JP2016042126A - Radiation-sensitive resin composition, interlayer insulation film of display element, method of forming the same, and display element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a radiation-sensitive resin composition for forming an interlayer insulation film for a display element, the radiation-sensitive resin composition sufficiently satisfying general properties such as sensitivity, and having high adhesion to substrate, excellent heat resistance, alkali resistance, and transparency, and provide an interlayer insulation film formed from the radiation-sensitive resin composition and a method of forming the same, and a display element comprising the interlayer insulation film.SOLUTION: The present invention provides a radiation-sensitive resin composition for forming an interlayer insulation film in a display element, comprising (A) a polymer having a polymerizable group, (B) a photoacid generator, (C) a photoradical polymerization initiator, and (D) a polyfunctional acrylate.SELECTED DRAWING: None

Description

  The present invention relates to a radiation-sensitive resin composition, a method for forming an interlayer insulating film, a method for forming the same, and a display element. In particular, the present invention relates to a radiation-sensitive resin composition suitable as a material for forming an interlayer insulating film for display elements, and a display element including an interlayer insulating film formed therefrom.

In recent years, liquid crystal display elements have advantages such as low power consumption and easy miniaturization and flattening. Therefore, liquid crystal display elements can be used from small liquid crystal display devices such as mobile phones to large screen liquid crystals such as liquid crystal televisions. It is applied to a wide range of uses up to display devices.
As drive modes of liquid crystal display devices, TN (Super Twisted Nematic), STN (Super Twisted Nematic), IPS (In-Plane Switching), and FFS (Fringe Field Switching) are currently used according to changes in the alignment (alignment) state of liquid crystal molecules. VA (Vertical Alignment) and the like are known.
An IPS (In-Plane Switching) type liquid crystal in which the driving direction of the liquid crystal when applying an electric field is only in the in-plane direction of the substrate by arranging the electrode pairs in a comb-like shape on the surface of one substrate in these driving modes. It is known that an FFS (Fringe Field Switching) type liquid crystal display element in which the display element and the IPS type electrode structure are changed to increase the aperture ratio of the display element portion to improve the luminance is excellent in viewing angle characteristics ( JP, 56-91277, U.S. Pat. No. 5,928,733, JP 2008-216572). It is also known that liquid crystal is always aligned parallel to the substrate, so that liquid crystal disturbance due to external pressure is small and display defects such as unevenness are unlikely to occur. Therefore, the application of the IPS and FFS systems to applications such as mobile phones and tablet PCs equipped with a touch panel function has been spreading.
In an FFS mode liquid crystal display panel, a pair of electrodes consisting of a common electrode and a pixel electrode are arranged in different layers through an insulating film, and a slit-like opening is provided in the common electrode or pixel electrode on the liquid crystal layer side. A substantially horizontal electric field passing through the aperture is applied to the liquid crystal layer. The FFS type liquid crystal display panel is widely used in recent years because it has an effect that a wide viewing angle and an image contrast can be improved.

Among these, the FFS mode liquid crystal display panel in which the common electrode and the pixel electrode are both disposed above the TFT (Thin Film Transistor) is covered with an interlayer insulating film, and the surface of the interlayer insulating film is an electrode. A lower electrode made of a transparent conductive material and an upper electrode having a slit-like opening are formed with an intermediate insulating film interposed therebetween. Both the upper electrode and the lower electrode can be operated as either a pixel electrode or a common electrode. As the transparent conductive material, a transparent conductive material such as ITO (Indium Tin Oxide) is usually used (see JP 2014-13411 A).
As described above, in the FFS mode liquid crystal display panel, a transparent electrode is formed on an interlayer insulating film, and a transparent electrode having a slit-like opening is formed with the inter-electrode insulating film interposed therebetween. For this reason, the interlayer insulating film is required to have heat resistance by heating in forming a transparent electrode and solvent resistance to strong acid and strong base when the transparent electrode is patterned into a slit shape.

JP 56-91277 A US Pat. No. 5,928,733 JP 2008-216572 A JP 2014-13411 A

  The present invention has been made based on the circumstances as described above, and its purpose is to sufficiently satisfy general characteristics such as sensitivity and to have high adhesion to a substrate, excellent heat resistance, alkali resistance, Provided is a radiation-sensitive resin composition for forming an interlayer insulating film for display elements having transparency, an interlayer insulating film formed from the radiation-sensitive resin composition, a method for forming the same, and a display element including the interlayer insulating film The purpose is to provide.

The invention made to solve the above problems is a radiation-sensitive resin composition for forming an interlayer insulating film in a display element,
(A) a polymer having a polymerizable group,
(B) a photoacid generator,
This is achieved by a radiation-sensitive resin composition comprising (C) a radical photopolymerization initiator and (D) a polyfunctional acrylate.
The present invention is achieved by a radiation-sensitive resin composition in which the polymer (A) is a polymer having a carboxyl group.
The present invention further provides (C) a radiation sensitive resin composition, wherein the photo radical polymerization initiator is at least one of an acetophenone photo radical polymerization initiator and an oxime ester photo radical polymerization initiator. Achieved.

  The present invention is further achieved by a radiation-sensitive resin composition comprising (E) a compound having a polymerizable group and an organic group having at least one of a fluorine atom and a silicon atom in one molecule. Is done.

  The present invention is further achieved by a radiation-sensitive resin composition containing (F) an antioxidant.

  The present invention is further achieved by a radiation-sensitive resin composition comprising a polymer containing at least one of a group represented by the following formula (1) and a group represented by the following formula (2). The

In Formula (1), R ¹ and R ² each independently represent a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms, or a part of the hydrogen atoms that the hydrocarbon group having 1 to 30 carbon atoms has Group substituted with a group, a halogen atom or a cyano group. However, there is no case where R ¹ and R ² are both hydrogen atoms. R ³ is a hydroxyl group, a halogen atom or a cyano group in which a part of hydrogen atoms of an oxyhydrocarbon group having 1 to 30 carbon atoms, a hydrocarbon group having 1 to 30 carbon atoms, or a hydrocarbon group having 1 to 30 carbon atoms is substituted. A group substituted with a group.

In formula (2), R ^{4 to} R ¹⁰ are each independently a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms. n is 1 or 2.

  Furthermore, another invention made in order to solve the above problems is a step of forming a coating film on a substrate using the radiation-sensitive resin composition, a step of irradiating at least a part of the coating film, It is the formation method of the interlayer insulation film including the process of developing the coating film irradiated with the said radiation, and the process of heating the said developed coating film.

  Further, the present invention is a liquid crystal display element including an interlayer insulating film formed by the above-described method for forming an interlayer insulating film.

    The present invention is a radiation-sensitive resin composition for forming an interlayer insulating film for a display element, which sufficiently satisfies general characteristics such as sensitivity, has high adhesion to a substrate, and has excellent heat resistance, alkali resistance, and transparency. And providing an interlayer insulating film formed from the radiation-sensitive resin composition, a method for forming the interlayer insulating film, and a display element including the interlayer insulating film.

<Radiation sensitive resin composition>
The radiation sensitive resin composition of the present invention comprises (A) a polymer having a polymerizable group, (B) a photoacid generator,
(C) A radiation-sensitive resin composition comprising a radical photopolymerization initiator and (D) a polyfunctional acrylate as essential components. The said radiation sensitive resin composition may contain another arbitrary component in the range which does not impair the effect of this invention. Hereinafter, each component will be described in detail.
<(A) Polymer having polymerizable group>
The radiation sensitive resin composition of the present invention contains (A) a polymer having a polymerizable group. Thereby, the heat resistance of the interlayer insulation film obtained from a radiation sensitive resin composition, adhesiveness to a board | substrate, sclerosis | hardenability, etc. can be improved.
Examples of the polymerizable group include an epoxy group, a (meth) acryloyl group, and a vinyl group.

Examples of such a polymer having an epoxy group include two or more oxiranyl groups, oxetanyl groups, glycidyl groups, 3,4-epoxycyclohexyl groups, 3,4-epoxytricyclo [5.2 in one molecule. .1.0 ^2.6 ] a polymer having a decyl group or the like.

  Specific examples of such an epoxy group-containing polymer include phenol novolac type epoxy resins, cresol novolac type epoxy resins, polyphenol type epoxy resins, bisphenol A type epoxy resins, cyclic aliphatic epoxy resins, and triphenylmethane type epoxy resins. Etc.

In addition, a monomer having an oxiranyl group, an oxetanyl group, a glycidyl group, a 3,4-epoxycyclohexyl group, a 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl group is polymerized. The resulting polymer may be used. Examples of such a polymer include a polymer having a structural unit represented by the following formula. In the following formula, R ²⁹ is a hydrogen atom or a methyl group.

Monomers that give such structural units include glycidyl (meth) acrylate, 3- (meth) acryloyloxymethyl-3-ethyloxetane, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3,4- An epoxy tricyclo [5.2.1.0 ^2.6 ] decyl (meth) acrylate etc. are mentioned.
(A) The polymer is preferably a polymer having a carboxyl group. By having a carboxyl group in the polymer, it is possible to impart alkali developability to the polymer, and in the heating step during the formation of the interlayer insulating film, the epoxy group and the carboxyl group in the polymer undergo a crosslinking reaction to cause crosslinking. It is possible to form an interlayer insulating film with a highly developed structure. An interlayer insulating film having excellent solvent resistance and heat resistance can be formed.
Other copolymerizable ethylenically unsaturated monomers such as an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter referred to as “unsaturated monomer (a1)”) and a monomer having an epoxy group A copolymer having an epoxy group and a carboxyl group can be obtained by copolymerization with a monomer (hereinafter referred to as “unsaturated monomer (a2)”).

  Examples of the unsaturated monomer (a1) include saturated monocarboxylic acid, unsaturated dicarboxylic acid, anhydride of unsaturated dicarboxylic acid, mono [(meth) acryloyloxyalkyl] ester of polyvalent carboxylic acid, both terminals Examples thereof include mono (meth) acrylates of polymers having a carboxyl group and a hydroxyl group, unsaturated polycyclic compounds having a carboxyl group, and anhydrides thereof.

  Examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, and crotonic acid. Examples of the unsaturated dicarboxylic acid include unsaturated dicarboxylic acid such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, and itaconic acid. As an anhydride, the anhydride of the compound illustrated as said dicarboxylic acid, etc. are mentioned, for example. An unsaturated monomer (a1) can be used individually or in mixture of 2 or more types.

  In the copolymer of the unsaturated monomer (a1) and the unsaturated monomer (a2), the copolymerization ratio of the unsaturated monomer (a1) in the polymer is preferably 5 to 50% by mass, More preferably, it is 10 to 40% by mass. By copolymerizing the unsaturated monomer (a1) in such a range, a composition excellent in alkali developability and storage stability can be obtained.

Among the unsaturated monomers (a2), examples of the monomer having an epoxy group include the above-described glycidyl (meth) acrylate, 3- (meth) acryloyloxymethyl-3-ethyloxetane, and 3,4-epoxycyclohexyl. Examples include methyl (meth) acrylate, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl (meth) acrylate, and the like.

  Specific examples of the copolymer of the unsaturated monomer (a1) and the unsaturated monomer (a2) include, for example, JP-A-7-140654, JP-A-8-259876, and JP-A-10-31308. Disclosed in Japanese Patent Application Laid-Open No. 10-300922, Japanese Patent Application Laid-Open No. 11-174224, Japanese Patent Application Laid-Open No. 11-258415, Japanese Patent Application Laid-Open No. 2000-56118, Japanese Patent Application Laid-Open No. 2004-101728, and Japanese Patent Application Laid-Open No. 4-352101. Can be mentioned.

In the present invention, examples of the polymer having a (meth) acryloyl group as the polymerizability include, for example, JP-A-5-19467, JP-A-6-230212, JP-A-7-207211, As disclosed in JP-A-09-325494, JP-A-11-140144, JP-A-2008-181095, and the like, containing a carboxyl group having a polymerizable unsaturated bond such as a (meth) acryloyl group in the side chain Polymers can also be used.
(A) The polymer can further contain at least one of a group represented by the following formula (1) and a group represented by the following formula (2). Such a group represented by the formula (1) and a group represented by the following formula (2) are acid-dissociable groups. This acid dissociable group acts as a protecting group for protecting a carboxy group or the like in the polymer. A polymer having such a protective group is usually insoluble or hardly soluble in an alkaline aqueous solution. Since this protecting group is an acid-dissociable group, this polymer becomes soluble in an alkaline aqueous solution when the protecting group is cleaved by the action of an acid.

In formula (1), R ¹ and R ² are each independently a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms, or at least a part of the hydrogen atoms of the hydrocarbon group is a hydroxyl group, a halogen atom or A group substituted with a cyano group. However, there is no case where R ¹ and R ² are both hydrogen atoms. R ³ represents a hydrocarbon group having 1 to 30 carbon atoms, a group containing an oxygen atom between carbon-carbon or a bond side terminal of the carbon hydrogen group, or at least a part of hydrogen atoms of these groups is a hydroxyl group, a halogen atom A group substituted by an atom or a cyano group. * Indicates a binding site.
In formula (2), R ⁴ to R ¹⁰ are each independently a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms. n is 1 or 2. When n is 2, the plurality of R ⁷ and R ⁸ may be the same or different. * Indicates a binding site.

  Examples of the structural unit having a group represented by the formula (1) include structural units represented by the following formulas (3-1) to (3-10).

In the above formulas (3-1) to (3-10), R ¹⁷ represents a hydrogen atom or a methyl group.

  Examples of monomers that give structural units represented by formulas (3-1) to (3-10) include 1-ethoxyethyl methacrylate, 1-butoxyethyl methacrylate, 1- (tricyclodecamethacrylate). Nyloxy) ethyl, 1- (pentacyclopentadecanylmethyloxy) ethyl methacrylate, 1- (pentacyclopentadecanyloxy) ethyl methacrylate, 1- (tetracyclododecanylmethyloxy) ethyl methacrylate, methacrylic acid 1- (adamantyloxy) ethyl and the like can be mentioned.

    Examples of the structural unit having a group represented by the above formula (2) include structural units represented by the following formulas (4-1) to (4-5).

In the above formulas (4-1) to (4-5), R ²⁰ represents a hydrogen atom or a methyl group.

  As a monomer which gives the structural unit represented by the above formula (2), tetrahydro-2H-pyran-2-yl methacrylate (4-3) is preferable.

  The polymer in the present invention has a polystyrene-equivalent weight average molecular weight measured by GPC (elution solvent: tetrahydrofuran) of usually 1,000 to 100,000, preferably 3,000 to 50,000. The ratio of the weight average molecular weight of the binder polymer in the present invention to the number average molecular weight in terms of polystyrene measured by GPC (elution solvent: tetrahydrofuran) is preferably 1.0 to 5.0, more preferably 1.0. To 3.0.

The polymer in the present invention can be produced by a known method, and disclosed in, for example, JP-A No. 2003-222717, JP-A No. 2006-259680, WO 07/029871, etc. The structure, Mw, and Mw / Mn can be controlled by the method.
<(B) Photoacid generator>
(B) As a photo-acid generator, it is a compound which generate | occur | produces an acid by irradiation of a radiation. Here, as the radiation, for example, visible light, ultraviolet light, far ultraviolet light, electron beam (charged particle beam), X-ray or the like can be used. The photoacid generator is not particularly limited as long as it is a compound that generates an acid (for example, carboxylic acid, sulfonic acid, etc.) by irradiation with radiation.

  Examples of the (B) photoacid generator include oxime sulfonate compounds, onium salts, sulfonimide compounds, halogen-containing compounds, diazomethane compounds, sulfone compounds, sulfonic acid ester compounds, carboxylic acid ester compounds, and quinone diazide compounds.

As said oxime sulfonate compound, the compound containing the oxime sulfonate group represented by a following formula is preferable. In the formula, R ²¹ represents an alkyl group, a cycloalkyl group, or an aryl group, and a part or all of the hydrogen atoms of these groups may be substituted with a substituent.

Specific examples of the oxime sulfonate compound include [(5-propylsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile], [(5H-octylsulfonyloxyimino-5H-thiophene-2- Ylidene)-(2-methylphenyl) acetonitrile], [(camphorsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile], [(5-p-toluenesulfonyloxyimino-5H- Thiophen-2-ylidene)-(2-methylphenyl) acetonitrile], 2- (octylsulfonyloxyimino) -2- (4-methoxyphenyl) acetonitrile, and the like.
In addition, the photoacid generators described in JP2011-227106A and JP2012-150494A can be used.

  Examples of the onium salt include diphenyliodonium salt, triphenylsulfonium salt, sulfonium salt, benzothiazonium salt, tetrahydrothiophenium salt, and sulfonimide compound.

  Examples of the sulfonimide compound include N- (trifluoromethylsulfonyloxy) succinimide, N- (camphorsulfonyloxy) succinimide, N- (4-methylphenylsulfonyloxy) succinimide, N- (2-trifluoromethyl). Phenylsulfonyloxy) succinimide, N- (4-fluorophenylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (camphorsulfonyloxy) phthalimide, N- (2-trifluoromethylphenylsulfonyloxy) Phthalimide, N- (2-fluorophenylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, N- (camphorsulfonyloxy) diph Cycloalkenyl maleimide, N- hydroxynaphthalimide - trifluoromethanesulfonic acid ester and the like.

  As other photoacid generators, the photoacid generators described in JP2011-215503A and WO2011 / 087011A1 can be used.

    The content of the (B) photoacid generator in the radiation-sensitive resin composition of the present embodiment is preferably 0.1 part by mass to 10 parts by mass with respect to 100 parts by mass of the component (A). 5 parts by mass is more preferable. The radiation sensitivity of the radiation sensitive resin composition of the present embodiment can be optimized, exhibits good patternability, and is suitable for forming the interlayer insulating film of the present embodiment.

  A quinonediazide compound can also be mentioned as (B) photoacid generator of the radiation sensitive resin composition of this embodiment. This quinonediazide compound can be particularly preferably used as a photoacid generator.

  A quinonediazide compound is a quinonediazide compound that generates a carboxylic acid upon irradiation with radiation. As the quinonediazide compound, a condensate of a phenolic compound or an alcoholic compound (hereinafter referred to as “mother nucleus”) and 1,2-naphthoquinonediazidesulfonic acid halide can be used.

  Examples of the mother nucleus include trihydroxybenzophenone, tetrahydroxybenzophenone, pentahydroxybenzophenone, hexahydroxybenzophenone, (polyhydroxyphenyl) alkane, and other mother nuclei.

  As the 1,2-naphthoquinone diazide sulfonic acid halide, 1,2-naphthoquinone diazide sulfonic acid chloride is preferable. Examples of 1,2-naphthoquinonediazide sulfonic acid chloride include 1,2-naphthoquinonediazide-4-sulfonic acid chloride, 1,2-naphthoquinonediazide-5-sulfonic acid chloride, and the like. Of these, 1,2-naphthoquinonediazide-5-sulfonic acid chloride is more preferred.

  In the condensation reaction of the phenolic compound or alcoholic compound (mother nucleus) and 1,2-naphthoquinonediazide sulfonic acid halide, preferably 30 mol% to the number of OH groups in the phenolic compound or alcoholic compound. 1,2-naphthoquinonediazide sulfonic acid halide corresponding to 85 mol%, more preferably 50 mol% to 70 mol% can be used. The condensation reaction can be carried out by a known method.

These quinonediazide compounds include 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol (1.0 mol) and 1,2-naphtho. A condensate of quinonediazide-5-sulfonic acid chloride (2.0 mol) is preferably used.

These quinonediazide compounds can be used alone or in combination of two or more.

  Moreover, it can also be used in combination with the oxime sulfonate compound, onium salt, sulfonimide compound, halogen-containing compound, diazomethane compound, sulfone compound, sulfonic acid ester compound and carboxylic acid ester compound described above.

As content of the quinonediazide compound in the radiation sensitive resin composition of this embodiment, Preferably it is 5 mass parts-100 mass parts with respect to 100 mass parts of (A) component, More preferably, it is 10 mass parts-50 masses. Part. By setting the content of the quinonediazide compound in the above range, the difference in solubility between the irradiated portion and the unirradiated portion with respect to the alkaline aqueous solution serving as the developer can be increased, and the patterning performance can be improved. Moreover, the solvent resistance of the interlayer insulation film obtained using this radiation sensitive resin composition can also be made favorable.
<(C) Photoradical polymerization initiator>
(C) A radical photopolymerization initiator is a component that generates radical species that can start polymerization of a compound having polymerizability in response to radiation. It becomes possible to improve the heat resistance and solvent resistance of the resulting interlayer insulating film by starting the crosslinking reaction of (D) polyfunctional acrylate described later.

    Examples of (C) photoradical polymerization initiators include O-acyloxime compounds, acetophenone compounds, biimidazole compounds, and the like. These compounds may be used alone or in combination of two or more.

  Examples of O-acyloxime compounds include 1,2-octanedione 1- [4- (phenylthio) -2- (O-benzoyloxime)], ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime) or ethanone-1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl } -9. H. -Carbazol-3-yl] -1- (O-acetyloxime) is preferred.

Examples of the acetophenone compound which is a specific example of the above-described (C) photoradical polymerization initiator include an α-aminoketone compound and an α-hydroxyketone compound.
Among the acetophenone compounds, α-aminoketone compounds are preferable, and 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one, 2-methyl More preferred are -1- (4-methylthiophenyl) -2-morpholinopropan-1-one and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1.

  As these (C) photoradical polymerization initiators, the photopolymerization initiators described in JP2013-164471A, JP2012-212114A, and JP2010-85929A can be used. .

(C) The content of the photopolymerization initiator exemplified as the photoradical polymerization initiator is preferably 1 part by mass to 40 parts by mass, more preferably 5 parts by mass with respect to 100 parts by mass of the component (A). 30 parts by mass. By setting the content of the radical photopolymerization initiator to 1 part by mass to 40 parts by mass, the radiation-sensitive resin composition of the present embodiment has high solvent resistance, high hardness and high even at a low exposure amount. A cured film having adhesiveness can be formed.
<(D) polyfunctional acrylate>
(D) The polyfunctional acrylate initiates a crosslinking reaction by radicals generated by the (C) photoradical polymerization initiator, and can improve the heat resistance and solvent resistance of the resulting interlayer insulating film.

  Examples of such polyfunctional acrylates include 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, and 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, penta Erythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol (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), reaction product of trimethylhexamethylene diisocyanate, hexamethylene diisocyanate and 2-hydroxyethyl (meth) acrylate, methylenebis (meth) acrylamide, (meth) Examples thereof include polyfunctional monomers such as acrylamide methylene ether, polyhydric alcohol and N-methylol (meth) acrylamide condensate, and triacryl formal. These polyfunctional monomers can be used alone or in combination of two or more.

The content of the polyfunctional acrylate is 100 parts by mass or less with respect to 100 parts by mass of the component (A), preferably 0.1 parts by mass or more and 80 parts by mass or less, and 0.5 parts by mass or more and 50 parts by mass or less. More preferably, it is more preferably 1 part by mass or more and 25 parts by mass or less. By using in this range, the heat resistance and solvent resistance of the interlayer insulation film formed from this radiation sensitive resin composition can be improved more.
The radiation-sensitive resin composition in the present invention becomes a positive radiation-sensitive resin composition by selecting the photoacid generators of the component (A) and the component (B), and the radical photopolymerization initiator of the component (C) ( By including the polyfunctional acrylate of component C), a negative radiation-sensitive resin composition can be obtained. The radiation sensitive resin composition in this invention turns into a radiation sensitive resin composition which has a positive type and a negative type component simultaneously.
For example, contact hole formation in an interlayer insulation film is performed by quinonediazide being exposed to light, a contact hole pattern is formed by a positive function, and photo radical polymerization initiator 2-methyl-1- (4-methylthiophenyl)- When 2-morpholinopropan-1-one is exposed to light, the crosslinking reaction of the unexposed part can be advanced by a negative function.
Thus, with one type of radiation sensitive resin composition, a positive type function and a negative type function can be expressed, a contact hole pattern can be formed, and the curability as an interlayer insulating film is improved, and the heat resistance, It becomes possible to further improve the solvent property.
<(E) Compound having a polymerizable group and an organic group having at least one of a fluorine atom or a silicon atom in one molecule>
(E) In one molecule, a compound having a polymerizable group and an organic group having at least one of a fluorine atom or a silicon atom (hereinafter also referred to as component (E)) is an organic compound having at least one of a fluorine atom or a silicon atom. The group tends to be unevenly distributed on the surface of the interlayer insulating film, and further having a polymerizable group can further promote the curability of the interlayer insulating film and the surface. The polymerizable group of component (E) is at least one selected from an epoxy group, a (meth) acryloyl group, and a vinyl group. The compound which overlaps with the component (A) is not the component (E).

  Examples of the organic group having at least one of a fluorine atom and a silicon atom include an alkyl group having 1 to 12 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, a methylene group, an alkylene group having 2 to 12 carbon atoms, and phenylene. A group in which one or more hydrogen atoms such as a group are substituted with fluorine atoms or silicon atoms.

Specific examples include compounds having an organic group having a fluorine atom and a polymerizable unsaturated group. For example, a polymerizable monomer having a poly (perfluoroalkylene ether) chain and polymerizable unsaturated groups at both ends thereof. Fluorine-based surface activity which is a copolymer obtained by copolymerizing a polymerizable monomer having an oxyalkylene group and a polymerizable unsaturated group as essential monomers is preferable.
As such fluorine-based surface activity, the fluorine-based surface activity described in WO2012 / 002361 A1 can be used.
Examples of the compound having an organic group having a silicon atom and a polymerizable unsaturated group include polyether-modified polydimethylsiloxane having a (meth) acryl group, and commercially available products include BYK-UV3500 and BYK. -UV3510, BYK-UV3530, BYK-UV3570 (manufactured by Big Cami) or the like can be used.

Further, polyorganosiloxane having an epoxy group can also be suitably used, and polyorganosiloxane having an epoxy group described in JP2012-168289A can be used.
The content of the component (E) is preferably 0.5 parts by mass or more and 30 parts by mass or less, and more preferably 1 part by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the component (A). By using in this range, the heat resistance and solvent resistance of the interlayer insulation film formed from this radiation sensitive resin composition can be improved more.
<(E) Antioxidant>
The (F) antioxidant (hereinafter also referred to as the (F) component) contained in the radiation-sensitive resin composition of the present embodiment suppresses oxidation of the formed cured film and improves the heat resistance of the interlayer insulating film. It becomes possible to do.

    Examples of the component (F) of the radiation-sensitive resin composition of the present embodiment include phenolic antioxidants, sulfur-based antioxidants, amine-based antioxidants, and the like, and phenolic antioxidants are particularly preferable.

Specific examples of the phenol-based antioxidant include styrenated phenol, 2,6-di-t-butyl-4-methylphenol, 2,6-di-t-butyl-p-ethylphenol, 2 , 4,6-tri-t-butylphenol, butylhydroxyanisole, 1-hydroxy-3-methyl-4-isopropylbenzene, mono-t-butyl-p-cresol, mono-t-butyl-m-cresol, 2, 4-dimethyl-6-tert-butylphenol, butylated bisphenol A, 2,2'-methylene-bis- (4-methyl-6-tert-butylphenol), 2,2'-methylene-bis- (4-ethyl- 6-t-butylphenol), 2,2'-methylene-bis (4-methyl-6-t-nonylphenol), 2,2'-isobutylidene-bis- (4,6-dimethyl) Tilphenol), 4,4′-butylidene-bis- (3-methyl-6-tert-butylphenol), 4,4′-methylene-bis- (2,6-di-tert-butylphenol), 2,2- Thio-bis- (4-methyl-6-tert-butylphenol), 4,4′-thio-bis- (3-methyl-6-tert-butylphenol), 4,4′-thio-bis- (2-methyl) -6-butylphenol), 4,4'-thio-bis- (6-tert-butyl-3-methylphenol), bis (3-methyl-4-hydroxy-5-tert-butylbenzene) sulfide, 2,2 -Thio [diethyl-bis-3- (3,5-di-t-butyl-4-hydroxyphenol) propionate], bis [3,3-bis (4'-hydroxy-3'-t-butylphenol) butyric Acid] Glycol S Ter, bis [2- (2-hydroxy-5-methyl-3-tert-butylbenzene) -4-methyl-6-tert-butylphenyl] terephthalate, 1,3,5-tris (3 ′, 5′- Di-t-butyl-4′-hydroxybenzyl) isocyanurate, N, N′-hexamethylene-bis (3,5-di-t-butyl-4-hydroxy-hydroxyamide), N-octadecyl-3- ( 4′-hydroxy-3 ′, 5′-di-t-butylphenol) propionate, tetrakis [methylene- (3 ′, 5′-di-t-butyl-4-hydroxyphenyl) propionate] methane, 1,1′- Bis (4-hydroxyphenyl) cyclohexane, mono (α-methylbenzene) phenol, di (α-methylbenzyl) phenol, tri (α-methylbenzyl) phenol, bis (2 ′ Hydroxy-3′-t-butyl-5′-methylbenzyl) 4-methyl-phenol, 2,5-di-t-amylhydroquinone, 2,6-di-butyl-α-dimethylamino-p-cresol, 2 , 5-di-t-butylhydroquinone, diethyl ester of 3,5-di-t-butyl-4-hydroxybenzyl phosphate, and the like.
These (F) antioxidants can be used alone or in combination of two or more. (F) As for content of antioxidant, 0.1 mass part-10 mass parts are preferable with respect to a total of 100 mass parts of (A) component contained in the radiation sensitive resin composition of this embodiment, Especially. Preferably they are 0.2 mass part-5 mass parts. By using in this range, the heat resistance of the interlayer insulation film formed from this radiation sensitive resin composition can be improved more.
<Other optional components>
The radiation-sensitive resin composition contains other optional components such as an acid diffusion controller, a surfactant, an adhesion assistant, and inorganic oxide particles as necessary, as long as the effects of the present invention are not impaired. Also good. Other optional components may be used alone or in combination of two or more.

  Surfactant is a component which improves the film-forming property of the said radiation sensitive resin composition. By containing the surfactant, the radiation sensitive resin composition can improve the surface smoothness of the coating film. As a result, the film thickness uniformity of the cured film formed from the radiation sensitive resin composition can be improved. It can be improved.

  The adhesion assistant is a component that improves the adhesion between the film formation target such as a substrate and the cured film. The adhesion assistant is particularly useful for improving the adhesion between the inorganic substrate and the cured film.

As the adhesion assistant, a functional silane coupling agent is preferable.
The acid diffusion control agent can be arbitrarily selected from those used in chemically amplified resists. By containing the acid diffusion control agent, the radiation sensitive resin composition can appropriately control the diffusion length of the acid generated from the radiation sensitive acid generator by exposure, and the pattern developability can be improved. As the acid diffusion control agent, an acid diffusion control agent described in JP 2011-232632 A can be used.
The inorganic oxide particle is an oxide containing at least one element selected from the group consisting of silicon, aluminum, zirconium, titanium, zinc, indium, tin, antimony, strontium, barium, cerium and hafnium. Can be used. Inorganic oxide particles described in JP2011-128385A can be used.
<Method for preparing radiation-sensitive resin composition>
The radiation-sensitive resin composition includes a polymer (A) component, a photoacid generator (B) component, a photoradical polymerization initiator (C) component, and a component (D) as a solvent. It is prepared in a dissolved or dispersed state by mixing a functional acrylate, if necessary, a suitable component and other optional components. For example, the said radiation sensitive resin composition can be prepared by mixing each component in a predetermined ratio in a solvent.
<Solvent>
As the solvent, a solvent that uniformly dissolves or disperses other components in the radiation-sensitive resin composition and does not react with the other components is preferably used. Examples of such solvents include alcohols, ethers, glycol ethers, ethylene glycol alkyl ether acetates, diethylene glycol alkyl ethers, propylene glycol monoalkyl ethers, propylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ether propionates, Aromatic hydrocarbons, ketones, other esters and the like can be mentioned. As the solvent, the solvents described in JP2011-232632 can be used.
<Method for forming cured film for display element>
The radiation-sensitive resin composition is preferable for forming an interlayer insulating film for display elements.

The method for forming an interlayer insulating film for a display element according to the present invention includes:
(1) The process of forming a coating film on a board | substrate using the said radiation sensitive resin composition,
(2) A step of irradiating at least a part of the coating film with radiation,
(3) a step of developing the coating film irradiated with the radiation; and (4) a step of heating the developed coating film.

According to the formation method of the present invention, it is possible to form an interlayer insulating film for a display element that is excellent in adhesion, heat resistance and solvent resistance. Hereinafter, each process is explained in full detail.
[Step (1)]
In this step, a transparent conductive film is formed on one surface of the transparent substrate, and a coating film of the radiation-sensitive resin composition is formed on the transparent conductive film. Examples of the transparent substrate include glass substrates such as soda lime glass and alkali-free glass, and resin substrates made of plastics such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, and polyimide.

  Examples of the transparent conductive film provided on one surface of the transparent substrate include a NESA film (registered trademark of PPG, USA) made of tin oxide (SnO2), an ITO film made of indium oxide-tin oxide (In2O3-SnO2), and the like.

  When a coating film is formed by a coating method, the coating film is preferably formed by heating (pre-baking) the coated surface after coating the solution of the radiation sensitive resin composition on the transparent conductive film. Can do. As solid content concentration of the composition solution used for a coating method, 5 mass%-50 mass% are preferable, 10 mass%-40 mass% are more preferable, 15 mass%-35 mass% are especially preferable. Examples of the application method of the radiation sensitive resin composition include spraying, roll coating, spin coating (spin coating), slit coating (slit die coating), bar coating, and ink jet coating. An appropriate method can be adopted. Of these, spin coating or slit coating is preferred.

The pre-baking conditions vary depending on the type of each component, the blending ratio, etc., but are preferably 70 ° C. to 120 ° C. and about 1 to 15 minutes. The film thickness after pre-baking of the coating film is preferably from 0.5 μm to 10 μm, more preferably from about 1.0 μm to 7.0 μm.
[Step (2)]
In this step, radiation is applied to at least a part of the formed coating film. At this time, when irradiating only a part of the coating film, for example, a method of irradiating through a photomask having a predetermined pattern can be used.

  Examples of radiation used for irradiation include visible light, ultraviolet light, and far ultraviolet light. Of these, radiation having a wavelength in the range of 250 nm to 550 nm is preferable, and radiation including ultraviolet light of 365 nm is more preferable.

Radiation dose (exposure dose), as a value measured by a luminometer intensity at a wavelength 365nm of the radiation emitted (OAI model 356, Optical Associates Ltd. Inc.), is 5,000J / ^{m 2} from 100 J / ^{m 2} Preferably, 200 J / m ² to 3,000 J / m ² is more preferable.

The radiation-sensitive resin composition has a higher sensitivity than conventionally known compositions, and a desired film thickness even when the radiation dose is 700 J / m ² or less, and even 600 J / m ² or less. It is possible to obtain an interlayer insulating film for display elements having a good shape, excellent adhesion and high hardness.
[Step (3)]
In this step, the coated film after irradiation is developed to remove unnecessary portions and form a predetermined pattern. Examples of the developer used for the development include aqueous solutions of alkaline compounds such as inorganic alkalis such as sodium hydroxide, potassium hydroxide and sodium carbonate, and quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide. Can be mentioned. An appropriate amount of a water-soluble organic solvent such as methanol or ethanol and / or a surfactant may be added to the aqueous solution of the alkaline compound.

The developing method may be any of a liquid filling method, a dipping method, a shower method, and the like, and the developing time is preferably about 10 seconds to 180 seconds at room temperature. Subsequent to the development processing, for example, washing with running water is performed for 30 seconds to 90 seconds, and then a desired pattern is obtained by air drying with compressed air or compressed nitrogen.
[Step (4)]
In this step, a cured film for display element is obtained by heating the obtained patterned coating film with a suitable heating device such as a hot plate or oven. The heating temperature is about 100 ° C to 250 ° C. The heating time is, for example, about 5 to 30 minutes on a hot plate and about 30 to 180 minutes for an oven.
<Method for manufacturing display element>
The present invention suitably includes a display element including the display element interlayer insulating film. As a method for manufacturing a display element, first, a pair (two) of transparent substrates having a transparent conductive film (electrode) on one side is prepared, and the radiation-sensitive resin composition is formed on the transparent conductive film of one of the substrates. Is used to form a spacer or a protective film or both in accordance with the method described above. Subsequently, an alignment film having liquid crystal alignment ability is formed on the transparent conductive film and the spacer or protective film of these substrates. These substrates are arranged facing each other with a certain gap (cell gap) so that the liquid crystal alignment direction of each alignment film is orthogonal or antiparallel, with the surface on which the alignment film is formed inside. A liquid crystal is filled in the cell gap defined by the surface of the substrate (alignment film) and the spacer, and the filling hole is sealed to constitute a liquid crystal cell. Then, the display element of the present invention is bonded to both outer surfaces of the liquid crystal cell such that the polarizing direction is aligned or orthogonal to the liquid crystal alignment direction of the alignment film formed on one surface of the substrate. can get.

  As another method, a pair of transparent substrates on which a transparent conductive film, an interlayer insulating film, a protective film, a spacer, or both, and an alignment film are formed are prepared in the same manner as described above. After that, along the edge of one substrate, an ultraviolet curable sealant is applied using a dispenser, and then the liquid crystal is dropped in the form of fine droplets using a liquid crystal dispenser, and the two substrates are bonded together under vacuum. . Then, both the substrates are sealed by irradiating the sealing agent part with ultraviolet rays using a high-pressure mercury lamp. Finally, the display element of the present invention is obtained by attaching polarizing plates to both outer surfaces of the liquid crystal cell.

  Examples of the liquid crystal used in each of the above methods include nematic liquid crystal and smectic liquid crystal. In addition, as a polarizing plate used outside the liquid crystal cell, a polarizing film in which a polarizing film called an “H film” that absorbs iodine while stretching and aligning polyvinyl alcohol is sandwiched between cellulose acetate protective films, or an H film Examples thereof include a polarizing plate made of itself.

<Synthesis of a polymer having a polymerizable group>
Synthesis Example 1 Polymer having 3,4-epoxycyclohexyl group and carboxyl group [A-2]
A flask equipped with a condenser and a stirrer was charged with 7 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts by mass of propylene glycol monomethyl ether acetate. Subsequently, 5 parts by mass of styrene, 20 parts by mass of methacrylic acid, 25 parts by mass of tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate, 30 parts by mass of 3,4-epoxycyclohexyl methacrylate, methacrylic acid After charging 20 parts by mass of tetrahydrofurfuryl acid and replacing with nitrogen, stirring was started gently. The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 5 hours to obtain a polymer solution containing the polymer [A-2]. The obtained polymer solution had a solid content concentration of 30.0% by mass, and the polymer had a weight average molecular weight of 18,000 (weight average molecular weight was GPC (gel permeation chromatography) HLC-8020. (Molecular weight in terms of polystyrene measured using Tosoh Corporation).

Synthesis Example 2 Polymer having glycidyl group and carboxyl group [A-3 ]
A flask equipped with a condenser and a stirrer was charged with 7 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol ethyl methyl ether. Subsequently, 5 parts by mass of styrene, 20 parts by mass of methacrylic acid, 25 parts by mass of tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate, 30 parts by mass of glycidyl methacrylate, tetrahydrofurfuryl methacrylate 20 Stirring was started gently after charging a mass part and substituting with nitrogen. The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 5 hours to obtain a polymer solution containing the polymer [A-3]. The obtained polymer solution had a solid content concentration of 31.0% by weight, and the polymer had a weight average molecular weight (Mw) of 20,000 (weight average molecular weight was GPC (gel permeation chromatography)). It is a polystyrene conversion molecular weight measured using HLC-8020 (manufactured by Tosoh Corporation).

Synthesis Example 3 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] polymer having decyl group and carboxyl group [A-4]
A flask equipped with a condenser and a stirrer was charged with 5 parts by mass of 2,2′-azobisisobutyronitrile and 200 parts by mass of propylene glycol monomethyl ether acetate. Subsequently, 10 parts by mass of styrene, 20 parts by mass of methacrylic acid, 30 parts by mass of tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate, 30 parts by mass of benzyl methacrylate, 3,4-epoxytri After 20 parts by mass of cyclo [5.2.1.0 ^2.6 ] decyl methacrylate was charged and purged with nitrogen, stirring was started gently. The temperature of the solution was raised to 90 ° C., and this temperature was maintained for 4 hours to obtain a polymer solution containing the polymer [A-4]. The solid content concentration of the obtained polymer solution was 31.0% by weight, and the polymer Mw was 21,000 (weight average molecular weight was GPC (gel permeation chromatography) HLC-8020 (Tosoh Corporation). (Made by Co., Ltd.) and measured in terms of polystyrene).

Synthesis Example 4 Polymer having methacryloyl group and carboxyl group [A-5]
A flask equipped with a condenser and a stirrer was charged with 4 parts by weight of 2,2′-azobisisobutyronitrile and 190 parts by weight of propylene glycol monomethyl ether acetate, followed by 85 parts by weight of methacrylic acid and 15 parts by weight of benzyl methacrylate. In addition, 2 parts by mass of α-methylstyrene dimer as a molecular weight regulator was added, and while stirring gently, the temperature of the solution was raised to 80 ° C., this temperature was maintained for 4 hours, and then increased to 100 ° C. Then, this temperature was maintained for 1 hour for polymerization to obtain a solution containing a copolymer. Next, 1.1 parts by mass of tetrabutylammonium bromide and 0.05 parts by mass of 4-methoxyphenol as a polymerization inhibitor were added to the solution containing this copolymer, and the mixture was stirred at 90 ° C. for 30 minutes in an air atmosphere. Polymer [A-5] was obtained by adding 74 mass parts of glycidyl acids and making it react at 90 degreeC for 10 hours (solid content concentration = 35.5%). Mw was 10,000.
Synthesis Example 5 Polymer having glycidyl group, carboxyl group and tetrahydro-2H-pyran-2-yl group [A-6]
A flask equipped with a condenser and a stirrer was charged with 7 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol ethyl methyl ether. Subsequently, 5 parts by weight of methacrylic acid, 40 parts by weight of tetrahydro-2H-pyran-2-yl methacrylate, 5 parts by weight of styrene, 40 parts by weight of glycidyl methacrylate, 10 parts by weight of 2-hydroxyethyl methacrylate and 3 parts by weight of α-methylstyrene dimer Was added, and the mixture was purged with nitrogen. The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 5 hours to obtain a polymer solution containing the polymer [A-6] as a copolymer. The polymer (A-5) had a polystyrene equivalent weight average molecular weight (Mw) of 9000. Moreover, solid content concentration of the obtained polymer solution was 31.3 mass%.
Synthesis Example 6 Component (E) Polysiloxane having an epoxy group 25 parts by mass of propylene glycol monomethyl ether was charged into a vessel equipped with a stirrer, and then 3-glycidoxypropyltrimethoxysilane (GPTMS) 40 Parts by mass (31.3 mol%), methyltrimethoxysilane (MTMS) 30 parts by mass (40.7 mol%), phenyltrimethoxysilane (PTMS) 30 parts by mass (28.0 mol%) and oxalic acid 0. 5 parts by mass were charged and heated until the solution temperature reached 60 ° C. After the solution temperature reached 60 ° C., 18 parts by mass of ion-exchanged water was charged, heated to 75 ° C. and held for 3 hours. Next, 28 parts by mass of methyl orthoformate was added as a dehydrating agent and stirred for 1 hour. Furthermore, the solution temperature was set to 40 ° C., and evaporation was performed while maintaining the temperature, thereby removing ion-exchanged water and methanol generated by hydrolysis and condensation. The hydrolysis condensate (E-1) was obtained by the above procedure. The solid content concentration of the hydrolysis-condensation product (E-1) was 39.5% by mass, Mw was 3,500, and Mw / Mn was 2.0.
<Preparation of radiation-sensitive resin composition>
[Example 1]
100 parts by weight of (A-1) triphenylmethane type epoxy resin (EPPN-501H made by Nippon Kayaku Co., Ltd.) as component (A), and (B-4) 4,4 ′-[1- [ 4- [1- [4-Hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol (1.0 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid chloride (2.0 mol) 2 parts by mass, (C-2) 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (IRGACURE369 manufactured by BASF) as component (B), (D) As a component, 100 parts by mass of succinic acid-modified pentaerythritol triacrylate (“Aronix TO-756” manufactured by Toagosei Co., Ltd.) is mixed so that the solid content concentration becomes 25% by mass. The radiation-sensitive resin composition were prepared using a propylene glycol monomethyl ether acetate (PGMEA).
Table 1 shows the details of the composition of the radiation-sensitive resin composition and the evaluation results shown below.
[Examples 1 to 6 and Comparative Examples 1 to 2]

In Table 1,
A-1: Triphenylmethane type epoxy resin (EPPN-501H manufactured by Nippon Kayaku Co., Ltd.)
<Photo acid generator>
B-1: 5-propylsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile (“IRGACURE PAG 103” from BASF)
B-2: (5-p-toluenesulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile (“IRGACURE PAG 121” from BASF)
B-3: N-hydroxynaphthalimide-trifluoromethanesulfonic acid ester B-4: 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol (1.0 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid chloride (2.0 mol) condensate <photo radical polymerization initiator>
C-1: 2-Methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (IRGACURE907 manufactured by BASF)
C-2: 2-Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (IRGACURE369 BASF)
C-3: 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)] (IRGACUREOX01 BASF)
<Multifunctional acrylate>
D-1: Mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (“KAYARAD DPHA” from Nippon Kayaku Co., Ltd.)
D-2: Succinic acid-modified pentaerythritol triacrylate (“Aronix TO-756” manufactured by Toagosei Co., Ltd.)
<Compound having a polymerizable group and an organic group having at least one of a fluorine atom or a silicon atom in one molecule>
E-1: Polysiloxane having an epoxy group obtained in Synthesis Example 6 E-2: Polyether-modified polydimethylsiloxane (BYK-UV3500, manufactured by Big Cami)
<Antioxidant>
F-1: Pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (ADK STAB AO-60, manufactured by ADEKA)
F-2: Tris- (3,5-di-tert-butyl-4-hydroxybenzyl) -isocyanurate (ADK STAB AO-20, manufactured by ADEKA)
Indicates.
<Evaluation of cured film>
Using the radiation-sensitive resin compositions prepared in Examples 1 to 7 and Comparative Examples 1 and 2, a cured film was formed as follows, and the characteristics were evaluated.
[Evaluation of light resistance]
A radiation sensitive resin composition was applied onto a silicon substrate using a spinner, and then prebaked on a hot plate at 90 ° C. for 2 minutes to form a coating film having a thickness of 3.0 μm. This silicon substrate was heated in a clean oven at 220 ° C. for 1 hour to obtain a cured film. Each of the obtained cured films was irradiated with an irradiance of 130 mW with a UV irradiation apparatus (Ushio "UVX-02516S1JS01"). It can be said that the light resistance of the cured film is good when the amount of film thickness reduction after irradiation is 3% or less compared to the film thickness before irradiation.

In the evaluation of light resistance, since the patterning of the cured film to be formed is unnecessary, the development process was omitted, and only the coating film forming process, the light resistance test, and the heating process were performed for evaluation.
[Evaluation of transmittance]
Similar to the light resistance evaluation, a coating film was formed on a silicon substrate using the radiation-sensitive resin composition. This silicon substrate was heated in a clean oven at 220 ° C. for 1 hour to form a cured film. About this cured film, the transmittance | permeability in wavelength 400nm was measured and evaluated using the spectrophotometer ("150-20 type double beam" by Hitachi, Ltd.). At this time, it can be said that the transparency is poor when the transmittance is less than 90%.
[Evaluation of adhesion]
Adhesion was evaluated after exposure. Specifically, first, a radiation sensitive resin composition is applied onto a glass substrate using a spinner, and then prebaked on a hot plate at 90 ° C. for 2 minutes to form a coating film having a thickness of 3.0 μm. did. Subsequently, 700 (J / m ² ) was passed through a mask having a 10 μm line-and-space (one-to-one) pattern using an exposure machine (“MPA-600FA (ghi line mixing)” manufactured by Canon Inc.). ). Thereafter, it was left in a clean room for 1 hour, and then developed with a 0.5 mass% aqueous solution of tetramethylammonium hydroxide at 25 ° C. for 80 seconds. Next, running water was washed with ultrapure water for 1 minute, and then dried to form a pattern on the glass substrate. After development, the substrate was observed with an optical microscope to confirm the presence or absence of pattern peeling. The criteria for determining pattern adhesion are shown below.

When pattern peeling is hardly seen: “○”
When pattern peeling is slightly seen: “△”
When the pattern is peeled off and almost no pattern remains on the substrate: “×”
[Heat resistance (film thickness stability during heating)]
A substrate having an interlayer insulating film was prepared in the same manner as in the evaluation of transmittance, heated in a clean oven at 250 ° C. for 1 hour, and the thickness of the protective film before and after heating was measured. The film thickness stability (%) was calculated according to the following formula. When this value is 95% or more, it can be said that the heat resistance of the protective film is good.

Film thickness stability during heating = ((film thickness after heating) / (film thickness before heating)) x 100 (%)
[Alkali resistance (film thickness stability when immersed in alkali)]
A substrate having an interlayer insulating film was prepared in the same manner as the evaluation of the transmittance, immersed in 5% NaOH at 30 ° C. for 30 minutes, and then the film thickness after removing moisture was measured. Table 1 shows the film thickness stability (%) at the time of alkali immersion calculated according to the following formula as an evaluation of alkali resistance. When this value is 95% or more, it can be said that the alkali resistance is good.

Alkali resistance = ((film thickness after moisture removal) / (film thickness before immersion)) × 100 (%)
As is clear from the results in Table 1, Examples 1 to 6 were excellent in light resistance, transmittance, heat resistance, and alkali resistance. On the other hand, in Comparative Examples 1 and 2, satisfactory results were not obtained with respect to light resistance, transmittance, heat resistance, and alkali resistance.

Claims (9)

A radiation-sensitive resin composition for forming an interlayer insulating film in a display element,
(A) a polymer having a polymerizable group,
(B) a photoacid generator,
A radiation-sensitive resin composition comprising (C) a radical photopolymerization initiator and (D) a polyfunctional acrylate.   3. The radiation sensitive resin composition according to claim 2, wherein the polymer (A) is a polymer further having a carboxyl group.   (C) The photoradical polymerization initiator is at least one of an acetophenone photoradical polymerization initiator and an oxime ester photoradical polymerization initiator, according to any one of claims 1 and 2. The radiation sensitive resin composition as described.   Furthermore, (E) The compound which has a polymeric group and the organic group which has at least one of a fluorine atom or a silicon atom in 1 molecule is contained, The any one of Claim 1 to 3 characterized by the above-mentioned. The radiation-sensitive resin composition according to item.   Furthermore, (F) antioxidant is contained, The radiation sensitive resin composition as described in any one of Claims 1-4 characterized by the above-mentioned. The polymer (A) is a polymer further comprising at least one of a group represented by the following formula (1) and a group represented by the following formula (2). The radiation-sensitive resin composition according to any one of 5.

(In formula (1), R ¹ and R ² are each independently a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms, or a part of hydrogen atoms possessed by a hydrocarbon group having 1 to 30 carbon atoms. A group substituted by a hydroxyl group, a halogen atom or a cyano group, provided that R ¹ and R ² are not both hydrogen atoms, R ³ is an oxyhydrocarbon group having 1 to 30 carbon atoms, 1 carbon atom A group obtained by substituting a part of hydrogen atoms of a hydrocarbon group having ˜30 or a hydrocarbon group having 1 to 30 carbon atoms with a hydroxyl group, a halogen atom or a cyano group.
In formula (2), R ^{4 to} R ¹⁰ are each independently a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms. n is 1 or 2. )   The sensitivity according to any one of claims 1 to 6, wherein the radiation-sensitive resin composition according to any one of claims 1 to 6 is a positive radiation-sensitive resin composition. Radiation resin composition.   The process of forming a coating film on a board | substrate using the radiation sensitive resin composition of any one of Claim 1 to 7, The process of irradiating a radiation to at least one part of the said coating film, The said radiation A method for forming an interlayer insulating film, comprising: a step of developing a coating film irradiated with a film; and a step of heating the developed coating film. A display element comprising an interlayer insulating film formed from the method for forming an interlayer insulating film according to claim 8.