JP6195456B2 - Radiation sensitive resin composition - Google Patents

Description

  The present invention relates to a radiation-sensitive resin composition, a method for forming a patterned resin film using the radiation-sensitive resin composition, an insulating film formed using the radiation-sensitive resin composition, and the insulating film It is related with a display apparatus provided with.

  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 radiation sensitive resin composition (photosensitive resin composition) which gives a transparent cured film by exposure is used. By selectively exposing such a radiation sensitive resin composition, a transparent cured film pattern can be formed.

  Examples of the radiation sensitive resin composition (photosensitive resin composition) capable of forming a transparent cured film include a composition containing a resin, a polymerizable compound, a polymerization initiator having a specific structure, and a solvent. It 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 radiation-sensitive resin composition containing a mixed solvent composed of 3-methoxy-1-butanol, propylene glycol monomethyl ether acetate, ethyl 3-ethoxypropionate, and 3-methoxybutyl acetate is disclosed.

JP 2012-58728 A

However, when the coating film of the radiation-sensitive resin composition described in Patent Document 1 is exposed and then the coating film is developed using an aqueous solution of tetramethylammonium hydroxide as an alkaline developer, the exposed portion to be left is It dissolves excessively and it is difficult to form a pattern with a desired shape. An aqueous solution of tetramethylammonium hydroxide is widely used as a developer in various processes using a radiation-sensitive resin composition. For this reason, if a radiation-sensitive resin composition that can form a pattern having a desired shape can be formed only with a developer other than an aqueous solution of tetramethylammonium hydroxide, the same line cannot be shared. It may be necessary to replace the liquid.
Therefore, in the radiation-sensitive resin composition, in the development after exposure, the exposed radiation-sensitive resin composition has a desired shape without being excessively dissolved by a developer of an aqueous solution of tetramethylammonium hydroxide. It is desirable to be able to form a pattern.

  The present invention has been made in view of the above-described problems, and can form a cured film having excellent transparency. Even if development is performed using an aqueous solution of tetramethylammonium hydroxide after exposure, the radiation-sensitive resin composition contains Of the exposed portion of the radiation-sensitive resin composition, a method for forming a patterned resin film using the radiation-sensitive resin composition, and the radiation-sensitive resin composition. Another object is to provide an insulating film and a display device including the insulating film.

  The inventors of the present invention provide the radiation-sensitive resin composition with (a1) a unit derived from an unsaturated carboxylic acid and a predetermined amount of (a2) a unit derived from an alicyclic skeleton-containing unsaturated compound having no epoxy group. And (A) an alkali-soluble resin comprising a copolymer containing, (B) a photopolymerizable compound, and (C) a photopolymerization initiator containing an oxime ester compound having a specific structure, The present inventors have found that the above problems can be solved and have completed the present invention.

（ｐは１〜５の整数であり、ｑは１〜８の整数であり、ｒは０〜（ｐ＋３）の整数であり、Ｒ^１は、置換基を有してもよい炭素数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、Ｒ^２は下記式（２）〜（４）：

で表される置換基のいずれかであり、Ｒ^３は炭素数１〜１１のアルキル基であり、Ｒ^４は置換基を有してもよいアリール基であり、Ｒ^５は水素原子、置換基を有してもよい炭素数１〜１０のアルキル基、又はアリール基であり、Ｒ^６は置換基を有してもよりアリール基である）
で表されるオキシムエステル化合物を含む、感放射線性樹脂組成物である。 The first aspect of the present invention includes (A) an alkali-soluble resin, (B) a photopolymerizable compound, and (C) a photopolymerization initiator,
The (A) alkali-soluble resin comprises (a1) a unit derived from an unsaturated carboxylic acid and (a2) a unit derived from an alicyclic skeleton-containing unsaturated compound having no epoxy group,
In the (A) alkali-soluble resin, the content of the unit derived from the (a2) alicyclic skeleton-containing unsaturated compound having no epoxy group is 10% by mass with respect to the mass of the (A) alkali-soluble resin. That's it,
The (C) photopolymerization initiator is represented by the following formula (1):

(P is an integer of 1 to 5, q is an integer of 1 to 8, r is an integer of 0 to (p + 3), and R ¹ may have a substituent having 1 to 11 carbon atoms. Or an aryl group which may have a substituent, and R ² represents the following formulas (2) to (4):

R ³ is an alkyl group having 1 to 11 carbon atoms, R ⁴ is an aryl group which may have a substituent, and R ⁵ is a hydrogen atom or a substituent. An alkyl group having 1 to 10 carbon atoms which may have an aryl group or an aryl group, and R ⁶ is an aryl group which may have a substituent.
It is a radiation sensitive resin composition containing the oxime ester compound represented by these.

A second aspect of the present invention is a coating step in which a radiation sensitive resin composition according to the first aspect is coated on a substrate to form a coating film,
It is a method for forming a patterned resin film, which includes an exposure step of exposing the coating film to a predetermined pattern, and a development step of developing the exposed coating film with an aqueous solution of tetramethylammonium hydroxide.

  The third aspect of the present invention is an insulating film formed using the radiation-sensitive resin composition according to the first aspect.

  4th aspect of this invention is a display apparatus provided with the insulating film which concerns on 3rd aspect.

  According to the present invention, a cured film having excellent transparency can be formed, and even if development is performed using an aqueous solution of tetramethylammonium hydroxide after exposure, the exposed portion in the radiation-sensitive resin composition is not excessively dissolved. A radiation-sensitive resin composition, a method for forming a patterned resin film using the radiation-sensitive resin composition, an insulating film formed using the radiation-sensitive resin composition, and the insulating film A display device.

≪Radiosensitive resin composition≫
The radiation-sensitive resin composition according to the present invention includes (A) an alkali-soluble resin containing specific units, (B) a photopolymerizable compound, and (C) a photopolymerization initiator containing an oxime ester compound having a specific structure. And containing. Hereinafter, each component contained in the radiation sensitive resin composition will be described.

<(A) Alkali-soluble resin>
(A) The alkali-soluble resin is a resin film having a resin concentration of 20% by mass (solvent: propylene glycol monomethyl ether acetate), and a resin film having a thickness of 1 μm is formed on the substrate, and 2.38% by mass at 23 ° C. When immersed in an aqueous tetramethylammonium hydroxide (TMAH) solution for 1 minute, it means a film that dissolves in a thickness of 0.01 μm or more.

  (A) As an alkali-soluble resin, (a1) a unit derived from an unsaturated carboxylic acid (hereinafter also referred to as (a1) unit) and (a2) an alicyclic skeleton-containing unsaturated compound having no epoxy group A copolymer containing a derived unit (hereinafter also referred to as (a2) unit) is used. By using (A) alkali-soluble resin containing (a1) unit and (a2) unit, a cured film having excellent transparency can be formed, and the exposed portion at the time of development after exposure is not excessively dissolved. It is easy to obtain a functional resin composition.

  The resin used as the component (A) is not particularly limited as long as it contains the (a1) unit and the (a2) unit. From the alkali-soluble resin conventionally used in various radiation-sensitive resin compositions. Can be appropriately selected and used.

  (A1) Unsaturated carboxylic acids that generate units include monocarboxylic acids such as (meth) acrylic acid and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, and itaconic acid; these dicarboxylic acids Anhydrous anhydride; and the like. Among these, (meth) acrylic acid and maleic anhydride are preferable in terms of copolymerization reactivity, alkali solubility of the resulting resin, availability, and the like. (A) The alkali-soluble resin may contain a combination of two or more units (a1) derived from these unsaturated carboxylic acids.

  The unit (a2) is not particularly limited as long as it is a unit derived from an alicyclic skeleton-containing unsaturated compound having no epoxy group. The alicyclic skeleton may be monocyclic or polycyclic. Examples of the monocyclic alicyclic group contained in the alicyclic skeleton-containing unsaturated compound include a cyclopentyl group and a cyclohexyl group. Examples of the polycyclic alicyclic group include an adamantyl group, a norbornyl group, an isobornyl group, a tricyclononyl group, a tricyclodecyl group, and a tetracyclododecyl group. (A) The alkali-soluble resin may contain a combination of two or more units (a2).

(A2) providing a unit, the alicyclic group-containing unsaturated compound having no epoxy group, for example, a compound represented by the following formula (a2-1) ~ (a2- 8) can be mentioned. In these, since it is easy to obtain the radiation sensitive resin composition with favorable developability, the compounds represented by the following formulas (a2-3) to (a2-8) are preferable, and the following formula (a2-3) Or the compound represented by (a2-4) is more preferable.

In the above formula, R ^a1 represents a hydrogen atom or a methyl group, R ^a2 represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, and R ^a3 represents a hydrogen atom or 1 to 5 carbon atoms. Represents an alkyl group. R ^a2 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 ^a3 is preferably a methyl group or an ethyl group.

  In addition to (a1) unit and (a2) unit, (A) alkali-soluble resin includes (a3) a unit derived from an alicyclic epoxy group-containing unsaturated compound (hereinafter also referred to as (a3) unit). It is preferable to include. (A) When alkali-soluble resin contains (a3) unit, when the coating film formed using a radiation sensitive resin composition is post-baked after exposure, it is easy to suppress an excessive shape change of the coating film. .

  In the unit (a3), the alicyclic group constituting the alicyclic epoxy group may be monocyclic or polycyclic. Examples of the monocyclic alicyclic group include a cyclopentyl group and a cyclohexyl group. Examples of the polycyclic alicyclic group include a norbornyl group, an isobornyl group, a tricyclononyl group, a tricyclodecyl group, and a tetracyclododecyl group. (A) The alkali-soluble resin may contain a combination of two or more (a3) units.

  (A3) Specific examples of the alicyclic epoxy group-containing unsaturated compound that gives a unit include compounds represented by the following formulas (a3-1) to (a3-16). Among these, in order to make the developability of the radiation-sensitive resin composition appropriate, compounds represented by the following formulas (a3-1) to (a3-6) are preferable, and the following formula (a3-1) ) To (a3-4) are more preferred.

In the above formula, R ^a4 represents a hydrogen atom or a methyl group, R ^a5 represents a divalent saturated aliphatic hydrocarbon group having 1 to ⁶ carbon atoms, and R ^a6 represents a divalent hydrocarbon having 1 to 10 carbon atoms. Represents a group, and n represents an integer of 0 to 10. R ^a5 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 ^a6 , 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.

  (A) The alkali-soluble resin may contain other units of the above (a1) unit, (a2) unit, and (a3) unit. Examples of compounds that give other units are the (meth) acrylic acid esters, (meth) acrylamides, allyl compounds, vinyl ethers, vinyl esters, styrenes, and epoxy groups having no alicyclic group. Examples thereof include unsaturated compounds. These compounds can be used alone or in combination of two or more.

  As (meth) acrylic acid esters, linear or branched chain such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, amyl (meth) acrylate, t-octyl (meth) acrylate, etc. Alkyl (meth) acrylates; chloroethyl (meth) acrylate, 2,2-dimethylhydroxypropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, trimethylolpropane mono (meth) acrylate, benzyl (meth) acrylate, furfuryl (Meth) acrylate; etc. are mentioned.

  (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.

  Examples of the epoxy group-containing unsaturated compound having no alicyclic group include glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, 6,7-epoxyheptyl ( (Meth) acrylate and other (meth) acrylic acid epoxy alkyl esters; α-ethyl acrylate glycidyl, α-n-propyl acrylate glycidyl, α-n-butyl acrylate glycidyl, α-ethyl acrylate 6,7-epoxy Α-alkyl acrylic acid epoxy alkyl esters such as heptyl; and the like. Among these, glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, and 6,7-epoxyheptyl (meth) acrylate are preferable.

  (A) The proportion of the (a1) unit, the proportion of the (a2) unit, and the proportion of the (a3) unit in the copolymer that is an alkali-soluble resin do not impair the purpose of the present invention. There is no particular limitation. (A) 5-25 mass% is preferable, and, as for the ratio of the said (a1) unit which occupies for the copolymer which is alkali-soluble resin, 8-20 mass% is more preferable. (A) 10-50 mass% is preferable and, as for the ratio of the said (a2) unit which occupies for the copolymer which is alkali-soluble resin, 11-30 mass% is more preferable. 10-70 mass% is preferable and, as for the ratio of the said (a3) unit occupied to the copolymer which is (A) alkali-soluble resin, 15-50 mass% is more preferable.

  (A) The mass average molecular weight of the alkali-soluble resin (Mw: measured value in terms of polystyrene of gel permeation chromatography (GPC). The same applies in the present specification) is preferably 2000 to 200000, more preferably 2000 to 18000, and 3000. ˜15000 is particularly preferred. By using the (A) alkali-soluble resin having a mass average molecular weight within the above range, the developability after exposure of the radiation-sensitive resin composition is likely to be particularly excellent.

  (A) The alkaline paper resin can be produced by a known radical polymerization method. That is, it can be produced by dissolving the monomer giving the above-described unit and a known radical polymerization initiator in a polymerization solvent and then stirring with heating.

<(B) Photopolymerizable compound>
As the (B) photopolymerizable compound (hereinafter also referred to as component (B)) contained in the radiation-sensitive resin composition, a compound having an ethylenically unsaturated group can be preferably used. The compound having an ethylenically unsaturated group 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 the polyfunctional monomer, 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 (meta Acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 2,2-bis (4- (meth) acryloxydi 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 ester di (meth) acrylate, glycerin triacrylate, glycerin polyglycidyl ether poly (Meth) acrylate, urethane (meth) acrylate (that is, tolylene diisocyanate), reaction product of trimethylhexamethylene diisocyanate and hexamethylene diisocyanate and 2-bidoxyethyl (meth) acrylate, methylenebis (meth) acrylamide, (meth) acrylamide methylene Ether, condensate of polyhydric alcohol and N-methylol (meth) acrylamide, triacryl formal, 2,4,6-trioxohexahydro-1,3,5-triazine-1,3,5-trisethanoltri Examples thereof include acrylates and 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 group, a polyfunctional monomer having three or more functional groups is preferable from the viewpoint of obtaining a radiation-sensitive resin composition that gives a cured product excellent in strength and adhesion to a substrate.

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

<(C) Photo heavy initiator>
The radiation-sensitive resin composition contains an oxime ester compound having a structure represented by the following formula (1) as (C) a photopolymerization initiator (hereinafter also referred to as (C) component). By using a combination of the oxime ester compound having the structure represented by the following formula (1) and the aforementioned component (A) as a photopolymerization initiator, a cured film having excellent transparency can be formed. Even if it develops using the aqueous solution of ammonium hydroxide, the radiation sensitive resin composition by which the exposed part is not melt | dissolved excessively can be obtained.

（ｐは１〜５の整数であり、ｑは１〜８の整数であり、ｒは０〜（ｐ＋３）の整数であり、Ｒ^１は、置換基を有してもよい炭素数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、Ｒ^２は下記式（２）〜（４）：

で表される置換基のいずれかであり、Ｒ^３は炭素数１〜１１のアルキル基であり、Ｒ^４は置換基を有してもよいアリール基であり、Ｒ^５は水素原子、置換基を有してもよい炭素数１〜１０のアルキル基、又はアリール基であり、Ｒ^６は置換基を有してもよりアリール基である。）

(P is an integer of 1 to 5, q is an integer of 1 to 8, r is an integer of 0 to (p + 3), and R ¹ may have a substituent having 1 to 11 carbon atoms. Or an aryl group which may have a substituent, and R ² represents the following formulas (2) to (4):

R ³ is an alkyl group having 1 to 11 carbon atoms, R ⁴ is an aryl group which may have a substituent, and R ⁵ is a hydrogen atom or a substituent. Or an aryl group having 1 to 10 carbon atoms or an aryl group, and R ⁶ may be a substituent or a more aryl group. )

  In the above formula (1), p is preferably 1 to 3, and more preferably 1 or 2. q is preferably 1 to 8, more preferably 1 to 4, and particularly preferably 2.

Preferred examples of the substituent that R ¹ may have when R ¹ is an alkyl group include a phenyl group and a naphthyl group. As the substituent that may be possessed when R ¹ is an aryl group, an alkyl group having 1 to 5 carbon atoms, an alkoxy group, a halogen atom and is preferably exemplified.

In the above formula (1), R ¹ is preferably exemplified by methyl group, ethyl group, propyl group, isopropyl group, butyl group, phenyl group, benzyl group, methylphenyl group, naphthyl group and the like. Among these, methyl A group or a phenyl group is more preferable.

In the above formula (1), as R ³ , a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a phenyl group and the like are preferably exemplified, and among these, a methyl group is more preferable.

In the above formulas (2) and (3), the aryl group represented by R ⁴ may have an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a halogen atom, or the like. Preferably exemplified. In the above formulas (2) and (3), preferred examples of the substituent that may be present when R ⁵ is an alkyl group include an alkoxy group having 1 to 5 carbon atoms, a phenyl group, and a naphthyl group. .

In the above formulas (2) and (3), R ⁴ is a phenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 2-ethylphenyl group, 3-ethylphenyl group, 4 -Ethylphenyl group, 2,3-dimethylphenyl group, 2,4-dimethylphenyl group, 2,5-dimethylphenyl group, 2,6-dimethylphenyl group, naphthyl group, 2-methoxy-1-naphthyl group, 9 -Anthracenyl group etc. are preferable.

In the above formulas (2) and (3), as R ⁵ , hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group , N-pentyl, n-hexyl group, phenyl group, 3-methylbutyl group, 3-methoxybutyl group and the like are preferred, and among these, ethyl group is more preferred.

In the above formula (4), examples of the substituent that the aryl group represented by R ⁶ may have include an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, and a halogen atom. . R ⁶ includes phenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 2-ethylphenyl group, 3-ethylphenyl group, 4-ethylphenyl group, 2,3-dimethylphenyl. Group, 2,4-dimethylphenyl group, 2,5-dimethylphenyl group, 2,6-dimethylphenyl group, naphthyl group, p-tert-butylphenyl group, p-methoxyphenyl group and the like are preferably exemplified. Of these, a phenyl group is more preferable.

More specifically, as the (C) photopolymerization initiator, compounds of the following formulas can be preferably exemplified.

  The radiation-sensitive resin composition may contain other photopolymerization initiator 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 radiation sensitive resin composition contains another photopolymerization initiator other than the oxime ester compound represented by the formula (1), the content of the other photopolymerizable compound does not hinder the object of the present invention. There is no particular limitation. In this case, the content of the other photopolymerization initiator is typically preferably 50% by mass or less, and preferably 30% by mass or less based on the total amount of the photopolymerization initiator contained in the radiation-sensitive resin composition. More preferred is 10% by mass or less.

  (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 radiation sensitive resin composition, and 0.5-10 mass parts is More preferred. By using the component (C) in an amount within the above range, the radiation sensitive resin composition can be sufficiently cured by radiation, and a radiation sensitive resin composition giving a cured film having excellent transparency can be obtained.

<(S) Solvent>
The radiation-sensitive resin composition according to the present invention preferably contains (S) an organic solvent (hereinafter also referred to as “(S) component”) in order to improve applicability and adjust 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) in the radiation-sensitive resin composition is not particularly limited, and is an amount within a range in which the radiation-sensitive resin composition can be applied to a substrate or the like, and is appropriately set according to the coating film thickness. The The viscosity of the radiation sensitive resin composition is preferably 0.9 to 500 cp, more preferably 1 to 50 cp, and further preferably 1 to 30 cp. Moreover, 1-80 mass% is preferable and, as for the solid content density | concentration of a radiation sensitive resin composition, 5-50 mass% is more preferable.

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

<Method for preparing radiation-sensitive resin composition>
The radiation-sensitive resin composition according to the present invention is prepared by stirring, mixing and dissolving the above components using a stirrer such as a magnetic stirrer and, if necessary, filtering through a filter such as a 0.2 μm membrane filter. be able to.

≪Method for forming patterned resin film≫
By using the radiation-sensitive resin composition described above, even if development is performed using an aqueous solution of tetramethylammonium hydroxide after exposure, the exposed portion in the radiation-sensitive resin composition is not excessively dissolved. Then, a patterned transparent resin film having a desired shape can be formed.

  Specifically, a coating process in which the above-described radiation-sensitive resin composition is applied onto a substrate to form a coating film, an exposure process in which the formed coating film is exposed to a predetermined pattern, and an exposed coating film A patterned resin film can be formed by a method including a developing step of developing the solution with an aqueous solution of tetramethylammonium hydroxide. Hereinafter, the coating process, the exposure process, and the development process will be described in order.

<Application process>
In the coating process, a radiation sensitive resin composition is formed on the substrate using a contact transfer type coating device such as a roll coater, reverse coater, bar coater, etc., or a non-contact type coating device such as a spinner (rotary coating device) or curtain flow coater. An object is applied, and if necessary, the solvent is removed by drying to form a coating film.

<Exposure process>
In the exposure step, the coating film formed in the coating step is selectively exposed according to the shape of the resin film pattern to be formed. The selective exposure method is not particularly limited, but it is preferable to expose the coating film through a negative mask. The coating film is exposed using radiation such as ArF excimer laser, KrF excimer laser, F ₂ excimer laser, extreme ultraviolet (EUV), vacuum ultraviolet (VUV), electron beam, X-ray, and soft X-ray. . The amount of exposure varies depending on the composition of the radiation-sensitive resin composition, but is preferably about 10 to 600 mJ / cm ² , for example.

  The above-mentioned radiation sensitive resin composition is hardly dissolved in an aqueous solution of tetramethylammonium hydroxide after exposure. For this reason, by using the above-mentioned radiation sensitive resin 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 good shape pattern.

<Development process>
In the developing step, the exposed coating film is developed with a developer, thereby removing the unexposed portion and forming 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. As the developer, an aqueous solution of tetramethylammonium hydroxide is used. The concentration of the aqueous solution of tetramethylammonium hydroxide is not particularly limited, and is appropriately selected from the concentration of the aqueous solution of tetramethylammonium hydroxide conventionally used as a developer. The concentration of the tetramethylammonium hydroxide aqueous solution is preferably 0.2 to 5% by mass, and more preferably 2.38% by mass.

  If necessary, the developed insulating film pattern is post-baked and cured by heating. The post-baking temperature is preferably 150 to 270 ° C.

  Since the patterned resin film manufactured in this way has an insulating property, it is useful as an insulating film. In particular, since a patterned resin film has excellent transparency, an insulating film for a display device that requires an insulating film with excellent transparency, such as an in-cell touch panel type liquid crystal display device, a UHA (Ultra High Aperture) panel, etc. Is preferably used.

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

[Examples 1-34 and Comparative Examples 1-11]
20 parts by mass of an alkali-soluble resin containing the units described in Table 1 or 2 at a mass ratio described in Table 1 or 2, 10 parts by mass of a photopolymerizable compound, 1.6 parts by mass of a photopolymerization initiator, and surface tension adjustment 0.4 parts by mass of an agent (BYK-310, polyester-modified polydimethylsiloxane, manufactured by Big Chemie Japan Co., Ltd.), 64 parts by mass of propylene glycol monomethyl ether acetate, and 43 parts by mass of diethylene glycol monomethyl ether are mixed uniformly. Radiation sensitive resin compositions of Examples 1 to 34 and Comparative Examples 1 to 11 were prepared as solutions.

Units I to IX constituting the alkali-soluble resin described in Tables 1 and 2 are units represented by the following formula.

  Examples of the photopolymerizable compound include 2,4,6-trioxohexahydro-1,3,5-triazine-1,3,5-trisethanol triacrylate and 2,4,6-trioxohexahydro-1 , 3,5-triazine-1,3,5-trisethanol diacrylate, M315 (manufactured by Toagosei Co., Ltd.) was used.

As the photopolymerization initiator, a compound represented by the following formula was used.

  About the radiation sensitive resin composition obtained in Examples 1-34 and Comparative Examples 1-11, according to the following method, evaluation of a residual film rate, heat resistance, and separation resolution, and a breakpoint (BP) Measurement was performed. The evaluation results are shown in Tables 1 and 2. In addition, about Comparative Examples 10 and 11, heat resistance evaluation was not performed.

(Residual film rate evaluation)
After spin-coating the radiation sensitive resin 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 120 seconds. Thus, a photosensitive radiation-sensitive resin layer was formed. Next, the radiation sensitive resin layer was exposed with an exposure amount of 100 mJ / cm ² using an exposure apparatus (MPA600FA, manufactured by Canon Inc.). Next, paddle development was performed at 23 ° C. for 60 seconds using an aqueous solution of tetramethylammonium hydroxide having a concentration of 2.38 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 6 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. Whether the remaining film rate was acceptable was determined according to the following criteria.
○: 80% or more.
X: Less than 80%.

(Heat resistance evaluation)
A pattern having a taper angle of 50 ° or more and 90 ° or less after development and a film thickness after post-baking of 6 μm was formed by the same method as the evaluation of the remaining film rate. From the cross-sectional photograph of the pattern after post-baking, the taper angle (°), which is an acute angle, among the angles formed by the substrate surface and the pattern surface was measured. Based on the measurement result of the taper angle, the heat resistance was determined according to the following criteria.
○: The taper angle is 30 to 70 °.
X: The taper angle is less than 30 ° or more than 70 °.

(Separation resolution)
Exposure and development were performed in the same manner as in the evaluation of the remaining film ratio, and a hole pattern having holes with a hole diameter of 10 μm was formed. After the post-bake treatment, it was observed whether or not the bottom of the hole reached the substrate. Based on the observation results of the holes, the separation resolution was determined according to the following criteria.
○: The bottom of the hole reached the substrate.
X: The bottom of the hole did not reach the substrate.

(Breakpoint measurement)
The radiation sensitive resin composition prepared in each of the above examples and comparative examples was spin-coated on a Si substrate with a spinner (Mikasa Spinner IH-360S, manufactured by Mikasa Co., Ltd.), and then the coating film was dried at 100 ° C. for 120 seconds. Thus, a photosensitive radiation-sensitive resin layer was formed. Next, the radiation sensitive resin layer was exposed with an exposure amount of 100 mJ / cm ² using an exposure apparatus (MPA600FA, manufactured by Canon Inc.). Next, using an aqueous solution of 2.38% by mass of tetramethylammonium hydroxide as a developing solution, paddle development is performed at 23 ° C. for 60 seconds, and the resist film disappears from the time when the developing solution contacts the substrate. Time was measured and used as a breakpoint.

  According to Examples 1 to 34 and Comparative Examples 1 to 11, (a1) a unit derived from an unsaturated carboxylic acid (unit I) and 10% by mass or more of (a2) an alicyclic group having no epoxy group A unit derived from a skeleton-containing unsaturated compound (unit II), (A) an alkali-soluble resin, (B) a photopolymerizable compound, and a structure represented by the above formula (1) If it is a radiation sensitive resin composition containing (C) photoinitiator containing an oxime ester compound, it turns out that an exposure part does not melt | dissolve excessively at the time of image development after exposure.

[Examples 35 and 36]
(Transparency evaluation)
15 parts by mass of an alkali-soluble resin used in Example 10, 7 parts by mass of a photopolymerizable compound, 1 part by mass of an oxime ester compound having the following structure, and a surface tension adjuster (BYK-310, polyester-modified polydimethylsiloxane, Big Chemie (Made in Japan) 0.2 parts by mass, 15 parts by mass of propylene glycol monomethyl ether acetate and 35 parts by mass of diethylene glycol monomethyl ether were mixed to obtain a uniform solution, and the radiation sensitive resins of Examples 35 and 36 A composition was prepared. The transparency of the insulating film formed using the radiation sensitive resin compositions of Examples 35 and 36 was evaluated.

  Examples of the photopolymerizable compound include 2,4,6-trioxohexahydro-1,3,5-triazine-1,3,5-trisethanol triacrylate and 2,4,6-trioxohexahydro-1 , 3,5-triazine-1,3,5-trisethanol diacrylate, M315 (manufactured by Toagosei Co., Ltd.) was used.

  Using the radiation-sensitive resin compositions of Examples 35 and 36, the post-baked radiation sensitivity was the same as the evaluation method for the remaining film ratio except that the exposure was not selectively performed during exposure. A cured film of the resin composition was formed. The film thickness of the cured film was 6 μm. When 240 degree transmittance | permeability in wavelength 400nm of the formed cured film was measured using MCPD-3000 (made by Otsuka Electronics Co., Ltd.), the transmittance | permeability of the cured film of the radiation sensitive resin composition of Example 35 was measured. Was 92.5%, and the transmittance of the cured film of the radiation-sensitive resin composition of Example 36 was 88.1%.

  From the above results, it can be seen that the radiation-sensitive resin composition containing the compound represented by the formula (1) as a photopolymerization initiator gives an insulating film having excellent transparency.

Claims (4)

(A) an alkali-soluble resin, (B) a photopolymerizable compound, (C) a photopolymerization initiator,
The (A) alkali-soluble resin comprises (a1) a unit derived from an unsaturated carboxylic acid (excluding those containing a structure derived from tetrahydrophthalic anhydride) , and (a2) an alicyclic ring having no epoxy group . A unit derived from an unsaturated compound containing a formula skeleton, and
In the (A) alkali-soluble resin, the content of the unit derived from the (a2) alicyclic skeleton-containing unsaturated compound having no epoxy group is 10% by mass with respect to the mass of the (A) alkali-soluble resin. More than 50 mass%,
The (C) photopolymerization initiator is represented by the following formula (1):

(P is an integer of 1 to 5, q is an integer of 1 to 8, r is an integer of 0 to (p + 3), and R ¹ may have a substituent having 1 to 11 carbon atoms. Or an aryl group which may have a substituent, and R ² represents the following formulas (2) to (4):

R ³ is an alkyl group having 1 to 11 carbon atoms, R ⁴ is an aryl group which may have a substituent, and R ⁵ is a hydrogen atom or a substituent. An alkyl group having 1 to 10 carbon atoms which may have an aryl group or an aryl group, and R ⁶ is an aryl group which may have a substituent.
An oxime ester compound represented by
The (a2) alicyclic skeleton-containing unsaturated compound having no epoxy group is represented by the following formulas (a2-3) to (a2-8):

(R ^a1 represents a hydrogen atom or a methyl group, R ^a2 represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, and R ^a3 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Is shown.)
The radiation sensitive resin composition which is a compound represented by these. Coating step of forming a coating film by coating the radiation-sensitive resin composition on a substrate,
An exposure step of exposing the coating film to a predetermined pattern, and a development step of developing the exposed coating film with an aqueous solution of tetramethylammonium hydroxide ,
The radiation sensitive resin composition includes (A) an alkali-soluble resin, (B) a photopolymerizable compound, and (C) a photopolymerization initiator,
The (A) alkali-soluble resin comprises (a1) a unit derived from an unsaturated carboxylic acid and (a2) a unit derived from an alicyclic skeleton-containing unsaturated compound having no epoxy group,
In the (A) alkali-soluble resin, the content of the unit derived from the (a2) alicyclic skeleton-containing unsaturated compound having no epoxy group is 10% by mass with respect to the mass of the (A) alkali-soluble resin. More than 50 mass%,
The (C) photopolymerization initiator is represented by the following formula (1):

(P is an integer of 1 to 5, q is an integer of 1 to 8, r is an integer of 0 to (p + 3), and R ¹ may have a substituent having 1 to 11 carbon atoms. Or an aryl group which may have a substituent, and R ² represents the following formulas (2) to (4):

R ³ is an alkyl group having 1 to 11 carbon atoms, R ⁴ is an aryl group which may have a substituent, and R ⁵ is a hydrogen atom or a substituent. An alkyl group having 1 to 10 carbon atoms which may have an aryl group or an aryl group, and R ⁶ is an aryl group which may have a substituent.
An oxime ester compound represented by
The (a2) alicyclic skeleton-containing unsaturated compound having no epoxy group is represented by the following formulas (a2-3) to (a2-8):

(R ^a1 represents a hydrogen atom or a methyl group, R ^a2 represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, and R ^a3 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Is shown.)
The formation method of the patterned resin film which is a compound represented by these .   The insulating film formed using the radiation sensitive resin composition of Claim 1.   A display device comprising the insulating film according to claim 3.