the KOH aqueous solution, the film thickness of 0.01 μm or more was dissolved.

The (A) alkali-soluble resin is not particularly limited as long as it satisfies the above requirements. A suitable example of an alkali-soluble resin For example, (A1) a resin having a cardo structure and (A2) an acrylic resin can be exemplified.

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

In the above 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 R ^a2 each independently represents a hydrogen atom or a methyl group, and W ^a represents a single bond or The group represented by the following formula (a-3).

Further, in the above formula (a-1), Y ^a represents a residue obtained by removing an acid anhydride group (-CO-O-CO-) from a dicarboxylic acid anhydride. As an example of the dicarboxylic anhydride, maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl bridged methylene four can be exemplified. Hydrogen phthalic anhydride, hexachlorotetramethylene phthalic anhydride, methyl tetrahydrophthalic anhydride, glutaric anhydride, and the like.

Further, in the above formula (a-1), Z ^a represents a residue obtained by removing two acid anhydride groups from tetracarboxylic dianhydride. Examples of the tetracarboxylic dianhydride include pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, and diphenyl ether tetracarboxylic dianhydride.

Further, in the above formula (a-1), m represents an integer of 0 to 20.

(A1) The mass average molecular weight of the resin having a fluorene structure is preferably from 1,000 to 40,000, more preferably from 2,000 to 30,000. By having the above range, it is possible to obtain good developability and to obtain sufficient heat resistance and film strength.

As the (A2) acrylic resin, those comprising a constituent unit derived from (meth)acrylic acid and/or a constituent unit derived from (meth)acrylic acid ester are used. (Meth)acrylic acid is acrylic acid or methacrylic acid. The (meth) acrylate is represented by the following formula (a-4), and is not particularly limited insofar as it does not impair the object of the present invention.

In the above formula (a-4), R ^a3 is a hydrogen atom or a methyl group, and R ^a4 is a monovalent organic group which does not contain an ethylenic or acetylene unsaturated bond. The organic group may contain a bond or a substituent other than a hydrocarbon group such as a hetero atom in the organic group. Further, the organic group may be any of a linear chain, a branched chain, and a ring.

The substituent other than the hydrocarbon group in the organic group of R ^a4 is not particularly limited insofar as it does not impair the effects of the present invention, and examples thereof include a halogen atom, a hydroxyl group, a mercapto group, a thioether group, a cyano group, an isocyano group, and a cyanogen. Oxyl, isocyanooxy, thiocyanato, isocyanothio, decyl, decyl, alkoxy, alkoxycarbonyl, amine carbaryl, thiamine, nitro, nitroso , carboxy, carboxylate, sulfhydryl, decyloxy, sulfinate, sulfonate, sulfonate, phosphino, phosphinyl, phosphonic, phosphonate, hydroxyimino, alkyl The ether group, the alkyl sulfide group, the aryl ether group, the aryl sulfide group, the amine group (-NH ₂ , -NHR, -NRR': R and R' each independently represent a hydrocarbon group) and the like. The hydrogen atom contained in the above substituent may be substituted by a hydrocarbon group. Further, the hydrocarbon group contained in the substituent may be any of a linear chain, a branched chain, and a cyclic group.

As R ^a4 , an alkyl group, an aryl group, an arylalkyl group or a heterocyclic group is preferred, and these groups may be substituted by a halogen atom, a hydroxyl group, an alkyl group or a heterocyclic group. Further, when the group is an alkyl group-containing moiety, the alkyl group 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 is preferably from 1 to 20, more preferably from 1 to 15, and particularly preferably from 1 to 10. As examples of suitable alkyl groups, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, and iso are illustrated. Pentyl, sec-pentyl, tert-pentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, sec-octyl, tert-octyl, n-fluorenyl, isodecyl, N-fluorenyl, isodecyl, and the like.

When the alkyl group is an alicyclic group or a group containing an alicyclic group, as a suitable alicyclic group contained in the alkyl group, a monocyclic alicyclic ring such as a cyclopentyl group or a cyclohexyl group can be exemplified. a polycyclic alicyclic group such as a ruthenyl group, an adamantyl group, a fluorenyl group, an isodecyl group, a tricyclodecyl group, a tricyclodecyl group, or a tetracyclododecyl group.

A suitable example of the (meth) acrylate in which the alkyl group is an alicyclic group or an alicyclic group is, for example, a compound represented by the following formulas (a4-1) to (a4-7). Among these, a photosensitive resin composition excellent in developability is easily obtained, and a compound represented by the following formulas (a4-3) to (a4-8) is preferable, and the following formula (a4-3) is used. The compound represented by or (a4-4) is further preferred.

In the above formulae (a4-1) to (a4-8), R ^a3 represents a hydrogen atom or a methyl group, and R ^a5 represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, and R ^{a6 is a} system. It represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. As the R ^a5 single bond, linear or branched alkyl group, for example, methylene, ethyl, propyl, tetramethylene, ethyl ethyl, pentamethylene, and hexa A methyl group is preferred. As R ^a6 , for example, a methyl group or an ethyl group is preferred.

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

The aralkyl group in R ^a4 is preferably an aralkyl group having 7 to 20 carbon atoms, and more preferably having 7 to 12 carbon atoms. As an example of the aralkyl group, a benzyl group, an α-methylbenzyl group, an α,α-dimethylbenzyl group, a phenylethyl group, a phenylvinyl group or the like can be exemplified.

The heterocyclic group in R ^a4 may, for example, be a heterocyclic group containing a nitrogen atom, a sulfur atom, and at least one atom of an oxygen atom, and a 5-membered ring or more (preferably a 5- to 7-membered ring). A condensed ring may also be included in the heterocyclic group. As an example of the heterocyclic group, a pyrrolyl group, an acridinyl group, a pyrimidinyl group, a furyl group, a thienyl group and the like can be exemplified.

Further, the (A2) acrylic resin may further polymerize other compounds 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, and styrenes. These compounds may be used singly or in combination of two or more.

As the (meth) acrylamide, (meth) acrylamide, N-alkyl (meth) acrylamide, N-aryl (meth) acrylamide, N, N-dioxane can be exemplified. (meth)acrylamide, N,N-aryl(meth)acrylamide, N-methyl-N-phenyl(meth)acrylamide, N-hydroxyethyl-N-methyl (Methyl) acrylamide and the like.

Examples of the unsaturated carboxylic acid 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 such dicarboxylic acids.

As the allyl compound, for example, allyl acetate and Allyl acrylate, allyl octylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetate, allyl lactate, etc. Ester; allyloxyethanol and the like.

Examples of the vinyl ethers include hexyl vinyl ether, octyl vinyl ether, mercapto vinyl ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether, and ethoxyethyl alkenyl ether. Chloroethyl vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl ether, 2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, Alkylethylene such as dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether or tetrahydrofurfuryl vinyl ether Vinyl phenyl ether, vinyl tolyl ether, vinyl chlorophenyl ether, vinyl-2,4-dichlorophenyl ether, vinyl naphthyl ether, vinyl decyl ether, etc. Aryl ether and the like.

As the vinyl esters, vinyl butyrate, vinyl butyrate, trimethyl vinyl acetate, diethyl vinyl acetate, vinyl valerate, vinyl hexanoate, vinyl chloroacetate, ethylene dichloroacetate can be exemplified. Ester, methoxyvinyl acetate, butoxy vinyl acetate, vinyl phenyl acetate, ethylene vinyl acetate, vinyl lactate, vinyl β-phenylbutyrate, vinyl benzoate, ethylene salicylate Ester, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, vinyl naphthoate, and the like.

As the styrene, styrene; methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, isopropyl styrene, butyl styrene, hexyl group can be exemplified. Styrene, cyclohexylstyrene, mercaptostyrene, benzylstyrene, chloromethylstyrene, three Alkyl styrene such as fluoromethylstyrene, ethoxymethylstyrene or ethoxymethylstyrene; methoxystyrene, 4-methoxy-3-methylstyrene, dimethyl Alkoxystyrene such as oxystyrene; chlorostyrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodine styrene, fluorine A halogenated styrene such as styrene, trifluorostyrene, 2-bromo-4-trifluoromethylstyrene or 4-fluoro-3-trifluoromethylstyrene.

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

(A2) The total amount of the constituent unit derived from (meth)acrylic acid in the acrylic resin and the amount of the constituent unit derived from (meth)acrylic acid are not within the range not impairing the object of the present invention. It is particularly limited, but it is preferably 5 to 100% by mass, and more preferably 10 to 50% by mass based on the mass of the (A2) acrylic resin. (A2) The acrylic resin is a photosensitive resin which is excellent in the halftone property by containing a constituent unit derived from (meth)acrylic acid and a constituent unit derived from (meth)acrylic acid in an amount in this range. Composition. Photosensitive resin group When the halftone characteristic of the object is excellent, exposure by a halftone mask can easily form a black column spacer having a sufficient height difference in response to light transmittance.

As the (A2) acrylic resin, those having an unsaturated bond can also be used. The method of preparing the acrylic resin having an unsaturated bond is not particularly limited, and examples thereof include a method of reacting at least a part of a carboxyl group of the acrylic resin with an epoxy group-containing unsaturated compound, which is contained in the acrylic resin. The carboxyl group is a carboxyl group derived from a constituent unit of (meth)acrylic acid and a resin derived from a constituent unit of (meth)acrylate.

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

As the (a-6) epoxy group-containing unsaturated compound having no alicyclic group, glycidyl (meth) acrylate, 2-methyl glycidyl (meth) acrylate, 3, (A) epoxyalkyl (meth)acrylates such as 4-epoxybutyl (meth) acrylate and 6,7-epoxyheptyl (meth) acrylate; α-ethyl glycidyl acrylate Α-alkylacrylic acid epoxyalkyl esters such as α-n-propyl glycidyl acrylate, α-n-butyl acrylate glycidyl ester, and α-ethyl acrylate 6,7-epoxyheptyl ester. Among these, glycidyl (meth) acrylate, 2-methyl glycidyl (meth) acrylate, and 6,7-epoxyheptyl (meth) acrylate are preferred. The (a-6) epoxy group-containing unsaturated The compounds may be used singly or in combination of two or more.

(a-6) The alicyclic epoxy group-containing unsaturated compound may be a monocyclic ring or a polycyclic ring. As the monocyclic alicyclic group, a cyclopentyl group, a cyclohexyl group or the like can be exemplified. Further, examples of the polycyclic alicyclic group include a thiol group, an isodecyl group, a tricyclodecyl group, a tricyclodecyl group, a tetracyclododecyl group, and the like. These (a-6) alicyclic epoxy group-containing unsaturated compounds may be used singly 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 make the developability of the photosensitive resin composition moderate, a compound represented by the following formula (a-6-1) to (a-6-6) is preferable, and the following formula (a) The compound represented by -6-1)~(a-6-4) is further preferred.

In the above formula, 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, and R ^a10 represents a carbon atom. A divalent hydrocarbon group of 1 to 10, and n represents an integer of 0 to 10. The linear alkyl or branched alkyl group of R ^a8 is, for example, a methylene group, an ethylidene group, a propyl group, a tetramethylene group, an ethyl group ethyl group, a pentamethylene group or a hexamethylene group. Preferably. As R ¹³ , for example, a methylene group, an ethyl group, a propyl group, a tetramethylene group, an ethyl group, an ethyl group, a pentamethylene group, a hexamethylene group, a phenylene group, a cyclohexyl group, and a —CH ₂ — Ph-CH ₂ - (Ph represents a phenylene group) is preferred.

When the (A2) acrylic resin has an unsaturated bond, the amount of the constituent unit having an unsaturated bond in the acrylic resin is preferably from 1 to 20% by mass based on the mass of the (A2) acrylic resin. It is also preferably from 1 to 10% by mass. When the acrylic resin containing the constituent unit of the unsaturated bond in the range is used as the (A2) acrylic resin, a photosensitive resin composition excellent in halftone characteristics can be easily obtained.

The mass average molecular weight of the (A2) acrylic resin is preferably from 2,000 to 200,000, more preferably from 5,000 to 30,000. By the above range, it is easy to obtain a balance between the film forming ability of the photosensitive resin composition and the developability after exposure.

(A) The alkali-soluble resin may contain other alkali-soluble resins conventionally known, in addition to the above-mentioned (A1) resin having a fluorene structure and the above (A2) acrylic resin.

In the (A) alkali-soluble resin, the total ratio of the resin having an anthracene structure (A1) to the (A2) acrylic resin is preferably 80% by mass or more, more preferably 90% by mass or more, most preferably Good is 100% by mass.

(A) The amount of the resin having a fluorene structure in the above (A1) is preferably from 10 to 100 parts by mass, and more preferably from 20 to 100 parts by mass, per 100 parts by mass of the alkali-soluble resin.

The content of the alkali-soluble resin (A) is preferably 20 to 85% by mass, and more preferably 30 to 75% by mass based on the solid content of the photosensitive resin composition. By becoming the above range, development is easy The tendency to balance sex.

<(B) Photopolymerizable monomer>

The photosensitive resin composition contains (B) a photopolymerizable monomer. (B) The photopolymerizable monomer is a combination of a (B1) tetrafunctional or higher polyfunctional monomer and a (B2) bifunctional monomer and/or a trifunctional monomer.

In the following, (B) the photopolymerizable monomer is described as "(B) component", and the (B1) tetrafunctional or higher polyfunctional monomer is also referred to as "(B1) component", and (B2) is also functional. The monomer and/or trifunctional monomer is described as "(B3) component".

Thereby, the photosensitive resin composition is used, and the elastic recovery rate is high, and a smooth film can be easily formed. Moreover, when the photosensitive resin composition is used to form the black pillar spacer, the photosensitive resin layer is exposed by using a halftone mask, and the black pillar spacer having a sufficient height difference can be easily formed. In this case, the highly different black column spacers can be formed by one exposure.

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

As a suitable example of the component (B1), trimethylolpropane tetra(meth)acrylate, diglycerin tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol-6 (a) can be exemplified. A acrylate, a pentaerythritol tetra(meth) acrylate, a condensate of a polyol and N-methylol (meth) acrylamide, and the like.

Among the components (B2), examples of the bifunctional monomer include (B2-1) a di(meth)acrylate of an alkanediol having 2 to 6 carbon atoms, and (B2-2)- A di(meth)acrylate or the like in which a (meth)acrylinyl group is bonded to both ends of a divalent group represented by O(-R ^b1 -O)p-.

Further, 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. p is preferably 2 or more and 20 or less. When p is an integer of 2 or more, the plurality of R ^b1 may be the same or different.

Examples of the (B2-1) di(meth) acrylate of the alkanediol having 2 to 6 carbon atoms include ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, and 1,3. -propylene glycol di(meth)acrylate, 1,4-butanediol (di(meth)acrylate, 1,3-butanediol di(meth)acrylate (butanediol di(meth)acrylic acid) Ester), 1,5-pentanediol di(meth)acrylate, 2,2-dimethyl-1,3-propanediol di(meth)acrylate (pentaerythritol di(meth)acrylate ), and 1,6-hexanediol (meth) acrylate, and the like.

A di(meth)acrylate obtained by bonding a (meth)acryloyl group to both ends of a divalent group represented by (B2-2)-O(-R ^b1 -O)p- can be exemplified Polyethylene glycol diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, ethylene oxide having a repeat number of 5 or more Polypropylene glycol having a repeating number of 5 or more of di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, tetrapropylene glycol di(meth)acrylate, or propyleneoxy group Di(meth)acrylate, and di(meth)acrylate of ethoxylated polypropylene glycol.

The di(meth) acrylate which is an ethoxylated polypropylene glycol, for example, which is a propyleneoxy group 12 and an ethyleneoxy unit of 6 can be obtained by 1206PE (made by Hinghe Co., Ltd.).

Other than the above, a bifunctional monomer which can be suitably used as the component (B2) is exemplified by glycerol di(meth)acrylate, pentaerythritol di(meth)acrylate, and 2,2-bis(4-(methyl). Propylene methoxy diethoxy phenyl) propane, 2,2-bis(4-(methyl) propylene oxypolyethoxy phenyl) propane, phthalic acid di(meth) acrylate, Cyclohexane 1,4-dimethanol di(meth) acrylate, cyclohexane 1,3-dimethanol di(meth) acrylate, tricyclodecane dimethanol di(meth) acrylate, 2- Hydroxy-3-(meth)acryloxypropyl (meth) acrylate, ethylene glycol diglycidyl ether di(meth) acrylate, diethylene glycol diglycidyl ether di(meth) acrylate Ester, diglycidyl phthalate di(meth) acrylate, trimethyl hexamethylene diisocyanate and hexamethylene diisocyanate and 2-hydroxyethyl (methyl) Acrylate reactant, methylene bis(meth) acrylamide, (meth) acrylamide, methylene ether, and 1,3,5-(2'-hydroxyethyl)isocyanuric acid Di(meth)acrylate and the like.

Among the components (B2), as a suitable example of the trifunctional monomer, trimethylolpropane (meth) acrylate or bistrihydroxymethyl can be exemplified. Propane (meth) acrylate, pentaerythritol tri (meth) acrylate, glycerol tri (meth) acrylate, diglycerin tri (meth) acrylate, poly glycerol tri (meth) acrylate, glycerol tricondensate Glycerol ether tri(meth)acrylate, tripropenyl formal, and the like.

The component (B) may contain a (B3) monofunctional monomer (hereinafter also referred to as a component (B3)) in addition to the (B1) component and the (B2) component, within a range that does not impair the desired effect.

As the component (B3), (meth) acrylamide, hydroxymethyl (meth) acrylamide, methoxymethyl (meth) acrylamide, ethoxymethyl (meth) propylene can be exemplified. Indoleamine, propoxymethyl (meth) acrylamide, butoxymethoxymethyl (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-methylol (Meth) acrylamide, (meth)acrylic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, crotonic acid, 2-propenylamine- 2-methylpropanesulfonic acid, tert-butylacrylamide, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (Meth) acrylate, cyclohexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate Ester, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 3-phenoxy-2-hydroxypropyl (meth) acrylate, 2-(methyl) propylene decyloxy-2 -hydroxypropyl phthalate, glycerol mono(meth)acrylate, tetrahydrofurfuryl (meth) acrylate, two Methylaminoethyl (meth) acrylate, glycidyl (meth) acrylate, 2, 2, 2-trifluoroethyl (meth) acrylate, 2, 2, 3, 3-tetrafluoro Propyl (Meth) acrylate, a (meth) acrylate half ester of a phthalic acid derivative, or the like. These monofunctional monomers may be used singly or in combination of two or more.

Further, the following alicyclic monofunctional monomer can also be suitably used.

(B) The content of the component (B2) in the photopolymerizable monomer is preferably 80% by mass or less, and more preferably 50% by mass based on the total mass of the component (B1) and the mass of the component (B2). the following.

In addition, the content of the component (B2) is preferably 1% by mass or more, and more preferably 5% by mass or more based on the total mass of the component (B1) and the mass of the component (B2).

(B) The mass of the photopolymerizable monomer, the ratio of the mass of the component (B1) to the total mass of the component (B2) is preferably 70% by mass or more, and more preferably 80% by mass or more, particularly preferably 90% by mass or more, most Good is 100% by mass.

The content of the photopolymerizable monomer (B) is preferably from 1 to 30% by mass, and more preferably from 5 to 20% by mass, based on the solid content of the photosensitive resin composition. When it is in the above range, it tends to easily obtain a balance between sensitivity, developability, and resolution.

<(C) Photopolymerization initiator>

The photopolymerization initiator is not particularly limited, and a conventional photopolymerization initiator can be used.

As the photopolymerization initiator, specifically, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethyl) can be exemplified. Oxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropan-1-one, bis(4-dimethylaminophenyl)one, 2,4,6-trimethyl Benzomidine diphenylphosphine oxide, 4-benzylidene-4'-methyldimethyl sulfide, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, Ethyl 4-dimethylaminobenzoate, butyl 4-dimethylaminobenzoate, 4-dimethylamino-2-ethylhexylbenzoic acid, 4-dimethylamino-2- Isoamylbenzoic acid, benzyl-β-methoxyethyl acetal, benzyl dimethyl ketal, 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)肟, o-o-benzoyl benzoic acid methyl ester, 2,4-diethyl thioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 1-chloro-4-propoxy Thiophenone ketone 2-chlorosulfur 2,4-diethyl sulphide 2-methylsulfide 2-isopropylsulfur , 2-ethyl hydrazine, octamethyl hydrazine, 1,2-benzopyrene, 2,3-diphenyl fluorene, azobisisobutyronitrile, benzammonium peroxide, hydrogen peroxidation Alkene, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o -Chlorophenyl)-4,5-bis(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-triaryl Imidazole dimer, benzophenone, 2-chlorobenzophenone, 4,4'-bisdimethylaminobenzophenone (ie, mazinone), 4,4'-bis Ethylaminobenzophenone (ie, ethyl melamine), 4,4'-dichlorobenzophenone, 3,3-dimethyl-4-methoxybenzophenone, benzyl Base, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, benzoin Ether, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloro Ethyl ketone, p-tert-butylacetophenone, p-dimethylaminoacetophenone, p-tert-butyltrichloroacetophenone, p-tert-butyldichloroacetophenone, α, α-Dichloro-4-phenoxyacetophenone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, dibenzosuberone, pentyl-4- Dimethylamino benzoate, 9-phenyl acridine, 1,7-bis-(9-acridinyl) heptane, 1,5-bis-(9-acridinyl)pentane, 1 ,3-bis-(9-acridinyl)propane, p-methoxytriazine, 2,4,6-glucos(trichloromethyl)-s-triazine, 2-methyl-4,6- Bis(trichloromethyl)-s-triazine, 2-[2-(5-methylfuran-2-yl)vinyl]-4,6-bis(trichloromethyl)-s-triazine, 2 -[2-(furan-2-yl)vinyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(4-diethylamino-2-methyl) Phenyl)vinyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(3,4-dimethoxyphenyl)vinyl]-4,6-double (trichloromethyl)-s-triazine, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxybenzene Vinyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-n-butoxyphenyl)-4,6-bis(trichloromethyl)-s-three Oxazine, 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-triazine, "IRGACURE OXE02", "IRGACURE OXE01", "IRGACURE 369", "IRGACURE 651", "IRGACURE 907" (trade name: BASF), "NCI-831" (trade name: made by ADEKA). These photopolymerization initiators can be used singly or in combination of two or more.

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

As a preferable example of the oxime-based photopolymerization initiator, a photopolymerization initiator represented by the following formula (c-1) can be exemplified.

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.

The heterocyclic group in R ^c1 may, for example, be a heterocyclic group containing a nitrogen atom, a sulfur atom, and at least one atom of an oxygen atom, and a 5-membered ring or more (preferably a 5-membered ring or a 6-membered ring). Examples of the heterocyclic group include a nitrogen-containing 5-membered ring group of a pyrrolyl group, an imidazolyl group, a pyrazolyl group, and the like; a nitrogen-containing 6-membered ring group such as an acridinyl group, a pyrazinyl group, a pyrimidinyl group, or a pyridazinyl group; a nitrogen-containing sulfur-containing group such as a thiazolyl group or an isothiazolyl group; a nitrogen-containing oxygen group such as an oxazolyl group or an isoxazolyl group; a sulfur-containing group such as a thienyl group or a thiopyranyl group; a furyl group and a pyran group; An oxy group or the like of a group or the like. Among them, it is preferred to contain one of a nitrogen atom or a sulfur atom. A condensed ring may also be included in the heterocyclic ring. As an example of the heterocyclic group containing a condensed ring, a benzothienyl group etc. are illustrated.

The condensed cyclic aromatic group in R ^c1 may, for example, be a naphthyl group, an anthracenyl group or a phenanthryl group. Further, examples of the aromatic group in R ^c1 include a phenyl group.

The heterocyclic group, the condensed cyclic aromatic group, or the aromatic group may have a substituent. In particular, when R ^c1 is an aromatic group, it preferably has a substituent. As such a substituent, -NO ₂ , -CN, -SO ₂ R ^c5 , -COR ^c5 , -NR ^c6 R ^c7 , -R ^c8 , -OR ^c8 , -OR ^c9 -OR ^c10 and the like can be exemplified.

R ^c5 independently represents an alkyl group, which may be substituted by a halogen atom or interrupted by an ether bond, a thioether bond or an ester bond. The alkyl group in R ^c5 is preferably a carbon number of 1 to 5, 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, which may be substituted by a halogen atom, and the alkyl group of the alkyl group and the alkoxy group may be an ether bond or sulfur. The ether bond or the ester bond is interrupted. Further, R ^c6 and R ^c7 may be bonded to each other to form a ring structure. The alkyl group or alkoxy group in R ^c6 and R ^c7 is preferably a carbon number of 1 to 5, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, and a methoxy group. , ethoxy, propoxy, and the like.

As the ring structure which can be formed by bonding R ^c6 and R ^c7 , a hetero ring can be exemplified. The heterocyclic ring may, for example, be a heterocyclic ring containing at least a nitrogen atom of a 5-membered ring or more (preferably a 5- to 7-membered ring). A condensed ring may also be included in the heterocyclic ring. As an example of the hetero ring, a piperidine ring, a morpholine ring, a thiomorpholine ring or the like can be exemplified. Among these, a morpholine ring is preferred.

R ^c8 represents an alkyl group in which part or all of a hydrogen atom may be substituted by a halogen atom. The alkyl group in R ^c8 is preferably a carbon number of 1 to 6, 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 by a halogen atom or interrupted by an ether bond, a thioether bond or an ester bond. The preferred number of carbon atoms or this specific example is the same as described above for R ^c1 .

Among these, as a preferable example of R ^c1 , a pyrrolyl group, an acridinyl group, a thienyl group, a thiopyranyl group, a benzothienyl group, a naphthyl group, or a substituted phenyl group can be exemplified.

In the above formula (c-1), R ^c2 represents a monovalent organic group. The organic group is preferably a group represented by -R ^c11 , -OR ^c11 , -COR ^c11 , -SR ^c11 and -NR ^c11 R ^c12 . R ^c11 and R ^c12 each independently represent an alkyl group, an alkenyl group, an aryl group, an arylalkyl group or a heterocyclic group, which may be substituted by a halogen atom, an alkyl group or a heterocyclic group, and the alkyl group and The alkylene moiety of 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 and form a ring structure together with a nitrogen atom.

The alkyl group in R ^c11 and R ^c12 preferably has 1 to 20 carbon atoms, and more preferably 1 to 5 carbon atoms. As an example of the alkyl group, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl can be exemplified. , sec-pentyl, tert-pentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, sec-octyl, tert-octyl, n-fluorenyl, isodecyl, n- A linear or branched chain group such as a fluorenyl group or an isomeric fluorenyl group. Further, the alkyl group may have a substituent. Examples of the alkyl group having a substituent include a methoxyethoxyethyl group, an ethoxyethoxyethyl group, a propoxyethoxyethyl group, a methoxypropyl group and the like.

The alkenyl group in R ^c11 and R ^c12 preferably has 1 to 20 carbon atoms, and more preferably 1 to 5 carbon atoms. 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 or an acryl group. Further, the alkenyl group may have a substituent. As an example of the alkenyl group having a substituent, 2-(benzoxazol-2-yl)vinyl group or the like can be exemplified.

The aryl group in R ^c11 and R ^c12 preferably has 6 to 20 carbon atoms, and more preferably 6 to 10 carbon atoms. As an example of the aryl group, a phenyl group, a tolyl group, a xylyl group, an ethylphenyl group, a naphthyl group, an anthracenyl group

The aralkyl group in R ^c11 and R ^c12 preferably has 7 to 20 carbon atoms, and more preferably 7 to 12 carbon atoms. As an example of the aralkyl group, a benzyl group, an α-methylbenzyl group, an α,α-dimethylbenzyl group, a phenylethyl group, a phenylvinyl group or the like can be exemplified.

The heterocyclic group in R ^c11 and R ^c12 may, for example, be a heterocyclic group containing a nitrogen atom, a sulfur atom or at least one atom of an oxygen atom and having a 5-membered or more ring (preferably a 5- to 7-membered ring). A condensed ring may be included in the heterocyclic group. As an example of the heterocyclic group, a pyrrolyl group, an acridinyl group, a pyrimidinyl group, a furyl group, a thienyl group and the like can be exemplified.

Among the R ^c11 and R ^c12 , the alkyl group 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, a ring structure which can be formed by bonding R ^c11 and R ^c12 can be exemplified by a hetero ring. The heterocyclic ring may, for example, be a heterocyclic ring containing at least a nitrogen atom of a 5-membered ring or more (preferably a 5- to 7-membered ring). A condensed ring may also be included in the heterocyclic ring. As an example of the hetero ring, a piperidine ring, a morpholine ring, a thiomorpholine ring or the like can be exemplified.

Among these, R ^{c2 is} 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 is preferably 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 of a group. As the substituent, the same substituent as in the case of the above R ^c1 can be exemplified. Examples of the aryl group having 6 to 12 carbon atoms include a phenyl group, a naphthyl group, an anthracenyl group, and a phenanthryl group.

[11] -R ^c13 -R ^c14 (c-2)

In the above formula (c-2), R ^c13 represents an alkylene group having 1 to 5 carbon atoms which can be interrupted by an oxygen atom. As such an alkylene group, a methylene group, an ethyl group, an n-propyl group, an exopropyl group, an n-butylene group, an isobutylene group, a sec-butylene group, and an n-stretching group can be exemplified. A linear or branched chain group such as a benzyl group, an iso-pentyl group or a sec-amyl group. Among these, R ^{c13 is} most preferably an exo-propyl 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 the organic groups, as long as the structure of R ^c14 is a structure represented by the following formula (c-3), it is preferable from the viewpoint of improving the solubility of the photopolymerization initiator.

In the above formula (c-3), R ^c17 and R ^c18 each independently represent an alkyl group having 1 to 5 carbon atoms. As such an alkyl group, 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 isoprene can be exemplified. Base, sec-pentyl, tert-pentyl, and the like. Among these, R ^c17 and R ^{c18 are} most preferably a methyl group.

The heterocyclic group in R ^c3 may, for example, be a heterocyclic group containing a nitrogen atom, a sulfur atom or at least one atom of an oxygen atom and having a 5-membered or more ring (preferably a 5-membered ring or a 6-membered ring). Examples of the heterocyclic group include a nitrogen-containing 5-membered ring group of a pyrrolyl group, an imidazolyl group, a pyrazolyl group, and the like; a nitrogen-containing 6-membered ring group such as an acridinyl group, a pyrazinyl group, a pyrimidinyl group, or a pyridazinyl group; a nitrogen-containing sulfur-containing group such as a thiazolyl group or an isothiazolyl group; a nitrogen-containing oxygen-containing group such as an oxazolyl group or an isoxazolyl group; a sulfur-containing group such as a thienyl group or a thiopyranyl group; a furyl group or a pyranyl group; Containing oxygen and the like. Among them, it is preferred to contain one of a nitrogen atom or a sulfur atom. A condensed ring may also be included in the heterocyclic ring. As an example of the heterocyclic group containing a condensed ring, a benzothienyl group etc. are illustrated.

Further, the heterocyclic group may have a substituent. As the substituent, the same substituent as in the case of the above R ^c1 can be exemplified.

In the above formula (c-1), R ^c4 represents a monovalent organic group. Among them, an alkyl group having 1 to 5 carbon atoms is preferred. As such an alkyl group, 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 isoprene can be exemplified. Base, sec-pentyl, tert-pentyl, and the like. Among these, R ^{c4 is} most preferably a methyl group.

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

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

R ^c31 , R ^c32 , and R ^c33 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or a carbon atom. A number of 2 to 20 heterocyclic groups. A hydrogen atom of an alkyl group, an aryl group, an arylalkyl group, and a heterocyclic group may be further ^exemplified by 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 ^c42 R ^c43 , a carboxyl group, or an epoxy group. R ^c41 , R ^c42 and R ^c43 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or a carbon atom. A number of 2 to 20 heterocyclic groups.

The methylene group of the alkyl group of the substituents in the above R ^c31 , R ^c32 , R ^c33 , R ^c41 , R ^c42 , and R ^c43 may be an unsaturated bond, an ether bond, a thioether bond, an ester bond, or The thioester bond, the guanamine bond, or the urethane bond is interrupted 1 to 5 times, and the alkyl moiety of the above substituent may be a branched chain or a cyclic alkyl group, and the alkyl terminal of the above substituent may be The saturation bond, in addition, R ^c32 and R ^c33 , and R ^c42 and R ^c43 may also be bonded to each other to form a ring structure.

In the above formula (c-4), R ^c23 and R ^c24 each independently represent 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. The a and b are independent integers representing 0 to 4, respectively.

R ^c23 can be bonded to one carbon atom of the adjacent benzene ring through -X ^c2 - and form a ring structure, and R ^c23 and R ^c24 can also bond and form a ring structure.

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 each independently represent R ^c31 , OR ^c31 , COR ^c31 , SR ^c31 , CONR ^c32 R ^c33 , or CN. R ^c51 , R ^c53 , and R ^c54 may independently form a ring structure together with any adjacent benzene ring.

In the above formula (c-4), ^examples of the alkyl group in R ^c31 , R ^c32 , R ^c33 , R ^c41 , R ^c42 and R ^c43 include a methyl group, an ethyl group, an n-propyl group and an isopropyl group. N-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, tert-pentyl, and the like.

In the above formula (c-4), ^examples of the aryl group in R ^c31 , R ^c32 , R ^c33 , R ^c41 , R ^c42 and R ^c43 include a phenyl group, a tolyl group, a xylyl group, and an ethylphenyl group. Chlorophenyl, naphthyl, anthryl, phenanthryl and the like.

In the above formula (c-4), ^examples of the aralkyl group in R ^c31 , R ^c32 , R ^c33 , R ^c41 , R ^c42 and R ^c43 include a benzyl group, a chlorobenzyl group, and an α-methylbenzyl group. α,α-dimethylbenzyl, phenylethyl, phenylvinyl, and the like.

In the above formula (c-4), as the heterocyclic group in R ^c31 , R ^c32 , R ^c33 , R ^c41 , R ^c42 and R ^c43 , an ^acridinyl group, a pyrimidinyl group, a furyl group or a thienyl group is preferably exemplified. , tetrahydrofuranyl, dioxoranyl, benzoxazol-2-yl, tetrahydropyranyl, pyrrolidyl, imidazolidinyl, pyrazolidyl, thiazolyl, A 5-7 membered ring of isothiazolyl, oxazolidyl, oxazolidyl, piperidinyl, pyrazinyl or morpholinyl.

In the above formula (c-4), a ring which can be formed by bonding R ^c32 and R ^c33 , a ring which can be formed by bonding R ^c42 and R ^c43 , and a ring which R ^c23 and an adjacent benzene ring can form together can be formed. 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 or an indoleamine ring can be exemplified.

^Further , when X ^c2 is NR ^c53 and R ^c23 is bonded to one carbon atom of the adjacent benzene ring, and forms a 5-membered ring structure together with X ^c2 , the photopolymerization initiator will have a carbazole skeleton.

In the above formula (c-4), as a halogen atom which can substitute R ^c31 , R ^c32 , R ^c33 , R ^c41 , R ^c42 and R ^c43 , and a halogen atom in R ^c24 and R ^c25 , a fluorine atom can be exemplified. Chlorine atom, bromine atom, iodine atom.

The methylene group of the alkyl group of the above substituent may be interrupted 1 to 5 times by an unsaturated bond, an ether bond, a thioether bond, an ester bond, a thioester bond, a guanamine bond, or a urethane bond. In this case, the interrupted bonding group may be one or more types, and in the case of a continuously interruptable group, two or more consecutive and interrupted. Further, the alkyl moiety of the above substituent may be a branched chain or a cyclic alkyl group, and the alkyl terminal of the above substituent may be an unsaturated bond.

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

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

In the formula (c-5), R ¹ is a hydrogen atom, a nitro group or a monovalent organic group. The 6-membered aromatic ring to which R ¹ is bonded to the anthracene ring of the formula (c-5) is different from the 6-membered aromatic ring bonded to the group represented by -(CO) _m -. In the formula (c-5), R ¹ is not particularly limited to the bonding position of the anthracene ring. For synthesis of compounds of formula When the compound (c-5) represented as having the one or ^more, R ^1, the easiness of the formula (c-5) represented by the other, one or more among R ¹ 1 Preferably, the second bit is bonded to the anthracene ring. When R ¹ is a complex number, a plurality of R ^{1 's} may be the same or different.

When R ¹ is an organic group, R ^{1 is} not particularly limited, and may be appropriately selected from various organic groups, within the range not impairing the object of the present invention. As a suitable example in the case where R ¹ is an organic group, an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic fluorenyl group, an alkoxycarbonyl group, a saturated aliphatic decyloxy group, a phenyl group which may have a substituent, a phenoxy group which may have a substituent, a benzamyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, a benzyl fluorenyl group which may have a substituent, may have a phenylalkyl group of a substituent, a naphthyl group which may have a substituent, a naphthyloxy group which may have a substituent, a naphthoquinone which may have a substituent, a naphthyloxycarbonyl group which may have a substituent, and a naphthalene which may have a substituent A methyloxy group, a naphthylalkyl group which may have a substituent, a heterocyclic group which may have a substituent, a heterocyclic carbonyl group which may have a substituent, an amine group substituted with 1 or 2 organic groups, morpholine- 1-yl, piperazin-1-yl and the like.

When R ¹ is an alkyl group, the alkyl group preferably has 1 to 20 carbon atoms and 1 to 6 carbon atoms. Further, when R ¹ is an alkyl group, it may be a straight chain or a branched chain. Specific examples of when R ¹ is an alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-. Pentyl, isopentyl, sec-pentyl, tert-pentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, sec-octyl, tert-octyl, n-fluorenyl, Isoindolyl, n-fluorenyl, and isodecyl. Further, when R ¹ is an alkyl group, the alkyl group may contain an ether bond (-O-) in the carbon chain. As an example of the alkyl group having an ether bond in the carbon chain, a methoxyethyl group, an ethoxyethyl group, a methoxyethoxyethyl group, an ethoxyethoxyethyl group, a propoxy group B can be exemplified. Oxyethyl, methoxypropyl and the like.

When R ¹ is an alkoxy group, the alkoxy group preferably has 1 to 20 carbon atoms, and more preferably 1 to 6 carbon atoms. Further, when R ¹ is an alkoxy group, it may be a straight chain or a branched chain. Specific examples of when R ¹ is an alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, and a sec-butoxy group. , tert-butoxy, n-pentyloxy, isopentyloxy, sec-pentyloxy, tert-pentyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, isooctyl An oxy group, a sec-octyloxy group, a tert-octyloxy group, an n-decyloxy group, an isodecyloxy group, an n-decyloxy group, an isodecyloxy group or the like. Further, when R ¹ is an alkoxy group, the alkoxy group may contain an ether bond (-O-) in the carbon chain. As an example of the alkoxy group having an ether bond in the carbon chain, a methoxyethoxy group, an ethoxyethyloxy group, a methoxyethoxyethoxy group, an ethoxyethoxyethoxy group can be exemplified. A group, a propoxyethoxyethyloxy group, a methoxypropoxy 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 from 3 to 10, and more preferably from 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, and a cyclooctyl group. Specific examples of the case where R ¹ is a cycloalkoxy group include a cyclopropoxy group, a cyclobutoxy group, a cyclopentyloxy group, a cyclohexyloxy group, a cycloheptyloxy group, and a cyclooctyloxy group.

When R ¹ is a saturated aliphatic fluorenyl group or a saturated aliphatic fluorenyloxy group, the saturated aliphatic fluorenyl group or the saturated aliphatic fluorenyloxy group preferably has 2 to 21 carbon atoms, and more preferably 2 to 7 carbon atoms. Specific examples of when R ¹ is a saturated aliphatic fluorenyl group include an ethyl hydrazino group, a propyl fluorenyl group, an n-butyl fluorenyl group, a 2-methyl propyl fluorenyl group, an n-pentamethylene group, and a 2,2-dimethyl group. Propyl, n-hexyl, n-heptyl, n-octyl, n-fluorenyl, n-fluorenyl, n-undecyl, n-taudecyl, n-tride Sulfhydryl, n-tetradecyl, n-pentadecanyl, and n-hexadecanyl. Specific examples of when R ¹ is a saturated aliphatic decyloxy group include an ethoxy group, a propenyloxy group, an n-butenyloxy group, a 2-methylpropoxy group, and an n-pentyloxy group. 2,2-Dimethylpropoxy, n-hexyloxy, n-heptyloxy, n-octyloxy, n-decyloxy, n-decyloxy, n- Eleven methoxy, n-dodecyloxy, n-tridecanyloxy, n-tetradecyloxy, n-pentadecanyloxy, and n-hexadecyloxy.

When R ¹ is an alkoxycarbonyl group, the alkoxycarbonyl group preferably has 2 to 20 carbon atoms, and more preferably 2 to 7 carbon atoms. Specific examples of when R ¹ is an alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, an isopropoxycarbonyl group, an n-butoxycarbonyl group, and an isobutoxy group. Carbonyl, sec-butoxycarbonyl, tert-butoxycarbonyl, n-pentyloxycarbonyl, isopentyloxycarbonyl, sec-pentyloxycarbonyl, tert-pentyloxycarbonyl, n-hexyloxycarbonyl, N-heptyloxycarbonyl, n-octyloxycarbonyl, isooctyloxycarbonyl, sec-octyloxycarbonyl, tert-octyloxycarbonyl, n-decyloxycarbonyl, isodecyloxycarbonyl, n-oxime An oxycarbonyl group, an isodecyloxycarbonyl group or the like.

When R ¹ is a phenylalkyl group, the phenylalkyl group preferably has 7 to 20 carbon atoms, and more preferably 7 to 10 carbon atoms. Further, when R ¹ is a naphthylalkyl group, the naphthylalkyl group preferably has 11 to 20 carbon atoms, and more preferably 11 to 14 carbon atoms. 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 when R ¹ is a naphthylalkyl group include α-naphthylmethyl group, β-naphthylmethyl group, 2-(α-naphthyl)ethyl group, and 2-(β-naphthyl)ethyl group. . When R ¹ is a phenylalkyl group or a naphthylalkyl group, R ¹ may further have a substituent on the phenyl group or the naphthyl group.

When R ¹ is a heterocyclic group, the heterocyclic group is a 5-membered or 6-membered monocyclic ring containing 1 or more of N, S, O, or the monocyclic ring or the monocyclic ring and the benzene ring are condensed. Ring base. When the heterocyclic group is a condensed ring, the number of rings is set to 3 or less. The heterocyclic group may be an aromatic group (heteroaryl group) or a non-aromatic group. Examples of the heterocyclic ring constituting the heterocyclic group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, and anthracene. Pyrazine, benzofuran, benzothiophene, anthracene, isoindole, pyridazine, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, anthracene, quinoline, isoquinoline , quinazoline, pyridazine, porphyrin, quinoxaline, piperidine, piperazine, morpholine, piperidine, tetrahydropyran, and tetrahydrofuran. When R ¹ is a heterocyclic group, the heterocyclic group may further have a substituent.

When R ¹ is a heterocyclic carbonyl group, the heterocyclic group contained in the heterocyclic carbonyl group is the same as the case where R ¹ is a heterocyclic group.

When R ¹ is an amine group substituted with 1 or 2 organic groups, as a suitable example of the organic group, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, and carbon can be exemplified. a saturated aliphatic fluorenyl group having 2 to 21 atoms, a phenyl group which may have a substituent, a benzamyl group which may have a substituent, a phenylalkyl group having 7 to 20 carbon atoms which may have a substituent, may have a substitution The naphthyl group of the group, the naphthoquinone which may have a substituent, the naphthylalkyl group having 11 to 20 carbon atoms which may have a substituent, and a heterocyclic group. Specific examples of such suitable organic groups are the same as R ¹ . Specific examples of the amine group substituted with 1 or 2 organic groups include methylamino group, ethylamino group, diethylamino group, n-propylamino group, and di-n-propylamino group. , isopropylamino, n-butylamino, di-n-butylamino, n-pentylamino, n-hexylamino, n-heptylamino, n-octylamino, N-decylamino, n-decylamino, phenylamino, naphthylamino, etidylamino, propylamino, n-butylamino, n-pentamethyleneamine, N-hexylamino group, n-heptylamino group, n-octylamino group, n-decylamino group, benzamidine amine group, α-naphthylmethylamino group, and β-naphthalene Carbenylamine and the like.

When the phenyl group, the naphthyl group, and the heterocyclic group contained in R ¹ further have a substituent, examples of the substituent include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and carbon. a saturated aliphatic fluorenyl group having 2 to 7 atoms, an alkoxycarbonyl group having 2 to 7 carbon atoms, a saturated aliphatic fluorenyloxy group having 2 to 7 carbon atoms, and a single alkyl group having 1 to 6 carbon atoms An alkylamino group, a dialkylamino group having an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, a halogen, a nitro group, and a cyano group. When the phenyl group, the naphthyl group, and the heterocyclic group contained in R ¹ further have a substituent, the number of the substituents is not limited within the range not detracting from the object of the present invention, but is 1 to 4 good. When the phenyl group, the naphthyl group, and the heterocyclic group contained in R ¹ have a plurality of substituents, the plurality of substituents may be the same or different.

Among the above-described bases, R ^{1 is} preferably a group represented by a nitro group or R ⁶ -CO- from the viewpoint of enhancing the sensitivity. R ^{6 is} not particularly limited insofar as it does not impair the object of the present invention, and can be selected from various organic groups. Examples of suitable bases for R ⁶ include an alkyl group having 1 to 20 carbon atoms, a phenyl group which may have a substituent, a naphthyl group which may have a substituent, and a heterocyclic group which may have a substituent. As R ⁶ , particularly preferred among these groups are 2-methylphenyl, thiophen-2-yl, and α-naphthyl.

Further, from the viewpoint of a tendency to improve transparency, R ^{1 is} preferably a hydrogen atom. When R ¹ is a hydrogen atom and R ⁴ is a group represented by the formula (R4-2) to be described later, the transparency tends to be more excellent.

In the formula (c-5), R ² and R ³ each independently represent a chain alkyl group which may have a substituent, a cyclic organic group which may have a substituent, or a hydrogen atom. R ² and R ³ may be bonded to each other to form a ring. Among these groups, R ² and R ^{3 are} preferably a chain alkyl group which may have a substituent. When R ² and R ³ are a chain alkyl group which may have a substituent, the chain alkyl group may be a linear alkyl group or a branched alkyl group.

When R ² and R ³ are a chain alkyl group having no substituent, the number of carbon atoms of the chain alkyl group is preferably from 1 to 20, more preferably from 1 to 10, particularly preferably from 1 to 6. Specific examples of the case where R ² and R ³ are a chain alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl. Base, n-pentyl, isopentyl, sec-pentyl, tert-pentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, sec-octyl, tert-octyl, n - anthracenyl, isodecyl, n-fluorenyl, and isodecyl. Further, when R ² and R ³ are an alkyl group, the alkyl group may contain an ether bond (-O-) in the carbon chain. As an example of the alkyl group having an ether bond in the carbon chain, a methoxyethyl group, an ethoxyethyl group, a methoxyethoxyethyl group, an ethoxyethoxyethyl group, a propoxy group B can be exemplified. Oxyethyl, methoxypropyl and the like.

When R ² and R ³ are a chain alkyl group having a substituent, the number of carbon atoms of the chain alkyl group is preferably from 1 to 20, more preferably from 1 to 10, particularly preferably from 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 a linear chain.

The substituent which the alkyl group may have is not particularly limited insofar as it does not impair the object of the present invention. As a suitable example of the substituent, a cyano group, a halogen atom, a cyclic organic group, and an alkoxycarbonyl group can be exemplified. The halogen atom may, for example, be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. Among these, a fluorine atom, a chlorine atom or a bromine atom is preferred. The cyclic organic group may, for example, be a cycloalkyl group, an aromatic hydrocarbon group or a heterocyclic group. Specific examples of the cycloalkyl group are the same as those in the case where R ¹ is a cycloalkyl group. Specific examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, a biphenyl group, an anthracenyl group, and a phenanthryl group. Specific examples of the heterocyclic group are the same as those in the case where R ¹ is a heterocyclic group. When R ¹ is an alkoxycarbonyl group, the alkoxy group contained in the alkoxycarbonyl group may be linear or branched, and is preferably linear. The alkoxy group contained in the alkoxycarbonyl group preferably has 1 to 10 carbon atoms, and more preferably 1 to 6 carbon atoms.

When the chain alkyl group has a substituent, the number of the substituent is not particularly limited. The number of preferred substituents can be adjusted to vary the number of carbon atoms of the chain alkyl group. The number of substituents is typically from 1 to 20, preferably from 1 to 10, and more preferably from 1 to 6.

When R ² and R ³ are a cyclic organic group, the cyclic organic group may be an alicyclic group or an aromatic group. The cyclic organic group may, for example, be an aliphatic cyclic hydrocarbon group, an aromatic hydrocarbon group or a heterocyclic group. When R ² and R ³ are a cyclic organic group, the substituent which the cyclic organic group may have is the same as when R ² and R ³ are a chain alkyl group.

When R ² and R ³ are an aromatic hydrocarbon group, the aromatic hydrocarbon group is preferably a phenyl group, or a group formed by bonding a plurality of benzene rings through a carbon-carbon bond, or a group formed by condensation of a plurality of benzene rings. . When the aromatic hydrocarbon group is a phenyl group or a group in which a plurality of benzene rings are bonded or condensed, the number of rings of the benzene ring contained in the aromatic hydrocarbon group is not particularly limited, and is preferably 3 or less, and more preferably 2 or less, especially preferably 1. Preferable examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, a biphenyl group, an anthracenyl group, and a phenanthryl group.

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 from 3 to 20, and more preferably from 3 to 10. Examples of the monocyclic cyclic hydrocarbon group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a decyl group, an isodecyl group, a tricyclodecyl group, and a trisole. Cyclodecyl, tetracyclododecyl, and adamantyl.

When R ² and R ³ are a heterocyclic group, the heterocyclic group is a 5-membered or 6-membered monocyclic ring containing 1 or more of N, S, O, or the monocyclic ring or the monocyclic ring and the benzene ring via Condensed heterocyclic group. When the heterocyclic group is a condensed ring, the number of rings is set to 3 or less. The heterocyclic group may be an aromatic group (heteroaryl group) or a non-aromatic group. Examples of the heterocyclic ring constituting the heterocyclic group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, and anthracene. Pyrazine, benzofuran, benzothiophene, anthracene, isoindole, pyridazine, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, anthracene, quinoline, isoquinoline , quinazoline, pyridazine, porphyrin, quinoxaline, piperidine, piperazine, morpholine, piperidine, tetrahydropyran, and tetrahydrofuran.

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

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

As an example of a suitable base among R ² and R ³ described above, a group represented by the formula -A ¹ -A ² can be exemplified. In the formula, A ¹ is a linear alkylene group, and A ² is an alkoxy group, a cyano group, a halogen atom, a halogenated alkyl group, a cyclic organic group, or an alkoxycarbonyl group.

The linear alkyl group of A ¹ preferably has 1 to 10 carbon atoms, and more preferably 1 to 6 carbon atoms. When A ² is an alkoxy group, the alkoxy group may be linear or branched, and is preferably a linear chain. The alkoxy group preferably has 1 to 10 carbon atoms, and more preferably 1 to 6 carbon atoms. When A ² is a halogen atom, it 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. When A ² is a halogenated alkyl group, the halogen atom contained in the halogenated alkyl group is preferably a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and more preferably a fluorine atom, a chlorine atom or a bromine atom. The halogenated alkyl group may be linear or branched, and is preferably a linear chain. When A ² is a cyclic organic group, an example of the cyclic organic group is the same as the cyclic organic group which is a substituent in R ² and R ³ . When A ² is an alkoxycarbonyl group, an alkoxycarbonyl group Examples thereof are the same as the alkoxycarbonyl group which is a substituent in R ² and R ³ .

Specific examples of suitable examples of R ² and R ³ include an alkyl group of an ethyl group, an n-propyl group, an n-butyl group, an n-hexyl group, an n-heptyl group, and an n-octyl group; 2-methoxy Ethyl ethyl, 3-methoxy-n-propyl, 4-methoxy-n-butyl, 5-methoxy-n-pentyl, 6-methoxy-n-hexyl, 7-A Oxy-n-heptyl, 8-methoxy-n-octyl, 2-ethoxyethyl, 3-ethoxy-n-propyl, 4-ethoxy-n-butyl, 5 An alkoxyalkyl group such as ethoxy-n-pentyl, 6-ethoxy-n-hexyl, 7-ethoxy-n-heptyl, and 8-ethoxy-n-octyl; 2-cyanoethyl, 3-cyano-n-propyl, 4-cyano-n-butyl, 5-cyano-n-pentyl, 6-cyano-n-hexyl, 7-cyano -n-heptyl, and cyanoalkyl such as 8-cyano-n-octyl; 2-phenylethyl, 3-phenyl-n-propyl, 4-phenyl-n-butyl, a phenylalkyl group such as 5-phenyl-n-pentyl, 6-phenyl-n-hexyl, 7-phenyl-n-heptyl, and 8-phenyl-n-octyl; 2-cyclohexyl Ethyl, 3-cyclohexyl-n-propyl, 4-cyclohexyl-n-butyl, 5-cyclohexyl-n-pentyl, 6-cyclohexyl-n-hexyl, 7-cyclohexyl-n-g , 8-cyclohexyl-n-octyl, 2-cyclopentylethyl, 3-cyclopentyl-n-propyl, 4-cyclopentyl-n- a cycloalkoxy group such as 5-cyclopentyl-n-pentyl, 6-cyclopentyl-n-hexyl, 7-cyclopentyl-n-heptyl, and 8-cyclopentyl-n-octyl Alkylalkyl; 2-methoxycarbonylethyl, 3-methoxycarbonyl-n-propyl, 4-methoxycarbonyl-n-butyl, 5-methoxycarbonyl-n-pentyl, 6 -methoxycarbonyl-n-hexyl, 7-methoxycarbonyl-n-heptyl, 8-methoxycarbonyl-n-octyl, 2-ethoxycarbonylethyl, 3-ethoxycarbonyl- N-propyl, 4-ethoxycarbonyl-n-butyl, 5-ethoxycarbonyl-n-pentyl, 6-ethoxycarbonyl-n-hexyl, 7-ethoxycarbonyl-n-g And alkoxycarbonylalkyl groups such as 8-ethoxycarbonyl-n-octyl; 2-chloroethyl, 3-chloro-n-propyl, 4-chloro-n-butyl, 5-chloro -n-pentyl, 6-chloro-n-hexyl, 7-chloro-n-heptyl, 8-chloro-n-octyl, 2-bromoethyl, 3-bromo-n-propyl, 4-bromo -n-butyl, 5-bromo-n-pentyl, 6-bromo-n-hexyl, 7-bromo-n-heptyl, 8-bromo-n-octyl, 3,3,3-trifluoropropene And a halogenated alkyl group such as 3,3,4,4,5,5,5-heptafluoro-n-pentyl.

As R ² and R ³ , the above is also a suitable base ethyl, n-propyl, n-butyl, n-pentyl, 2-methoxyethyl, 2-cyanoethyl, 2 -phenylethyl, 2-cyclohexylethyl, 2-methoxycarbonylethyl, 2-chloroethyl, 2-bromoethyl, 3,3,3-trifluoropropyl, and 3,3, 4,4,5,5,5-heptafluoro-n-pentyl.

As an example of a suitable organic group for R ⁴ , the same as R ¹ , an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic fluorenyl group, an alkoxycarbonyl group, a saturated aliphatic hydrazine can be exemplified. An oxy group, a phenyl group which may have a substituent, a phenoxy group which may have a substituent, a benzamyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, a benzamidineoxy group which may have a substituent a phenylalkyl group which may have a substituent, a naphthyl group which may have a substituent, a naphthyloxy group which may have a substituent, a naphthoquinone which may have a substituent, a naphthyloxycarbonyl group which may have a substituent, may have a substitution a naphthylmethoxycarbonyl group, a naphthylalkyl group which may have a substituent, a heterocyclic group which may have a substituent, a heterocyclic carbonyl group which may have a substituent, an amine group substituted with 1 or 2 organic groups, Morpholin-1-yl, piperazin-1-yl and the like. Specific examples of such group, the same as those described for R ^1. Further, as R ⁴ , a cycloalkyloxyalkyl 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 substituent which the phenoxyalkyl group and the phenylthioalkyl group may have is the same as the substituent which the phenyl group contained in R ¹ may have.

Among the organic groups, as R ⁴ , an alkyl group, a cycloalkyl group, a phenyl group which may have a substituent, or a cycloalkoxyalkyl group, and a phenylthioalkyl group which may have a substituent on the aromatic ring are preferable. base. The alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, particularly preferably an alkyl group having 1 to 4 carbon atoms, and most preferably a methyl group. Among the phenyl groups which may have a substituent, a methylphenyl group is preferred, and a 2-methylphenyl group is also preferred. The number of carbon atoms of the cycloalkyl group contained in the cycloalkoxyalkyl 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 cycloalkoxyalkyl group is preferably from 1 to 8, more preferably from 1 to 4, particularly preferably 2. Among the cycloalkyloxyalkyl groups, a cyclopentylethyl group is preferred. The number of carbon atoms of the alkylene group contained in the phenylthioalkyl group which may have a substituent on the aromatic ring is preferably from 1 to 8, more preferably from 1 to 4, particularly preferably 2. Among the phenylthioalkyl groups which may have a substituent on the aromatic ring, 2-(4-chlorophenylthio)ethyl group is preferred.

Further, as R ⁴ , a group represented by -A ³ -CO-OA ⁴ is also preferred. A ³ is a divalent organic group, preferably a divalent hydrocarbon group, and an alkyl group is preferred. A ⁴ is a monovalent organic group, preferably a monovalent hydrocarbon group.

When A ³ is an alkylene group, the alkyl group may be linear or branched, and is preferably a linear chain. When A ³ is an alkylene group, the alkyl group has preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 4 carbon atoms.

As a suitable example of A ⁴ , 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 can be exemplified. Specific examples of suitable A ⁴ include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, N-hexyl, phenyl, naphthyl, benzyl, phenethyl, α-naphthylmethyl, and β-naphthylmethyl.

As a suitable example of the group represented by -A ³ -CO-OA ⁴ , 2-methoxycarbonylethyl, 2-ethoxycarbonylethyl, 2-n-propoxycarbonylethyl, 2-n-butoxycarbonylethyl, 2-n-pentyloxycarbonylethyl, 2-n-hexyloxycarbonylethyl, 2-benzyloxycarbonylethyl, 2-phenoxycarbonylethyl , 3-methoxycarbonyl-n-propyl, 3-ethoxycarbonyl-n-propyl, 3-n-propoxycarbonyl-n-propyl, 3-n-butoxycarbonyl-n- Propyl, 3-n-pentyloxycarbonyl-n-propyl, 3-n-hexyloxycarbonyl-n-propyl, 3-benzyloxycarbonyl-n-propyl, and 3-phenoxycarbonyl -n-propyl and the like.

Although R ^{4 has} been described above, R ^{4 is} preferably a group represented by the following formula (R4-1) or (R4-2).

(In the formulae (R4-1) and (R4-2), R ⁷ and R ⁸ are each an organic group, and p is an integer of 0 to 4, and when R ⁷ and R ⁸ are present in an adjacent position on the benzene ring; R ⁷ and R ⁸ may be bonded to each other to form a ring, q is an integer of 1 to 8, r is an integer of 1 to 5, s is an integer of 0 to (r+3), and R ⁹ is an organic group).

Examples of the organic group of R ⁷ and R ⁸ in the formula (R4-1) are the same as those of R ¹ . As R ⁷ , an alkyl group or a phenyl group is preferred. When R ⁷ is an alkyl group, the number of carbon atoms is preferably from 1 to 10, more preferably from 1 to 5, particularly preferably from 1 to 3, most preferably 1. In other words, R ^{7 is} most preferably a methyl group. When R ⁷ and R ^{8 are} bonded to form a ring, the ring may be an aromatic ring or an aliphatic ring. As a group represented by the formula (R4-1), and R ⁷ and R ⁸ are suitable examples of the group forming the ring, naphthalene-1-yl or 1,2,3,4-tetrahydronaphthalene-5 can be exemplified. - Base, etc. 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. As the organic group, the same ones as those exemplified for R ¹ can be exemplified. Among the organic groups, an alkyl group is preferred. The alkyl group may be linear or branched. The alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and particularly preferably 1 to 3 carbon atoms. As R ⁹ , a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group or the like is preferable, and among them, a methyl group is 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), preferably an integer of 0 to 3, and more preferably an integer of 0 to 2, and particularly preferably 0. 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, particularly preferably 1 or 2.

In the 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. The substituent which may be possessed when R ⁵ is an alkyl group is preferably exemplified by a phenyl group, a naphthyl group or the like. 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 or the like is preferably exemplified.

In the formula (c-5), as R ⁵ , preferred are, for example, a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a phenyl group, a benzyl group or a methylphenyl group. And naphthyl and the like, among these, a methyl group or a phenyl group is preferred.

The compound represented by formula (c-5) can be used alone or When two or more types are used, when two or more types are used, the following (i) to (iii) are preferable.

(I) with a compound R ¹ R ¹ is a combination of a hydrogen atom of a nitro compound; combination of a compound of the compound (II) R ⁴ is of formula (R4-1) and R ⁴ is of formula (R4-2) of; (iii) R ⁴ is a compound of the formula (R4-1) or the formula (R4-2) and the compound wherein R ⁴ is an alkyl group having 1 to 4 carbon atoms.

Among them, from the viewpoint of improving the characteristics of the sensitivity and the transmittance of the cured product, etc., it is preferable that the combination of the above (i) satisfies the combination of the above (i), (ii) or (iii).

The blending ratio (mass ratio) of each compound in the combination of the above (i) to (iii) can be appropriately adjusted depending on the characteristics such as the sensitivity of the object, for example, from 1:99 to 99:1. Good, 10:90~90:10 is better, 30:70~70:30 is better.

The method for producing the compound represented by the formula (c-5) is not particularly limited. The compound represented by the formula (c-5) can be preferably produced by a method comprising the following steps: the thiol group (=N) contained in the compound represented by the following formula (c-6) The step of converting -OH) to the oxime ester group represented by =NO-COR ⁵ . The R ⁵ system 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 the formula (c-5). n is an integer of 0 to 4, and m is 0 or 1).

Therefore, the compound represented by the above formula (c-6) can be used as a synthesis intermediate of the compound represented by the formula (c-5).

The method of converting the thiol group (=N-OH) to the oxime ester group represented by =NO-COR ⁵ is not particularly limited. Typically, a method of reacting a deuteration agent imparted with a mercapto group represented by COR ⁵ with a hydroxyl group in a mercapto group can be exemplified. The acidifying agent may, for example, be an acid anhydride represented by (R ⁵ CO) ₂ O or an acid halide represented by R ⁵ COHal (Hal is a halogen atom).

When m of the compound represented by the general formula (c-5) is 0, for example, the synthesis can be carried out in accordance with the following Scheme 1. In the scheme 1, an anthracene 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, a substituent ( ¹⁾ can be obtained by introducing a substituent R ^{1 to} an anthracene derivative substituted with R ² and R ³ at the 9th position by a conventional method. 1) The anthracene derivative represented. The ninth place is an anthracene derivative substituted with R ² and R ³ . For example, when R ² and R ³ are an alkyl group, the presence of an alkali metal hydroxide is as described in JP-A-06-234668. It can be obtained by reacting hydrazine with an alkylating agent in an aprotic polar organic solvent. Further, an alkylating agent such as a halogenated alkyl group, an aqueous solution of an alkali metal hydroxide, and a phase transfer catalyst such as tetrabutylammonium iodide or potassium t-butoxide are added to the organic solvent solution of the hydrazine. The 9,9-alkyl substituted anthracene can be obtained by carrying out an alkylation reaction.

For the anthracene derivative represented by the formula (1-1), a thiol group represented by -CO-R ⁴ is introduced by a Friedel-Crafts deuteration reaction, and the formula (1) can be obtained. -3) The anthracene derivative represented. The deuteration agent for introducing a mercapto group represented by -CO-R ⁴ may be a halocarbonyl compound or an acid anhydride. As the halogenating agent, a halogenated carbonyl compound represented by the formula (1-2) is preferred. In the formula (1-2), Hal is a halogen atom. The position at which the sulfhydryl group is introduced on the ankle ring can be appropriately changed by the conditions of the Friedel-Crafts reaction or by applying protection and deprotection at other positions in the deuteration position. .

Next, the group represented by -CO-R ⁴ in the anthracene derivative represented by the obtained formula (1-3) is converted into a group represented by -C(=N-OH)-R ⁴ to give a formula ( 1-4) The hydrazine compound represented. The method of converting the group represented by -CO-R ⁴ into a group represented by -C(=N-OH)-R ⁴ is not particularly limited, but is preferably a hydrazine group. An anthracene compound represented by the formula (1-4), an acid anhydride represented by the following formula (1-5) ((R ⁵ CO) ₂ O), or an acid halide represented by the following general formula (1-6) ( When R ⁵ COHal and Hal are a halogen atom, a compound represented by the following formula (1-7) can be obtained.

Further, 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 those of the formula (c-5).

Further, in the scheme 1, R ⁴ contained in each of the formula (1-2), the formula (1-3), and the formula (1-4) may be the same or different. In other words, R ⁴ in the formula (1-2), the formula (1-3), and the formula (1-4) may be chemically modified in the synthesis process shown in Scheme 1. Examples of the chemical modification include esterification, etherification, deuteration, guanidation, halogenation, and substitution of a hydrogen atom in an amine group with an organic group. The chemical modification that R ⁴ can be subjected to is not limited to this.

<Process 1>

When m of the compound represented by the formula (c-5) is 1, for example, it can be synthesized according to the following Scheme 2. In the scheme 2, an anthracene derivative represented by the following formula (2-1) is used as a raw material. The anthracene derivative represented by the formula (2-1) is introduced into the -CO-CH for the compound represented by the formula (1-1) by the Friedel-Crafts reaction by the same method as in the first scheme. Available as a thiol group represented by _{2 -} R ⁴ . As the halogenating agent, a carboxylic acid halide represented by the formula (1-8): Hal-CO-CH ₂ -R ⁴ is preferred. Next, the methylene group existing between R ⁴ and the carbonyl group in the compound represented by the formula (2-1) is deuterated to obtain a ketoxime compound represented by the following formula (2-3). The method of purifying the methylene group is not particularly limited, but it is preferably a nitrite represented by the following general formula (2-2) in the presence of hydrochloric acid (RONO, R is an alkane having 1 to 6 carbon atoms) Base) method of reaction. Next, a ketoxime compound represented by the following formula (2-3), an acid anhydride represented by the following formula (2-4) ((R ⁵ CO) ₂ O), or the following general formula (2-5) The acid halide (R ⁵ COHal, Hal is a halogen atom) is reacted to obtain a compound represented by the following formula (2-6). Further, in the following formulae (2-1), (2-3), (2-4), (2-5), and (2-6), R ¹ , R ² , R ³ , R ⁴ , and The R ⁵ system is the same as the formula (c-5).

When m is 1, the use of the photosensitive resin composition containing the compound represented by the formula (c-5) tends to lower the generation of foreign matter in the formed pattern.

Further, in the scheme 2, R ⁴ contained in the formula (1-8), the formula (2-1), and the formula (2-3) may be the same or different. In other words, R ⁴ in the formula (1-8), the formula (2-1), and the formula (2-3) may be chemically modified in the synthesis process shown in Scheme 2. Examples of the chemical modification include esterification, etherification, deuteration, guanidation, halogenation, and substitution of a hydrogen atom in an amine group with an organic group. The chemical modification that R ⁴ can be subjected to is not limited to this.

<Process 2>

Specific examples of suitable compounds of 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 based on 100 parts by mass of the solid content of the photosensitive resin composition. By the above range, sufficient heat resistance and chemical resistance can be obtained, and the coating film forming ability can be improved and the hardening failure can be suppressed.

<(D) Sunscreen>

The photosensitive resin composition according to the present invention contains an opacifier. As the light shielding agent, a black pigment is preferably used. Examples of the black pigment used as the opacifier include metal oxides of carbon black, lanthanum pigment, silver tin alloy, titanium black, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, silver, and the like. Oxides, metal sulfides, metal sulfates or metal carbonates, etc., regardless of organic or inorganic pigments. These black pigments can be used in combination of two or more kinds.

As the (D) light-shielding agent, it is preferable to contain an anthraquinone-based pigment because the adhesion between the black column spacer formed by the photosensitive resin composition and the substrate is likely to be excellent. The content of the lanthanoid pigment in the light-shielding agent (D) is preferably 85% by mass or more, more preferably 90% by mass or more, and particularly preferably 100% by mass or more based on the total mass of the (D) light-shielding agent.

Specific examples of the fluorene-based pigments include the fluorene-based pigments represented by the following general formula (d-1) and the fluorene-based pigments represented by the following general formula (d-2). Further, as for the commercially available product, it is preferable to use the product names K0084, K0086, or Pigment Black 21, 30, 31, 32, 33, and 34 manufactured by BASF Corporation.

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

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

For the compound represented by the above formula (d-1) and the compound represented by the general formula (d-2), for example, the method described in JP-A-62-21753 and JP-A-63-26784 can be used. To synthesize. That is, the hydrazine-3,5,9,10-tetracarboxylic acid or the dianhydride and the amine are used as a raw material, and the reaction is carried out in water or an organic solvent. Then, the obtained crude product is reprecipitated in sulfuric acid or recrystallized from water, an organic solvent or a mixed solvent thereof to obtain a desired product.

Further, in the photosensitive resin composition, in order to disperse the fluorene-based pigment well, the average particle diameter of the quinone-based pigment is 10 to 1000 nm. good.

Further, in the purpose of adjusting the color tone or the like, (D) the light-shielding agent may be a black pigment or a coloring matter of a hue with red, blue, green, yellow, purple or the like. A pigment of a color other than the black pigment can be appropriately selected from the conventional dyes. The amount of the other coloring matter of the coloring matter other than the black pigment is preferably 15% by mass or less, and preferably 10% by mass or less based on the total mass of the (D) opacifier.

The content of the (D) light-shielding agent in the photosensitive resin composition can be appropriately selected within the range not impairing the object of the present invention, and it is preferably preferred to the solid content of the photosensitive resin composition. It is 5 to 50% by mass. By using the amount of the light-shielding agent in the range, the light-blocking property of the black column spacer obtained by using the photosensitive resin composition is good, and at the same time, the exposure failure can be easily suppressed when the photosensitive resin composition is exposed. Poor hardening.

<(E) Light Absorber>

The photosensitive resin composition according to the present invention preferably contains a light absorbing agent.

The light absorbing agent is not particularly limited, and a light absorbing agent capable of absorbing light that is exposed can be used, but a light absorbing agent that absorbs light in the wavelength range of 200 to 450 nm is particularly preferable. For example, a naphthalene compound, a dinaphthyl compound, an anthraquinone compound, a phenanthroline compound, a dye, etc.

Specifically, cinnamic acid-2-ethylhexyl ester, p-methoxycinnamic acid-2-ethylhexyl ester, methoxy cinnamic acid isopropyl ester, methoxy laurel can be exemplified. A cinnamic acid derivative such as isoamyl citrate; α-naphthol, β-naphthol, α-naphthol methyl ether, α-naphthol ethyl ether, 1,2-dihydroxynaphthalene, 1,3- Dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,3-dihydroxy Naphthalene derivatives such as naphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene; anthracene, 9,10-dihydroxyindole, etc.; and azo dyes, benzophenones Dyes such as dyes, aminoketone dyes, quinoline dyes, anthraquinone dyes, diphenylcyanoacrylate dyes, triazine dyes, p-aminobenzoic acid dyes, and the like. Among these, a cinnamic acid derivative or a naphthalene derivative is preferably used, and a cinnamic acid derivative is particularly preferably used. These light absorbers can be used singly or in combination of two or more.

The content of the light absorbing agent (E) is preferably 0.5 to 20 parts by mass based on 100 parts by mass of the solid content of the photosensitive resin composition. By setting it as the above range, the fracture strength after hardening can be kept good, and the ratio of the change in film thickness at the time of changing the exposure amount can be increased.

<(S) organic solvent>

The photosensitive resin composition according to the present invention preferably contains an organic solvent for dilution. The organic solvent may, for example, be ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol-n-propyl ether, ethylene glycol mono-n-butyl ether or diethylene glycol monomethyl. Ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol single Ethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol (poly) of monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, etc. Alkylene glycol monoalkyl ethers; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl (poly)alkylene glycol monoalkyl ether acetates such as ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate; diethylene glycol dimethyl ether, diethylene glycol Other ethers such as alcohol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone; Alkyl lactate such as methyl hydroxypropionate or ethyl 2-hydroxypropionate; ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, 3-methoxypropane Ethyl acetate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3 -methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, ethyl acetate, B Acid n-propyl ester, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl formate, isoamyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate Ester, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetate, ethyl acetate, 2-oxobutyric acid Other esters such as ethyl ester; aromatic hydrocarbons such as toluene and xylene; N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethyl B Indoleamine, N,N-dimethylisobutylamine, N,N-diethylacetamide, N,N-diethylformamide, N-methylcaprolactam, 1,3- A nitrogen-containing polar organic solvent such as dimethyl-2-imidazolidinone, pyridine or N,N,N',N'-tetramethylurea or the like.

Among these, an alkanediol monoalkyl ether, an alkylene glycol monoalkyl ether acetate, the above other ethers, an alkyl lactate, and the above other esters are preferred. Alkylene glycol monoalkyl ether acetates, the above other ethers, and the above other esters are further preferred. Further, the (S) organic solvent preferably contains a nitrogen-containing polar organic solvent from the viewpoints of solubility of each component or (D) dispersibility of the light-shielding agent. As the nitrogen-containing polar organic solvent, N, N, N', N'-tetramethylurea is preferred.

These solvents may be used singly or in combination of two or more.

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

<Other ingredients>

The photosensitive resin composition according to the present invention may contain various additives as needed. As the additive, a sensitizer, a hardening accelerator, a filler, an adhesion promoter, an antioxidant, an aggregation inhibitor, a thermal polymerization inhibitor, an antifoaming agent, a surfactant, and the like can be exemplified.

<Modulation Method of Photosensitive Resin Composition>

The photosensitive resin composition according to the present invention is prepared by mixing the above components with a stirrer. Further, in order to make the prepared photosensitive resin composition uniform, it is also possible to perform filtration using a membrane filter or the like.

≪ spacer, display device, black column spacer forming method≫

The black column spacer according to the present invention is the same as the conventional black column spacer except that it is formed of the photosensitive resin composition according to the present invention. Moreover, the display device according to the present invention is the same as the conventional display device except that the spacer formed of the photosensitive resin composition according to the present invention is provided. Only the method of forming the black column spacer will be described below.

A suitable method for forming a black pillar spacer, comprising: applying a photosensitive resin composition according to the present invention to a substrate, thereby forming a photosensitive resin layer (coating step); and corresponding to the specified spacer The pattern is used to expose the photosensitive resin layer (exposure step); and the exposed photosensitive resin layer is developed to form a pattern of the spacer (developing step).

First, in the coating step, a contact transfer type coating device such as roll coating, reverse roll, or bar coating, or a non-contact type such as a rotary cloth coating machine (rotary coating device) or curtain coating is used. In the coating apparatus, the photosensitive resin composition according to the present invention is applied onto a substrate on which a black column spacer is to be formed, and the solvent is removed by drying as needed to form a photosensitive resin layer.

Next, in the exposure step, the photosensitive resin layer is irradiated with an active energy ray such as ultraviolet light or excimer laser light through a negative mask, and the photosensitive resin layer is partially exposed in accordance with the pattern of the black column spacer. A high-pressure mercury lamp, an ultra-high pressure mercury lamp, a xenon lamp, a carbon arc lamp, or the like, which emits ultraviolet light, can be used for the exposure. The exposure amount varies depending on the composition of the photosensitive resin composition, but is preferably, for example, about 10 to 600 mJ/cm ² .

Further, when the substrate is a TFT substrate or the like, the element is formed on the substrate, and the black pillar spacer must be formed on the element or on the opposite portion of the element on which the substrate on which the element is formed is the counter substrate. In this case, it is necessary to change the height of the black column spacer between the portion where the element is formed and the other portion, considering the height of the element. Here, in such a case, it is preferable to perform exposure by transmitting a halftone mask. As long as the photosensitive resin composition according to the present invention is used and exposed through a halftone mask, it is possible to easily form black pillar spacers having different heights.

Next, in the developing step, the exposed photosensitive resin layer is developed by a developing solution to form a black column spacer. The development method is not particularly limited, and a dipping method, a spray method, or the like can be used. Specific examples of the developer include an organic developer such as monoethanolamine, diethanolamine or triethanolamine, or an aqueous solution of sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia or a quaternary ammonium salt.

Thereafter, post-baking is applied to the developed black column spacer to heat-harden. The post-baking is preferably carried out at 150 to 250 ° C for 15 to 60 minutes.

[Examples]

Hereinafter, the examples are shown to further illustrate the present invention, but the scope of the present invention is not limited to the examples.

<Examples 1 to 5, and Comparative Examples 1 to 4>

5 parts by mass of (A) alkali-soluble resin, 2 parts by mass of (B1) component, 0.8 parts by mass of (B2) component or (B3) component, and (C) photopolymerization initiator 2.5 parts by mass, and pigment dispersion The liquid (pigment: 4.64 parts by mass of ruthenium black) and 0.05 parts by mass of α-naphthol were dispersed and dissolved in a solvent so that the solid content was 20% by mass to prepare a photosensitive resin composition.

Further, the composition of the solvent in the photosensitive composition is 10% by mass of methoxybutyl acetate, 10% by mass of N,N,N',N'-tetramethylurea, and propylene glycol monomethyl ether. The adjustment was carried out in such a manner that the acetate was 80% by mass.

Further, as the components of the photosensitive resin composition, the following were used.

((A) alkali soluble resin)

As the (A) alkali-soluble resin, the following resin A-1 was used.

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.

The compound described in Table 1 was used as the component (B2). The compounds described in Table 1 are as follows.

B2-1: Tetraethylene glycol dimethacrylate

B2-2: Dimethacrylate of ethoxylated polypropylene glycol (containing propyleneoxy unit 12, and ethyleneoxy unit 6.1206PE (manufactured by Xinghe Co., Ltd.))

B2-3: Diacrylate compound of the following structure

B2-4: 1,3,5-(2'-hydroxyethyl)isocyanuric acid diacrylate

B2-5: 1,3,5-(2'-hydroxyethyl)isocyanuric acid triacrylate

The compound described in Table 1 was used as the component (B3). B3-1, B3-2, B3-3, and B3-4 of the component (B3) described in Table 1 are as follows.

((C) Photopolymerization initiator)

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

The synthesis method of the above resin (A-1) is as follows.

First, a 500 ml four-necked flask was charged with 235 g of bisphenolphthalein type epoxy resin (epoxy equivalent 235), 110 mg of tetramethylammonium chloride, and 100 mg of 2,6-di-tert-butyl-4-methylphenol. 72.0 g of acrylic acid was blown into the air at a rate of 25 ml/min while being heated and dissolved at 90 to 100 °C. Next, the solution was slowly heated while the solution was cloudy, and heated to 120 ° C to be completely dissolved. At this point, the solution gradually became transparent and viscous, but continued to stir. At this time, the acid value was measured, and heating and stirring were continued until it was less than 1.0 mgKOH/g. It takes 12 hours for the acid price to reach the target value. Subsequently, the mixture was cooled to room temperature to obtain a bisphenolphthalein type epoxy acrylate represented by the following formula (a-7) which was colorless, transparent and solid.

Next, 600 g of 3-methoxybutyl acetate was added to 307.0 g of the above-mentioned bisphenol fluorene-type epoxy acrylate, and after dissolving, 80.5 g of benzophenone tetracarboxylic dianhydride and bromine were mixed. 1 g of tetraethylammonium chloride was slowly 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 the reaction was carried out 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.

Further, the resin (A-1) corresponds to the resin represented by the above formula (a-1).

Using the obtained photosensitive resin composition, the halftone characteristics (?H) and the pattern adhesion were evaluated according to the following methods. The evaluation results of these are shown in Table 1.

<Surface roughness Ra evaluation method>

The surface roughness was evaluated by using an atomic force microscope ("AFM (apparatus name)", manufactured by SIINano Technology Co., Ltd.) on the cured film which was cured at an exposure amount of 70 mJ/cm ² by the method described in the halftone characteristic evaluation method described later. Ra). The results are shown in Table 1.

<Evaluation method of elastic recovery rate>

The elastic recovery rate of the cured film which was cured at an exposure amount of 70 mJ/cm ² was measured using a hardness meter FISCHERSCOPE HM2000 (manufactured by FISCHER Instruments) by the method described in the halftone characteristic evaluation method described later. The results are shown in Table 1.

<Halftone characteristic evaluation method>

The photosensitive resin composition was applied onto a glass substrate of 10 cm × 10 cm, and then 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, two photosensitive resin layers formed on the glass substrate were prepared in total.

Next, the photosensitive resin layer was passed through an exposure machine using a high-pressure mercury lamp and passed through a negative mask having a mask size of 30 μm, with an exposure amount of 70 mJ/cm ² for one photosensitive layer resin layer and the other photosensitive layer resin layer for the other photosensitive layer resin layer. The exposure was 6.3 mJ/cm ² for selective exposure.

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 resulting black column spacer was post-baked at 230 ° C for 20 minutes.

Film thickness was measured at an exposure amount of 70mJ / cm ² is formed of a black bar spacers (height, H _FT), with an exposure amount of a film thickness of 6.3mJ / cm ² is formed of a black bar spacers (height, H _HT) According to the following formula, the value of ΔH is obtained.

△H(Å)=H _FT -H _HT

When the value of ΔH is 2500 Å or more, it is judged that the halftone characteristics are good.

As can be seen from the examples of Table 1, when the photosensitive resin composition is a polyfunctional monomer containing (B1) 4 or more functional groups, and (B2) a bifunctional monomer and/or a trifunctional monomer, elasticity can be formed. Black column spacers with high recovery rate and less wrinkles.

Further, the photosensitive resin composition of the examples was also excellent in halftone characteristics.

On the other hand, as seen from the comparative example, the photosensitive resin composition is a combination of a (B1) tetrafunctional or higher polyfunctional monomer, a (B3) monofunctional monomer, or only (B1)4. In the case of a polyfunctional monomer having a functional group or more, the photosensitive resin composition has a low elastic recovery rate and is inferior in halftone characteristics.

Claims (8)

A photosensitive resin composition for a black column spacer, comprising (A) an alkali-soluble resin, (B) a photopolymerizable monomer, (C) a photopolymerization initiator, and (D) an opacifier, (B) The photopolymerizable single system includes (B1) a tetrafunctional or higher polyfunctional monomer, and a (B2) bifunctional monomer and/or a trifunctional monomer. The photosensitive resin composition for a black column spacer according to claim 1, wherein the (D) opacifier comprises an anthraquinone black pigment. The photosensitive resin composition for a black column spacer according to claim 1, further comprising (E) a light absorbing agent. The photosensitive resin composition for a black column spacer according to claim 1, wherein the photosensitive resin layer formed of the photosensitive resin composition for the black column spacer is exposed to a predetermined exposure amount by a ghi line, and After developing at 25 ° C for 70 seconds using a 0.05% by mass aqueous KOH solution, post-baking was performed at 230 ° C for 20 minutes to obtain a black column spacer having a film thickness of 2.5 μm or more, and the black column spacer was designated as described above. the exposure amount of 70mJ / cm ² of _{the FT} a thickness H, and the aforementioned exposure amount specified for 6.3mJ / cm ² of the film thickness H _HT difference _{△ H (= H FT -H HT} ) of 2500 ~ 6000Å . A black column spacer formed of a cured product of a photosensitive resin composition of the black column spacer of claim 1. A display device having the black column spacer of claim 5. A method for forming a black column spacer, comprising: The black column spacer of claim 1 is coated on the substrate with a photosensitive resin composition to form a photosensitive resin layer; the photosensitive resin layer is exposed in accordance with a pattern of the specified spacer; The subsequent photosensitive resin layer is developed to form a pattern of the spacer. A method of forming a black column spacer according to claim 7, wherein the exposure is exposed through a halftone mask.