JP2016218353A - Photosensitive composition, pattern forming method, cured film, insulation film, and display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive composition providing a cured film having sufficient transmissivity and sensitivity to light exposure, a pattern forming method using the photosensitive composition, a cured film and an insulation film formed by using the photosensitive composition and a display device having the insulation film.SOLUTION: There is provided a photosensitive composition containing (A) a crosslinkable group-containing resin, (B) a photopolymerizable monomer and (C) a photoinitiator which is represented by the formula (1).SELECTED DRAWING: None

Description

  The present invention relates to a photosensitive composition, a pattern forming method using the photosensitive composition, a cured film and an insulating film formed using the photosensitive composition, and a display device including the insulating film.

  In a display device such as a liquid crystal display device, an insulating film or a material such as a spacer needs to efficiently transmit light emitted from a light source such as a backlight. For this reason, in order to form the pattern of an insulating film or a spacer, the photosensitive composition which gives a transparent cured film by exposure is used. By selectively exposing such a photosensitive composition, a transparent cured film pattern can be formed.

  As a photosensitive composition capable of forming a transparent cured film, for example, a composition containing a resin, a polymerizable compound, a polymerization initiator having a specific structure, and a solvent has been proposed (Patent Document 1). . Specifically, Examples of Patent Document 1 include a copolymer of methacrylic acid and an acrylate having an alicyclic epoxy group, dipentaerythritol hexaacrylate, a polymerization initiator represented by the following formula, A photosensitive composition comprising a mixed solvent comprising 3-methoxy-1-butanol, propylene glycol monomethyl ether acetate, ethyl 3-ethoxypropionate, and 3-methoxybutyl acetate is disclosed.

  The photosensitive composition is cured by the photopolymerization initiator contained as a part of its components generating radicals upon exposure and polymerizing the polymerizable compound contained in the photosensitive composition. Therefore, it is known that the sensitivity of the photosensitive composition is affected by the type of photopolymerization initiator contained therein. As a photopolymerization initiator capable of improving the sensitivity of the photosensitive composition, Patent Document 2 proposes an oxime ester compound having a cycloalkyl group. In the examples described in Patent Document 2, compounds represented by the following chemical formulas (a) and (b) are specifically disclosed.

JP 2012-58728 A Published patent gazette No. 101508744 in the People's Republic of China

  However, the cured film formed using the photosensitive composition described in Patent Document 1 or Patent Document 2 has insufficient transmittance and sensitivity to exposure.

  The present invention has been made in view of the above-described problems, and includes a photosensitive composition that provides a cured film with sufficient transmittance and sensitivity to exposure, a pattern formation method using the photosensitive composition, and the photosensitive property. It aims at providing the cured film and insulating film which are formed using a composition, and a display apparatus provided with the said insulating film.

  The present inventors include (A) a crosslinkable group-containing resin, (B) a photopolymerizable monomer, and (C) a photopolymerization initiator containing a compound having a specific structure in the photosensitive composition. Thus, the inventors have found that the above-described problems can be solved, and have completed the present invention.

（Ｒ^１は水素原子、ニトロ基又は１価の有機基であり、Ｒ^２及びＲ^３は、それぞれ、鎖状アルキル基、環状炭化水素基、又はヘテロアリール基であり、Ｒ^２とＲ^３とは相互に結合してスピロ環を形成してもよく、Ｒ^４は１価の有機基であり、Ｒ^５は、水素原子、置換基を有してもよい炭素原子数１〜１１のアルキル基、又は置換基を有してもよいアリール基であり、ｍは０又は１である。）
で表される化合物を含む、感光性組成物である。 The first aspect of the present invention includes (A) a crosslinkable group-containing resin, (B) a photopolymerizable monomer, and (C) a photopolymerization initiator,
The (C) photopolymerization initiator is represented by the following formula (1):

(R ¹ is a hydrogen atom, a nitro group or a monovalent organic group, R ² and R ³ are each a chain alkyl group, a cyclic hydrocarbon group, or a heteroaryl group, and R ² and R ³ are ^May combine with each other to form a spiro ring, R ⁴ is a monovalent organic group, and R ⁵ is a hydrogen atom or an alkyl group having 1 to 11 carbon atoms that may have a substituent. Or an aryl group which may have a substituent, and m is 0 or 1.)
It is a photosensitive composition containing the compound represented by these.

  The second aspect of the present invention is to form a coating film or a molded body using the photosensitive composition according to the first aspect, irradiate the coating film or the molded body with electromagnetic waves in a predetermined pattern, and develop It is a pattern formation method including doing.

  The third aspect of the present invention is a cured film formed using the photosensitive composition according to the first aspect.

  A fourth aspect of the present invention is an insulating film formed using the photosensitive composition according to the first aspect.

  A fifth aspect of the present invention is a display device including the insulating film according to the fourth aspect.

  According to the present invention, a photosensitive composition that provides a cured film with sufficient transmittance and sensitivity to exposure, a pattern forming method using the photosensitive composition, and a cured film formed using the photosensitive composition And an insulating film, and a display device including the insulating film can be provided.

≪Photosensitive composition≫
The photosensitive composition according to the present invention contains (A) a crosslinkable group-containing resin, (B) a photopolymerizable monomer, and (C) a photopolymerization initiator containing a specific compound. Hereinafter, each component contained in the photosensitive composition will be described.

<(A) Crosslinkable group-containing resin>
The photosensitive composition according to the present invention contains (A) a crosslinkable group-containing resin (hereinafter, also referred to as “component (A)”), so that a cured film using the photosensitive composition can be formed. To. (A) The crosslinkable group-containing resin is a resin having a crosslinkable group, and preferably contains a unit derived from a (meth) acrylic acid ester having a crosslinkable group. The crosslinkable group is not particularly limited as long as it is a functional group capable of crosslinking the (A) crosslinkable group-containing resin mainly by heating, but an epoxy group or an ethylenically unsaturated double bond is preferable. The crosslinkable group includes, for example, at least one selected from the group consisting of a unit derived from a (meth) acrylic acid ester having an epoxy group and a unit having an ethylenically unsaturated double bond. It can introduce | transduce into crosslinkable group containing resin.

  (A) As crosslinkable group containing resin, resin containing the unit derived from the (meth) acrylic acid ester which has an epoxy group is preferable. By having such a unit, the adhesiveness and mechanical strength of the insulating film formed using the photosensitive composition to the substrate can be improved.

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

  The (meth) acrylic acid ester having an epoxy group may have an aromatic group. In this specification, an aromatic group is a group having an aromatic ring. 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, 2-glycidyloxyphenyl (meta ) Acrylate, 4-glycidyloxyphenylmethyl (meth) acrylate, 3-glycidyloxyphenylmethyl (meth) acrylate, 2-glycidyloxyphenylmethyl (meth) acrylate, and the like.

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

  Examples of (meth) acrylic acid ester having a chain aliphatic epoxy group include an ester group (—O—CO—) such as epoxy alkyl (meth) acrylate and epoxyalkyloxyalkyl (meth) acrylate. (Meth) acrylic acid ester in which a chain aliphatic epoxy group is bonded to the oxy group (—O—). 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 chain aliphatic epoxy group include glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, 6,7- Epoxyalkyl (meth) acrylates such as epoxyheptyl (meth) acrylate; 2-glycidyloxyethyl (meth) acrylate, 3-glycidyloxy-n-propyl (meth) acrylate, 4-glycidyloxy-n-butyl (meth) acrylate And epoxyalkyloxyalkyl (meth) acrylates such as 5-glycidyloxy-n-hexyl (meth) acrylate and 6-glycidyloxy-n-hexyl (meth) acrylate.

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

In the above formula, R ^d4 represents a hydrogen atom or a methyl group, R ^d5 represents a divalent aliphatic saturated hydrocarbon group having 1 to ⁶ carbon atoms, and R ^d6 represents a divalent hydrocarbon having 1 to 10 carbon atoms. Represents a group, and n represents an integer of 0 to 10. R ^d5 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 ^d6 , for example, methylene group, ethylene group, propylene group, tetramethylene group, ethylethylene group, pentamethylene group, hexamethylene group, phenylene group, cyclohexylene group, —CH ₂ —Ph—CH ₂ — (Ph is A phenylene group) is preferred.

  When the (meth) acrylic acid ester having an epoxy group is a (meth) acrylic acid ester having an alicyclic epoxy group as described above, compared to a (meth) acrylic acid ester having a chain aliphatic epoxy group, The (A) crosslinkable group-containing resin containing a unit derived from the (meth) acrylic acid ester, which is excellent in storage stability of the photosensitive composition, and can be prebaked at the time of forming an insulating film or the like (prebaked (Temperature margin) is widened, which is preferable.

  (A) As a crosslinkable group-containing resin, a resin containing a unit having an ethylenically unsaturated double bond as a crosslinkable group (in this specification, “resin having an ethylenically unsaturated double bond”) May be). The ethylenically unsaturated double bond is preferably a part constituting a (meth) acryloyloxy group.

Examples of the resin having an ethylenically unsaturated double bond include a resin having a (meth) acryloyloxy group.
The resin having a (meth) acryloyloxy group is, for example, a (meth) acrylic acid ester having at least a part of a carboxy group contained in a polymer containing a unit derived from an unsaturated carboxylic acid and the alicyclic epoxy group. And / or it can prepare by making it react with the (meth) acrylic acid ester which has the said chain | strand-shaped aliphatic epoxy group.

  (A) When the crosslinkable group-containing resin is a resin having an ethylenically unsaturated double bond, it may have photopolymerizability. (A) The crosslinkable group-containing resin can improve the curability of the photosensitive composition and facilitate pattern formation by containing a photopolymerizable resin having such an ethylenically unsaturated double bond. .

  (A) In the crosslinkable group-containing resin, the amount of the unit derived from the (meth) acrylic acid ester having a crosslinkable group is preferably 20 to 80% by mass, and 30 to 70% by mass with respect to the mass of the resin. % Is more preferable, 33 to 65% by mass is further preferable, and the amount of the unit derived from the (meth) acrylic acid ester having an epoxy group is preferably 10 to 80% by mass, more preferably 15 to 70% by mass, and 20 -65 mass% is still more preferable, 15-40 mass% is preferable and, as for the quantity of the unit which has an ethylenically unsaturated double bond, 20-35 mass% is more preferable. (A) The crosslinkable group-containing resin is preferably a polymer of at least one monomer selected from (meth) acrylic acid and (meth) acrylic acid ester. Content of the unit derived from the (meth) acrylic acid ester having a crosslinkable group in the coalescence is the same as described above with respect to the mass of the resin.

  (A) The crosslinkable group-containing resin may include both a unit derived from a (meth) acrylic acid ester having an epoxy group and a unit having an ethylenically unsaturated double bond. It may contain either a unit derived from a (meth) acrylic acid ester having a unit or a unit having an ethylenically unsaturated double bond, and the (meth) acrylic acid ester having an epoxy group as a crosslinkable group Those containing only derived units are preferred.

  (A) The crosslinkable group-containing resin is preferably a resin having a crosslinkable group and an alkali-soluble resin. The photosensitive composition can impart alkali developability to the photosensitive composition by blending such an alkali-soluble resin.

  In this specification, the alkali-soluble resin means that a resin film having a film thickness of 1 μm is formed on a substrate with a resin solution (solvent: propylene glycol monomethyl ether acetate) having a resin concentration of 20% by mass, and KOH having a concentration of 0.05% by mass. When immersed in an aqueous solution for 1 minute, it means one that dissolves to a thickness of 0.01 μm or more.

  (A) When the crosslinkable group-containing resin is also an alkali-soluble resin, it usually has an alkali-soluble group. The alkali-soluble group is not particularly limited as long as it is a functional group that imparts solubility to the alkali in the (A) crosslinkable group-containing resin, but is preferably a carboxy group or a group that generates a carboxy group by deprotection. By containing a unit derived from an unsaturated carboxylic acid described later, and by polymerizing a monomer containing a (meth) acrylic acid ester that imparts an alkali-soluble group, (A) a crosslinkable group-containing resin Can be introduced. In this specification, the (meth) acrylic acid ester that imparts the alkali-soluble group does not include the (meth) acrylic acid ester having the crosslinkable group described above.

  When (A) the crosslinkable group-containing resin is also an alkali-soluble resin, (A) a functional group that suppresses or inhibits the solubility of the crosslinkable group-containing resin in the alkali (hereinafter referred to as “alkali dissolution inhibiting group” or “ Although it may be a resin having no “dissolution-inhibiting group”), a resin having an alkali-soluble group and a dissolution-inhibiting group is preferred. The dissolution inhibiting group can be said to be an alkali hardly soluble group in that it has a function of reducing the solubility of (A) the crosslinkable group-containing resin in alkali. (A) Crosslinkable group containing resin can adjust the solubility with respect to an alkali by having an alkali-soluble group and a dissolution inhibiting group, and can adjust the alkali developability of the photosensitive composition by this. . Examples of the dissolution inhibiting group include styrene or styrene derivatives described later; unsaturated imides; (meth) acrylic acid ester having an alicyclic skeleton (excluding those having an epoxy group); benzyl (meth) acrylate And (meth) acrylic acid ester having an aromatic group such as In this specification, the (meth) acrylic acid ester that imparts the dissolution inhibiting group does not include the (meth) acrylic acid ester having the crosslinkable group described above.

  (A) Among the crosslinkable group-containing resins, the monomer having an ethylenically unsaturated double bond is excellent in film-forming properties and easy to adjust the characteristics of the resin by selecting the monomer. Polymers are preferred. As monomers having an ethylenically unsaturated double bond, (meth) acrylic acid; (meth) acrylic acid ester; (meth) acrylic acid amide; crotonic acid; maleic acid, fumaric acid, citraconic acid, mesaconic acid, Itaconic acid, anhydrides of these dicarboxylic acids; such as allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, allyl lactate, and allyloxyethanol Allyl compounds; hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethyl hexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl ether, 2- Tilbutyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether, vinyl phenyl ether, vinyl tolyl ether, vinyl chlorophenyl ether, vinyl-2,4 -Vinyl ethers such as dichlorophenyl ether, vinyl naphthyl ether, and vinyl anthranyl ether; vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl valerate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, Vinyl methoxyacetate, Vinyls such as nylbutoxy acetate, vinyl phenyl acetate, vinyl acetoacetate, vinyl lactate, vinyl-β-phenylbutyrate, vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, and vinyl naphthoate Esters: 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, ethoxymethyl styrene, Acetoxymethylstyrene, methoxystyrene, 4-methoxy-3-methylstyrene, dimethoxystyrene, chlorostyrene, dichlorostyrene , Trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethylstyrene, and 4-fluoro-3-trifluoromethylstyrene Styrene or styrene derivatives such as: ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4- Methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene 1-octadecene, and 1-olefins such as eicosene; maleimide, N- phenylmaleimide, unsaturated imides such as N- cyclohexyl maleimide; and the like.

  (A) When the crosslinkable group-containing resin is a polymer of a monomer having an ethylenically unsaturated double bond, it usually contains a unit derived from an unsaturated carboxylic acid. 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. . The amount of the unit derived from the unsaturated carboxylic acid in the resin used as the alkali-soluble resin is preferably 5 to 25% by mass, more preferably 8 to 16% by mass, based on the mass of the resin, (A) When the crosslinkable group-containing resin has a dissolution inhibiting group described later, these amounts are particularly preferable. (A) When the crosslinkable group-containing resin does not have a dissolution inhibiting group described later, the amount of the unit derived from the unsaturated carboxylic acid in the resin is preferably 50 to 80% by mass with respect to the mass of the resin. 60-70 mass% is more preferable.

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

  The (meth) acrylic acid ester used for the preparation of a polymer of one or more monomers selected from (meth) acrylic acid and (meth) acrylic acid ester is particularly within the range not hindering the object of the present invention. It is not limited, It selects suitably from well-known (meth) acrylic acid ester.

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

  Moreover, among polymers of one or more monomers selected from (meth) acrylic acid and (meth) acrylic acid esters, it is easy to form an insulating film with high transmittance using a photosensitive composition. Therefore, a resin containing a unit derived from a (meth) acrylic acid ester having an alicyclic skeleton is also preferable. In this specification, the (meth) acrylic acid ester having an alicyclic skeleton does not include the (meth) acrylic acid ester having the above-described crosslinkable group.

  In the (meth) acrylic acid ester having an alicyclic skeleton, the group having an alicyclic skeleton is preferably a group having an alicyclic hydrocarbon group. 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.

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

In the above formula, R ^d1 represents a hydrogen atom or a methyl group, R ^d2 represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, and R ^d3 represents a hydrogen atom or 1 carbon atom. Represents an alkyl group of ~ 5. R ^d2 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 ^d3 is preferably a methyl group or an ethyl group.

  (A) The crosslinkable group-containing resin is a (meth) acryl having a unit derived from one or more monomers selected from (meth) acrylic acid and (meth) acrylic ester, and an alicyclic epoxy group. A resin containing a unit derived from an acid ester is preferable. Such a resin may further be a resin including a unit derived from a (meth) acrylic acid ester having an alicyclic skeleton, and in that case, a (meth) acrylic acid ester having an alicyclic skeleton in the resin. The amount of the unit derived from may be 10 to 35% by mass, 15 to 30% by mass, or 20 to 25% by mass.

  Moreover, in the polymer of the 1 or more types of monomer selected from the (meth) acrylic acid and (meth) acrylic acid ester containing the unit derived from the (meth) acrylic acid ester which has an alicyclic skeleton. A resin containing a unit derived from (meth) acrylic acid and a unit derived from a (meth) acrylic acid ester having an alicyclic epoxy group is preferred. A film formed using such a photosensitive composition containing (A) a crosslinkable group-containing resin is excellent in adhesion to a substrate. Further, when such a resin is used, it is possible to cause a self-reaction between a carboxy group contained in the resin and an alicyclic epoxy group. Therefore, when a photosensitive composition containing such a resin is used, a film formed by causing a self-reaction between a carboxy group and an alicyclic epoxy group using a method of heating the film or the like. It is possible to improve mechanical properties such as hardness.

  In the resin containing a unit derived from (meth) acrylic acid (excluding those having a crosslinkable group) and a unit derived from a (meth) acrylic acid ester having an alicyclic epoxy group, the former in the resin 1-95 mass% is preferable and, as for the quantity of the unit derived from (meth) acrylic acid, 10-70 mass% is more preferable. In the resin containing the unit derived from the (meth) acrylic acid and the unit derived from the (meth) acrylic acid ester having an alicyclic epoxy group, the (meth) acrylic having an alicyclic epoxy group in the resin 1-95 mass% is preferable and, as for the quantity of the unit derived from an acid ester, 10-50 mass% is more preferable.

  One type selected from (meth) acrylic acid and (meth) acrylic acid ester, including a unit derived from (meth) acrylic acid and a unit derived from a (meth) acrylic acid ester having an alicyclic epoxy group Among the above polymer of monomers, it has a unit derived from (meth) acrylic acid, a unit derived from a (meth) acrylic acid ester having an alicyclic hydrocarbon group, and an alicyclic epoxy group. It may be a resin containing a unit derived from a (meth) acrylic acid ester.

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

(A) The mass average molecular weight of the crosslinkable group-containing resin (Mw: measured value in terms of polystyrene by gel permeation chromatography (GPC). The same applies in this specification) is preferably 2000 to 200000, and 2000 to 18000. It is more preferable that By setting it as the above range, there is a tendency that the film forming ability of the photosensitive composition and the developability after exposure are easily balanced.

  The content of the (A) crosslinkable group-containing resin in the photosensitive composition is preferably 15 to 95 mass%, more preferably 35 to 85 mass%, and more preferably 50 to 70 mass% in the solid content of the photosensitive composition. Is particularly preferred.

<(B) Photopolymerizable monomer>
As the (B) photopolymerizable monomer (hereinafter also referred to as “component (B)”) contained in the photosensitive composition, a compound having an ethylenically unsaturated double bond can be preferably used. The compound having an ethylenically unsaturated double bond includes a monofunctional compound and a polyfunctional compound.

  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 monomers can be used alone or in combination of two or more.

On the other hand, as a polyfunctional monomer,
1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1, 10-decanediol di (meth) acrylate, 1,12-dodecanediol di (meth) acrylate, ethoxylated hexanediol di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, 2-hydroxy-3- ( (Meth) acryloyloxypropyl (meth) acrylate, dipentaerythritol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol (Meth) acrylate, ethoxylated neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, poly (ethylene-propylene) glycol di (meth) acrylate, polytetramethylene glycol di (meth) acrylate, ethoxylated bisphenol A di (meth) acrylate, propoxylated bisphenol A di (meth) acrylate, propoxylated ethoxylated bisphenol A di (meth) acrylate, 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, di Pentaerythritol 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) acryloxydiethoxyphenyl) 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 (meth) acrylate, urethane (meth) acrylate (ie, tolylene diisocyanate), trimethylhexamethylene diisocyanate and hexamethylene diisocyanate and the like 2- Reaction product with bidoxyethyl (meth) acrylate, methylenebis (meth) acrylamide, (meth) acrylamide methylene ether, A condensate of a monohydric alcohol and N-methylol (meth) acrylamide, triacryl formal, 2,4,6-trioxohexahydro-1,3,5-triazine-1,3,5-trisethanol triacrylate, and Examples include 2,4,6-trioxohexahydro-1,3,5-triazine-1,3,5-trisethanol diacrylate. These polyfunctional monomers can be used alone or in combination of two or more.

Among these compounds having an ethylenically unsaturated double bond, a polyfunctional monomer having three or more functional groups is preferable from the viewpoint of obtaining a photosensitive composition that provides a cured product excellent in strength and adhesion to a substrate.
From the viewpoint of controlling the glass transition point (Tg), a monofunctional monomer or a bifunctional monomer may be used in combination with a trifunctional or higher polyfunctional monomer. Among these, 1,6-hexanediol di (meth) acrylate is preferable.

  (B) 5-60 mass% is preferable with respect to solid content of a photosensitive composition, and, as for content of a component, 10-50 mass% is more preferable. By making content of (B) component in a photosensitive composition into said range, there exists a tendency which is easy to balance the sensitivity of a photosensitive composition, developability, and resolution.

<(C) Photopolymerization initiator>
The photosensitive composition according to the present invention includes (C) a photopolymerization initiator (hereinafter referred to as “(C), which includes a compound represented by the following formula (1)” (also referred to as “oxime ester compound” in the present specification). ) "Component"). Since the photosensitive composition of this invention contains the compound represented by following formula (1) as (C) photoinitiator, it is excellent in a sensitivity. For this reason, by using the photosensitive composition of the present invention, a pattern having a desired shape can be formed with a low exposure amount. Moreover, by using the photosensitive composition according to the present invention having excellent sensitivity, pattern peeling at the time of pattern formation can be suppressed, and occurrence of rattling that occurs at the edge of the pattern when forming a line pattern can be suppressed. .

  Further, depending on the type of the photopolymerization initiator, the pattern transmittance may be lowered by post-baking the pattern formed using the photosensitive composition. However, when a photosensitive composition containing a compound represented by the following formula (1) is used as the photopolymerization initiator (C), the transmittance of the pattern is hardly reduced by heating.

（Ｒ^１は水素原子、ニトロ基又は１価の有機基であり、Ｒ^２及びＲ^３は、それぞれ、鎖状アルキル基、環状炭化水素基、又はヘテロアリール基であり、Ｒ^２とＲ^３とは相互に結合してスピロ環を形成してもよく、Ｒ^４は１価の有機基であり、Ｒ^５は、水素原子、置換基を有してもよい炭素原子数１〜１１のアルキル基、又は置換基を有してもよいアリール基であり、ｍは０又は１である。）

(R ¹ is a hydrogen atom, a nitro group or a monovalent organic group, R ² and R ³ are each a chain alkyl group, a cyclic hydrocarbon group, or a heteroaryl group, and R ² and R ³ are ^May combine with each other to form a spiro ring, R ⁴ is a monovalent organic group, and R ⁵ is a hydrogen atom or an alkyl group having 1 to 11 carbon atoms that may have a substituent. Or an aryl group which may have a substituent, and m is 0 or 1.)

In Formula (1), R ¹ is a hydrogen atom, a nitro group, or a monovalent organic group. R ¹ is bonded to a 6-membered aromatic ring different from the 6-membered aromatic ring bonded to the group represented by — (CO) _m — on the fluorene ring in the formula (1). In formula (1), the bonding position of R ^{1 to} the fluorene ring is not particularly limited. The bonding position of R ^{1 to} the fluorene ring is preferably the 2-position in the fluorene ring because the synthesis of the compound represented by formula (1) is easy.

When R ¹ is an organic group, R ¹ is not particularly limited as long as the object of the present invention is not impaired, and is appropriately selected from various organic groups. Preferable examples when R ¹ is an organic group include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, an alkoxycarbonyl group, a saturated aliphatic acyloxy group, and a substituent. An optionally substituted phenyl group, an optionally substituted phenoxy group, an optionally substituted benzoyl group, an optionally substituted phenoxycarbonyl group, an optionally substituted benzoyloxy A group, a phenylalkyl group which may have a substituent, a naphthyl group which may have a substituent, a naphthoxy group which may have a substituent, a naphthoyl group which may have a substituent, a substituent An optionally substituted naphthoxycarbonyl group, an optionally substituted naphthoyloxy group, an optionally substituted naphthylalkyl group, an optionally substituted heterocyclyl group, a substituted Examples include a heterocyclylcarbonyl group which may have a group, an amino group substituted with 1 or 2 organic groups, a morpholin-1-yl group, and a piperazin-1-yl group.

When R ¹ is an alkyl group, number of carbon atoms in the alkyl group is preferably from 1 to 20, 1 to 6 is more preferable. Further, when R ¹ is an alkyl group, it may be linear or branched. Specific examples in the case where R ¹ is an alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, and an n-pentyl group. , Isopentyl group, sec-pentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, n-nonyl group, isononyl group, An n-decyl group, an isodecyl group, etc. are mentioned. When R ¹ is an alkyl group, the alkyl group may include 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.

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

When R ¹ is a cycloalkyl group or a cycloalkoxy group, the number of carbon atoms of the cycloalkyl group or the cycloalkoxy group is preferably 3 to 10, and more preferably 3 to 6. Specific examples of when R ¹ is a cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Specific examples when R ¹ 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 ¹ is a saturated aliphatic acyl group or a saturated aliphatic acyloxy group, the number of carbon atoms of the saturated aliphatic acyl group or the saturated aliphatic acyloxy group is preferably 2 to 21, and more preferably 2 to 7. Specific examples when R ¹ 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 ¹ 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 ¹ is an alkoxycarbonyl group, the number of carbon atoms of the alkoxycarbonyl group is preferably 2-20, and more preferably 2-7. Specific examples in the case where R ¹ 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, i Examples include a sononyloxycarbonyl group, an n-decyloxycarbonyl group, and an isodecyloxycarbonyl group.

When R ¹ is a phenylalkyl group, the number of carbon atoms of the phenylalkyl group is preferably 7 to 20, and more preferably 7 to 10. Moreover, when R < ¹ > is a naphthyl alkyl group, 11-20 are preferable and, as for the carbon atom number of a naphthyl alkyl group, 11-14 are more preferable. Specific examples when R ¹ is a phenylalkyl group include a benzyl group, a 2-phenylethyl group, a 3-phenylpropyl group, and a 4-phenylbutyl group. Specific examples in the case where R ¹ 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 ¹ is a phenylalkyl group or a naphthylalkyl group, R ¹ may further have a substituent on the phenyl group or naphthyl group.

When R ¹ 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 rings are condensed. Heterocyclyl group. When the heterocyclyl group is a condensed ring, the ring number is up to 3. The heterocyclyl group may be an aromatic group (heteroaryl group) or a non-aromatic group. 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 ¹ is a heterocyclyl group, the heterocyclyl group may further have a substituent.

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

When R ¹ is an amino group substituted with an organic group having 1 or 2, suitable examples of the organic group include alkyl groups having 1 to 20 carbon atoms, cycloalkyl groups having 3 to 10 carbon atoms, and carbon atoms. A saturated aliphatic acyl group having 2 to 21 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 ¹ . 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- Examples include a decanoylamino group, a benzoylamino group, an α-naphthoylamino group, and a β-naphthoylamino group.

In the case where the phenyl group, naphthyl group, and heterocyclyl group included in R ¹ further have a substituent, the substituent is an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or 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 included in R ¹ further have a substituent, the number of the substituent is not limited as long as the object of the present invention is not impaired, but 1 to 4 is preferable. When the phenyl group, naphthyl group, and heterocyclyl group contained in R ¹ have a plurality of substituents, the plurality of substituents may be the same or different.

Among the groups described above, R ¹ is preferably a nitro group or a group represented by R ⁶ —CO— because the sensitivity tends to be improved. R ⁶ is not particularly limited as long as the object of the present invention is not impaired, and can be selected from various organic groups. Examples of a group suitable as R ⁶ include an alkyl group having 1 to 20 carbon atoms, a phenyl group which may have a substituent, a naphthyl group which may have a substituent, and a substituent. Or a heterocyclyl group that may be used. Among these groups, R ⁶ is particularly preferably a 2-methylphenyl group, a thiophen-2-yl group, or an α-naphthyl group.
In addition, it is preferable that R ¹ is a hydrogen atom because the transmittance tends to be excellent. When R ¹ is a hydrogen atom and R ⁴ is (R4-2) described later, the transmittance tends to be more excellent.

In Formula (1), R ² and R ³ are each a chain alkyl group, a cyclic hydrocarbon group, or a heteroaryl group. Among these groups, R ² and R ³ are preferably chain alkyl groups.

When R ² and R ³ are chain alkyl groups, the chain alkyl group may be a linear alkyl group or a branched alkyl group. When R ² and R ³ are chain alkyl groups, the chain alkyl group preferably has 1 to 20 carbon atoms, and more preferably 1 to 6 carbon atoms. Further, when R ¹ is an alkyl group, it may be linear or branched. Specific examples in the case where R ¹ is an alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, and an n-pentyl group. , Isopentyl group, sec-pentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, n-nonyl group, isononyl group, An n-decyl group, an isodecyl group, etc. are mentioned. When R ¹ is an alkyl group, the alkyl group may include 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 ² and R ³ are cyclic hydrocarbon groups, the cyclic hydrocarbon group may be an aliphatic cyclic hydrocarbon group or an aromatic cyclic hydrocarbon group.

When R ² and R ³ are aromatic cyclic hydrocarbon groups, the aromatic cyclic hydrocarbon group is a phenyl group or a group formed by bonding a plurality of benzene rings via a carbon-carbon bond. It is preferably a group formed by condensation of a plurality of benzene rings. When the aromatic cyclic hydrocarbon group is a phenyl group or a group formed by bonding or condensing a plurality of benzene rings, the number of benzene rings included in the aromatic cyclic hydrocarbon group is particularly limited. 3 or less is preferable, 2 or less is more preferable, and 1 is particularly preferable. Preferable specific examples of the aromatic cyclic hydrocarbon group include a phenyl group, a naphthyl group, a biphenylyl group, an anthryl group, and a phenanthryl group.

When R ² and R ³ are aliphatic cyclic hydrocarbon groups, the aliphatic cyclic hydrocarbon group may be monocyclic or polycyclic. Although the carbon atom number of an aliphatic cyclic hydrocarbon group is not specifically limited, 3-20 are preferable and 3-10 are more preferable. Examples of monocyclic cyclic hydrocarbon groups are cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, norbornyl, isobornyl, tricyclononyl, tricyclodecyl, Examples include a tetracyclododecyl group and an adamantyl group.

When R ² and R ³ are heteroaryl groups, the heteroaryl group is a 5- or 6-membered monocycle containing one or more N, S, O, such monocycles, or such monocycles It is a heteroaryl group condensed with a benzene ring. When the heteroaryl group is a condensed ring, the number of rings is limited to 3. Examples of the heterocyclic ring constituting the heteroaryl group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, pyridazine, benzofuran, benzothiophene, and indole. , Isoindole, indolizine, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalazine, cinnoline, quinoxaline and the like.

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

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

Examples of suitable organic groups for R ⁴ include, similarly to R ¹ , 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, An optionally substituted naphthoxycarbonyl group, an optionally substituted naphthoyloxy group, an optionally substituted naphthylalkyl group, and an optionally substituted heterocyclyl group An optionally substituted heterocyclyl group, 1, or an amino group substituted with two organic groups, morpholin-1-yl group, and piperazine-1-yl group. Specific examples of these groups are the same as those described for R ¹ . R ⁴ is also preferably a cycloalkylalkyl group, a phenoxyalkyl group optionally having a substituent on the aromatic ring, or a phenylthioalkyl group optionally having a substituent on the aromatic ring. The substituent that the phenoxyalkyl group and the phenylthioalkyl group may have is the same as the substituent that the phenyl group contained in R ¹ may have.

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

（式（Ｒ４−１）及び（Ｒ４−２）中、Ｒ^６及びＲ^７はそれぞれ有機基であり、ｐは０〜４の整数であり、Ｒ^６及びＲ^７がベンゼン環上の隣接する位置に存在する場合、Ｒ^６とＲ^７とが互いに結合して環を形成してもよく、ｑは１〜８の整数であり、ｒは１〜５の整数であり、ｓは０〜（ｒ＋３）の整数であり、Ｒ^８はアルキル基である。）
Ｒ^４が上記式（Ｒ４−１）又は（Ｒ４−２）で表される基である場合、感度及び透過率がより優れる。 Having described ^{R 4,} as is ^{R 4,} preferably a group represented by the following formula (R4-1) or (R4-2).

(In formulas (R4-1) and (R4-2), R ⁶ and R ⁷ are each an organic group, p is an integer of 0 to 4, and R ⁶ and R ⁷ are adjacent positions on the benzene ring. R ⁶ and R ⁷ may be bonded to each other to form a ring, q is an integer of 1 to 8, r is an integer of 1 to 5, and s is 0 to (r + 3). ) And R ⁸ is an alkyl group.)
When R ⁴ is a group represented by the above formula (R4-1) or (R4-2), sensitivity and transmittance are more excellent.

Examples of the organic group for R ⁶ and R ^{7 in} formula (R4-1) are the same as those for R ¹ . R ⁶ is preferably an alkyl group or a phenyl group. When R ⁶ is an alkyl group, the number of carbon atoms is preferably 1 to 10, more preferably 1 to 5, particularly preferably 1 to 3, and most preferably 1. That is, R ⁶ is most preferably a methyl group. When R ⁶ and R ⁷ are combined to form a ring, the ring may be an aromatic ring or an aliphatic ring. Preferable examples of the group represented by the formula (R4-1) in which R ⁶ and R ⁷ form a ring include a naphthalen-1-yl group, 1, 2, 3, 4-tetrahydronaphthalen-5-yl group etc. are mentioned. In said formula (R4-1), p is an integer of 0-4, it is preferable that it is 0 or 1, and it is more preferable that it is 0.

In the above formula (R4-2), ^{R 8} is an alkyl group. 1-10 are preferable, as for the carbon atom number of an alkyl group, 1-5 are more preferable, and 1-3 are especially preferable. As R ⁸ , a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group and the like are preferably exemplified, and among these, a methyl group is more preferable.

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

In Formula (1), R ⁵ is a hydrogen atom, an alkyl group having 1 to 11 carbon atoms which may have a substituent, or an aryl group which may have a substituent. Preferred examples of the substituent that may be present when R ⁵ is an alkyl group include a phenyl group and a naphthyl group. In addition, preferred examples of the substituent that R ¹ may have when it is an aryl group include an alkyl group having 1 to 5 carbon atoms, an alkoxy group, and a halogen atom.

In formula (1), preferred examples of R ⁵ include a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a phenyl group, a benzyl group, a methylphenyl group, and a naphthyl group. Among these, a methyl group or a phenyl group is more preferable.

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

  The fluorene derivative represented by the formula (1-1) is acylated by the Friedel-Crafts reaction using the halocarbonyl compound represented by the formula (1-2), and represented by the formula (1-3). A fluorene derivative is obtained. In formula (1-2), Hal is a halogen atom. The position acylated by the compound represented by the formula (1-2) on the fluorene ring can be changed by appropriately changing the conditions of the Friedel-Crafts reaction, or the compound represented by the formula (1-2) on the fluorene ring. It can be selected by a method in which protection and deprotection are performed at other positions to be acylated by.

Next, the resulting fluorene derivative represented by the formula (1-3) is oximed with hydroxylamine to obtain an oxime compound represented by the following formula (1-4). An oxime compound of the formula (1-4) and an acid anhydride ((R ⁵ CO) ₂ O) represented by the following formula (1-5) or an acid halide represented by the following general formula (1-6) A compound represented by the following formula (1-7) can be obtained by reacting (R ⁵ COHal, Hal is a halogen atom).

In the formulas (1-1), (1-2), (1-3), (1-4), (1-5), (1-6), and (1-7), R ¹ , R ² , R ³ , R ⁴ , and R ⁵ are the same as those in the formula (1).

<Scheme 1>

When m is 1, the compound represented by the formula (1) can be synthesized, for example, according to the following scheme 2. In Scheme 2, a fluorene derivative represented by the following formula (2-1) is used as a raw material. The fluorene derivative represented by the formula (2-1) is obtained by acylating the compound represented by the formula (1-1) by a Friedel-Crafts reaction in the same manner as in Scheme 1. A nitrite ester (RONO, R is an alkyl group having 1 to 6 carbon atoms) represented by the following general formula (2-2) in the presence of hydrochloric acid is added to the fluorene derivative represented by the formula (2-1). By reacting, a ketoxime compound represented by the following formula (2-3) is obtained. Next, a ketoxime compound represented by the following formula (2-3) and an acid anhydride ((R ⁵ CO) ₂ O) represented by the following formula (2-4), or the following general formula (2-5) A compound represented by the following formula (2-6) can be obtained by reacting with an acid halide represented by the formula (R ⁵ COHal, Hal is a halogen atom). In the following formulas (2-1), (2-3), (2-4), (2-5), and (2-6), R ¹ , R ² , R ³ , R ⁴ , and R ⁵ is the same as in the general formula (1).
When m is 1, the generation of foreign matters in a pattern formed using the photosensitive composition containing the compound represented by the formula (1) can be further reduced, and the sensitivity tends to increase. , M is preferably 1.

<Scheme 2>

Preferable specific examples of the compound represented by the formula (1) include the following compounds 1 to 25.

  The photosensitive composition may contain other photopolymerization initiators other than the oxime ester compound represented by the formula (1) as necessary, as long as the object of the present invention is not impaired. Specific examples of other photopolymerization initiators include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) phenyl]- 2-hydroxy-2-methyl-1-propan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4-dodecylphenyl) -2-hydroxy 2-methylpropan-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one, bis (4-dimethylaminophenyl) ketone, 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, eta 1,1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl], 1- (o-acetyloxime), 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 4- Benzoyl-4'-methyldimethylsulfide, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, butyl 4-dimethylaminobenzoate, 4-dimethylamino-2-ethylhexylbenzoic acid 4-dimethylamino-2-isoamylbenzoic acid, benzyl-β-methoxyethyl acetal, benzyldimethyl ketal, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, o-benzoylbenzoic acid Methyl, 2,4-diethylthioxanthone, 2-chlorothioxone Sandone, 2,4-dimethylthioxanthone, 1-chloro-4-propoxythioxanthone, thioxanthene, 2-chlorothioxanthene, 2,4-diethylthioxanthene, 2-methylthioxanthene, 2-isopropylthioxanthene, 2-ethylanthraquinone , Octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-diphenylanthraquinone, azobisisobutyronitrile, benzoyl peroxide, cumene peroxide, 2-mercaptobenzoimidar, 2-mercaptobenzoxazole, 2-mercapto Benzothiazole, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di (methoxyphenyl) imidazole dimer, 2- (o-fluoro Enyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer 2,4,5-triarylimidazole dimer, benzophenone, 2-chlorobenzophenone, 4,4′-bisdimethylaminobenzophenone (ie, Michler's ketone), 4,4′-bisdiethylaminobenzophenone (ie, ethyl Michler's) Ketone), 4,4'-dichlorobenzophenone, 3,3-dimethyl-4-methoxybenzophenone, benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ester Ter, benzoin butyl ether, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p-tert-butylacetophenone, p-dimethylaminoacetophenone, p-tert -Butyltrichloroacetophenone, p-tert-butyldichloroacetophenone, α, α-dichloro-4-phenoxyacetophenone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, dibenzosuberone, pentyl-4-dimethylaminobenzoate, 9- Phenylacridine, 1,7-bis- (9-acridinyl) heptane, 1,5-bis- (9-acridinyl) pentane, 1,3-bis- ( -Acridinyl) propane, p-methoxytriazine, 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2- [2- ( 5-methylfuran-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) ethenyl] -4,6-bis (trichloromethyl) -S-triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4-dimethoxyphenyl) Ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4 -Ethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-n-butoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-bis- Trichloromethyl-6- (3-bromo-4-methoxy) phenyl-s-triazine, 2,4-bis-trichloromethyl-6- (2-bromo-4-methoxy) phenyl-s-triazine, 2,4- Bis-trichloromethyl-6- (3-bromo-4-methoxy) styrylphenyl-s-triazine, 2,4-bis-trichloromethyl-6- (2-bromo-4-methoxy) styrylphenyl-s-triazine, etc. Is mentioned. Among these, it is particularly preferable in terms of sensitivity to use an oxime-based photopolymerization initiator. These photopolymerization initiators can be used alone or in combination of two or more.

When the photosensitive composition contains another photopolymerization initiator other than the oxime ester compound represented by the formula (1), the content of the other photopolymerization initiator is particularly within the range not hindering the object of the present invention. It is not limited. In this case, the content of the other photopolymerization initiator is typically preferably 99% by mass or less, more preferably 50% by mass or less, with respect to the total amount of the photopolymerization initiator contained in the photosensitive composition. 30% by mass or less is particularly preferable.
Moreover, the photosensitive composition may contain only 1 type as an oxime ester compound represented by Formula (1), and may contain two or more different types.

  (C) As for content of the photoinitiator which is a component, 0.1-50 mass parts is preferable with respect to a total of 100 mass parts of solid content of a photosensitive composition, and 0.5-10 mass parts is more preferable. . By using the component (C) in an amount within the above range, the photosensitive composition can be sufficiently cured by radiation or electromagnetic waves, and a photosensitive composition giving a cured film having excellent transmittance can be obtained.

<Other ingredients>
The photosensitive composition concerning this invention may contain alkali-soluble resin (henceforth "(D) alkali-soluble resin") other than (A) crosslinkable group containing resin. Although (D) alkali-soluble resin is mix | blended with a photosensitive composition, the alkali developability of a photosensitive composition may be able to be improved, The photosensitive composition of this invention is (D) alkali-soluble resin. Even if it does not contain, it can have alkali developability by using the above-mentioned resin which is also alkali-soluble resin as (A) crosslinkable group containing resin.

The photosensitive composition according to the present invention may contain various additives as necessary. Specifically, a solvent, a surface conditioner, a sensitizer, a curing accelerator, a photocrosslinking agent, a photosensitizer, a dispersion aid, a filler, an adhesion promoter, an antioxidant, an ultraviolet absorber, and an aggregation inhibitor. , Thermal polymerization inhibitors, antifoaming agents, surfactants, chain transfer agents and the like. 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.
Examples of the chain transfer agent include mercaptan-based, halogen-based, quinone-based compounds, α-methylstyrene dimer, and the like. By containing the chain transfer agent, the pattern shape (in particular, the CD change of the hole pattern and the exposure margin) can be controlled well. Of these, 2,4-diphenyl-4-methyl-1-pentene (α-methylstyrene dimer) is preferable in that it can reduce sublimates, coloring, and odor in addition to the above effects.

  Examples of the solvent used in the photosensitive composition according to the present invention include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol. Monoethyl ether, 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 (Poly) alkylene glycol mono, such as coal monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether Alkyl ethers: (poly) alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate acetate Other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether and tetrahydrofuran; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone and 3-heptanone; methyl 2-hydroxypropionate and ethyl 2-hydroxypropionate Alkyl lactates such as ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, Hydroxyethyl acetate, 2-hydroxy-3-methyl methyl carbonate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl pro Pionate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl formate, isopentyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate , Other esters such as methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate and ethyl 2-oxobutanoate; aromatic hydrocarbons such as toluene and xylene; N-methylpyrrolidone Amides such as N, N-dimethylformamide and N, N-dimethylacetamide. These solvents may be used alone or in combination of two or more.

  Among the above solvents, propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, and 3-methoxybutyl acetate are the above-mentioned (A ) Component and (B) component are excellent in solubility, and the dispersibility of the component (C) can be improved. Propylene glycol monomethyl ether acetate and 3-methoxybutyl acetate are preferably used. It is particularly preferred. The solvent may be appropriately determined according to the use of the photosensitive composition. As an example, the solvent may be about 50 to 900 parts by mass with respect to a total of 100 parts by mass of the solid content of the photosensitive composition.

  Examples of the thermal polymerization inhibitor used in the photosensitive composition according to the present invention include hydroquinone and hydroquinone monoethyl ether. Further, examples of the antifoaming agent include compounds such as silicone and fluorine, and examples of the surfactant include compounds such as anion, cation and nonion.

<Method for preparing photosensitive composition>
The photosensitive composition according to the present invention can be prepared by stirring, mixing and dissolving the above components using a magnetic stirrer, and filtering with a filter such as a 0.2 μm membrane filter as necessary.

≪Insulating film≫
The insulating film according to the present invention is the same as the conventional insulating film formed using the photosensitive composition except that the above-described photosensitive composition is used. Only the method for forming the insulating film will be described below.

  The method for forming the insulating film using the above-described photosensitive composition is not particularly limited, and can be appropriately selected from conventionally employed methods. As a preferable method for forming an insulating film, the above-described photosensitive composition is applied onto a substrate, and a photosensitive resin layer is formed, and the photosensitive resin layer is exposed according to a predetermined insulating film pattern. Examples include a method including an exposure step and a development step of developing the exposed photosensitive resin layer to form a pattern of an insulating film.

  First, in the coating process, a contact transfer type coating device such as a roll coater, reverse coater, and bar coater, a non-contact type coating such as a spinner (rotary coating device), a curtain flow coater, etc. is applied on a substrate on which an insulating film is to be formed. The photosensitive composition which concerns on this invention is apply | coated using an apparatus, a solvent is removed by drying (prebaking) as needed, and the photosensitive resin layer is formed. The photosensitive resin layer may be, for example, a coating film or a molded body.

Next, the substrate having the photosensitive resin layer formed on the surface is subjected to an exposure process. In the exposure process, an ArF excimer laser, KrF excimer laser, F ₂ excimer laser, extreme ultraviolet (EUV), vacuum ultraviolet (VUV), electron beam, X-ray, soft X is applied to the photosensitive resin layer through a negative mask. The photosensitive resin layer is partially exposed according to a pattern of a predetermined insulating film by irradiating radiation or electromagnetic waves such as lines, g-lines, i-lines, and h-lines. The amount of exposure varies depending on the composition of the photosensitive composition, but is preferably about 10 to 600 mJ / cm ² , for example.

  The above-mentioned photosensitive composition is hardly dissolved in an alkali developer after exposure. For this reason, by using the above-mentioned photosensitive composition, it is easy to form a pattern having an exposed portion as a convex portion and an unexposed portion as a concave portion as a pattern having a good shape.

  In the development step, the exposed photosensitive resin layer is developed with a developer to form an insulating film having a predetermined pattern. 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.

  Then, if necessary, a cured film can be obtained by post-baking and heat-curing the pattern of the insulating film after development. The post-baking temperature is preferably 150 to 270 ° C.

  Since the insulating film formed using the above-described photosensitive composition has excellent transmittance, a display that requires an insulating film having excellent transparency, such as an in-cell touch panel type liquid crystal display device or a UHA (Ultra High Aperture) panel. It is suitably used as an insulating film for devices.

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

[Examples 1-42 and Comparative Examples 1-3]
15 parts by mass of a crosslinkable group-containing resin composed of the units shown in Table 1, 7 parts by mass of a photopolymerizable monomer, 0.5 parts by mass of a photopolymerization initiator, and a surface conditioner (BYK-310, polyester modified) Polydimethylsiloxane, manufactured by Big Chemie Japan Co., Ltd.) 0.5 parts by mass, 15 parts by mass of propylene glycol monomethyl ether acetate, 0.4 parts by mass of 2,4-diphenyl-4-methyl-1-pentene, and diethylene glycol methyl 35 parts by mass of ethyl ether was mixed to obtain a uniform solution, and photosensitive compositions of Examples 1 to 42 and Comparative Examples 1 to 3 were prepared.

  Units I to III constituting the crosslinkable group-containing resin described in Table 1 are units represented by the following formula. Regarding the crosslinkable group-containing resin, the numerical values shown in Table 1 represent a mass ratio. Any crosslinkable group-containing resin had a mass average molecular weight (Mw) of 7000 determined by gel permeation chromatography (GPC).

  Dipentaerythritol hexaacrylate was used as the photopolymerizable monomer.

As the photopolymerization initiator, initiators 1 to 6 represented by the following formula were used as shown in Table 1.

As comparative photopolymerization initiators, 1.2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)] (OXE-01), ethanone, 1- [9-ethyl-6] Initiator 7 represented by-(2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (0-acetyloxime) (OXE-02) or the following structure was used as shown in Table 1. .

  About the photosensitive composition obtained by each Example and the comparative example, according to the following method, evaluation and measurement of chemical resistance, a residual film rate, a break point (BP), a sensitivity, and the transmittance | permeability were performed. The evaluation results are shown in Table 1.

(Chemical resistance (NMP swelling rate))
Using the photosensitive composition, a cured film of the post-baked photosensitive composition was formed in the same manner as in the method for evaluating the remaining film ratio. The formed cured film was measured using a stylus type surface shape measuring instrument (Dektak 3st, manufactured by ULVAC, Inc.). The film thickness of the cured film was 3 μm. Thereafter, the substrate was immersed in NMP heated to 70 ° C. for 10 minutes, taken out, rinsed with pure water, and dried by air blow. The film was measured using a stylus type surface shape measuring instrument (Dektak 3st, manufactured by ULVAC, Inc.), and the swelling ratio when the original film thickness was 100% was determined.

(Residual film rate evaluation)
After spin-coating the photosensitive composition prepared in each of the above Examples and Comparative Examples on a glass substrate with a spinner (Mikasa Spinner IH-360S, manufactured by Mikasa Co., Ltd.), the coating film was dried at 100 ° C. for 100 seconds. A photosensitive resin layer was formed. Subsequently, the photosensitive resin layer was exposed with an exposure amount of 100 mJ / cm ² using an exposure apparatus (MPA600FA, manufactured by Canon Inc.). Subsequently, paddle development was performed at 23 ° C. for 100 seconds using an aqueous solution of tetramethylammonium hydroxide having a concentration of 2.38% by mass as a developer to form a pattern. After development, the pattern was post-baked at 230 ° C. for 20 minutes. The film thickness of the pattern after post-baking was 3 μm. The film thickness of the pattern was measured using a stylus type surface shape measuring instrument (Dektak 3st, manufactured by ULVAC, Inc.). The film thickness after post-baking / film thickness before development was measured to determine the remaining film ratio.

(Breakpoint measurement)
After spin-coating the photosensitive composition prepared in each of the above Examples and Comparative Examples on a substrate with a spinner (Mikasa Spinner IH-360S, manufactured by Mikasa Corporation), the coating film was dried at 100 ° C. for 100 seconds, A photosensitive resin layer was formed. Subsequently, the photosensitive resin layer was exposed with an exposure amount of 100 mJ / cm ² using an exposure apparatus (MPA600FA, manufactured by Canon Inc.). Subsequently, using an aqueous solution of tetramethylammonium hydroxide having a concentration of 2.38% by mass as a developing solution, paddle development is performed at 23 ° C. for 100 seconds, and the resist film disappears from the time when the developing solution contacts the substrate. Time was measured and used as a breakpoint (BP).

(sensitivity)
Exposure and development were performed in the same manner as in the evaluation of the remaining film ratio, and a hole pattern having holes within a pore diameter range of 10 μm was formed. The exposure amount that the post-baking treatment and the hole diameter at the bottom of the hole was 8 μm was determined as the appropriate sensitivity.

(Transmittance)
Using the photosensitive composition, a cured film of the post-baked photosensitive composition was formed in the same manner as in the method for evaluating the remaining film ratio. The thickness of the cured film was 3 μm. The transmittance | permeability in wavelength 400nm of the formed cured film was measured using MCPD-3000 (made by Otsuka Electronics Co., Ltd.).

According to Examples 1-42 and Comparative Examples 1-3, if it is a photosensitive resin containing (C) a photopolymerization initiator in the present invention, a cured film having high transmittance and sufficient sensitivity to exposure is obtained. It has been found that there are cases where at least one of chemical resistance, remaining film rate and breakpoint (BP) can be further improved depending on the obtained resin and the crosslinkable group-containing resin to be used.
In the crosslinkable group-containing resin, as the crosslinkable group, a polymer including a unit derived from a (meth) acrylic acid ester having an epoxy group of I-1 to I-3 is particularly better in terms of the remaining film rate, Moreover, it turned out that what uses any one of III-1 to III-4 as a dissolution inhibiting group is especially good at the point of a break point (BP).

Claims (11)

(A) a crosslinkable group-containing resin, (B) a photopolymerizable monomer and (C) a photopolymerization initiator,
The (C) photopolymerization initiator is represented by the following formula (1):

(R ¹ is a hydrogen atom, a nitro group or a monovalent organic group, R ² and R ³ are each a chain alkyl group, a cyclic hydrocarbon group, or a heteroaryl group, and R ² and R ³ are ^May combine with each other to form a spiro ring, R ⁴ is a monovalent organic group, and R ⁵ is a hydrogen atom or an alkyl group having 1 to 11 carbon atoms that may have a substituent. Or an aryl group which may have a substituent, and m is 0 or 1.)
The photosensitive composition containing the compound represented by these.   2. The photosensitive composition according to claim 1, wherein the crosslinkable group contained in the (A) crosslinkable group-containing resin is at least one selected from the group consisting of an epoxy group and an ethylenically unsaturated double bond.   The photosensitive composition according to claim 1 or 2, wherein the (A) crosslinkable group-containing resin further has an alkali-soluble group.   The photosensitive composition according to claim 1, wherein the (A) crosslinkable group-containing resin further has an alkali dissolution inhibiting group. The photosensitive composition of any one of Claims 1-4 whose said R < ⁴ > is group represented by a following formula (R4-1) or (R4-2).

(In formulas (R4-1) and (R4-2), R ⁶ and R ⁷ are each an organic group, p is an integer of 0 to 4, and R ⁶ and R ⁷ are adjacent positions on the benzene ring. R ⁶ and R ⁷ may be bonded to each other to form a ring, q is an integer of 1 to 8, r is an integer of 1 to 5, and s is 0 to (r + 3). ) And R ⁸ is an alkyl group.)   The photosensitive composition of any one of Claims 1-5 whose said m is 1. Wherein R ¹ is a hydrogen atom, photosensitive composition according to any one of claims 1 to 6.   A coating film or a molded body is formed using the photosensitive composition according to any one of claims 1 to 7, and the coating film or the molded body is irradiated with electromagnetic waves in a predetermined pattern and developed. A pattern forming method.   The cured film formed using the photosensitive composition of any one of Claims 1-7.   The insulating film formed using the photosensitive composition of any one of Claims 1-7.   A display device comprising the insulating film according to claim 10.