JP5890464B2 - Photosensitive resin composition - Google Patents

Description

  The present invention combines (A) an alkali-soluble resin having a specific functional group, (B) a photopolymerizable compound containing a compound having a specific structure, and (C) a photopolymerization initiator which is an oxime ester compound. It is related with the photosensitive resin composition containing. The present invention also relates to an insulating film, a color filter, a black matrix, and a black column spacer formed using the photosensitive resin composition. Furthermore, the present invention relates to a display device including the above-described insulating film or including at least one of the above-described color filter, black matrix, and black column spacer.

  Conventionally, in an electronic component such as a liquid crystal display element, an integrated circuit element, and a solid-state imaging element, an insulating film or the like is formed between the wirings in order to insulate the wirings arranged in layers. As a method of forming such an insulating film, there is a method of forming using a photosensitive resin composition.

  The photosensitive resin composition used to form such an insulating film includes an alkali-soluble resin having a specific structure, a photopolymerizable monomer, a photopolymerization initiator, and a base that generates a base by the action of light. There is known a composition containing a compound having a structure of (Patent Document 1).

  The photosensitive resin composition is also used for forming color filters, black matrices, black column spacers and the like in panels for liquid crystal display devices. The photosensitive resin composition used for forming a color filter, a black matrix, a black column spacer or the like is usually colored with a colorant. As such a photosensitive resin composition, for example, as a photosensitive resin composition for forming a black column spacer, an alkali-soluble resin, a photopolymerizable monomer, a photopolymerization initiator, and a perylene-based black pigment and a silver tin alloy There is known a composition containing a light-shielding agent containing (Patent Document 2).

JP 2013-228862 A JP 2013-134264 A

  In general, when forming a pattern such as an insulating film, a color filter, a black matrix, or a black column spacer using a photosensitive resin composition, the cross-sectional shape of the pattern is preferably rectangular, and the surface of the pattern is fine. It is preferably smooth without wrinkles.

  However, when forming a pattern such as an insulating film, a color filter, a black matrix, or a black column spacer using the photosensitive resin composition described in Patent Documents 1 and 2, due to the influence of heating during pattern formation, Due to the deformation of the pattern, it may be difficult to form a pattern having a rectangular cross-sectional shape, or fine wrinkles may be generated on the surface of the formed pattern. Moreover, when forming a pattern using the photosensitive resin composition described in Patent Documents 1 and 2, there is a problem that it is difficult to form a pattern having excellent straightness or that the pattern is easily peeled off from the substrate after development. There is.

  The present invention has been made in view of the above-described problems, and has a rectangular shape with a good cross-sectional shape, has no fine wrinkles on the surface, has excellent straightness, and can form a pattern that does not easily peel off from the substrate after development. Photosensitive resin composition, insulating film, color filter, black matrix, and black column spacer formed using the photosensitive resin composition, insulating film, color filter, black matrix, or black An object is to provide a display device including a column spacer.

  The present inventors include (A) an alkali-soluble resin having a specific functional group, (B) a photopolymerizable compound containing a compound having a specific structure, and (C) a photopolymerization initiator that is an oxime ester compound. The present inventors have found that the above-mentioned problems can be solved by using a photosensitive resin composition containing the present invention, and have completed the present invention.

（式（Ｉ）中、Ｒ^１は炭素原子数２〜４のアルキレン基であり、Ｘは、下式（ＩＩ）：

で表される基又は水素原子であり、Ｒ^２は炭素原子数２〜４のアルキレン基であり、Ｒ^３は、下式（ＩＩＩ）：

で表される基であり、ｐは０〜４の整数であり、ｑは０〜５の整数であり、式（Ｉ）中の６つのＸのうちの式（ＩＩ）で表される基の数は４〜６の整数であり、式（Ｉ）中の複数の式（ＩＩ）で表される基は、それぞれ同一であっても異なっていてもよく、式（Ｉ）で表される化合物中の−（Ｒ^１−Ｏ）−で表される２価基の数と−（Ｒ^２−Ｏ）−で表される２価基の数との合計は１以上であり、式（ＩＩＩ）中、Ｒ^４は、水素原子又はメチル基である。）
The first aspect of the present invention comprises (A) an alkali-soluble resin, (B) a photopolymerizable compound, and (C) a photopolymerization initiator, and (A) the alkali-soluble resin is an acryloyl group or an epoxy. A photosensitive resin composition having a group, wherein (B) the photopolymerizable compound includes a compound represented by the following formula (I), and (C) the photopolymerization initiator is an oxime ester compound.

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

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

P is an integer of 0 to 4, q is an integer of 0 to 5, and the group represented by the formula (II) among the six Xs in the formula (I) The number is an integer of 4 to 6, and a plurality of groups represented by the formula (II) in the formula (I) may be the same or different, and the compound represented by the formula (I) The sum of the number of divalent groups represented by — (R ¹ —O) — and the number of divalent groups represented by — (R ² —O) — is 1 or more, and the formula (III) R ⁴ is a hydrogen atom or a methyl group. )

  The 2nd aspect of this invention is the photosensitive resin composition concerning a 1st aspect, Comprising: (D) The insulating film formed using the photosensitive resin composition which does not contain a coloring agent.

  3rd aspect of this invention is a display apparatus provided with the insulating film concerning 2nd aspect.

  4th aspect of this invention is the photosensitive resin composition concerning 1st aspect, Comprising: It is a color filter formed using the photosensitive resin composition containing (D) coloring agent.

  A fifth aspect of the present invention is a photosensitive resin composition according to the first aspect, which is a black matrix formed using a photosensitive resin containing a light-shielding agent as a colorant (D).

  The sixth aspect of the present invention is a photosensitive resin composition according to the first aspect, which is a black column spacer formed using a photosensitive resin containing a light-shielding agent as a colorant (D).

  A seventh aspect of the present invention is a display comprising at least one selected from the group consisting of a color filter according to the fourth aspect, a black matrix according to the fifth aspect, and a black column spacer according to the sixth aspect. Device.

  According to the present invention, a photosensitive resin composition capable of forming a pattern having a rectangular shape with a good cross-sectional shape, no fine wrinkles on the surface, excellent straightness, and difficult to peel off from a substrate after development, and the photosensitive resin composition. Provided are an insulating film, a color filter, a black matrix, and a black column spacer that are formed using a conductive resin composition, and a display device that includes the insulating film, the color filter, the black matrix, or the black column spacer. be able to.

≪Photosensitive resin composition≫
The photosensitive resin composition includes (A) an alkali-soluble resin having a specific functional group, (B) a photopolymerizable compound containing a compound having a specific structure, and (C) a photopolymerization initiator which is an oxime ester compound. including. The photosensitive resin composition may contain (D) a coloring agent, and may contain (D) a coloring agent. The photosensitive resin composition may contain (S) an organic solvent for the purpose of adjusting coating properties. Hereinafter, essential or optional components contained in the photosensitive resin composition and a method for preparing the photosensitive resin composition will be described in order.

<(A) Alkali-soluble resin>
(A) An alkali-soluble resin (hereinafter also referred to as “component (A)”) is a resin solution having a resin concentration of 20% by mass (solvent: propylene glycol monomethyl ether acetate). When the film is immersed in a KOH aqueous solution having a concentration of 0.05% by mass for 1 minute, the film thickness is 0.01 μm or more.

  (A) The alkali-soluble resin has a (meth) acryloyl group or an epoxy group. The (A) alkali-soluble resin is not particularly limited as long as it has a (meth) acryloyl group or an epoxy group and exhibits the above-described alkali solubility, and can be appropriately selected from conventionally known resins.

  (A) As resin suitable as alkali-soluble resin, (A1) resin which has a cardo structure is mentioned. (A) A photosensitive resin composition containing a combination of (A1) a resin having a cardo structure as an alkali-soluble resin and (D) a light-shielding agent as a colorant described later is a black matrix or a black column spacer. It is particularly preferable for use in forming a light shielding member.

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

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

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

In the formula (a-1), Y ^a represents a residue obtained by removing an acid anhydride group (—CO—O—CO—) from a dicarboxylic acid anhydride. Examples of dicarboxylic acid anhydrides include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, chlorendic anhydride, methyltetrahydro Examples thereof include phthalic anhydride and glutaric anhydride.

Further, in the above formula ^(a-1), Z a represents a residue obtained by removing two acid anhydride groups from a tetracarboxylic acid dianhydride. Examples of tetracarboxylic dianhydrides include pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, biphenyl ether tetracarboxylic dianhydride, and the like.
Moreover, in said formula (a-1), m shows the integer of 0-20.

  (A1) The mass average molecular weight of the resin having a cardo structure is preferably 1000 to 40000, and more preferably 2000 to 30000. By setting it as the above range, sufficient heat resistance and film strength can be obtained while obtaining good developability.

  The (A) alkali-soluble resin is a monomer polymer having an ethylenically unsaturated double bond, which contains a unit derived from an unsaturated carboxylic acid, and is a (meth) acryloyloxy group or an epoxy group. Also preferred is a resin having Hereinafter, a polymer of a monomer having an ethylenically unsaturated double bond, including a unit derived from an unsaturated carboxylic acid and having a (meth) acryloyloxy group or an epoxy group (A2) Also described as coalescence.

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

  (A2) Among the copolymers, one having a good balance of transparency, film-forming property, hardness of the film to be formed, etc. is selected from (meth) acrylic acid and (meth) acrylic acid ester A monomer polymer containing the above is preferred. Hereinafter, a monomer polymer containing (meth) acrylic acid and one or more selected from (meth) acrylic acid esters will be described.

  As described above, the (A) alkali-soluble resin has a (meth) acryloyl group or an epoxy group. When the polymer comprising a monomer containing (meth) acrylic acid and one or more selected from (meth) acrylic acid esters is a resin having an epoxy group, the resin is a group having an epoxy group. It is preferable that it is resin containing the unit derived from the (meth) acrylic acid ester which has this.

  The (meth) acrylic acid ester having a group having an epoxy group is a (meth) acrylic acid having a group having a chain aliphatic epoxy group even if it is a (meth) acrylic acid ester having an aromatic group and an epoxy group. Even an acid ester may be a (meth) acrylic acid ester having a group having an alicyclic epoxy group.

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

  From the viewpoint of the transparency of the film formed using the photosensitive resin composition, the (meth) acrylic acid ester having a group having an epoxy group preferably does not contain an aromatic group.

  Examples of (meth) acrylic acid ester having a group having a chain aliphatic epoxy group include an ester group (—O—CO, such as epoxyalkyl (meth) acrylate, epoxyalkyloxyalkyl (meth) acrylate, and the like. (Meth) acrylic acid ester in which a chain aliphatic epoxy group is bonded to the oxy group (—O—) in —). Such a chain aliphatic epoxy group possessed by the (meth) acrylate ester may contain one or a plurality of oxy groups (—O—) in the chain. The number of carbon atoms of the chain aliphatic epoxy group is not particularly limited, but is preferably 3 to 20, more preferably 3 to 15, and particularly preferably 3 to 10.

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

  As the (meth) acrylic acid ester having a group having an alicyclic epoxy group, compounds represented by formulas (a3-1) to (a3-15) described later are preferable.

  In a polymer of a monomer containing (meth) acrylic acid containing a unit derived from a (meth) acrylic acid ester having a group having an epoxy group, and one or more selected from (meth) acrylic acid ester The content of the unit derived from the (meth) acrylic acid ester having a group having an epoxy group is preferably 1 to 95% by mass and more preferably 30 to 70% by mass with respect to the mass of the resin.

  Moreover, in the polymer of the monomer containing (meth) acrylic acid and 1 or more types selected from (meth) acrylic acid ester, the insulating film which is excellent in transparency using the photosensitive resin composition is used. A resin containing a unit derived from a (meth) acrylic acid ester having a group having an alicyclic skeleton is also preferable because it is easy to form.

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

  Of the (meth) acrylic acid ester having a group having an alicyclic skeleton, examples of the (meth) acrylic acid ester having a group having an alicyclic hydrocarbon group include the following formulas (a2-1) to (a2- The compound represented by 8) is mentioned. Among these, compounds represented by the following formulas (a2-3) to (a2-8) are preferable, and compounds represented by the following formula (a2-3) or (a2-4) are more preferable.

In the above formula, R ^a3 represents a hydrogen atom or a methyl group, R ^a4 represents a single bond or a divalent saturated aliphatic hydrocarbon group having 1 to 6 carbon atoms, and R ^a5 represents a hydrogen atom or 1 carbon atom. Represents an alkyl group of ~ 5. R ^a4 is preferably a single bond or a linear or branched alkylene group such as a methylene group, an ethylene group, a propylene group, a tetramethylene group, an ethylethylene group, a pentamethylene group or a hexamethylene group. R ^a5 is preferably a methyl group or an ethyl group.

  Among the (meth) acrylic acid ester having a group having an alicyclic skeleton, specific examples of the (meth) acrylic acid ester having a group having an alicyclic epoxy group include, for example, the following formulas (a3-1) to ( and a compound represented by a3-15). Among these, in order to make the developability of the photosensitive resin composition appropriate, compounds represented by the following formulas (a3-1) to (a3-5) are preferable, and the following formula (a3-1) The compound represented by (a3-3) is more preferable.

In the above ^{formulas, R a6} represents a hydrogen atom or a methyl ^{group, R a7} represents a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon ^{atoms, R a8} are the divalent 1 to 10 carbon atoms A hydrocarbon group is shown, n shows the integer of 0-10. R ^a7 is preferably a linear or branched alkylene group such as a methylene group, an ethylene group, a propylene group, a tetramethylene group, an ethylethylene group, a pentamethylene group, or a hexamethylene group. As R ^a8 , for example, a methylene group, an ethylene group, a propylene group, a tetramethylene group, an ethylethylene group, a pentamethylene group, a hexamethylene group, a phenylene group, a cyclohexylene group, —CH ₂ —Ph—CH ₂ — (Ph is A phenylene group) is preferred.

  A unit derived from a (meth) acrylic acid ester in which a polymer of a monomer containing (meth) acrylic acid and at least one selected from (meth) acrylic acid esters has a group having an alicyclic skeleton. When the amount of the unit derived from the (meth) acrylic acid ester having a group having an alicyclic skeleton in the resin is preferably 5 to 95% by mass, more preferably 10 to 90% by mass, 30-70 mass% is further more preferable.

  Moreover, the monomer containing (meth) acrylic acid containing the unit derived from the (meth) acrylic acid ester which has group which has alicyclic skeleton, and 1 or more types selected from (meth) acrylic acid ester Among these polymers, a resin containing a unit derived from (meth) acrylic acid and a unit derived from a (meth) acrylic acid ester having a group having an alicyclic epoxy group is preferable. Such a resin is excellent in adhesion to the substrate. When such a resin is used, it is possible to cause a self-reaction between a carboxyl group contained in the resin and an alicyclic epoxy group. Therefore, when a photosensitive resin composition containing such a resin is used, it is formed by causing a self-reaction between a carboxyl group and an alicyclic epoxy group using a method of heating a film or the like. Mechanical properties such as film hardness can be improved.

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

  Selected from (meth) acrylic acid and (meth) acrylic acid ester, including units derived from (meth) acrylic acid and units derived from (meth) acrylic acid ester having a group having an alicyclic epoxy group In the monomer polymer containing one or more of the above, a unit derived from (meth) acrylic acid, a unit derived from a (meth) acrylic acid ester having an alicyclic hydrocarbon group, and fat A resin containing a unit derived from a (meth) acrylic acid ester having a group having a cyclic epoxy group is preferred.

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

  The polymer of the monomer containing (meth) acrylic acid and one or more selected from (meth) acrylic acid ester has a group having an epoxy group as a unit derived from (meth) acrylic acid ester. Units derived from (meth) acrylic acid esters other than (meth) acrylic acid esters and (meth) acrylic acid esters having a group having an alicyclic skeleton may be included.

  Suitable examples of (meth) acrylic acid esters other than (meth) acrylic acid having a group having an epoxy group and (meth) acrylic acid ester having a group having an alicyclic skeleton include methyl (meth) acrylate, Linear or branched alkyl (meth) acrylates such as ethyl (meth) acrylate, propyl (meth) acrylate, amyl (meth) acrylate, t-octyl (meth) acrylate; chloroethyl (meth) acrylate, 2,2 -Dimethylhydroxypropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, trimethylolpropane mono (meth) acrylate, benzyl (meth) acrylate, and furfuryl (meth) acrylate.

  Monomers used for the preparation of a polymer of monomers containing (meth) acrylic acid and one or more selected from (meth) acrylic acid esters are (meth) acrylic acid and (meth) acrylic. A monomer having an ethylenically unsaturated double bond other than the acid ester may be included.

  Monomers having ethylenically unsaturated double bonds other than (meth) acrylic acid and (meth) acrylic acid include (meth) acrylamides, allyl compounds, vinyl ethers, vinyl esters, styrenes and the like. Can be mentioned. These compounds can be used alone or in combination of two or more.

  (Meth) acrylamides include (meth) acrylamide, N-alkyl (meth) acrylamide, N-aryl (meth) acrylamide, N, N-dialkyl (meth) acrylamide, N, N-aryl (meth) acrylamide, N -Methyl-N-phenyl (meth) acrylamide, N-hydroxyethyl-N-methyl (meth) acrylamide and the like.

  Examples of the allyl compound include allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, allyl lactate, etc .; allyloxyethanol; Can be mentioned.

  Examples of vinyl ethers include hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethyl hexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl ether, 2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether. Alkyl vinyl ethers such as diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether; vinyl phenyl ether, vinyl tolyl ether, vinyl chlorophenyl ether, vinyl-2,4-dichloropheny And the like; ethers, vinyl naphthyl ether, vinyl aryl ethers such as vinyl anthranyl ether.

  Vinyl esters include vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl valate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxyacetate, vinyl butoxyacetate, vinyl phenyl Examples include acetate, vinyl acetoacetate, vinyl lactate, vinyl-β-phenylbutyrate, vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, and vinyl naphthoate.

  Styrenes include: styrene; methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, isopropyl styrene, butyl styrene, hexyl styrene, cyclohexyl styrene, decyl styrene, benzyl styrene, chloromethyl styrene, trifluoromethyl styrene, ethoxy Alkyl styrene such as methyl styrene and acetoxymethyl styrene; alkoxy styrene such as methoxy styrene, 4-methoxy-3-methyl styrene and dimethoxy styrene; chlorostyrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, Dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethyl Styrene, halostyrenes such as 4-fluoro-3-trifluoromethyl styrene; and the like.

  Among polymers of monomers containing (meth) acrylic acid and one or more selected from (meth) acrylic acid esters, the transparency and mechanical properties of the film formed using the photosensitive resin composition From the viewpoint of physical properties, a monomer polymer comprising (meth) acrylic acid and one or more selected from (meth) acrylic acid esters is preferred.

  (A2) The copolymer is a polymer comprising a monomer containing (meth) acrylic acid and one or more selected from (meth) acrylic acid esters, and has a (meth) acryloyl group. In the case of a resin, for example, a resin described below can be used.

  Specifically, a part of the carboxyl group contained in the polymer of the monomer containing (meth) acrylic acid and one or more selected from (meth) acrylic acid ester has the aforementioned epoxy group. A polymer having a (meth) acryloyl group in the side chain obtained by reacting with a (meth) acrylic acid ester having a group can be used as a polymer having a (meth) acryloyl group.

  Moreover, the polymer of the monomer containing (meth) acrylic acid and 1 or more types selected from (meth) acrylic acid ester is 2,2-dimethylhydroxypropyl (meth) acrylate, 2-hydroxyethyl ( When a unit derived from a monomer having a hydroxyl group such as (meth) acrylate and hydroxyethyl vinyl ether is included, the hydroxyl group in the side chain of the polymer is a (meth) acryloyl halide (eg, (meth) acryloyl chloride). By reacting with an acylating agent, a polymer having a (meth) acryloyl group in the side chain is obtained.

  (Meth) acrylic acid and a polymer comprising a monomer containing at least one selected from (meth) acrylic acid esters, and (meth) acrylic in a resin having a (meth) acryloyl group 1-95 mass% is preferable with respect to the mass of resin, and, as for the quantity of the unit derived from an acid, 10-50 mass% is more preferable. A polymer comprising (meth) acrylic acid and a monomer comprising at least one selected from (meth) acrylic acid esters, and (meth) acryloyl in a resin having a (meth) acryloyl group 1-95 mass% is preferable with respect to the mass of resin, and, as for the quantity of the unit which has group, 10-70 mass% is more preferable.

  (A2) The weight average molecular weight of the copolymer (Mw: measured value in terms of polystyrene of gel permeation chromatography (GPC). Same in this specification) is preferably 2000 to 200000, and preferably 5000 to 30000. It is more preferable. By setting it as the above range, the film forming ability of the photosensitive resin composition and the developability after exposure tend to be easily balanced.

  (A) The content of the alkali-soluble resin is preferably 30 to 90% by mass and more preferably 45 to 75% by mass with respect to the solid content of the photosensitive resin composition. By setting it as the above range, there is a tendency that developability is easily balanced.

（式（Ｉ）中、Ｒ^１は炭素原子数２〜４のアルキレン基であり、Ｘは、下式（ＩＩ）：

で表される基又は水素原子であり、Ｒ^２は炭素原子数２〜４のアルキレン基であり、Ｒ^３は、下式（ＩＩＩ）：

で表される基であり、ｐは０〜４の整数であり、ｑは０〜５の整数であり、式（Ｉ）中の６つのＸのうちの式（ＩＩ）で表される基の数は４〜６の整数であり、式（Ｉ）中の複数の式（ＩＩ）で表される基は、それぞれ同一であっても異なっていてもよく、式（Ｉ）で表される化合物中の−（Ｒ^１−Ｏ）−で表される２価基の数と−（Ｒ^２−Ｏ）−で表される２価基の数との合計は１以上であり、式（ＩＩＩ）中、Ｒ^４は、水素原子又はメチル基である。） <(B) Photopolymerizable compound>
The photosensitive resin composition contains a compound represented by the following formula (I) as a photopolymerizable compound (B).

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

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

P is an integer of 0 to 4, q is an integer of 0 to 5, and the group represented by the formula (II) among the six Xs in the formula (I) The number is an integer of 4 to 6, and a plurality of groups represented by the formula (II) in the formula (I) may be the same or different, and the compound represented by the formula (I) The sum of the number of divalent groups represented by — (R ¹ —O) — and the number of divalent groups represented by — (R ² —O) — is 1 or more, and the formula (III) R ⁴ is a hydrogen atom or a methyl group. )

R ¹ in formula (I) is an alkylene group having 2 to 4 carbon atoms. Specific examples of the alkylene group having 2 to 4 carbon atoms include ethylene group, propane-1,3-diyl group, propane-1,2-diyl group, butane-1,4-diyl group, butane-1,3. -Diyl group, butane-2,3-diyl group, butane-1,2-diyl group, and 2-methylpropane-1,3-diyl group. Among these divalent groups, an ethylene group, a propane-1,2-diyl group, and a propane-1,3-diyl group are preferable, and an ethylene group and a propane-1,2-diyl group are more preferable. In the divalent group represented by —R ¹ —O—, any of the two bonds of R ^{1 that} is an alkylene group may be bonded to an oxygen atom.

P which is the repeating number of the bivalent group represented by -R < ¹ > -O- in Formula (I) is an integer of 0-4. As the compound represented by the formula (I), a compound in which p is 0 is preferable. When p is 0, the number of divalent groups represented by —R ¹ —O— and the number of divalent groups represented by —R ² —O— in the compound represented by formula (I) Therefore, the compound represented by the formula (I) always has one or more divalent groups represented by —OR ² —O— in six Xs.

X contained in the compound represented by the formula (I) is a hydrogen atom or a group represented by the formula (II). Of the six Xs contained in the compound represented by formula (I), the number of groups represented by formula (II) is an integer of 4-6. R ³ present at the terminal of the group represented by the formula (II) is a hydrogen atom or a group represented by the formula (III). In the formula (III), R ⁴ is a hydrogen atom or a methyl group. That is, the group represented by the formula (III) is an acryloyl group or a methacryloyl group.

The group represented by Formula ^(II), include divalent groups represented by -R 2 -O-. Expression contained in the compound represented by ^(I), 2 divalent group the number of which is represented by -R 2 -O- is preferably 0-10, more preferably 1-8, 2-6 is particularly preferred.

Moreover, it is also preferable that q is 0 for the groups represented by formula (II) of 4 to 6 which the compound represented by formula (I) has. The sum of the number of divalent groups represented by — (R ¹ —O) — and the number of divalent groups represented by — (R ² —O) — in the compound represented by formula (I) is: Since it is 1 or more, in this case, p in the formula (I) is an integer of 1 to 4. That is, the compound represented by the formula (I) does not have an alkylene oxide repeating unit represented by —R ² —O— in the side chain, and 1 to 4 —R ¹ —O at the center thereof. It has an alkylene oxide repeating unit represented by-.

（式（Ｉ−１）中、Ｒ^４は式（ＩＩＩ）と同様であり、ｑ１、ｑ２、ｑ３、ｑ４、ｑ５、及びｑ６はそれぞれ０〜５の整数であり、ｑ１、ｑ２、ｑ３、ｑ４、ｑ５、及びｑ６の和は、２〜６の整数である。） Among the compounds represented by the formula (I), a compound represented by the following formula (I-1) is preferable.

(In the formula (I-1), R ⁴ is the same as in the formula (III), q1, q2, q3, q4, q5, and q6 are each an integer of 0 to 5, q1, q2, q3, q4 , Q5, and q6 are integers of 2 to 6.)

  (B) The photopolymerizable compound may contain a photopolymerizable compound other than the compound represented by the formula (I) together with the compound represented by the formula (I). Photopolymerizable compounds that can be used with the compound represented by formula (I) include monofunctional compounds and polyfunctional compounds.

  Monofunctional compounds include (meth) acrylamide, methylol (meth) acrylamide, methoxymethyl (meth) acrylamide, ethoxymethyl (meth) acrylamide, propoxymethyl (meth) acrylamide, butoxymethoxymethyl (meth) acrylamide, N-methylol ( (Meth) acrylamide, N-hydroxymethyl (meth) acrylamide, (meth) acrylic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, crotonic acid, 2-acrylamide- 2-methylpropanesulfonic acid, tert-butylacrylamidesulfonic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate , Cyclohexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2- ( (Meth) acryloyloxy-2-hydroxypropyl phthalate, glycerin mono (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dimethylamino (meth) acrylate, glycidyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) ) Acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, and half (meth) acrylate of a phthalic acid derivative. These monofunctional compounds can be used alone or in combination of two or more.

  On the other hand, as polyfunctional compounds, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butylene glycol Di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexane glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerin di (meth) acrylate, pentaerythritol triacrylate, pentaerythritol Tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol di (meth) Acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 2,2-bis (4- (meth) acryloxy) Ethoxyphenyl) propane, 2,2-bis (4- (meth) acryloxypolyethoxyphenyl) propane, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, ethylene glycol diglycidyl ether di (meth) Acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, diglycidyl phthalate di (meth) acrylate, glycerin triacrylate, glycerin polyglycidyl ether poly ( ) Acrylate, urethane (meth) acrylate (ie, tolylene diisocyanate), reaction product of trimethylhexamethylene diisocyanate, hexamethylene diisocyanate and 2-hydroxyethyl (meth) acrylate, methylenebis (meth) acrylamide, (meth) acrylamide methylene Examples thereof include polyfunctional compounds such as condensates of ether, polyhydric alcohol and N-methylol (meth) acrylamide, and triacryl formal. These polyfunctional compounds can be used alone or in combination of two or more.

  As the polymerizable compound used together with the compound represented by the formula (I), dipentaerythritol hexa (meth) acrylate is preferable.

  In addition, as the photopolymerizable compound (B), together with the compound represented by the formula (I), alkyl (meth) acrylate, alkanediol monoalkyl ether mono (meth) acrylate, alkanediol di (meth) acrylate, poly It is also preferable to use monoalkyl ether mono (meth) acrylate of alkylene oxide or di (meth) acrylate of polyalkylene oxide.

  (B) The photopolymerizable compound, together with the compound represented by formula (I), alkyl (meth) acrylate, alkanediol monoalkyl ether mono (meth) acrylate, alkanediol di (meth) acrylate, polyalkylene oxide When the monoalkyl ether mono (meth) acrylate or polyalkylene oxide di (meth) acrylate is included, excessive deformation of the pattern due to heating during pattern formation and generation of fine wrinkles on the pattern surface are suppressed. It is preferable in terms of easy.

  Here, the “polyalkylene oxide” has an alkyleneoxy group or a chain in which two or more alkyleneoxy groups are repeated, and a hydrogen atom is bonded to an oxygen atom at one end of the chain, It means a compound in which a hydroxyl group is bonded to the other terminal carbon atom.

  Regarding the alkyl (meth) acrylate, the alkyl ester may be a linear alkyl ester or a branched alkyl ester, and is preferably a linear alkyl ester. Although the carbon atom number of the alkyl group which comprises alkylester is not specifically limited, 1-8 are preferable, 1-6 are more preferable, and 1-4 are especially preferable.

  For the monoalkyl ether mono (meth) acrylate of alkanediol and the monoalkyl ether mono (meth) acrylate of polyalkylene oxide, the monoalkyl ether may be a linear alkyl ether or a branched alkyl ether, Preferably there is. The number of carbon atoms of the alkyl group constituting the monoalkyl ether is not particularly limited, but is preferably 1 to 8, more preferably 1 to 6, particularly preferably 1 to 4, and most preferably 1.

（式（ＩＶ）及び式（Ｖ）中、Ｒ^５は炭素原子数２〜４のアルキレン基であり、Ｒ^６は水素原子又はメチル基であり、Ｒ^７は炭素原子数１〜８の直鎖アルキル基であり、ｓは０〜９の整数であり、ｔは１〜９の整数である。） n-alkyl (meth) acrylate, monoalkyl ether mono (meth) acrylate of alkanediol, di (meth) acrylate of alkanediol, monoalkyl ether mono (meth) acrylate of polyalkylene oxide, or di (meta) of polyalkylene oxide The acrylate is preferably a compound represented by the following formula (IV) or a compound represented by (V).

(In Formula (IV) and Formula (V), R ⁵ is an alkylene group having 2 to 4 carbon atoms, R ⁶ is a hydrogen atom or a methyl group, and R ⁷ is a straight chain having 1 to 8 carbon atoms. An alkyl group, s is an integer of 0 to 9, and t is an integer of 1 to 9.)

In formula (IV) and formula (IV), the alkylene group having 2 to 4 carbon atoms as R ^{5 is the same} as R ¹ in formula (I). As the alkylene group as R ⁵ , an ethylene group, a propane-1,2-diyl group, and a propane-1,3-diyl group are preferable, and a propane-1,2-diyl group and an ethylene group are more preferable. In formula (IV), when s is 0, R ⁷ is preferably a linear alkyl group having 2 to 8 carbon atoms, and more preferably a linear alkyl group having 2 to 6 carbon atoms. In formula (IV), when s is an integer of 1 to 8, R ⁷ is preferably a methyl group or an ethyl group, and more preferably a methyl group.

  (B) In the photopolymerizable compound, alkyl (meth) acrylate, monoalkyl ether mono (meth) acrylate of alkanediol, di (meth) acrylate of alkanediol, monoalkyl ether mono (meth) acrylate of polyalkylene oxide, Alternatively, the content of the poly (alkylene oxide) di (meth) acrylate is not particularly limited, and is preferably more than 20% by mass with respect to the mass of the (B) photopolymerizable compound, and is 20 to 50% by mass. Is more preferable, and it is especially preferable that it is 20-30 mass%.

  Alkyl (meth) acrylates, alkanediol monoalkyl ether mono (meth) acrylates, alkanediol di (meth) acrylates, polyalkylene oxide monoalkyl ether mono (meth) acrylates, or polyalkylenes in such range amounts When a photosensitive resin composition containing (B) a photopolymerizable compound containing di (meth) acrylate of oxide is used, excessive deformation of the pattern due to heating during pattern formation and generation of fine wrinkles on the pattern surface And is particularly easy to suppress.

  (B) 0.5-15 mass% is preferable with respect to solid content of the photosensitive resin composition, and, as for content of a photopolymerizable compound, 2-10 mass% is more preferable.

<(C) Photopolymerization initiator>
The photosensitive resin composition contains (C) a photopolymerization initiator that is an oxime ester compound. The oxime ester compound is a compound in which two organic groups are bonded through an oxime ester bond represented by ═N—O—CO—. By blending the photosensitive resin composition in combination with (B) a photopolymerizable compound containing the compound represented by the above formula (I) and (C) a photopolymerization initiator which is an oxime ester compound. In particular, the exposure sensitivity can be made favorable.

It does not specifically limit as (C) photoinitiator which is an oxime ester compound, A conventionally well-known thing can be used. Among the oxime ester compounds, compounds represented by the following formula (c1) are preferable.

In the above formula (c1), R ^c1 is an ^optionally substituted alkyl group having 1 to 10 carbon atoms, an optionally substituted phenyl group, or an optionally substituted carbazolyl. Indicates a group. a is 0 or 1. R ^c2 represents an alkyl group having 1 to 10 carbon atoms which may have a substituent, a phenyl group which may have a substituent, or a carbazolyl group which may have a substituent. R ^c3 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group which may have a substituent.

When R ^c1 is an alkyl group having 1 to 10 carbon atoms that may have a substituent, the type of substituent that the alkyl group has is not particularly limited as long as the object of the present invention is not impaired.

  Examples of suitable substituents that the alkyl group having 1 to 10 carbon atoms may have include an alkoxy group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, and 3 to 3 carbon atoms. 10 cycloalkoxy groups, saturated aliphatic acyl groups having 2 to 20 carbon atoms, alkoxycarbonyl groups having 2 to 20 carbon atoms, saturated aliphatic acyloxy groups having 2 to 20 carbon atoms, and substituents. Good phenyl group, optionally substituted phenoxy group, optionally substituted phenylthio group, optionally substituted benzoyl group, optionally substituted phenoxycarbonyl group, substituted Benzoyloxy group which may have a group, phenylalkyl group having 7 to 20 carbon atoms which may have a substituent, naphthyl group which may have a substituent, naphthoxy which may have a substituent Group, substituent An optionally substituted naphthoyl group, an optionally substituted naphthoxycarbonyl group, an optionally substituted naphthoyloxy group, and an optionally substituted naphthylalkyl having 11 to 20 carbon atoms Group, optionally substituted heterocyclyl group, optionally substituted heterocyclylcarbonyl group, amino group, amino group substituted with 1 or 2 organic groups, morpholin-1-yl group, and piperazine Examples include a -1-yl group, a halogen, a nitro group, and a cyano group.

  The alkyl group having 1 to 10 carbon atoms may be linear or branched. In this case, 1-8 are preferable and, as for the carbon atom number of an alkyl group, 1-5 are more preferable.

When R ^c1 is a phenyl group which may have a substituent, the type of the substituent is not particularly limited as long as the object of the present invention is not impaired. Suitable examples of the substituent that the phenyl group may have include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, an alkoxycarbonyl group, a saturated aliphatic acyloxy group, and a substituent. A phenyl group which may have a substituent, a phenoxy group which may have a substituent, a benzoyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, and a substituent A good benzoyloxy group, a phenylalkyl group which may have a substituent, a naphthyl group which may have a substituent, a naphthoxy group which may have a substituent, a naphthoyl group which may have a substituent, A naphthoxycarbonyl group which may have a substituent, a naphthoyloxy group which may have a substituent, a naphthylalkyl group which may have a substituent, a heterocycle which may have a substituent Group, an amino group, 1 or 2 of the organic amino group substituted with groups, morpholin-1-yl group, and piperazine-1-yl group, a halogen, and nitro group, and a cyano group. When R ^c1 is a phenyl group which may have a substituent, and the phenyl group has a plurality of substituents, the plurality of substituents may be the same or different.

When the substituent which a phenyl group has is an alkyl group, 1-20 are preferable, 1-10 are more preferable, 1-10 are more preferable, 1-6 are more preferable, 1-3 are especially preferable, and 1 is the most preferable. . In addition, the alkyl group may be linear or branched. Specific examples when the substituent of the phenyl group is an alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, n-pentyl group, isopentyl group, sec-pentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, n-nonyl group , Isononyl group, n-decyl group, and isodecyl group. The alkyl group may contain an ether bond (—O—) in the carbon chain. In this case, examples of the substituent that the phenyl group has include an alkoxyalkyl group and an alkoxyalkoxyalkyl group. When the substituent that the phenyl group has is an alkoxyalkyl group, a group represented by -R ^c4 -O-R ^c5 is preferable. R ^c4 is an alkylene group which may be a straight chain or branched chain having 1 to 10 carbon atoms. R ^c5 is an alkyl group which may be a straight chain or branched chain having 1 to 10 carbon atoms. 1-8 are preferable, as for the carbon atom number of ^Rc4 , 1-5 are more preferable, and 1-3 are especially preferable. The number of carbon atoms in R ^c5 is 1-8, more preferably 1 to 5, particularly preferably 1 to 3, and most preferably 1. Examples of the alkyl group having an ether bond in the carbon chain include a methoxyethyl group, an ethoxyethyl group, a methoxyethoxyethyl group, an ethoxyethoxyethyl group, a propyloxyethoxyethyl group, and a methoxypropyl group.

  When the substituent which a phenyl group has is an alkoxy group, 1-20 are preferable and 1-6 are more preferable. Further, the alkoxy group may be linear or branched. Specific examples when the substituent of the phenyl group is an alkoxy group include methoxy group, ethoxy group, n-propyloxy group, isopropyloxy group, n-butyloxy group, isobutyloxy group, sec-butyloxy group, tert- Butyloxy group, n-pentyloxy group, isopentyloxy group, sec-pentyloxy group, tert-pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, isooctyloxy group, sec Examples include -octyloxy group, tert-octyloxy group, n-nonyloxy group, isononyloxy group, n-decyloxy group, and isodecyloxy group. The alkoxy group may contain an ether bond (—O—) in the carbon chain. Examples of alkoxy groups having ether linkages in the carbon chain include methoxyethoxy groups, ethoxyethoxy groups, 2-methoxy-1-methylethoxy groups, methoxyethoxyethoxy groups, ethoxyethoxyethoxy groups, propyloxyethoxyethoxy groups, and A methoxypropyloxy group etc. are mentioned.

  When the substituent which a phenyl group has is a cycloalkyl group or a cycloalkoxy group, 3-10 are preferable and 3-6 are more preferable. Specific examples when the substituent of the phenyl group 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 when the substituent of the phenyl group is a cycloalkoxy group include a cyclopropyloxy group, a cyclobutyloxy group, a cyclopentyloxy group, a cyclohexyloxy group, a cycloheptyloxy group, and a cyclooctyloxy group. It is done.

  When the substituent which a phenyl group has is a saturated aliphatic acyl group or a saturated aliphatic acyloxy group, 2-20 are preferable and 2-7 are more preferable. Specific examples when the substituent of the phenyl group is a saturated aliphatic acyl group include acetyl group, propanoyl group, n-butanoyl group, 2-methylpropanoyl group, n-pentanoyl group, 2,2-dimethylpropanoyl group. Noyl group, n-hexanoyl group, n-heptanoyl group, n-octanoyl group, n-nonanoyl group, n-decanoyl group, n-undecanoyl group, n-dodecanoyl group, n-tridecanoyl group, n-tetradecanoyl group, Examples include an n-pentadecanoyl group and an n-hexadecanoyl group. Specific examples when the substituent of the phenyl group is a saturated aliphatic acyloxy group include acetyloxy group, propanoyloxy group, n-butanoyloxy group, 2-methylpropanoyloxy group, n-pentanoyloxy Group, 2,2-dimethylpropanoyloxy group, n-hexanoyloxy group, n-heptanoyloxy group, n-octanoyloxy group, n-nonanoyloxy group, n-decanoyloxy group, n-undecanoyl Examples include an oxy group, an n-dodecanoyloxy group, an n-tridecanoyloxy group, an n-tetradecanoyloxy group, an n-pentadecanoyloxy group, and an n-hexadecanoyloxy group.

  When the substituent which a phenyl group has is an alkoxycarbonyl group, 2-20 are preferable and, as for the carbon atom number, 2-7 are more preferable. Specific examples when the substituent of the phenyl group is an alkoxycarbonyl group include methoxycarbonyl group, ethoxycarbonyl group, n-propyloxycarbonyl group, isopropyloxycarbonyl group, n-butyloxycarbonyl group, isobutyloxycarbonyl group , Sec-butyloxycarbonyl group, tert-butyloxycarbonyl group, n-pentyloxycarbonyl group, isopentyloxycarbonyl group, sec-pentyloxycarbonyl group, tert-pentyloxycarbonyl group, n-hexyloxycarbonyl group, n -Heptyloxycarbonyl group, n-octyloxycarbonyl group, isooctyloxycarbonyl group, sec-octyloxycarbonyl group, tert-octyloxycarbonyl group, n-nonyloxy group Aryloxycarbonyl group, isononyl oxycarbonyl group, n- decyl oxycarbonyl group, and the like isodecyl oxycarbonyl group.

  When the substituent which a phenyl group has is a phenylalkyl group, 7-20 are preferable and 7-10 are more preferable. Moreover, when the substituent which a phenyl group has is a naphthyl alkyl group, 11-20 are preferable and 11-14 are more preferable. Specific examples when the substituent of the phenyl group is a phenylalkyl group include a benzyl group, a 2-phenylethyl group, a 3-phenylpropyl group, and a 4-phenylbutyl group. Specific examples when the substituent of the phenyl group is a naphthylalkyl group include an α-naphthylmethyl group, a β-naphthylmethyl group, a 2- (α-naphthyl) ethyl group, and 2- (β-naphthyl) ethyl. Groups. When the substituent that the phenyl group has is a phenylalkyl group or a naphthylalkyl group, the substituent may further have a substituent on the phenyl group or naphthyl group.

  When the substituent of the phenyl group is a heterocyclyl group, the heterocyclyl group is a 5-membered or 6-membered monocycle containing one or more N, S, and O, such monocycles, or such monocycles and benzene. A heterocyclyl group condensed with a ring. When the heterocyclyl group is a condensed ring, the ring number is up to 3. Examples of the heterocyclic ring constituting the heterocyclyl group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, pyridazine, benzofuran, benzothiophene, indole, Examples include isoindole, indolizine, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalazine, cinnoline, and quinoxaline. When the substituent that the phenyl group has is a heterocyclyl group, the heterocyclyl group may further have a substituent.

  When the substituent of the phenyl group is an amino group substituted with 1 or 2 organic groups, suitable examples of the organic group include alkyl groups having 1 to 20 carbon atoms and cycloalkyl having 3 to 10 carbon atoms. Group, a saturated aliphatic acyl group having 2 to 20 carbon atoms, a saturated aliphatic acyloxy group having 2 to 20 carbon atoms, a phenyl group which may have a substituent, a benzoyl group which may have a substituent, An optionally substituted phenylalkyl group having 7 to 20 carbon atoms, an optionally substituted naphthyl group, an optionally substituted naphthoyl group, and an optionally substituted carbon Examples thereof include a naphthylalkyl group having 11 to 20 atoms and a heterocyclyl group. Specific examples of these suitable organic groups include the same ones as described above for the substituent of the phenyl group. Specific examples of the amino group substituted with 1 or 2 organic groups include methylamino group, ethylamino group, diethylamino group, n-propylamino group, di-n-propylamino group, isopropylamino group, n- Butylamino group, di-n-butylamino group, n-pentylamino group, n-hexylamino group, n-heptylamino group, n-octylamino group, n-nonylamino group, n-decylamino group, phenylamino group, Naphthylamino group, acetylamino group, propanoylamino group, n-butanoylamino group, n-pentanoylamino group, n-hexanoylamino group, n-heptanoylamino group, n-octanoylamino group, n- Decanoylamino group, benzoylamino group, α-naphthoylamino group, β-naphthoylamino group, and N-acetyl-N-a And a cetyloxyamino group.

  In the case where the phenyl group, naphthyl group, and heterocyclyl group further include a substituent contained in the substituent of the phenyl group, the substituent includes an alkyl group having 1 to 6 carbon atoms and an alkoxy having 1 to 6 carbon atoms. Group, a saturated aliphatic acyl group having 2 to 7 carbon atoms, an alkoxycarbonyl group having 2 to 7 carbon atoms, a saturated aliphatic acyloxy group having 2 to 7 carbon atoms, and an alkyl group having 1 to 6 carbon atoms. Examples thereof include a monoalkylamino 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 heterocyclyl group included in the substituent that the phenyl group has further have a substituent, the number of the substituents is not limited as long as the object of the present invention is not hindered. Is preferred. When the phenyl group, the naphthyl group, and the heterocyclyl group contained in the substituent that the phenyl group has have a plurality of substituents, the plurality of substituents may be the same or different.

As mentioned above, although the substituent in case ^Rc1 is the phenyl group which may have a substituent was ^demonstrated , in these substituents, an alkyl group or an alkoxyalkyl group is preferable.

When R ^c1 is a phenyl group which may have a substituent, the number of substituents and the bonding position of the substituent are not particularly limited as long as the object of the present invention is not impaired. In the case where R ^c1 is a phenyl group which may have a substituent, the phenyl group which may have a substituent is an o- which may have a substituent in terms of excellent base generation efficiency. A tolyl group is preferred.

When R ^c1 is a carbazolyl group which may have a substituent, the type of the substituent is not particularly limited as long as the object of the present invention is not impaired. Examples of suitable substituents that the carbazolyl group may have on the carbon atom include an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and a cycloalkyl having 3 to 10 carbon atoms. Group, a cycloalkoxy group having 3 to 10 carbon atoms, a saturated aliphatic acyl group having 2 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, a saturated aliphatic acyloxy group having 2 to 20 carbon atoms, A phenyl group which may have a substituent, a phenoxy group which may have a substituent, a phenylthio group which may have a substituent, a phenylcarbonyl group which may have a substituent, and a substituent An optionally substituted benzoyl group, an optionally substituted phenoxycarbonyl group, an optionally substituted benzoyloxy group, an optionally substituted phenylalkyl group having 7 to 20 carbon atoms, a substituted group A naphthyl group which may have a substituent, a naphthoxy group which may have a substituent, a naphthylcarbonyl group which may have a substituent, a naphthoyl group which may have a substituent, and a substituent A good naphthoxycarbonyl group, an optionally substituted naphthoyloxy group, an optionally substituted naphthylalkyl group having 11 to 20 carbon atoms, an optionally substituted heterocyclyl group, a substituted group An optionally substituted heterocyclylcarbonyl group, an amino group, an amino group substituted with one or two organic groups, a morpholin-1-yl group, and a piperazin-1-yl group, a halogen, a nitro group, and a cyano group Etc.

When R ^c1 is a carbazolyl group which may have a substituent, examples of suitable substituents that the carbazolyl group may have on the nitrogen atom include alkyl groups having 1 to 20 carbon atoms, carbon atoms A cycloalkyl group having 3 to 10 carbon atoms, a saturated aliphatic acyl group having 2 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, a phenyl group which may have a substituent, and a substituent. A benzoyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, a phenylalkyl group having 7 to 20 carbon atoms which may have a substituent, a naphthyl group which may have a substituent, a substituent An optionally substituted naphthoyl group, an optionally substituted naphthoxycarbonyl group, an optionally substituted naphthylalkyl group having 11 to 20 carbon atoms, and an optionally substituted heterocyclyl group , And substituents Examples thereof include a heterocyclylcarbonyl group which may be included. Among these substituents, an alkyl group having 1 to 20 carbon atoms is preferable, an alkyl group having 1 to 6 carbon atoms is more preferable, and an ethyl group is particularly preferable.

Specific examples of the substituent that the carbazolyl group may have include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, an alkoxycarbonyl group, a saturated aliphatic acyloxy group, and a substituent. R ^c1 is substituted for an ^optionally substituted phenylalkyl group, an optionally substituted naphthylalkyl group, an optionally substituted heterocyclyl group, and an amino group substituted with 1 or 2 organic groups. In the case of a phenyl group which may have a group, it is the same as the example of the substituent which the phenyl group has.

Examples of the substituent when the phenyl group, the naphthyl group, and the heterocyclyl group included in the substituent that the carbazolyl group has in R ^c1 further have a substituent include an alkyl group having 1 to 6 carbon atoms; An alkoxy group having 1 to 6 carbon atoms; a saturated aliphatic acyl group having 2 to 7 carbon atoms; an alkoxycarbonyl group having 2 to 7 carbon atoms; a saturated aliphatic acyloxy group having 2 to 7 carbon atoms; a phenyl group; a naphthyl group; A benzoyl group; a naphthoyl group; a benzoyl group substituted by a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, and a phenyl group; a carbon atom A monoalkylamino group having an alkyl group of 1 to 6; a dialkylamino group having an alkyl group of 1 to 6 carbon atoms; morpholin-1-yl Group; piperazin-1-yl group; halogen; nitro group; cyano group. When the phenyl group, naphthyl group, and heterocyclyl group contained in the substituent of the carbazolyl group further have a substituent, the number of the substituent is not limited as long as the object of the present invention is not impaired, but 1-4 is preferable. When the phenyl group, naphthyl group, and heterocyclyl group have a plurality of substituents, the plurality of substituents may be the same or different.

R ^c2 is an ^optionally substituted alkyl group having 1 to 10 carbon atoms, an optionally substituted phenyl group, or an optionally substituted carbazolyl group.

When R ^c2 is an alkyl group having 1 to 10 carbon atoms which may have a substituent, the alkyl group may be linear or branched. In this case, 1-8 are preferable and, as for the carbon atom number of an alkyl group, 1-5 are more preferable.

In R ^c2 , the substituent that the alkyl group or the phenyl group has is not particularly limited as long as the object of the present invention is not impaired.
Examples of suitable substituents that the alkyl group may have on the carbon atom include an alkoxy group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, and a cyclohexane having 3 to 10 carbon atoms. An alkoxy group, a saturated aliphatic acyl group having 2 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, a saturated aliphatic acyloxy group having 2 to 20 carbon atoms, and an optionally substituted phenyl group A phenoxy group which may have a substituent, a phenylthio group which may have a substituent, a benzoyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, and a substituent. Benzoyloxy group which may have a substituent, phenylalkyl group having 7 to 20 carbon atoms which may have a substituent, naphthyl group which may have a substituent, naphthoxy group which may have a substituent, substituted Even if it has a group Naphthoyl group, optionally substituted naphthoxycarbonyl group, optionally substituted naphthoyloxy group, optionally substituted naphthylalkyl group having 11 to 20 carbon atoms, substituted A heterocyclyl group which may have a group, a heterocyclylcarbonyl group which may have a substituent, an amino group, an amino group substituted with 1 or 2 organic groups, a morpholin-1-yl group, and piperazine-1- Yl group, halogen, nitro group, cyano group and the like.
Examples of suitable substituents that the phenyl group may have on the carbon atom include, in addition to the groups exemplified above as suitable substituents that the alkyl group may have on the carbon atom, the number of carbon atoms 1-20 alkyl groups are mentioned.

Specific examples of the substituent that the alkyl group or the phenyl group may have include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, an alkoxycarbonyl group, a saturated aliphatic acyloxy group, and a substituent. For a phenylalkyl group which may have a substituent, a naphthylalkyl group which may have a substituent, a heterocyclyl group which may have a substituent, and an amino group substituted with one or two organic groups, R ^This is the same as the example of the substituent that the phenyl group has when ^c1 is a phenyl group that may have a substituent.

In R ^c2 , examples of the substituent when the phenyl group, naphthyl group, and heterocyclyl group included in the substituent of the alkyl group or the phenyl group further have a substituent include an alkyl group having 1 to 6 carbon atoms; An alkoxy group having 1 to 6 carbon atoms; a saturated aliphatic acyl group having 2 to 7 carbon atoms; an alkoxycarbonyl group having 2 to 7 carbon atoms; a saturated aliphatic acyloxy group having 2 to 7 carbon atoms; a phenyl group; A benzoyl group substituted by a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, and a phenyl group A monoalkylamino group having an alkyl group having 1 to 6 carbon atoms; a dialkylamino group having an alkyl group having 1 to 6 carbon atoms; morpholine -1-yl group; piperazin-1-yl group; halogen; nitro group; cyano group. When the phenyl group, naphthyl group, and heterocyclyl group contained in the substituent of the alkyl group or phenyl group further have a substituent, the number of substituents is not limited as long as the object of the present invention is not impaired. ~ 4 is preferred. When the phenyl group, naphthyl group, and heterocyclyl group have a plurality of substituents, the plurality of substituents may be the same or different.

When R ^c2 is a carbazolyl group which may have a substituent, the type of substituent that the carbazolyl group has is not particularly limited as long as the object of the present invention is not impaired. Preferable examples of the substituent that the carbazolyl group may have are the same as those of the substituent in the case where R ^c1 is a carbazolyl group that may have a substituent.

又は、下記式（ｃ３）：

で表される基が好ましい。 From the viewpoint of the reactivity of the compound represented by the formula (c1), R ^c2 is represented by the following formula (c2):

Or the following formula (c3):

The group represented by these is preferable.

In formula (c2), R ^c6 and R ^c7 are each a monovalent organic group, and b is 0 or 1. In formula (c3), R ^c8 is a group selected from the group consisting of a monovalent organic group, amino group, halogen, nitro group, and cyano group, A is S or O, and c is 0 to 0. It is an integer of 4.

R ^c6 in formula (c2) can be selected from various organic groups as long as the object of the present invention is not ^impaired . Preferable examples of R ^c6 include a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a saturated aliphatic acyl group having 2 to 20 carbon atoms, and 2 carbon atoms. ~ 20 alkoxycarbonyl groups, optionally substituted phenyl groups, optionally substituted benzoyl groups, optionally substituted phenoxycarbonyl groups, optionally substituted carbons A phenylalkyl group having 7 to 20 atoms, a naphthyl group which may have a substituent, a naphthoyl group which may have a substituent, a naphthoxycarbonyl group which may have a substituent, and a substituent Examples thereof include a naphthylalkyl group having 11 to 20 carbon atoms, a heterocyclyl group which may have a substituent, and a heterocyclylcarbonyl group which may have a substituent.

Among R ^c6 , an alkyl group having 1 to 20 carbon atoms is preferable, an alkyl group having 1 to 6 carbon atoms is more preferable, and an ethyl group is particularly preferable.

R ^c7 in formula (c2) is not particularly limited as long as the object of the present invention is not ^impaired , and can be selected from various organic groups. Specific examples of the group suitable as R ^c7 include a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a phenyl group which may have a substituent, a naphthyl group which may have a substituent, and a substituent. And a heterocyclyl group which may have As R ^c7 , among these groups, a phenyl group which may have a substituent and a naphthyl group which may have a substituent are more preferable, and a 2-methylphenyl group and a naphthyl group are particularly preferable.

In the case where the phenyl group, naphthyl group, and heterocyclyl group contained in R ^c6 or R ^c7 further have a substituent, the substituent includes an alkyl group having 1 to 6 carbon atoms and an alkoxy group having 1 to 6 carbon atoms. , Monocyclic compounds having a saturated aliphatic acyl group having 2 to 7 carbon atoms, an alkoxycarbonyl group having 2 to 7 carbon atoms, a saturated aliphatic acyloxy group having 2 to 7 carbon atoms, and an alkyl group having 1 to 6 carbon atoms Examples include 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, naphthyl group, and heterocyclyl group included in R ^c6 or R ^c7 further have a substituent, the number of the substituent is not limited as long as the object of the present invention is not impaired, but 1-4 is preferable. When the phenyl group, naphthyl group, and heterocyclyl group contained in R ^c6 or R ^c7 have a plurality of substituents, the plurality of substituents may be the same or different.

When R ^c8 in formula (c3) is an organic group, R ^c8 can be selected from various organic groups as long as the object of the present invention is not ^impaired . In the formula (c3), when R ^c8 is an organic group, preferred examples include an alkyl group having 1 to 6 carbon atoms; an alkoxy group having 1 to 6 carbon atoms; and a saturated aliphatic group having 2 to 7 carbon atoms. An acyl group; an alkoxycarbonyl group having 2 to 7 carbon atoms; a saturated aliphatic acyloxy group having 2 to 7 carbon atoms; a phenyl group; a naphthyl group; a benzoyl group; a naphthoyl group; an alkyl group having 1 to 6 carbon atoms; A benzoyl group substituted by a group selected from the group consisting of a -1-yl group, a piperazin-1-yl group, and a phenyl group; a monoalkylamino group having an alkyl group having 1 to 6 carbon atoms; Dialkylamino groups having 1-6 alkyl groups; morpholin-1-yl groups; piperazin-1-yl groups; halogens; nitro groups; cyano groups; 4- (piperazin-1-yl) phenylcarbonyl group; 4- (phenyl) phenylcarbonyl group.

In ^Rc8 , it is substituted by a group selected from the group consisting of a benzoyl group; a naphthoyl group; an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, and a phenyl group. Benzoyl group; nitro group is preferred, benzoyl group; naphthoyl group; 2-methylphenylcarbonyl group; 4- (piperazin-1-yl) phenylcarbonyl group; 4- (phenyl) phenylcarbonyl group is more preferred.

In the formula (c3), c is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and particularly preferably 0 or 1. when c is 1, the binding position of R ^c8, relative bond which the phenyl group R ^c8 is bonded is bonded to the sulfur atom is preferably in the para position.

R ^c3 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an optionally substituted phenyl group. When it is a phenyl group which may have a substituent, the substituent which the phenyl group may have is the same as the case where R ^c1 is a phenyl group which may have a substituent. R ^c3 is preferably a methyl group, an ethyl group, or a phenyl group, and more preferably a methyl group or a phenyl group.

When a is 0, the oxime ester compound represented by the above formula (c1) can be synthesized, for example, by the method described below. First, a ketone compound represented by R ^c2 —CO—R ^c1 is ^oximed with hydroxylamine to obtain an oxime compound represented by R ^c2 — (C═N—OH) —R ^c1 . Next, the obtained oxime compound is acylated with an acid halide represented by R ^c3 —CO—Hal (Hal represents halogen) or an acid anhydride represented by (R ^c3 CO) ₂ O, An oxime ester compound represented by the above formula (c1) in which a is 0 is obtained.

Moreover, when a is 1, the oxime ester compound represented by the said formula (c1) is compoundable by the method demonstrated below, for example. First, a ketone compound represented by R ^c2 —CO—CH ₂ —R ^c1 is reacted with a nitrite in the presence of hydrochloric acid, and represented by R ^c2 —CO— (C═N—OH) —R ^c1. An oxime compound is obtained. Next, the obtained oxime compound is acylated with an acid halide represented by R ^c3 —CO—Hal (Hal represents halogen) or an acid anhydride represented by (R ^c3 CO) ₂ O, An oxime ester compound represented by the above formula (c1) in which a is 1 is obtained.

Examples of the compound represented by the formula (c1) include a compound represented by the following formula (c4).

In the above formula (c4), a, R ^c2 and R ^c3 are as described above. R ^c9 is a group selected from the group consisting of a monovalent organic group, amino group, halogen, nitro group, and cyano group, and d is an integer of 0-4.

In the above formula (c4), R ^c9 is not particularly limited as long as the object of the present invention is not ^impaired , and when it is an organic group, it is appropriately selected from various organic groups. Preferable examples of R ^c9 include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, an alkoxycarbonyl group, a saturated aliphatic acyloxy group, a phenyl group which may have a substituent, It may have a phenoxy group that may have a substituent, a benzoyl group that may have a substituent, a phenoxycarbonyl group that may have a substituent, a benzoyloxy group that may have a substituent, and a substituent. An optionally substituted phenylalkyl group, an optionally substituted naphthyl group, an optionally substituted naphthoxy group, an optionally substituted naphthoyl group, and an optionally substituted naphtho Xyloxycarbonyl group, optionally substituted naphthoyloxy group, optionally substituted naphthylalkyl group, optionally substituted heterocyclyl group, amino group, 1 or 2 Examples include an amino group substituted with an organic group, morpholin-1-yl group, piperazin-1-yl group, halogen, nitro group, and cyano group. When s is an integer of 2 to 4, R ^c9 may be the same or different. Further, the number of carbon atoms of the substituent does not include the number of carbon atoms of the substituent that the substituent further has.

When R ^c9 is an alkyl group, 1 to 20 carbon atoms are preferable, and 1 to 6 carbon atoms are more preferable. Further, when R ^c99 is an alkyl group, it may be linear or branched. Specific examples when R ^c9 is an alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, and an n-pentyl group. , Isopentyl group, sec-pentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, n-nonyl group, isononyl group, An n-decyl group, an isodecyl group, etc. are mentioned. When R ^c9 is an alkyl group, the alkyl group may contain an ether bond (—O—) in the carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include a methoxyethyl group, an ethoxyethyl group, a methoxyethoxyethyl group, an ethoxyethoxyethyl group, a propyloxyethoxyethyl group, and a methoxypropyl group.

When R ^c9 is an alkoxy group, 1 to 20 carbon atoms are preferable, and 1 to 6 carbon atoms are more preferable. Further, when R ^c9 is an alkoxy group, it may be linear or branched. Specific examples when R ^c9 is an alkoxy group include methoxy group, ethoxy group, n-propyloxy group, isopropyloxy group, n-butyloxy group, isobutyloxy group, sec-butyloxy group, tert-butyloxy group, n -Pentyloxy group, isopentyloxy group, sec-pentyloxy group, tert-pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, isooctyloxy group, sec-octyloxy group Tert-octyloxy group, n-nonyloxy group, isononyloxy group, n-decyloxy group, and isodecyloxy group. When R ^c9 is an alkoxy group, the alkoxy group may include an ether bond (—O—) in the carbon chain. Examples of the alkoxy group having an ether bond in the carbon chain include a methoxyethoxy group, an ethoxyethoxy group, a methoxyethoxyethoxy group, an ethoxyethoxyethoxy group, a propyloxyethoxyethoxy group, and a methoxypropyloxy group.

When R ^c9 is a cycloalkyl group or a cycloalkoxy group, 3 to 10 carbon atoms are preferable, and 3 to 6 carbon atoms are more preferable. Specific examples in the case where R ^c9 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 in the case where R ^c9 is a cycloalkoxy group include a cyclopropyloxy group, a cyclobutyloxy group, a cyclopentyloxy group, a cyclohexyloxy group, a cycloheptyloxy group, and a cyclooctyloxy group.

When R ^c9 is a saturated aliphatic acyl group or a saturated aliphatic acyloxy group, 2 to 20 carbon atoms are preferable, and 2 to 7 carbon atoms are more preferable. Specific examples when R ^c9 is a saturated aliphatic acyl group include acetyl group, propanoyl group, n-butanoyl group, 2-methylpropanoyl group, n-pentanoyl group, 2,2-dimethylpropanoyl group, n -Hexanoyl group, n-heptanoyl group, n-octanoyl group, n-nonanoyl group, n-decanoyl group, n-undecanoyl group, n-dodecanoyl group, n-tridecanoyl group, n-tetradecanoyl group, n-pentadecane Examples include a noyl group and an n-hexadecanoyl group. Specific examples when R ^c9 is a saturated aliphatic acyloxy group include acetyloxy group, propanoyloxy group, n-butanoyloxy group, 2-methylpropanoyloxy group, n-pentanoyloxy group, 2, 2-dimethylpropanoyloxy group, n-hexanoyloxy group, n-heptanoyloxy group, n-octanoyloxy group, n-nonanoyloxy group, n-decanoyloxy group, n-undecanoyloxy group, n -Dodecanoyloxy group, n-tridecanoyloxy group, n-tetradecanoyloxy group, n-pentadecanoyloxy group, n-hexadecanoyloxy group and the like.

When R ^c9 is an alkoxycarbonyl group, the number of carbon atoms is preferably 2 to 20, and more preferably 2 to 7 carbon atoms. Specific examples in the case where R ^c9 is an alkoxycarbonyl group include methoxycarbonyl group, ethoxycarbonyl group, n-propyloxycarbonyl group, isopropyloxycarbonyl group, n-butyloxycarbonyl group, isobutyloxycarbonyl group, sec-butyl. Oxycarbonyl group, tert-butyloxycarbonyl group, n-pentyloxycarbonyl group, isopentyloxycarbonyl group, sec-pentyloxycarbonyl group, tert-pentyloxycarbonyl group, n-hexyloxycarbonyl group, n-heptyloxycarbonyl Group, n-octyloxycarbonyl group, isooctyloxycarbonyl group, sec-octyloxycarbonyl group, tert-octyloxycarbonyl group, n-nonyloxycarbonyl group, Examples include an isononyloxycarbonyl group, an n-decyloxycarbonyl group, and an isodecyloxycarbonyl group.

When R ^c9 is a phenylalkyl group, 7 to 20 carbon atoms are preferable, and 7 to 10 carbon atoms are more preferable. Further, when R ^c9 is a naphthylalkyl group, the number of carbon atoms is preferably from 11 to 20, and more preferably from 11 to 14 carbon atoms. Specific examples in the case where R ^c9 is a phenylalkyl group include a benzyl group, a 2-phenylethyl group, a 3-phenylpropyl group, and a 4-phenylbutyl group. Specific examples in the case where R ^c9 is a naphthylalkyl group include an α-naphthylmethyl group, a β-naphthylmethyl group, a 2- (α-naphthyl) ethyl group, and a 2- (β-naphthyl) ethyl group. . When R ^c9 is a phenylalkyl group or a naphthylalkyl group, R ^c9 may further have a substituent on the phenyl group or naphthyl group.

When R ^c9 is a heterocyclyl group, the heterocyclyl group is a 5-membered or 6-membered monocycle containing one or more N, S, and O, or such monocycles are fused with each other, or such monocycle and a benzene ring. Heterocyclyl group. When the heterocyclyl group is a condensed ring, the ring number is up to 3. Examples of the heterocyclic ring constituting the heterocyclyl group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, pyridazine, benzofuran, benzothiophene, indole, Examples include isoindole, indolizine, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalazine, cinnoline, and quinoxaline. When R ^c9 is a heterocyclyl group, the heterocyclyl group may further have a substituent.

When R ^c9 is an amino group substituted with an organic group having 1 or 2, suitable examples of the organic group include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, and a carbon atom. A saturated aliphatic acyl group having 2 to 20 carbon atoms, a phenyl group which may have a substituent, a benzoyl group which may have a substituent, a phenylalkyl having 7 to 20 carbon atoms which may have a substituent A naphthyl group which may have a substituent, a naphthyl group which may have a substituent, a naphthylalkyl group having 11 to 20 carbon atoms which may have a substituent, a heterocyclyl group, and the like. . Specific examples of these suitable organic groups are the same as those for R ^c9 . Specific examples of the amino group substituted with one or two organic groups include methylamino group, ethylamino group, diethylamino group, n-propylamino group, di-n-propylamino group, isopropylamino group, and n-butyl. Amino group, di-n-butylamino group, n-pentylamino group, n-hexylamino group, n-heptylamino group, n-octylamino group, n-nonylamino group, n-decylamino group, phenylamino group, naphthyl Amino group, acetylamino group, propanoylamino group, n-butanoylamino group, n-pentanoylamino group, n-hexanoylamino group, n-heptanoylamino group, n-octanoylamino group, n-deca Examples thereof include a noylamino group, a benzoylamino group, an α-naphthoylamino group, and a β-naphthoylamino group.

In the case where the phenyl group, the naphthyl group, and the heterocyclyl group included in R ^c9 further have a substituent, the substituent includes an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and a carbon atom. A monoalkylamino group having a saturated aliphatic acyl group having 2 to 7 carbon atoms, an alkoxycarbonyl group having 2 to 7 carbon atoms, a saturated aliphatic acyloxy group having 2 to 7 carbon atoms, and an alkyl group having 1 to 6 carbon atoms And 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, naphthyl group, and heterocyclyl group contained in R ^c9 further have a substituent, the number of the substituent is not limited as long as the object of the present invention is not impaired, but 1 to 4 is preferable. When the phenyl group, naphthyl group, and heterocyclyl group included in R ^c9 have a plurality of substituents, the plurality of substituents may be the same or different.

Among R ^c9 , an alkyl group having 1 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms because it is chemically stable, has few steric hindrances, and is easy to synthesize an oxime ester compound. A group selected from the group consisting of 6 alkoxy groups and saturated aliphatic acyl groups having 2 to 7 carbon atoms is preferred, alkyls having 1 to 6 carbon atoms are more preferred, and methyl groups are particularly preferred.

Position R ^c9 is bonded to the phenyl group, the phenyl group R ^c9 is attached, the position of the bond to the main chain of the phenyl group and the oxime ester compound as a 1-position, if the 2-position of the position of the methyl group 4th or 5th is preferable, and 5th is more preferable. D is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and particularly preferably 0 or 1.

R ^c3 in the above formula (c4) is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group which may have a substituent. Specific examples of R ^c3 are as described above for the formula (c1). As R ^c3 in formula (c4), a methyl group, an ethyl group, and a phenyl group are preferable, and a methyl group and a phenyl group are more preferable.

Among the oxime ester compounds used as the component (C), preferred examples of the compounds that are included in the formula (c1) but are not included in the formula (c4) include the following compounds.

Among the oxime ester compounds represented by formula (c4) that are particularly suitable as oxime ester compounds, particularly preferred compounds include compounds of the following formulae.

  The (C) photopolymerization initiator preferably contains only the oxime ester compound, but may contain a small amount of other compounds of the oxime ester compound as long as the object of the present invention is not impaired. Specifically, (C) the photopolymerization initiator is 10% by mass or less, preferably 5% by mass or less, more preferably 3% by mass or less, based on the total mass of (C) the photopolymerization initiator. Other compounds of the compound may be included.

  (C) It is preferable that content of a photoinitiator is 0.5-20 mass% with respect to the mass of solid content in the photosensitive resin composition. By setting it as said range, it is easy to prepare the photosensitive resin composition which has favorable applicability | paintability and sclerosis | hardenability.

<(D) Colorant>
As the photosensitive resin composition, those containing no (D) colorant are preferred, and those containing (D) a colorant are also preferred. (D) Since the photosensitive resin composition which does not contain a coloring agent can form a transparent cured film, it is useful in the formation of a transparent insulating film, for example. The photosensitive resin composition containing (D) the colorant can form a cured film colored in various hues according to the hue of the (D) colorant, and is useful in the formation of color filters and black column spacers. .

  The colorant (D) contained in the photosensitive resin composition according to the present invention is not particularly limited. For example, in the color index (CI; issued by The Society of Dyers and Colorists), pigment (Pigment) It is preferable to use a compound classified under (), specifically, a compound with a color index (CI) number as shown below.

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

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

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

  Examples of red pigments that can be suitably used include C.I. I. Pigment Red 1 (hereinafter, “CI Pigment Red” is the same, and only the number is described) 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 40, 41, 42, 48: 1, 48: 2, 48: 3, 48: 4, 49: 1, 49: 2, 50: 1, 52: 1, 53: 1, 57: 1, 57: 1, 57: 2, 58: 2, 58: 4, 60: 1, 63: 1, 63: 2, 64: 1, 81: 1, 83, 88, 90: 1, 97, 101, 102, 104, 105, 106, 108, 112, 113, 114, 122, 123, 144, 146, 149, 150, 151, 155, 166, 168, 170, 171, 172, 174, 175, 176, 177, 1 8, 179, 180, 185, 187, 188, 190, 192, 193, 194, 202, 206, 207, 208, 209, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 242, 243, 245, 254, 255, 264, and 265.

  Examples of blue pigments that can be suitably used include C.I. I. Pigment Blue 1 (hereinafter, “CI Pigment Blue” is the same, and only the number is described) 2, 15, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64 , And 66.

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

  The colorant (D) is preferably a light-shielding agent. (D) By using a photosensitive resin composition containing a light-shielding agent as a colorant, a black column spacer, a black matrix, or the like having suitable characteristics can be formed. When the colorant is a light-shielding agent, it is preferable to use a black pigment or a purple pigment as the light-shielding agent. Examples of black pigments and purple pigments include carbon black, perylene pigments, titanium black, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, silver and other metal oxides, composite oxides, metal sulfides In addition, various pigments can be mentioned regardless of organic matter or inorganic matter such as metal sulfate or metal carbonate. Among these, it is preferable to use carbon black having high light shielding properties.

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

  As the carbon black, carbon black subjected to a treatment for introducing an acidic group is also preferable. The acidic group introduced into carbon black is a functional group that exhibits acidity according to the Bronsted definition. Specific examples of the acidic group include a carboxyl group, a sulfonic acid group, and a phosphoric acid group. The acidic group introduced into the carbon black may form a salt. The cation that forms a salt with the acidic group is not particularly limited as long as the object of the present invention is not impaired. Examples of the cation include various metal ions, cations of nitrogen-containing compounds, ammonium ions, and the like, and alkali metal ions such as sodium ion, potassium ion, lithium ion, and ammonium ion are preferable.

  Among the carbon blacks that have been treated to introduce acidic groups as described above, the light-blocking cured film formed using the photosensitive resin composition has a low relative dielectric constant, and thus has a carboxylic acid group and a carboxylic acid group. Carbon black having one or more functional groups selected from the group consisting of a base, a sulfonic acid group, and a sulfonic acid group is preferable.

The method for introducing an acidic group into carbon black is not particularly limited. Examples of the method for introducing an acidic group include the following methods.
1) A method of introducing a sulfonic acid group into carbon black by a direct substitution method using concentrated sulfuric acid, fuming sulfuric acid, chlorosulfonic acid, or the like, or an indirect substitution method using sulfite, bisulfite, or the like.
2) A method of diazo coupling an organic compound having an amino group and an acidic group with carbon black.
3) A method of reacting an organic compound having a halogen atom and an acidic group with carbon black having a hydroxyl group by Williamson's etherification method.
4) A method of reacting an organic compound having a halocarbonyl group and an acidic group protected by a protecting group with carbon black having a hydroxyl group.
5) A method of performing deprotection after performing a Friedel-Crafts reaction on carbon black using an organic compound having a halocarbonyl group and an acidic group protected by a protecting group.

  Among these methods, the method 2) is preferred because the acidic group introduction treatment is easy and safe. As the organic compound having an amino group and an acidic group used in the method 2), a compound in which an amino group and an acidic group are bonded to an aromatic group is preferable. Examples of such compounds include aminobenzene sulfonic acids such as sulfanilic acid and aminobenzoic acids such as 4-aminobenzoic acid.

  The number of moles of acidic groups introduced into carbon black is not particularly limited as long as the object of the present invention is not impaired. 1-200 mmol is preferable with respect to 100 g of carbon black, and, as for the number of moles of the acidic group introduce | transduced into carbon black, 5-100 mmol is more preferable.

Carbon black introduced with acidic groups may be coated with a resin.
When a photosensitive resin composition containing carbon black coated with a resin is used, it is easy to form a light-shielding cured film having excellent light-shielding properties and insulating properties and low surface reflectance. In addition, the bad influence with respect to the dielectric constant of the light-shielding cured film formed using a photosensitive resin composition does not produce especially by the coating process by resin. Examples of resins that can be used to coat carbon black include thermosetting resins such as phenolic resin, melamine resin, xylene resin, diallyl phthalate resin, glyphtal resin, epoxy resin, alkylbenzene resin, polystyrene, polycarbonate, polyethylene terephthalate, poly Examples thereof include thermoplastic resins such as butylene terephthalate, modified polyphenylene oxide, polysulfone, polyparaphenylene terephthalamide, polyamideimide, polyimide, polyamino bismaleimide, polyether sulfopolyphenylene sulfone, polyarylate, and polyether ether ketone. The coating amount of the resin on the carbon black is preferably 1 to 30% by mass with respect to the total mass of the carbon black and the mass of the resin.

  A perylene pigment is also preferable as the light-shielding agent. Specific examples of the perylene pigment include the perylene pigment represented by the following formula (d-1), the perylene pigment represented by the following formula (d-2), and the following formula (d-3). Perylene pigments. As commercial products, product names K0084 and K0086 manufactured by BASF, Pigment Black 21, 30, 31, 32, 33, 34, and the like can be preferably used as perylene pigments.

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

In 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 Represents an acetyl group.

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

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

式（ｄ−３）中、Ｒ^ｄ７及びＲ^ｄ８は、それぞれ独立に、水素原子、炭素原子数１〜２２のアルキル基であり、Ｎ，Ｏ、Ｓ、又はＰのヘテロ原子を含んでいてもよい。Ｒ^ｄ７及びＲ^ｄ８がアルキル基である場合、当該アルキル基は、直鎖状であっても、分岐鎖状であってもよい。

In formula (d-3), R ^d7 and R ^d8 each independently represent a hydrogen atom or an alkyl group having 1 to 22 carbon atoms, and may contain N, O, S, or P heteroatoms. Good. When R ^d7 and R ^d8 are alkyl groups, the alkyl group may be linear or branched.

  Examples of the compound represented by the formula (d-1), the compound represented by the formula (d-2), and the compound represented by the formula (d-3) include, for example, JP-A-62-17353. Can be synthesized using the method described in JP-B 63-26784. That is, perylene-3,5,9,10-tetracarboxylic acid or a dianhydride thereof and an amine are used as raw materials, and a heating reaction is performed in water or an organic solvent. The target product can be obtained by reprecipitation of the obtained crude product in sulfuric acid or recrystallization in water, an organic solvent or a mixed solvent thereof.

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

  The light-shielding agent may contain a dye having a hue such as red, blue, green, and yellow together with the black pigment and the purple pigment for the purpose of adjusting the color tone. The pigment of other hues of the black pigment and the purple pigment can be appropriately selected from known pigments. For example, the above-mentioned various pigments can be used as the coloring matter of other hues of black pigments and purple pigments. The amount of the dye having a hue other than the black pigment or the purple pigment is preferably 15% by mass or less and more preferably 10% by mass or less with respect to the total mass of the light shielding agent.

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

  In addition, each of the inorganic pigment and the organic pigment may be used alone or in combination of two or more. It is preferably used in the range, and more preferably in the range of 20 to 40% by mass.

  The amount of the colorant (D) used in the photosensitive resin composition can be appropriately selected within a range that does not impair the object of the present invention. Typically, the amount used is 5 with respect to the mass of the solid content in the photosensitive resin composition. -70 mass% is preferable, and 25-60 mass% is more preferable.

  (D) It is preferable to add the colorant to the photosensitive resin composition after making the dispersion liquid dispersed at an appropriate concentration using a dispersant.

<(S) Organic solvent>
The photosensitive resin composition according to the present invention preferably contains (S) an organic solvent (hereinafter, also referred to as “component (S)”) for improving coating properties and adjusting viscosity.

  Specific examples of the organic solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n- Propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether , Dipropylene glycol monomethyl ether, (Poly) alkylene glycol monoalkyl ethers such as propylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether; ethylene (Poly) alkylene glycol monoalkyl ether acetates such as glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate Diethylene Other ethers such as recall dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone; methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, etc. Alkyl 2-lactic acid esters; ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, hydroxy Ethyl acetate, methyl 2-hydroxy-3-methylbutanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3- Methoxybutyl propionate, ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-pentyl formate, i-pentyl acetate, n-butyl propionate, ethyl butyrate, n-butyrate Other esters such as -propyl, i-propyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxobutanoate; toluene, xylene Aromatic hydrocarbons such as N-methylpyrrolidone, N, N-dimethylformamide, amides such as N, N-dimethylacetamide, and the like. Among these, alkylene glycol monoalkyl ethers, alkylene glycol monoalkyl ether acetates, other ethers described above, alkyl lactate esters, and other esters described above are preferable, alkylene glycol monoalkyl ether acetates described above. Other ethers and other esters described above are more preferred. These solvents can be used alone or in combination of two or more.

  The content of the component (S) is not particularly limited, and is a concentration that can be applied to a substrate or the like, and is appropriately set according to the coating film thickness. The viscosity of the photosensitive resin composition is preferably 5 to 500 cp, more preferably 10 to 50 cp, and still more preferably 20 to 30 cp. Moreover, it is preferable that solid content concentration is 5-100 mass%, and it is more preferable that it is 20-50 mass%.

<Other ingredients>
The photosensitive resin composition according to the present invention may contain additives such as a surfactant, an adhesion improver, a thermal polymerization inhibitor, and an antifoaming agent as necessary. Any additive can be used as the additive. Examples of the surfactant include anionic, cationic, and nonionic compounds, examples of the adhesion improver include conventionally known silane coupling agents, and examples of the thermal polymerization inhibitor include hydroquinone and hydroquinone mono Examples of the antifoaming agent include silicone-based and fluorine-based compounds.

<Method for preparing photosensitive resin composition>
The photosensitive resin composition according to the present invention is prepared by mixing (dispersing and kneading) each of the above components with a stirrer such as a three-roll mill, a ball mill, or a sand mill and, if necessary, filtering with a filter such as a 5 μm membrane filter. can do.

≪Insulating film, color filter, black matrix, black column spacer, formation method thereof, and display device including them≫
The insulating film is the same as the conventional insulating film except that it is formed using a photosensitive resin composition not containing (D) a colorant. The color filter is the same as the conventional color filter except that it is formed using a photosensitive resin composition containing (D) a colorant. The black matrix and the black column spacer are the same as the conventional black matrix and the black column spacer except that the black matrix and the black column spacer are formed from a photosensitive resin composition containing a light-shielding agent as a colorant (D). The display device is the same as the conventional display device except that the display device includes the above-described insulating film or includes at least one of the above-described color filter, black matrix, and black column spacer.

  A method for forming the insulating film, the color filter, the black matrix, and the black column spacer using the above-described photosensitive resin composition is not particularly limited. As a typical method for forming an insulating film, a color filter, a black matrix, and a black column spacer, a photosensitive resin composition is applied on a predetermined substrate, and a photosensitive resin layer is formed. There is a method including an exposure step of exposing the resin layer according to a predetermined black column spacer pattern and a development step of developing the exposed photosensitive resin layer to form a black column spacer pattern.

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

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

  When a black column spacer is formed on a substrate having an element on its surface, such as a TFT substrate, the black column is placed on the element or at a position facing the element on the substrate that is paired with the element-formed substrate. It may be necessary to form spacers. In such a case, it is necessary to change the height of the black column spacer between the part where the element is formed and the other part in consideration of the height of the element. Therefore, in such a case, it is preferable to perform exposure through a halftone mask.

  Next, in the developing step, the exposed photosensitive resin layer is developed with a developer, thereby forming an insulating film, a color filter, a black matrix, or a black column spacer patterned in a predetermined shape. The development method is not particularly limited, and an immersion method, a spray method, or the like can be used. Specific examples of the developer include organic ones such as monoethanolamine, diethanolamine, and triethanolamine, and aqueous solutions such as sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, and quaternary ammonium salts.

  Thereafter, the black column spacer after development is post-baked and cured by heating. Post baking is preferably performed at 150 to 250 ° C. for 15 to 60 minutes.

  The color filter, black matrix, and black column spacer formed in this manner are prevented from being peeled off from the substrate after development, and the shape change or surface change due to post-baking or heating during panel processing. Since it is difficult to cause generation of fine wrinkles, it is preferably used as a constituent member of a panel for an image display device. In particular, when the photosensitive resin composition described above is used, a pattern having excellent straightness can be formed. Therefore, a color filter or a black matrix is suitable as a constituent member of a panel for an image display device from the viewpoint of straightness of the pattern.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples.

<Alkali-soluble resin>
In Examples and Comparative Examples, R1 to R4 were used as alkali-soluble resins. R1 was prepared according to the following synthesis example. R2 to R3 are resins represented by the following formula. In the following formula, the number on the lower right of each unit means the content (% by mass) of each unit in the resin. The mass average molecular weights of R1 to R4 are as follows.
(Mass average molecular weight of R1 to R4)
R1: 3,000
R2: 15,000
R3: 8,000
R4: 15,000

（Ｒ３において、Ｚは、下記Ｚ１又はＺ２である）

(In R3, Z is the following Z1 or Z2)

[Resin (R1) Synthesis Example]
First, in a 500 ml four-necked flask, 235 g of bisphenolfluorene type epoxy resin (epoxy equivalent 235), 110 mg of tetramethylammonium chloride, 100 mg of 2,6-di-tert-butyl-4-methylphenol, and 72.0 g of acrylic acid Was heated and dissolved at 90 to 100 ° C. while blowing air at a rate of 25 ml / min. Next, the temperature was gradually raised while the solution was clouded, and the solution was heated to 120 ° C. to be completely dissolved. At this time, the solution gradually became transparent and viscous, but stirring was continued as it was. During this time, the acid value was measured, and heating and stirring were continued until the acid value was less than 1.0 mgKOH / g. It took 12 hours for the acid value to reach the target value. And it cooled to room temperature and obtained the bisphenol fluorene type epoxy acrylate represented by the following transparent formula (a-4) colorless and transparent.

  Next, after adding 600 g of 3-methoxybutyl acetate to 307.0 g of the bisphenolfluorene type epoxy acrylate thus obtained and dissolving, 80.5 g of benzophenonetetracarboxylic dianhydride and 1 g of tetraethylammonium bromide were added. The mixture was gradually heated and reacted at 110 to 115 ° C. for 4 hours. After confirming disappearance of the acid anhydride group, 38.0 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed and reacted at 90 ° C. for 6 hours to obtain a resin (R1). The disappearance of the acid anhydride group was confirmed by IR spectrum. In addition, this resin (R1) is corresponded to resin represented by the said Formula (a-1).

（式（Ｉ−２）中、ｑ１、ｑ２、ｑ３、ｑ４、ｑ５、及びｑ６はそれぞれ０〜５の整数であり、ｑ１、ｑ２、ｑ３、ｑ４、ｑ５、及びｑ６の和は、２〜６の整数である。） <Photopolymerizable compound>
As the photopolymerizable compound, HM1 to HM3, which are compounds represented by the following formula (I-2), and HM4 (dipentaerythritol hexaacrylate) were used as hexafunctional compounds. For HM1, the sum of q1, q2, q3, q4, q5, and q6 is 2. For HM2, the sum of q1, q2, q3, q4, q5, and q6 is 4. For HM3, the sum of q1, q2, q3, q4, q5, and q6 is 6. The following MM1 to MM3 and DM1 to DM3 were used as mono- or bifunctional compounds.

(In Formula (I-2), q1, q2, q3, q4, q5, and q6 are each an integer of 0-5, and the sum of q1, q2, q3, q4, q5, and q6 is 2-6. Is an integer.)

MM1: diethylene glycol monomethyl ether monoacrylate MM2: n-butyl acrylate MM3: tetraethylene glycol monomethyl ether monoacrylate DM1: diethylene glycol diacrylate DM2: 1,4-butanediol diacrylate DM3: tetraethylene glycol diacrylate

<Photopolymerization initiator>
In Examples and Comparative Examples, the following PI-A and PI-B were used as photopolymerization initiators.

<Colorant>
In Examples and Comparative Examples, carbon black (CF black, manufactured by Gokoku Dye) was used as a colorant.

[Examples 1 to 19 and Comparative Examples 1 to 6 (non-colored photosensitive resin composition)]
(A) Alkali-soluble resin (component (A)), (B) photopolymerizable compound (component (B)), and (C) photopolymerization initiator ((C), each of the types and amounts listed in Table 1. Ingredients) are dissolved in a mixed solvent (composition: methyl ethyl diglycol 60% by mass, propylene glycol monomethyl ether 40% by mass) so that the solid content concentration is 15% by mass. A functional resin composition was obtained.

<Pattern straightness evaluation>
The photosensitive resin composition was applied onto a glass substrate (100 mm × 100 mm) using a spin coater and pre-baked at 90 ° C. for 120 seconds to form a coating film having a thickness of 1.0 μm. Next, using a mirror projection aligner (product name: TME-150 RTO, manufactured by Topcon Corporation), the exposure gap was 50 μm, and the coating film was irradiated with ultraviolet rays through a negative mask having a line pattern with a width of 10 μm. The exposure amount was set in four stages of ²⁰ , 40, 60, and 80 mJ / cm ² . The exposed coating film was developed with a 0.04 mass% KOH aqueous solution at 26 ° C. for 40 seconds and then post-baked at 230 ° C. for 30 minutes to form a line pattern.
The formed line pattern was observed with an optical microscope, and pattern straightness was evaluated. The straightness of the pattern was evaluated as “◯” when the edge of the line is not wobbled, and “x” when the line is wobbled. Table 2 shows the evaluation results of the pattern straightness.

<Pattern peeling evaluation>
In the same manner as the pattern straightness evaluation, a line pattern was formed by changing the exposure amount into four stages of 40, 60, 80, and 120 mJ / cm ² . The line pattern was observed with an optical microscope, and the presence or absence of peeling of the line pattern from the substrate or chipping of the line pattern was confirmed. The case where no peeling or chipping of the line pattern was observed was evaluated as “◯”, and the case where the peeling or chipping of the line pattern was observed was evaluated as “x”. The evaluation results of pattern peeling are shown in Table 2.

<Pattern shape after heating>
A line pattern was formed in the same manner as the pattern straightness evaluation except that the exposure amount was 120 mJ / cm ² .
The cross section of the pattern after post-baking was observed with an electron microscope, and the taper angle, which is an acute angle among the angles formed by the substrate surface and the pattern side surfaces, was determined. From the obtained taper angle, the quality of the pattern shape after heating was evaluated according to the following criteria. Table 2 shows the evaluation results of the shape of the pattern after heating.
◎: Taper angle of 80 ° or more and 90 ° or less ○: Taper angle of 60 ° or more and less than 80 ° Δ: Taper angle of 40 ° or more and less than 60 ° ×: Taper angle of less than 40 °

<Surface condition of pattern after heating>
A pattern was formed in the same manner as the evaluation of the pattern shape after heating.
The surface roughness of the pattern after heating was measured with a stylus type film thickness measuring device (manufactured by Dektak Bruker). From the measured surface roughness (Ra (Å)), the quality of the surface state of the pattern after heating was evaluated according to the following criteria. The evaluation results of the surface state of the pattern after heating are shown in Table 2.
◎: Ra is 35 Å or less ○: Ra is more than 35 Å 45 Å or less Δ: Ra is more than 45 Å 55 or less ×: Ra is more than 55 Å

  According to Examples 1 to 19, (A) an alkali-soluble resin having a (meth) acryloyl group or an epoxy group, and (B) a photopolymerizable compound containing the compound represented by the above formula (I), By using a photosensitive resin composition containing (C) a photopolymerization initiator that is an oxime ester compound, the cross-sectional shape is a good rectangle, there are no fine wrinkles on the surface, excellent straightness, and after development. It can be seen that a pattern that is difficult to peel off from the substrate can be formed.

  According to Examples 5 to 19, (B) As the photopolymerizable compound, a compound represented by the formula (I) and a monofunctional or bifunctional compound such as MM1 to MM3 and DM1 to DM3 are used in combination. Thus, it can be seen that it is particularly easy to form a pattern having a favorable cross-sectional shape and having no fine wrinkles on the surface.

  According to Comparative Examples 1 to 3, the photosensitive resin composition includes (A) an alkali-soluble resin having a (meth) acryloyl group or an epoxy group, and (C) a photopolymerization initiator that is an oxime ester compound. However, when the compound represented by the formula (I) is not contained as the photopolymerizable compound (B), the taper angle in the pattern cross section is remarkably lowered by heating during pattern formation, and the rectangularity of the pattern is greatly impaired. I understand.

  According to Comparative Examples 4 to 6, when the photosensitive resin composition does not contain (A) an alkali-soluble resin having a (meth) acryloyl group or an epoxy group, it is excellent in straightness at low exposure and peeled from the substrate. It can be seen that a pattern in which the pattern is suppressed cannot be formed, and the rectangularity of the pattern after heating is greatly impaired.

[Examples 20 to 39 and Comparative Examples 7 to 11 (non-colored photosensitive resin composition)]
(A) Alkali-soluble resin (component (A)), (B) photopolymerizable compound (component (B)), and (C) photopolymerization initiator ((C), each of the types and amounts listed in Table 3 Component) and the amount of (D) colorant (component (D)) described in Table 3 in a mixed solvent (composition: 60% by mass of methyl ethyl diglycol, propylene, so that the solid concentration is 15% by mass) Glycol monomethyl ether 20% by mass, cyclohexanone 20% by mass) to obtain photosensitive resin compositions of Examples and Comparative Examples.

Using the obtained photosensitive resin composition, the pattern straightness, pattern peeling, the pattern shape after heating, and the surface state of the pattern after heating were evaluated according to the methods described above. In addition, the exposure amount at the time of pattern straightness evaluation was changed to 30, 60, 90, 120 mJ / cm ² . These evaluation results are shown in Table 4.

  According to Examples 20 to 39, even when the photosensitive resin composition contains (D) a colorant, the photosensitive resin composition has a (meth) acryloyl group or an epoxy group (A) alkali. If a soluble resin, (B) a photopolymerizable compound containing the compound represented by the formula (I) and (C) a photopolymerization initiator which is an oxime ester compound are contained, the cross-sectional shape is good. It can be seen that a rectangular pattern having no fine wrinkles on the surface, excellent straightness, and difficult to peel off from the substrate after development can be formed.

  According to Examples 23 to 39, as the photopolymerizable compound (B), a compound represented by the formula (I) and a monofunctional or bifunctional compound such as MM1 to MM3 and DM1 to DM3 are used in combination. Thus, it can be seen that it is particularly easy to form a pattern having a favorable cross-sectional shape and having no fine wrinkles on the surface.

  According to Comparative Examples 7 and 8, the photosensitive resin composition includes (A) an alkali-soluble resin having a (meth) acryloyl group or an epoxy group, and (C) a photopolymerization initiator which is an oxime ester compound. However, when the compound represented by the formula (I) is not contained as the photopolymerizable compound (B), the taper angle in the pattern cross section is remarkably lowered by heating during pattern formation, and the rectangularity of the pattern is greatly impaired. I understand.

  According to Comparative Examples 9 to 11, when the photosensitive resin composition does not contain (A) an alkali-soluble resin having a (meth) acryloyl group or an epoxy group, it is excellent in straightness at low exposure and peeled from the substrate. It can be seen that a pattern in which the pattern is suppressed cannot be formed, and the rectangularity of the pattern after heating is greatly impaired.

Claims (13)

(A) an alkali-soluble resin, (B) a photopolymerizable compound, and (C) a photopolymerization initiator,
The (A) alkali-soluble resin has an acryloyl group or an epoxy group,
The photopolymerizable compound (B) includes a compound represented by the following formula (I):
The (C) photopolymerization initiator is represented by the following formula (c4):

(R ^c9 is a group selected from the group consisting of a monovalent organic group, amino group, halogen, nitro group, and cyano group, a is 0 or 1, and d is an integer of 0-4. , R ^c2 is a phenyl group which may have a substituent, or a carbazolyl group which may have a substituent, and R ^c3 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a substituent Which may have a phenyl group.)
The photosensitive resin composition which is an oxime ester compound containing the oxime ester compound represented by these.

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

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

P is an integer of 0 to 4, q is an integer of 0 to 5, and the group represented by the formula (II) among the six Xs in the formula (I) The number is an integer of 4 to 6, and the groups represented by the plurality of formulas (II) in the formula (I) may be the same or different, and the plurality of formulas in the formula (I) In the group represented by (II), not all q are 0, and the number of divalent groups represented by-(R ¹ -O)-in the compound represented by formula (I) and- The total number of divalent groups represented by (R ² —O) — is 1 or more, and in formula (III), R ⁴ is a hydrogen atom or a methyl group. )   The photosensitive resin composition of Claim 1 whose said p is 0. Further, an alkyl (meth) acrylate, a monoalkyl ether mono (meth) acrylate of an alkanediol, a di (meth) acrylate of an alkanediol, a monoalkyl ether mono (meth) acrylate of a polyalkylene oxide, or a di (meta) of a polyalkylene oxide The photosensitive resin composition of Claim 1 or 2 containing an acrylate. Alkyl (meth) acrylate, monoalkyl ether mono (meth) acrylate of alkanediol, di (meth) acrylate of alkanediol, monoalkyl ether mono (meth) acrylate of polyalkylene oxide, or di (meth) of polyalkylene oxide The photosensitive resin composition according to claim 3 , wherein the acrylate is at least one of a compound represented by the following formula (IV) or a compound represented by (V).

(In Formula (IV) and Formula (V), R ⁵ is an alkylene group having 2 to 4 carbon atoms, R ⁶ is a hydrogen atom or a methyl group, and R ⁷ is a straight chain having 1 to 8 carbon atoms. An alkyl group, s is an integer of 0 to 9, and t is an integer of 1 to 9.) (D) The photosensitive resin composition of any one of Claims 1-4 which does not contain a coloring agent. Furthermore, (D) The photosensitive resin composition of any one of Claims 1-4 containing a coloring agent. The photosensitive resin composition of Claim 6 whose said (D) coloring agent is a light-shielding agent. An insulating film formed using the photosensitive resin composition according to claim 5 . A display device comprising the insulating film according to claim 8 . Color filter formed using the photosensitive resin composition according to claim 6 or 7. A black matrix formed using the photosensitive resin composition according to claim 7 . A black column spacer formed using the photosensitive resin composition according to claim 7 . The color filter according to claim 10, the display device comprising at least one selected from the group consisting of black column spacer according black matrix, and to claim 12 of claim 11.