JP2009276742A - Method of forming photosensitive resin film, method of forming silica-based coating film, and device and member including silica-based coating film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method of forming a photosensitive resin film with which a silica-based coating film usable as an interlayer dielectric is relatively easily formed and which is excellent in process margin and makes a formed silica-based film excellent in resolution and heat resistance, and to provide a method of forming a silica-based coating film using the same. <P>SOLUTION: The method of forming the photosensitive resin film includes a step of coating the top of a substrate with a photosensitive resin composition comprising a siloxane resin obtained by hydrolytic condensation of a specific silane compound, a solvent in which the siloxane resin dissolves and a naphthoquinonediazidesulfonic acid ester and carrying out vacuum drying to form a photosensitive resin film. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a method for forming a photosensitive resin film, a method for forming a silica-based coating, and a semiconductor device, a flat display device, and an electronic device member including the silica-based coating formed by the method.

  In the production of flat display devices such as liquid crystal display devices and semiconductor devices, interlayer insulating films are used. In general, the interlayer insulating film is formed into a pattern by etching a film formed by deposition or coating from the gas phase through a photoresist. When a fine pattern is formed, gas phase etching is usually used. However, vapor phase etching has a problem that the apparatus cost is high and the processing speed is slow.

  Therefore, development of photosensitive materials for interlayer insulating films has been carried out for the purpose of cost reduction. In particular, in a liquid crystal display device, it is necessary to form a contact hole in an interlayer insulating film used for insulation between a pixel electrode and a gate / drain wiring and device flattening. There is a need for a photosensitive material for an interlayer insulating film. Further, the interlayer insulating film in the liquid crystal display device is required to be transparent. Further, when the patterned film is used as an interlayer insulating film, it is desired that the film has a low dielectric constant.

In order to meet these requirements, for example, methods for forming an interlayer insulating film disclosed in Patent Documents 1 and 2 have been proposed. Patent Document 1 includes a step of forming a coating film of a photosensitive polysilazane composition containing polysilazane and a photoacid generator, a step of irradiating the coating film with light in a pattern, and the irradiation of the coating film. And a method of forming an interlayer insulating film, which includes a step of dissolving and removing the portion. Patent Document 2 discloses an interlayer insulating film formed from a composition containing a siloxane resin and a compound that generates an acid or a base upon irradiation with radiation.
JP 2000-181069 A JP 2004-107562 A

  However, when the film described in Patent Document 1 is used as an interlayer insulating film, it is necessary to hydrolyze polysilazane to convert the polysilazane structure into a polysiloxane structure. At this time, there is a problem that the hydrolysis does not proceed sufficiently if the moisture in the film is insufficient. Furthermore, in the hydrolysis of polysilazane, highly volatile ammonia is generated, which causes problems such as corrosion of the production apparatus.

  In addition, an interlayer insulating film formed from a composition containing a siloxane resin described in Patent Document 2 and a compound that generates an acid or a base upon irradiation with radiation has a problem that heat resistance and resolution are not sufficient. is there.

  Therefore, the present invention is a photosensitive resin film in which the formation of a silica-based film that can be used as an interlayer insulating film is relatively easy, the process margin is excellent, and the formed silica-based film is excellent in resolution and heat resistance. It is an object of the present invention to provide a method for forming a silica film and a method for forming a silica-based film using the same. Furthermore, an object of the present invention is to provide a semiconductor device, a flat display device, and a member for an electronic device provided with a silica-based film formed by the method.

［式（１）中、Ｒ^１は、Ｈ原子若しくはＦ原子、又は、Ｂ原子、Ｎ原子、Ａｌ原子、Ｐ原子、Ｓｉ原子、Ｇｅ原子若しくはＴｉ原子を含む基、又は有機基を示し、Ｘは加水分解性基を示し、ｎは０〜２の整数を示し、同一分子内の複数のＸは同一でも異なっていてもよく、ｎが２であるとき、同一分子内の複数のＲ^１は同一でも異なっていてもよい。］ In order to achieve the above object, the present invention comprises (a) component: a siloxane resin obtained by hydrolytic condensation of a silane compound containing a compound represented by the following general formula (1), and (b) component: ( a step of applying a photosensitive resin composition containing a solvent in which component a is dissolved and component (c): naphthoquinonediazide sulfonic acid ester on a substrate and then vacuum drying to form a photosensitive resin film; A method for forming a photosensitive resin film is provided.

[In Formula (1), R ¹ represents a group containing an H atom or F atom, or a B atom, N atom, Al atom, P atom, Si atom, Ge atom or Ti atom, or an organic group, and Represents a hydrolyzable group, n represents an integer of 0 to 2, a plurality of X in the same molecule may be the same or different, and when n is 2, a plurality of R ¹ in the same molecule is It may be the same or different. ]

  Since a siloxane resin is used as a constituent component of the photosensitive resin composition, the method described in Patent Document 1 can omit the step of converting an essential polysilazane structure into a polysiloxane structure. A silica-based film can be formed.

  Furthermore, after applying the photosensitive resin composition to the substrate, it is possible to obtain a photosensitive resin film in which the difference in dissolution rate between the unexposed part and the exposed part in the alkaline aqueous solution increases by drying under reduced pressure conditions. Therefore, it is possible to form a silica-based coating film that has an excellent process margin and also has excellent resolution and heat resistance. The reason why such an effect can be obtained by the silica-based film formed from the photosensitive resin film of the present invention is not necessarily clear, but the present inventors consider as follows.

  That is, in such a photosensitive resin composition, since the component (a) is excellent in heat resistance, the formed silica-based film is considered to be excellent in heat resistance. In addition, since the compound represented by the general formula (1) has a hydrolyzable group, the siloxane resin obtained by hydrolyzing it has a silanol group, so that it is soluble in an alkaline aqueous solution. Is expensive. Here, in order to form a patterned silica-based coating, it is necessary to increase the difference in solubility in the alkaline aqueous solution between the unexposed portion and the exposed portion of the coating, and the larger the difference, the better the resolution. It will be a thing. After the photosensitive resin composition is applied to a substrate, the solvent contained in the photosensitive resin film is reduced by drying under reduced pressure, and the naphthoquinone diazide sulfonic acid ester compound that is a silanol group in the siloxane resin and a photosensitive agent Is promoted, and the solubility of the unexposed portion in the alkaline aqueous solution is significantly reduced. This is presumably because the silanol group is protected by the naphthoquinone diazide sulfonic acid ester compound, so that the solubility in an alkaline aqueous solution is lowered. On the other hand, the exposed portion can be easily dissolved in an alkaline aqueous solution during development by a photoreaction of a naphthoquinone diazide sulfonic acid ester compound. For this reason, it is considered that the difference in solubility between the unexposed area and the exposed area with respect to the aqueous alkali solution is increased, the resolution is improved, and the influence of process conditions (temperature, etc.) is less likely. And the effect mentioned above can be expressed effectively and the silica-type film which was especially excellent in process margin, resolution, and heat resistance can be formed.

  The photosensitive resin composition preferably further contains (d) component: a siloxane resin obtained by hydrolytic condensation of a compound represented by the following general formula (2). Thereby, the photosensitive resin film excellent in a softness | flexibility can be formed, and the crack tolerance of the silica-type film finally formed improves.

［式（２）中、Ｒ^２は有機基を示し、Ａは２価の有機基を示し、Ｘは加水分解性基を示し、同一分子内の複数のＸは同一でも異なっていてもよい。］

[In Formula (2), R ² represents an organic group, A represents a divalent organic group, X represents a hydrolyzable group, and a plurality of X in the same molecule may be the same or different. ]

  The component (b) preferably contains at least one solvent selected from the group consisting of ether acetate solvents, ether solvents, ester solvents, alcohol solvents, and ketone solvents. Thereby, the coating nonuniformity and repelling at the time of apply | coating this photosensitive resin composition on a board | substrate can be suppressed, and also a solvent can be easily removed under vacuum.

  The component (c) is preferably an ester of a monovalent or polyhydric alcohol and naphthoquinone diazide sulfonic acid. Thereby, the transparency of the silica-type film formed from this photosensitive resin composition improves.

  The present invention also provides a heat treatment step for further obtaining a coating film by heat-treating the photosensitive resin film produced by the method for forming the photosensitive resin film at normal pressure, and a first exposure step for exposing a predetermined portion of the coating film. And a method of forming a silica-based coating, comprising: a removing step of removing the exposed predetermined portion of the coating film; and a heating step of heating the coating film from which the predetermined portion has been removed. According to such a method for forming a silica-based film, since the above-described photosensitive resin film is used, it is possible to obtain a silica-based film that is excellent in process margin and further excellent in resolution and heat resistance.

  The present invention also provides a heat treatment step for further obtaining a coating film by heat-treating the photosensitive resin film produced by the method for forming the photosensitive resin film at normal pressure, and a first exposure step for exposing a predetermined portion of the coating film. A removal step of removing the exposed predetermined portion of the coating film, a second exposure step of exposing the coating film from which the predetermined portion has been removed, and a heating step of heating the coating film from which the predetermined portion has been removed. A method for forming a silica-based coating having According to such a method for forming a silica-based film, since the above-described photosensitive resin composition is used, it is possible to obtain a silica-based film that is excellent in process margin and further excellent in resolution and heat resistance. Furthermore, the component (c) having optical absorption in the visible light region is decomposed in the second exposure step, and a compound having sufficiently small optical absorption in the visible light region is generated. Therefore, the transparency of the resulting silica-based coating is improved.

  The present invention provides a semiconductor device, a flat panel display device, and an electronic device member comprising a substrate and a silica-based film formed on the substrate by the above-described forming method. Since these semiconductor devices, flat display devices, and electronic device members include the silica-based coating formed from the above-described photosensitive resin film as an interlayer insulating film, they exhibit excellent effects.

  According to the present invention, a photosensitive resin in which the formation of a silica-based film that can be used as an interlayer insulating film is relatively easy, the process margin is excellent, and the formed silica-based film is excellent in resolution and heat resistance. A method for forming a film and a method for forming a silica-based film using the same can be provided. In addition, the silica-based film formed from the photosensitive resin film of the present invention is excellent in insulating properties, low dielectric properties and, in some cases, transparency, and can be easily thickened. Furthermore, this invention can provide a semiconductor device, a flat display apparatus, and a member for electronic devices provided with the silica-type film formed by the said silica-type film formation method.

  Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings as the case may be. However, the present invention is not limited to the following embodiments. In the drawings, the same or corresponding parts are denoted by the same reference numerals, and redundant description is omitted.

  In the present specification, the weight average molecular weight is measured by gel permeation chromatography (hereinafter referred to as “GPC”) and converted using a standard polystyrene calibration curve.

Here, the weight average molecular weight (Mw) can be measured using GPC under the following conditions, for example.
(conditions)
Sample: 10 μL
Standard polystyrene: Standard polystyrene manufactured by Tosoh Corporation (molecular weight: 190000, 17900, 9100, 2980, 578, 474, 370, 266)
Detector: manufactured by Hitachi, Ltd., RI-monitor, trade name “L-3000”
Integrator: Hitachi, Ltd., GPC integrator, product name “D-2200”
Pump: manufactured by Hitachi, Ltd., trade name “L-6000”
Degassing device: Showa Denko Co., Ltd., trade name "Shodex DEGAS"
Column: Hitachi Chemical Co., Ltd., trade names “GL-R440”, “GL-R430”, “GL-R420” connected in this order and used as eluent: tetrahydrofuran (THF)
Measurement temperature: 23 ° C
Flow rate: 1.75 mL / min Measurement time: 45 minutes

(Photosensitive resin composition)
The photosensitive resin composition according to the present invention contains a component (a), a component (b) and a component (c), and preferably further contains a component (d). Hereinafter, each component will be described.

<(A) component>
The component (a) is a siloxane resin obtained by hydrolytic condensation of a silane compound containing a compound represented by the following general formula (1).

［式（１）中、Ｒ^１は、Ｈ原子若しくはＦ原子、又は、Ｂ原子、Ｎ原子、Ａｌ原子、Ｐ原子、Ｓｉ原子、Ｇｅ原子若しくはＴｉ原子を含む基、又は有機基を示し、Ｘは加水分解性基を示し、ｎは０〜２の整数を示し、同一分子内の複数のＸは同一でも異なっていてもよく、ｎが２であるとき、同一分子内の複数のＲ^１は同一でも異なっていてもよい。］

[In Formula (1), R ¹ represents a group containing an H atom or F atom, or a B atom, N atom, Al atom, P atom, Si atom, Ge atom or Ti atom, or an organic group, and Represents a hydrolyzable group, n represents an integer of 0 to 2, a plurality of X in the same molecule may be the same or different, and when n is 2, a plurality of R ¹ in the same molecule is It may be the same or different. ]

In the formula (1), examples of the organic group represented by R ² include an amino group, an aromatic ring, a group having an amino group or an epoxy group, an alicyclic hydrocarbon group, and an alkyl group having 1 to 20 carbon atoms. It is done. Among these, a group having an amino group or an epoxy group and a methyl group are preferable from the viewpoint of adhesiveness.

In the formula (1), the organic group having 1 to 20 carbon atoms represented by R ¹ may have, for example, an aliphatic hydrocarbon group which may have a substituent and a substituent. An aromatic hydrocarbon group is mentioned. Among these, a linear or branched aliphatic hydrocarbon group having 1 to 6 carbon atoms, a group in which a part thereof is substituted with an F atom, and a phenyl group are preferable.

  In the formula (1), examples of the hydrolyzable group represented by X include an alkoxy group, a halogen atom, an acetoxy group, an isocyanate group, and a hydroxyl group. Among these, an alkoxy group is preferable from the viewpoint of liquid stability of the composition itself, coating characteristics, and the like.

  Examples of the compound (alkoxysilane) of the general formula (1) in which the hydrolyzable group X is an alkoxy group include tetraalkoxysilane, trialkoxysilane, and diorganodialkoxysilane.

  Examples of the tetraalkoxysilane include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-iso-propoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane, and tetra-tert-butoxysilane. And tetraphenoxysilane.

  Examples of the trialkoxysilane include trimethoxysilane, triethoxysilane, tripropoxysilane, fluorotrimethoxysilane, fluorotriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, and methyltri-iso. -Propoxysilane, methyltri-n-butoxysilane, methyltri-iso-butoxysilane, methyltri-tert-butoxysilane, methyltriphenoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltri-n-propoxysilane, ethyltri-iso -Propoxysilane, ethyltri-n-butoxysilane, ethyltri-iso-butoxysilane, ethyltri-tert-butoxysilane, ethyltriphenoxy N-propyltrimethoxysilane, n-propyltriethoxysilane, n-propyltri-n-propoxysilane, n-propyltri-iso-propoxysilane, n-propyltri-n-butoxysilane, n-propyltri -Iso-butoxysilane, n-propyltri-tert-butoxysilane, n-propyltriphenoxysilane, iso-propyltrimethoxysilane, iso-propyltriethoxysilane, iso-propyltri-n-propoxysilane, iso-propyl Tri-iso-propoxysilane, iso-propyltri-n-butoxysilane, iso-propyltri-iso-butoxysilane, iso-propyltri-tert-butoxysilane, iso-propyltriphenoxysilane, n-butyltrimethyl Xylsilane, n-butyltriethoxysilane, n-butyltri-n-propoxysilane, n-butyltri-iso-propoxysilane, n-butyltri-n-butoxysilane, n-butyltri-iso-butoxysilane, n-butyltri-tert -Butoxysilane, n-butyltriphenoxysilane, sec-butyltrimethoxysilane, sec-butyltriethoxysilane, sec-butyltri-n-propoxysilane, sec-butyltri-iso-propoxysilane, sec-butyltri-n-butoxy Silane, sec-butyltri-iso-butoxysilane, sec-butyltri-tert-butoxysilane, sec-butyltriphenoxysilane, t-butyltrimethoxysilane, t-butyltriethoxysilane, t-butylto Ri-n-propoxysilane, t-butyltri-iso-propoxysilane, t-butyltri-n-butoxysilane, t-butyltri-iso-butoxysilane, t-butyltri-tert-butoxysilane, t-butyltriphenoxysilane, Phenyltrimethoxysilane, phenyltriethoxysilane, phenyltri-n-propoxysilane, phenyltri-iso-propoxysilane, phenyltri-n-butoxysilane, phenyltri-iso-butoxysilane, phenyltri-tert-butoxysilane, Phenyltriphenoxysilane, trifluoromethyltrimethoxysilane, pentafluoroethyltrimethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxy Run, and the like.

  Examples of the diorganodialkoxysilane include dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldi-n-propoxysilane, dimethyldi-iso-propoxysilane, dimethyldi-n-butoxysilane, dimethyldi-sec-butoxysilane, and dimethyldi-tert. -Butoxysilane, dimethyldiphenoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethyldi-n-propoxysilane, diethyldi-iso-propoxysilane, diethyldi-n-butoxysilane, diethyldi-sec-butoxysilane, diethyldi-tert- Butoxysilane, diethyldiphenoxysilane, di-n-propyldimethoxysilane, di-n-propyldiethoxysilane, di-n-propyldi-n-propoxy Di-n-propyldi-iso-propoxysilane, di-n-propyldi-n-butoxysilane, di-n-propyldi-sec-butoxysilane, di-n-propyldi-tert-butoxysilane, di-n- Propyl diphenoxy silane, di-iso-propyl dimethoxy silane, di-iso-propyl diethoxy silane, di-iso-propyl di-n-propoxy silane, di-iso-propyl di-iso-propoxy silane, di-iso-propyl di- n-butoxysilane, di-iso-propyldi-sec-butoxysilane, di-iso-propyldi-tert-butoxysilane, di-iso-propyldiphenoxysilane, di-n-butyldimethoxysilane, di-n-butyldi Ethoxysilane, di-n-butyldi-n-propoxy Silane, di-n-butyldi-iso-propoxysilane, di-n-butyldi-n-butoxysilane, di-n-butyldi-sec-butoxysilane, di-n-butyldi-tert-butoxysilane, di-n- Butyldiphenoxysilane, di-sec-butyldimethoxysilane, di-sec-butyldiethoxysilane, di-sec-butyldi-n-propoxysilane, di-sec-butyldi-iso-propoxysilane, di-sec-butyldi- n-butoxysilane, di-sec-butyldi-sec-butoxysilane, di-sec-butyldi-tert-butoxysilane, di-sec-butyldiphenoxysilane, di-tert-butyldimethoxysilane, di-tert-butyldi Ethoxysilane, di-tert-butyldi-n-propoxysila Di-tert-butyldi-iso-propoxysilane, di-tert-butyldi-n-butoxysilane, di-tert-butyldi-sec-butoxysilane, di-tert-butyldi-tert-butoxysilane, di-tert- Butyldiphenoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldi-n-propoxysilane, diphenyldi-iso-propoxysilane, diphenyldi-n-butoxysilane, diphenyldi-sec-butoxysilane, diphenyldi-tert -Butoxysilane, diphenyldiphenoxysilane, bis (3,3,3-trifluoropropyl) dimethoxysilane, methyl (3,3,3-trifluoropropyl) dimethoxysilane.

Examples of the compound represented by the general formula (1) in which X is an alkoxy group and R ² is an organic group having 1 to 20 carbon atoms include, for example, bis (trimethoxysilyl) methane in addition to the above compounds. Bis (triethoxysilyl) methane, bis (tri-n-propoxysilyl) methane, bis (tri-iso-propoxysilyl) methane, bis (trimethoxysilyl) ethane, bis (triethoxysilyl) ethane, bis (tri -N-propoxysilyl) ethane, bis (tri-iso-propoxysilyl) ethane, bis (trimethoxysilyl) propane, bis (triethoxysilyl) propane, bis (tri-n-propoxysilyl) propane, bis (tri- iso-propoxysilyl) propane, bis (trimethoxysilyl) benzene, bis (triethoxysilyl) ) Bissilylalkanes such as benzene, bis (tri-n-propoxysilyl) benzene, bis (tri-iso-propoxysilyl) benzene, and bissilylbenzene.

Examples of the compound represented by the general formula (1) in which X is an alkoxy group and R ² is a group having an aromatic ring include, for example, bis (trimethoxysilyl) benzene, bis (triethoxy Bissilylbenzene such as silyl) benzene, bis (tri-n-propoxysilyl) benzene, bis (triisopropoxysilyl) benzene and the like can be mentioned.

Examples of the compound represented by the general formula (1) in which X is an alkoxy group and R ² is a group having an amino group include 4-aminobutyltriethoxysilane, N- (2-aminoethyl)- 3-aminoisobutylmethylmethoxysilane, (aminoethylaminomethyl) phenethyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltri Methoxysilane, N- (6-aminohexyl) aminopropyltrimethoxysilane, 3- (m-aminophenoxy) propyltrimethoxysilane, aminophenyltrimethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-aminopropyltri Ethoxysilane, 3-aminopropyltrimethoxysilane , 6-azidosulfonylhexyltriethoxysilane and the like.

Examples of the compound represented by the general formula (1) in which X is an alkoxy group and R ² is a group having an epoxy group include 5,6-epoxyhexyltriethoxysilane, (3-glycidoxypropyl) ) Methyldiethoxysilane, (3-glycidoxypropyl) methyldimethoxysilane, (3-glycidoxypropyl) trimethoxysilane and the like.

  Among these compounds represented by the general formula (1), tetraethoxysilane, 3-aminopropyltriethoxysilane, and (3-glycidoxypropyl) methyldiethoxysilane are particularly preferable from the viewpoint of adhesiveness. . From the same viewpoint, a compound in which n is 0 is preferable, and tetraalkoxysilane is particularly preferable.

  These compounds represented by the general formula (1) are used singly or in combination of two or more.

  The hydrolysis condensation of the compound represented by the above general formula (1) can be performed, for example, under the following conditions.

  First, the amount of water used in the hydrolysis condensation is preferably 0.1 to 1000 mol, more preferably 0.5 to 100 mol, per 1 mol of the compound represented by the general formula (1). . If the amount of water is less than 0.1 mol, the hydrolysis-condensation reaction tends not to proceed sufficiently, and if the amount of water exceeds 1000 mol, gelation tends to occur during hydrolysis or condensation.

  In addition, a catalyst may be used in the hydrolysis condensation. As the catalyst, for example, an acid catalyst, an alkali catalyst, or a metal chelate compound can be used. Among these, an acid catalyst is preferable from the viewpoint of preventing gelation of the compound represented by the general formula (1).

  Examples of the acid catalyst include organic acids and inorganic acids. Examples of organic acids include formic acid, maleic acid, fumaric acid, phthalic acid, malonic acid, succinic acid, tartaric acid, malic acid, lactic acid, citric acid, acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid , Octanoic acid, nonanoic acid, decanoic acid, oxalic acid, adipic acid, sebacic acid, butyric acid, oleic acid, stearic acid, linoleic acid, linolenic acid, salicylic acid, benzenesulfonic acid, benzoic acid, p-aminobenzoic acid, p- Toluenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, trifluoroethanesulfonic acid and the like can be mentioned. Examples of the inorganic acid include hydrochloric acid, phosphoric acid, nitric acid, boric acid, sulfuric acid, and hydrofluoric acid. These are used singly or in combination of two or more. Further, the catalyst after hydrolysis condensation may be removed or deactivated in the same manner as described above.

  Examples of the alkali catalyst include inorganic alkalis and organic alkalis. Examples of the inorganic alkali include sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide and the like. Examples of the organic alkali include pyridine, monoethanolamine, diethanolamine, triethanolamine, dimethylmonoethanolamine, monomethyldiethanolamine, ammonia, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, methylamine, and ethylamine. , Propylamine, butylamine, pentylamine, hexylamine, hebutylamine, octylamine, nonylamine, decylamine, undecylamine, dodecylamine, cyclopentylamine, cyclohexylamine, N, N-dimethylamine, N, N-diethylamine, N , N-dipropylamine, N, N-dibutylamine, N, N-dipentylamine, , N-dihexylamine, N, N-dicyclopentylamine, N, N-dicyclohexylamine, trimethylamine, triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, tricyclopentylamine, tricyclohexylamine, etc. It is done. These are used singly or in combination of two or more.

  Examples of the metal chelate compound include trimethoxy mono (acetyl acetonate) titanium, triethoxy mono (acetyl acetonate) titanium, tri-n-propoxy mono (acetyl acetonate) titanium, tri-iso-propoxy mono ( Acetyl acetonate) titanium, tri-n-butoxy mono (acetyl acetonate) titanium, tri-sec-butoxy mono (acetyl acetonate) titanium, tri-tert-butoxy mono (acetyl acetonate) titanium, dimethoxy Mono (acetylacetonate) titanium, diethoxy-di (acetylacetonate) titanium, di-n-propoxy-di (acetylacetonate) titanium, diiso-propoxy-di (acetylacetonate) titanium, di-n-butoxy-di (Acetylacetonate) titanium, di-s c-butoxy-di (acetylacetonate) titanium, ditert-butoxy-di (acetylacetonate) titanium, monomethoxy-tris (acetylacetonate) titanium, monoethoxy-tris (acetylacetonate) titanium, mono-n- Propoxy tris (acetyl acetonate) titanium, mono iso-propoxy tris (acetyl acetonate) titanium, mono n-butoxy tris (acetyl acetonate) titanium, mono sec-butoxy tris (acetyl acetonate) titanium, mono tert-butoxy-tris (acetylacetonate) titanium, tetrakis (acetylacetonate) titanium, trimethoxy-mono (ethylacetoacetate) titanium, triethoxy-mono (ethylacetoacetate) titanium, tri-n-propoxy-mono (ethyl) Acetoacetate) titanium, tri-iso-propoxy mono (ethyl acetoacetate) titanium, tri-n-butoxy mono (ethyl acetoacetate) titanium, tri-sec-butoxy mono (ethyl acetoacetate) titanium, tri-tert -Butoxy mono (ethyl acetoacetate) titanium, dimethoxy mono (ethyl acetoacetate) titanium, diethoxy di (ethyl acetoacetate) titanium, di-n-propoxy di (ethyl acetoacetate) titanium, diiso-propoxy di (Ethyl acetoacetate) titanium, di-n-butoxy di (ethyl acetoacetate) titanium, disec-butoxy di (ethyl acetoacetate) titanium, di tert-butoxy di (ethyl acetoacetate) titanium, monomethoxy Lith (ethyl acetoacetate) titanium, monoethoxy tris (ethyl acetoacetate) titanium, mono n-propoxy tris (ethyl acetoacetate) titanium, monoiso-propoxy tris (ethyl acetoacetate) titanium, mono n-butoxy Metal chelate compounds having titanium such as tris (ethyl acetoacetate) titanium, mono sec-butoxy tris (ethyl acetoacetate) titanium, mono tert-butoxy tris (ethyl acetoacetate) titanium, tetrakis (ethyl acetoacetate) titanium, Examples thereof include compounds in which titanium of the metal chelate compound having titanium is substituted with zirconium, aluminum, or the like. These are used singly or in combination of two or more.

  The amount of such a catalyst used is preferably in the range of 0.0001 to 1 mol with respect to 1 mol of the compound represented by the general formula (1). If the amount used is less than 0.0001 mol, the reaction does not proceed substantially, and if it exceeds 1 mol, gelation tends to be promoted during hydrolysis condensation.

  In addition, when the above-mentioned catalyst is used in hydrolysis condensation, there is a possibility that the stability of the obtained photosensitive resin composition may be deteriorated, or that the influence of corrosion on other materials may be caused by including the catalyst. There is sex. Such adverse effects can be eliminated, for example, by removing the catalyst from the photosensitive resin composition after hydrolytic condensation, or by reacting the catalyst with other compounds to deactivate the function as a catalyst. it can. As a method for carrying out these operations, a conventionally known method can be used. Examples of the method for removing the catalyst include a distillation method and an ion chromatography column method. Moreover, as a method of deactivating the function as a catalyst by reacting the catalyst with another compound, for example, when the catalyst is an acid catalyst, a method of adding a base and neutralizing by an acid-base reaction can be mentioned.

  In addition, alcohol is by-produced during such hydrolysis condensation. Since this alcohol is a protic solvent and may adversely affect the physical properties of the photosensitive resin composition, it is preferably removed using an evaporator or the like.

  The siloxane resin thus obtained preferably has a weight average molecular weight of 500 to 1,000,000, more preferably 500 to 500,000 from the viewpoints of solubility in a solvent, mechanical properties, moldability, and the like. More preferably, it is 500-100000, It is especially preferable that it is 500-10000, It is very preferable that it is 500-5000. If this weight average molecular weight is 500 or more, the film-forming property of a silica-type film will improve, and if it is 1000000 or less, it will be excellent in compatibility with a solvent.

<(B) component>
The component (b) is a solvent that dissolves the component (a). Specific examples thereof include aprotic solvents and protic solvents. These may be used alone or in combination of two or more.

  Examples of the aprotic solvent include acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-iso-propyl ketone, methyl-n-butyl ketone, methyl-iso-butyl ketone, methyl-n-pentyl ketone, methyl-n- Hexyl ketone, diethyl ketone, dipropyl ketone, di-iso-butyl ketone, trimethylnonanone, cyclohexanone, cyclopentanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone, γ-butyrolactone, γ-valerolactone, etc. Ketone solvents; diethyl ether, methyl ethyl ether, methyl di-n-propyl ether, diisopropyl ether, tetrahydrofuran, methyltetrahydrofuran, dioxane, dimethyldioxane, ethylene glycol Dimethyl ether, ethylene glycol diethyl ether, ethylene glycol di-n-propyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol methyl mono-n-propyl ether, diethylene glycol methyl mono-n-butyl ether, Diethylene glycol di-n-propyl ether, diethylene glycol di-n-butyl ether, diethylene glycol methyl mono-n-hexyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, triethylene glycol methyl ethyl ether, triethylene glycol methyl mono-n- The Ether, triethylene glycol di-n-butyl ether, triethylene glycol methyl mono-n-hexyl ether, tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether, tetradiethylene glycol methyl ethyl ether, tetraethylene glycol methyl mono-n-butyl ether, diethylene glycol Di-n-butyl ether, tetraethylene glycol methyl mono-n-hexyl ether, tetraethylene glycol di-n-butyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol di-n-propyl ether, propylene glycol dibutyl ether, di Propylene glycol dimethyl ether, dipropylene Recall diethyl ether, dipropylene glycol methyl ethyl ether, dipropylene glycol methyl mono-n-butyl ether, dipropylene glycol di-n-propyl ether, dipropylene glycol di-n-butyl ether, dipropylene glycol methyl mono-n-hexyl ether , Tripropylene glycol dimethyl ether, tripropylene glycol diethyl ether, tripropylene glycol methyl ethyl ether, tripropylene glycol methyl mono-n-butyl ether, tripropylene glycol di-n-butyl ether, tripropylene glycol methyl mono-n-hexyl ether, tetra Propylene glycol dimethyl ether, tetrapropylene glycol diethyl ether, tetradipro Ether solvents such as pyrene glycol methyl ethyl ether, tetrapropylene glycol methyl mono-n-butyl ether, dipropylene glycol di-n-butyl ether, tetrapropylene glycol methyl mono-n-hexyl ether, tetrapropylene glycol di-n-butyl ether; Methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methyl pentyl acetate, 2-acetate Ethylbutyl, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methyl cyclohexyl acetate, nonyl acetate, methyl acetoacetate, ethyl acetoacetate, diethylene glycol monomethyl ether, vinegar Diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, glycol diacetate, methoxytriglycol acetate, ethyl propionate, n-butyl propionate, isoamyl propionate Ester solvents such as diethyl oxalate, di-n-butyl oxalate; ethylene glycol methyl ether propionate, ethylene glycol ethyl ether propionate, ethylene glycol methyl ether acetate, ethylene glycol ethyl ether acetate, diethylene glycol methyl ether acetate , Diethylene glycol ethyl ether acetate, diethylene glycol-n-butyl Ether acetate solvents such as ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, dipropylene glycol methyl ether acetate, dipropylene glycol ethyl ether acetate; acetonitrile, N-methylpyrrolidinone, N-ethyl Examples include pyrrolidinone, N-propylpyrrolidinone, N-butylpyrrolidinone, N-hexylpyrrolidinone, N-cyclohexylpyrrolidinone, N, N-dimethylformamide, N, N-dimethylacetamide, N, N-dimethylsulfoxide, toluene and xylene. Among these, an ether solvent, an ether acetate solvent, and a ketone solvent are preferable from the viewpoints that the formed silica-based film can be thickened and the solution stability of the photosensitive resin composition is improved. Among these, from the viewpoint of suppressing coating unevenness and repellency, an ether acetate solvent is most preferable, an ether solvent is next preferable, and a ketone solvent is next preferable. These may be used alone or in combination of two or more.

  Examples of the protic solvent include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-pentanol, isopentanol, 2-methylbutanol, sec-pen. Tanol, tert-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, sec-heptanol, n-octanol, 2-ethylhexanol, sec-octanol, n- Nonyl alcohol, n-decanol, sec-undecyl alcohol, trimethylnonyl alcohol, sec-tetradecyl alcohol, sec-heptadecyl alcohol, phenol, cyclohexanol, methyl chloride Alcohol solvents such as lohexanol, benzyl alcohol, ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol; ethylene glycol methyl ether, ethylene glycol ethyl Ether, ethylene glycol monophenyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol mono-n-hexyl ether, ethoxytriglycol, tetraethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether, Dipropylene glycol monomethyl ether , Dipropylene glycol monoethyl ether, ether solvents such as tripropylene glycol monomethyl ether; methyl lactate, ethyl lactate, n- butyl, ester solvents such as lactic acid n- amyl. Among these, alcohol-based solvents are preferable from the viewpoint of storage stability. Furthermore, ethanol, isopropyl alcohol, and propylene glycol propyl ether are preferable from the viewpoint of suppressing coating unevenness and repellency. These may be used alone or in combination of two or more.

  The type of the component (b) can be appropriately selected according to the types of the component (a), the component (c) and the component (d). For example, when the component (c) described later is an ester of naphthoquinone diazide sulfonic acid and a phenol and has low solubility in an aliphatic hydrocarbon solvent, an aromatic hydrocarbon solvent such as toluene is appropriately used. You can choose.

  The blending amount of the component (b) can be appropriately adjusted according to the types of the component (a), the component (b), and the component (d). For example, the solid content of the photosensitive resin composition 0.1-90 mass parts can be used with respect to 100 mass parts of the whole.

  As a method of adding the component (b) to the photosensitive resin composition, a conventionally known method can be used. Specific examples thereof include a method used as a solvent in preparing the component (a), a method of adding the component (a) after addition, a method of exchanging the solvent, and the component (a) removed by distilling off the solvent. The method etc. which add (b) component later are mentioned.

<(C) component>
(C) A component is a naphthoquinone diazide sulfonate ester. This component is for imparting positive photosensitivity to the photosensitive resin composition. Positive photosensitivity is manifested, for example, as follows.

  That is, the naphthoquinone diazide group contained in the naphthoquinone diazide sulfonate ester does not inherently exhibit solubility in an alkali developer, and further inhibits dissolution of the siloxane resin in the alkali developer. However, when irradiated with ultraviolet rays or visible light, the naphthoquinone diazide group changes to an indenecarboxylic acid structure and exhibits high solubility in an alkaline developer. Therefore, by incorporating the component (c), positive photosensitivity in which the exposed portion is removed by the alkali developer is developed.

  Examples of naphthoquinone diazide sulfonic acid esters include esters of naphthoquinone diazide sulfonic acid and phenols or alcohols. Among these, from the viewpoint of compatibility with the component (a) and transparency (sensitivity) of the silica-based coating formed, naphthoquinonediazidesulfonic acid, monovalent or polyhydric alcohols, phenols, or one or more An ester with an alcohol having an aryl group is preferable, and a monovalent or polyhydric alcohol and an ester are more preferable. Examples of naphthoquinonediazide sulfonic acid include naphthoquinone-1,2-diazide-5-sulfonic acid, naphthoquinone-1,2-diazide-4-sulfonic acid, and derivatives thereof.

  Specific examples of phenols and alcohols having an aryl group include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, p-ethylphenol, 2,3-xylenol, and 2,5-xylenol. 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, o-isopropylphenol, p-isopropylphenol, mesitol, o-propylphenol, m-propylphenol, p-propylphenol, 2,3, 5 trimethylphenol, 2,3,6 trimethylphenol, 2,4,6 trimethylphenol, o-methoxyphenol, m-methoxyphenol, p-methoxyphenol, o-ethoxyphenol, m-ethoxyphenol, p-ethoxyphenol, 2-Met Si-4-methylphenol, 2-methoxy-5-methylphenol, 3-methoxy-5-methylphenol, salicylic acid, methyl salicylate, ethyl salicylate, isopropyl salicylate, isobutyl salicylate, 4-hydroxycoumarin, 7-hydroxycoumarin, benzyl Alcohol, o-methylbenzyl alcohol, m-methylbenzyl alcohol, p-methylbenzyl alcohol, o-methoxybenzyl alcohol, m-methoxybenzyl alcohol, phenethyl alcohol, 2,5-dimethylbenzyl alcohol, 3,5-dimethylbenzyl alcohol 1- (2-methylphenyl) ethanol, 1- (4-methylphenyl) ethanol, 2-phenoxyethanol, 2- (4-methylphenyl) ethanol, 2- (p-tolyl) Ethanol, 1-phenyl-1-propanol, 2-phenyl-1-propanol, 2-phenyl-2-propanol, 3-phenyl-1-propanol, p-xylene-α, α'-diol, o-tert-butylphenol M-tert-butylphenol, p-tert-butylphenol, p-sec-butylphenol, 6-tert-butyl-m-cresol, 2-tert-butyl-p-cresol, o-cyclohexylphenol, 2,4-di- tert-butylphenol, 2,6-di-tert-butylphenol, o-allylphenol, 2,6-diisopropylphenol, 2,4,6-trimethylphenol, 2-isopropyl-5-methylphenol, 4-isopropyl-3- Methylphenol, 4-ter -Butyl-2-methylphenol, 2-tert-butyl-6-methylphenol, catechol, resorcinol, hydroquinone, 2,3-dihydroxytoluene, 2,6-dihydroxytoluene, 3,4-dihydroxytoluene, 3,5- Dihydroxytoluene, salicyl alcohol, o-hydroxybenzyl alcohol, m-hydroxybenzyl alcohol, p-hydroxybenzyl alcohol, 1,2-benzenedimethanol, 1,3-benzenedimethanol, 1,4-benzenedimethanol, 2 , 6-bis (hydroxymethyl) -p-cresol, 2,4-bis (hydroxymethyl) -m-cresol, 2,4,6-tris (hydroxymethyl) phenol, 1-naphthol, 2-naphthol, (1 , 3) -dihydroxynaphthalene, (1,4) -dihydroxynaphthalene, (1,5) -dihydroxynaphthalene, (1,6) -dihydroxynaphthalene, (2,3) -dihydroxynaphthalene, (2,6) -dihydroxynaphthalene, (2,7) -Dihydroxynaphthalene, 1-naphthalenemethanol, 2-naphthalenemethanol, 7-methoxy-2-naphthol, 4-methoxy-1-naphthol, 1- (1-naphthyl) ethanol, 1- (2-naphthyl) ethanol, 2- (1-naphthyl) ethanol, 1,4-naphthalenediethanol, 2,3-naphthalenediethanol, 2- (2-naphthoxy) ethanol, 2-hydroxybiphenyl, 3-hydroxybiphenyl, 4-hydroxybiphenyl, 2-biphenyl Ethanol, 4-biphenylmethanol, 2-benzylphenol Diol, benzhydrol, 2-methyl-3-biphenylmethanol, 1,1-diphenylethanol, 2,2-diphenylethanol, 1- (4-biphenylyl) ethanol, 2,2-bis (4-hydroxy) propane, 1,3-diphenoxypropan-2-ol, p-cumylphenol, 2- (4-biphenylyl) -2-propanol, 4- (4-biphenyl) -2-butanol, (2,3) biphenyldiol, (2,2 ′) biphenyldiol, (4,4 ′) biphenyldiol, 3-phenoxybenzyl alcohol, 4-4 ′ methylenediphenol, 2-benzyloxyphenol, 4-benzyloxyphenol, 1,2-diphenyl- 1,2-ethanediol, 4,4′-ethylidene diphenol, 4-benzyloxybenzene Dil alcohol, 1,3-diphenoxy-2-propanol, 4,4′-dimethoxybenzhydrol, 1′-hydroxy-2′-acetonaphthone, 1-acetonaphthol, 2,3,4-trihydroxydiphenylmethane, 4- Hydroxybiphenyl, 4-hydroxy-4′-propoxybiphenyl, 4-hydroxy-4′-butoxybiphenyl, diphenylmethane-2,4-diol, 4,4 ′, 4 ″ -trihydroxytriphenylmethane, 4,4 ′ -(1- (p- (4-hydroxy-α, α-dimethylbenzyl) phenyl) ethylidene) diphenol, 4,4 '-(2-hydroxybenzylidene) bis (2,3,6-trimethylphenol), 2 , 6-Bis (2-hydroxy-5-methylbenzyl) p-cresol, 1,1,1-tri (P- hydroxyphenyl) ethane, include 1,1,2,2-tetrakis (p- hydroxyphenyl) ethane.

  In addition, examples of phenols include the following compounds (all are trade names manufactured by Honshu Chemical Industry Co., Ltd.).

  As monovalent or polyhydric alcohols, those having 3 to 20 carbon atoms are preferred. When the carbon number of the monohydric or polyhydric alcohol is 1 or 2, the corresponding sulfonic acid ester can include naphthoquinone diazide sulfonic acid methyl ester, naphthoquinone diazide sulfonic acid ethyl ester, and the like. In addition, since the alkyl group portion is small and the crystallinity is high, it is likely to precipitate in the photosensitive resin composition solution, and the compatibility with the component (a) tends to be poor and mixing at a sufficient concentration tends to be impossible. In addition, when the number of carbon atoms of the monohydric or polyhydric alcohol exceeds 20, the proportion of the naphthoquinone diazide moiety in the naphthoquinone diazide sulfonic acid ester molecule is small, and thus the photosensitive property tends to be lowered.

  Specific examples of monohydric alcohols having 3 to 20 carbon atoms include 1-propanol, 2-propanol, 1-butanol, 2-butanol, 1-pentanol, 2-pentanol, 1-hexanol, 2-hexanol, 1-heptanol, 1-octanol, 1-decanol, 1-dodecanol, benzyl alcohol, cyclohexyl alcohol, cyclohexane methanol, cyclohexane ethanol, 2-ethylbutanol, 2-ethylhexanol, 3,5,5-trimethyl-1-hexanol, 1-adamantanol, 2-adamantanol, adamantanemethanol, norbornane-2-methanol, tetrafurfuryl alcohol, 2-methoxyethanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether , Ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, polyethylene glycol monomethyl ether with a polymerization degree of 2 to 10, polyethylene glycol monoethyl ether with a polymerization degree of 2 to 10, and polyprolene with a polymerization degree of 1 to 10 Glycol monomethyl ether, polyprolene glycol monoethyl ether having a polymerization degree of 1 to 10, and polyprolene glycol having a polymerization degree of 1 to 10 in which the alkyl group is propyl, isopropyl, butyl, isobutyl, tert-butyl, isoamyl, hexyl, cyclohexyl, etc. A monoalkyl ether is mentioned.

  Specific examples of the dihydric alcohol having 3 to 20 carbon atoms include 1,4-cyclohexanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and 1,7-heptanediol. 1,8-octanediol, 1,9-nonanediol, neopentyl glycol, p-xylylene glycol, 2,2-dimethyl-1,3-propanediol, 2,2,4-trimethyl-1,3- Pentanediol, 3,9-bis (1,1-dimethyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane, 2,2-diisoamyl-1,3-propane Diol, 2,2-diisobutyl-1,3-propanediol, 2,2-di-n-octyl-1,3-propanediol, 2-ethyl-2-methyl-1 3-propanediol, and 2-methyl-2-propyl-1,3-propanediol.

  Specific examples of alcohols having 3 to 20 carbon atoms and having a valence of 3 or more include glycerol, trimethylolethane, trimethylolpropane, pentaerythritol, 3-methylpentane-1,3,5-triol, sugars, Examples include polyhydric alcohol ethylene glycol, propylene glycol, polyethylene glycol, and polypropylene glycol adducts.

  Among these mono- or polyhydric alcohols, a compound selected from ethylene glycol, propylene glycol, and a polymer having a polymerization degree of 2 to 10 is used from the viewpoint of transparency of the formed silica-based film. It is preferable.

  The above-mentioned naphthoquinone diazide sulfonic acid ester can be obtained by a conventionally known method. For example, it can be obtained by reacting naphthoquinone diazide sulfonic acid chloride with an alcohol in the presence of a base.

  Examples of the base used in this reaction include tertiary alkylamines such as trimethylamine, triethylamine, tripropylamine, tributylamine, trihexylamine, trioctylamine, pyridine, 2,6-lutidine, sodium hydroxide, hydroxide. Examples include potassium, sodium hydride, potassium tert-butoxide, sodium methoxide, sodium carbonate, and potassium carbonate.

  Examples of the reaction solvent include aromatic solvents such as toluene and xylene, halogen solvents such as chloroform and carbon tetrachloride, ether solvents such as THF, 1,4-dioxane and diethyl ether, ethyl acetate and butyl acetate. Examples include ester solvents, ether acetate solvents such as propylene glycol monomethyl ether acetate, ketone solvents such as acetone and isobutyl ketone, hexane, and dimethyl sulfoxide.

  Further, the naphthoquinone diazide sulfonic acid ester as the component (c) is used by being dissolved in the solvent as the component (b) together with the siloxane resin as the component (a).

  The blending ratio of the component (c) in the photosensitive resin composition is 3 to 40% by mass based on the total solid content of the siloxane resin contained in the photosensitive resin composition from the viewpoint of photosensitive characteristics and the like. It is preferably 5 to 30% by mass, and more preferably 5 to 25% by mass. When the blending ratio of the component (c) is 3% by mass or more, the dissolution inhibiting action in an alkali developer is improved and the photosensitivity is excellent. Moreover, precipitation of the (c) component at the time of forming a coating film is suppressed as the compounding ratio of (c) component is 40 mass% or less, and a coating film tends to become uniform. On the other hand, when the blending ratio of the photosensitizer exceeds 40% by mass, the concentration of the component (c) as the photosensitizer is high and light absorption occurs only in the vicinity of the surface of the formed coating film. There is a tendency that the light characteristics do not reach and the photosensitive characteristics deteriorate.

<(D) component>
The component (d) is a siloxane resin obtained by hydrolytic condensation of a compound represented by the following general formula (2). This component (d) is preferably used in combination with the component (a) described above. Since the component (d) contains an acyloxy group in the siloxane resin, it is possible to obtain a film excellent in both photosensitive characteristics and insulating film characteristics. Since the acyloxy group is easily dissolved in an aqueous alkali solution, the solubility in the aqueous alkali solution used during development after exposure increases, and the contrast between the unexposed area and the exposed area increases, resulting in improved resolution. In addition, since the component (d) is a flexible component, cracks are unlikely to occur in the film after the heat treatment, and it is easy to increase the film thickness. Thereby, the crack tolerance of the silica-type film formed from this photosensitive resin composition can be improved.

［式（２）中、Ｒ^２は有機基を示し、Ａは２価の有機基を示し、Ｘは加水分解性基を示す。なお、同一分子内の複数のＸは同一でも異なっていてもよい。］

[In the formula (2), R ² represents an organic group, A represents a divalent organic group, and X represents a hydrolyzable group. A plurality of X in the same molecule may be the same or different. ]

In formula (2), examples of the organic group represented by R ² include an aliphatic hydrocarbon group and an aromatic hydrocarbon group. Among these, a linear, branched or cyclic aliphatic hydrocarbon group having 1 to 20 carbon atoms is preferable. Specific examples of the linear aliphatic hydrocarbon group having 1 to 20 carbon atoms include groups such as a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and an n-pentyl group. Specific examples of the branched aliphatic hydrocarbon group include groups such as isopropyl group and isobutyl group. Specific examples of the cyclic aliphatic hydrocarbon group include groups such as a cyclopentyl group, a cyclohexyl group, a cycloheptylene group, a norbornyl group, and an adamantyl group. Among these, a linear hydrocarbon group having 1 to 5 carbon atoms such as a methyl group, an ethyl group, and a propyl group is more preferable, and a methyl group is particularly preferable from the viewpoint of availability of raw materials.

  In the formula (2), examples of the divalent organic group represented by A include a divalent aromatic hydrocarbon group and a divalent aliphatic hydrocarbon group. Among these, from the viewpoint of availability of raw materials, a linear, branched or cyclic divalent hydrocarbon group having 1 to 20 carbon atoms is preferable.

  Preferable specific examples of the linear divalent hydrocarbon group having 1 to 20 carbon atoms include groups such as a methylene group, an ethylene group, a propylene group, a butylene group, and a pentylene group. Preferable specific examples of the branched divalent hydrocarbon group having 1 to 20 carbon atoms include groups such as isopropylene group and isobutylene group. Preferred examples of the cyclic divalent hydrocarbon group having 1 to 20 carbon atoms include groups such as a cyclopentylene group, a cyclohexylene group, a cycloheptylene group, a group having a norbornane skeleton, and a group having an adamantane skeleton. It is done. Among these, a linear divalent hydrocarbon group having 1 to 7 carbon atoms such as a methylene group, an ethylene group and a propylene group, a cyclic divalent carbon such as a cyclopentylene group and a cyclohexylene group. A hydrogen group and a cyclic divalent hydrocarbon group having a norbornane skeleton are particularly preferred.

  In the formula (2), examples of the hydrolyzable group represented by X include an alkoxy group, a halogen atom, an acetoxy group, an isocyanate group, and a hydroxyl group. Among these, an alkoxy group is preferable from the viewpoint of liquid stability of the photosensitive resin composition itself, coating properties, and the like.

  When hydrolyzing and condensing the silane compound, one type of the compound represented by the general formula (2) may be used alone, or two or more types may be used in combination. For example, a compound represented by the general formula (1) can be combined with two or more kinds.

A specific example of the structure of a siloxane resin obtained by hydrolytic condensation of a silane compound containing the compound represented by the general formula (1) and the compound represented by the general formula (2) is represented by the following general formula (3). Shown in In this specific example, two types of compounds represented by general formula (1) (R ¹ is a phenyl group and a methyl group, respectively) and one type of compound represented by general formula (2) (R ² is It is a structure of a siloxane resin obtained by hydrolytic condensation with a methyl group. Further, although the structure is shown in a plan view for simplification, as will be understood by those skilled in the art, an actual siloxane resin has a three-dimensional network structure. Further, the subscript “3/2” indicates that O atoms are bonded at a ratio of 3/2 to one Si atom.

  Here, in formula (3), a, b, and c represent the molar ratio (mol%) of the raw material corresponding to each site, a is 1 to 98, b is 1 to 98, and c is 1 to 98. It is. However, the sum of a, b and c is 100. Moreover, A in Formula (3) shows a bivalent organic group.

  The hydrolysis condensation of the above-mentioned silane compound can be performed, for example, under the following conditions.

  First, the amount of water used in the hydrolytic condensation is preferably 0.01 to 1000 mol, more preferably 0.05 to 100 mol, per 1 mol of the compound represented by the general formula (2). preferable. If the amount of water is less than 0.01 mol, the hydrolysis-condensation reaction tends not to proceed sufficiently, and if the amount of water exceeds 1000 mol, gelation tends to occur during hydrolysis or condensation.

  In addition, a catalyst may be used in the hydrolysis condensation. As a catalyst, the thing similar to what is used in the case of the hydrolysis condensation of the above-mentioned silane compound can be used, For example, an acid catalyst, an alkali catalyst, and a metal chelate compound are mentioned. Among these, an acid catalyst is preferable from the viewpoint of preventing hydrolysis of an acyloxy group in the compound represented by the general formula (2).

  The amount of such a catalyst used is preferably in the range of 0.0001 to 1 mol with respect to 1 mol of the compound represented by the general formula (2). If the amount used is less than 0.0001 mol, the reaction does not proceed substantially, and if it exceeds 1 mol, gelation tends to be promoted during hydrolysis condensation.

  In addition, when the above-mentioned catalyst is used in hydrolysis condensation, there is a possibility that the stability of the obtained photosensitive resin composition may be deteriorated, or that the influence of corrosion on other materials may be caused by including the catalyst. There is sex. Such adverse effects can be eliminated, for example, by removing the catalyst from the photosensitive resin composition after hydrolytic condensation, or by reacting the catalyst with other compounds to deactivate the function as a catalyst. it can. As a method for carrying out these operations, a conventionally known method can be used. Examples of the method for removing the catalyst include a distillation method and an ion chromatography column method. Moreover, as a method of deactivating the function as a catalyst by reacting the catalyst with another compound, for example, when the catalyst is an acid catalyst, a method of adding a base and neutralizing by an acid-base reaction can be mentioned.

  In addition, alcohol is by-produced during such hydrolysis condensation. Since this alcohol is a protic solvent and may adversely affect the physical properties of the photosensitive resin composition, it is preferably removed using an evaporator or the like.

  The siloxane resin thus obtained has a weight average molecular weight of preferably 500 to 1,000,000, more preferably 500 to 500,000, from the viewpoint of solubility in a solvent, moldability, and the like. It is more preferable that it is 100,000, and it is especially preferable that it is 500-50000. If the weight average molecular weight is less than 500, the film formability of the silica-based film tends to be inferior. If the weight average molecular weight exceeds 1000000, the compatibility with the solvent tends to be lowered.

  In addition, the blending ratio of the component (d) in the photosensitive resin composition is determined based on the solid content of the photosensitive resin composition from the viewpoint of solubility in a solvent, film thickness, moldability, photosensitive properties, solution stability, and the like. It is necessary to be 0 to 80% by mass based on the whole, more preferably 5 to 75% by mass, still more preferably 20 to 70% by mass, and 30 to 70% by mass. Is particularly preferred. When the blending ratio is 5% by mass or more, the silica film has excellent film formability and photosensitive characteristics, and when it is 80% by mass or less, the stability of the solution is excellent.

  When the photosensitive resin composition contains the above-mentioned component (d) in the above blending ratio, the formed silica-based film is further excellent in resolution. Furthermore, in such a photosensitive resin composition, since the component (d) described above is excellent in flexibility, the occurrence of cracks during the heat treatment of the formed silica-based film is prevented, so that the crack resistance is excellent. Furthermore, since the formed silica-based film is excellent in crack resistance, it is possible to increase the thickness of the silica-based film by using the photosensitive resin composition of the present invention.

  In addition, when using the above-mentioned photosensitive resin composition for an electronic component etc., it is desirable not to contain an alkali metal or an alkaline earth metal, and even if included, the concentration of those metal ions in the composition is 1000 ppm or less. It is preferable that it is 1 ppm or less. If the concentration of these metal ions exceeds 1000 ppm, the metal ions are liable to flow into an electronic component having a silica-based film obtained from the composition, which may adversely affect the electrical performance itself. Therefore, it is effective to remove alkali metal or alkaline earth metal from the composition using an ion exchange filter or the like, if necessary. However, when used for optical waveguides, other uses, etc., this is not limited as long as the purpose is not impaired.

  Moreover, although the above-mentioned photosensitive resin composition may contain water as needed, it is preferable that it is the range which does not impair the target characteristic.

(Formation method of photosensitive resin film)
The method for forming a photosensitive resin film of the present invention comprises a photosensitive resin composition containing the above-described components (a), (b) and (c) and, if necessary, a component (d) on a substrate. A step of applying and vacuum drying to form a photosensitive resin film is provided. Here, the “photosensitive resin film” in the present specification refers to a film preliminarily dried by removing a part of the solvent contained in the coating film made of the photosensitive resin composition.

<Application process>
First, a substrate for applying the photosensitive resin composition is prepared. The substrate may be one having a flat surface or one having electrodes or the like and having irregularities. Examples of materials for these substrates include organic polymers such as polyethylene terephthalate, polyethylene naphthalate, polyamide, polycarbonate, polyacryl, nylon, polyethersulfone, polyvinyl chloride, polypropylene, and triacetyl cellulose. Further, the organic polymer in the form of a film can be used as the substrate.

  The above-mentioned photosensitive resin composition can be applied onto such a substrate by a conventionally known method. Specific examples of the coating method include spin coating, spraying, roll coating, rotation, and slit coating. Among these, it is preferable to apply the photosensitive resin composition by a spin coating method that is generally excellent in film formability and film uniformity.

  When the spin coating method is used, the coating film is formed by spin-coating the above-described photosensitive resin composition on a substrate at 300 to 3000 rotations / minute, more preferably 400 to 2000 rotations / minute. If the rotational speed is less than 300 revolutions / minute, the film uniformity tends to deteriorate, and if it exceeds 3000 revolutions / minute, the film formability may deteriorate.

  The film thickness of the coating film thus formed can be adjusted as follows, for example. First, at the time of spin coating, the film thickness of the coating film can be adjusted by adjusting the number of rotations and the number of coatings. That is, the film thickness of the coating film can be increased by lowering the spin coating speed or increasing the number of coatings. Moreover, the film thickness of a coating film can be made thin by raising the rotation speed of a spin coat or reducing the frequency | count of application | coating.

  Furthermore, in the above-mentioned photosensitive resin composition, the film thickness of a coating film can also be adjusted by adjusting the density | concentration of (a) component. For example, the film thickness of the coating film can be increased by increasing the concentration of the component (a). Moreover, the film thickness of a coating film can be made thin by making the density | concentration of (a) component low.

  By adjusting the film thickness of the coating film as described above, the film thickness of the silica-based film that is the final product can be adjusted. The suitable film thickness of the silica-based coating varies depending on the intended use. For example, the thickness of the silica-based coating is 0.01 to 2 μm when used for an interlayer insulating film such as LSI; 2 to 40 μm when used for a passivation layer; 1 to 20 [mu] m; 0.1 to 2 [mu] m when used for a photoresist; preferably 1 to 50 [mu] m when used for an optical waveguide. In general, the thickness of the silica-based coating is preferably 0.01 to 10 μm, more preferably 0.01 to 5 μm, still more preferably 0.01 to 3 μm, and It is especially preferable that it is 05-3 micrometers, and it is very preferable that it is 0.1-3 micrometers. The photosensitive resin composition according to the present invention can be suitably used for a silica-based film having a thickness of 0.5 to 3.0 μm, and more preferably a silica-based film having a thickness of 0.5 to 2.5 μm. It can be used, and can be particularly suitably used for a silica-based film having a thickness of 1.0 to 2.5 μm.

  After forming the coating film on the substrate as described above, the solvent in the coating film is removed by vacuum drying under reduced pressure conditions to form a photosensitive resin film with a reduced amount of residual solvent. The degree of vacuum in vacuum drying is preferably 0.01 mmHg to 500 mmHg, more preferably 0.01 mmHg to 200 mmHg, and still more preferably 0.01 mmHg to 100 mmHg. By setting the degree of vacuum to 500 mmHg or less, the amount of residual solvent in the photosensitive resin film is reduced, and the influence of temperature in the subsequent heat treatment is reduced. Can be suppressed. Moreover, it is preferable to perform vacuum drying at normal temperature, and it is more preferable to carry out in 25-35 degreeC.

(Method for forming silica-based film)
The method for forming a silica-based film of the present invention includes a heat treatment step for obtaining a coating film by heat-treating the photosensitive resin film produced by the above-described method for forming a photosensitive resin film of the present invention at normal pressure, and a predetermined coating film. It has the 1st exposure process which exposes a part, the removal process which removes the predetermined part by which the coating film was exposed, and the heating process which heats the coating film from which the predetermined part was removed. Further, the method for forming a silica-based film of the present invention includes a heat treatment step of obtaining a coating film by heat-treating the photosensitive resin film produced by the above-described method for forming a photosensitive resin film of the present invention at normal pressure, and a coating film A first exposure step of exposing a predetermined portion of the film, a removal step of removing the predetermined portion of the coating film exposed, a second exposure step of exposing the coating film from which the predetermined portion has been removed, and the predetermined portion removed. A heating step of heating the coating film. Hereinafter, each step will be described.

<Heat treatment process>
The photosensitive resin film formed as described above is further heat-treated (dried) to further remove the solvent in the photosensitive resin film. A conventionally well-known method can be used for heat drying, for example, it can dry using a hotplate. The drying temperature is preferably 50 to 200 ° C, more preferably 80 to 180 ° C. If this drying temperature is less than 50 ° C., the organic solvent tends not to be sufficiently removed. On the other hand, when the drying temperature exceeds 200 ° C., the coating film is hardened and the solubility in the developer is lowered.

<First exposure step>
Next, the predetermined part of the obtained coating film is exposed. As a method for exposing a predetermined portion of the coating film, a conventionally known method can be used. For example, the predetermined portion can be exposed by irradiating the coating film with radiation through a mask having a predetermined pattern. .

Examples of the radiation used here include ultraviolet rays such as g-ray (wavelength 436 nm) and i-ray (wavelength 365 nm), far ultraviolet rays such as KrF excimer laser, X-rays such as synchrotron radiation, and charged particle beams such as electron beams. Can be mentioned. Of these, g-line and i-line are preferable. As an exposure amount, it is 10-2000 mJ / cm < ² > normally, Preferably it is 20-200 mJ / cm < ² >.

<Removal process>
Subsequently, the exposed predetermined portion (hereinafter also referred to as “exposed portion”) of the coating film is removed to obtain a coating film having a predetermined pattern. As a method for removing the exposed portion of the coating film, a conventionally known method can be used. For example, a coating film having a predetermined pattern is obtained by removing the exposed portion by developing with a developer. be able to.

  Examples of the developer used here include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium oxalate, and aqueous ammonia, primary amines such as ethylamine and n-propylamine, diethylamine, Secondary amines such as di-n-propylamine, tertiary amines such as triethylamine and methyldiethylamine, alcoholamines such as dimethylethanolamine and triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxy And quaternary ammonium salts such as choline, pyrrole, piperidine, 1,8-diazabicyclo- (5.4.0) -7-undecene, 1,5-diazabicyclo- (4.3.0) -5 -An alkaline aqueous solution in which cyclic amines such as nonane are dissolved in water is preferred. It is used. In addition, an appropriate amount of a water-soluble organic solvent, for example, alcohols such as methanol and ethanol, and a surfactant can be added to the developer. Furthermore, various organic solvents that dissolve the photosensitive resin composition according to the present embodiment can also be used as a developer.

  As a developing method, an appropriate method such as a liquid piling method, a dipping method, a rocking dipping method, or the like can be used. After the development process, the patterned film may be rinsed by running water cleaning, for example.

<Second exposure step>
Further, if necessary, the entire surface of the coating film remaining after the removing step is exposed. As a result, the component (d) having optical absorption in the visible light region is decomposed to produce a compound having sufficiently small optical absorption in the visible light region. Therefore, the transparency of the silica-based film that is the final product is improved. For the exposure, the same radiation as in the first exposure step can be used. Energy of exposure, it is necessary to completely disassemble the component (d), usually 100~3000mJ / cm ^2, preferably 200~2000mJ / cm ^2.

<Heating process>
Finally, the coating film remaining after the removing step is heated to perform final curing. By this heating step, a silica-based film that is the final product is obtained. For example, the heating temperature is preferably 250 to 500 ° C, and more preferably 250 to 400 ° C. If the heating temperature is less than 250 ° C., the coating film tends not to be cured sufficiently. If the heating temperature exceeds 500 ° C., if there is a metal wiring layer, the amount of heat input may increase and the wiring metal may be deteriorated.

  Note that the heating step is preferably performed in an inert atmosphere such as nitrogen, argon, or helium. In this case, the oxygen concentration is preferably 1000 ppm or less. Further, the heating time is preferably 2 to 60 minutes, more preferably 2 to 30 minutes. If the heating time is less than 2 minutes, the coating film tends not to be cured sufficiently. If the heating time exceeds 60 minutes, the heat input may be excessively increased and the wiring metal may be deteriorated.

  Furthermore, as a heating apparatus, it is preferable to use a heat treatment apparatus such as a quartz tube furnace or other furnace, a hot plate, rapid thermal annealing (RTA) or the like, or a heat treatment apparatus using both EB and UV.

  The silica-based film formed through the above-described process has, for example, sufficient heat resistance and high transparency even when heat treatment at 350 ° C. is performed, and is excellent in solvent resistance. In addition, a coating film formed from a composition containing a phenolic resin such as a novolak resin and a quinonediazide photosensitizer known in the related art or a composition containing an acrylic resin and a quinonediazide photosensitizer material is generally used. About 230 ° C. is the upper limit of the heat-resistant temperature, and when the heat treatment is performed beyond this temperature, it is colored yellow or brown, and the transparency is remarkably lowered.

  The silica-based film formed through the above-described steps can be suitably used as an interlayer insulating film of a flat display device such as a liquid crystal display element, a plasma display, an organic EL, or a field emission display. Such a silica-based film can also be suitably used as an interlayer insulating film for semiconductor elements and the like. Further, such silica-based coatings are used for semiconductor device wafer coating materials (surface protective film, bump protective film, MCM (multi-chip module) interlayer protective film, junction coating), package materials (sealing materials, die bonding materials), etc. It can use suitably also as a member for electronic devices.

  A specific example of the electronic component of the present invention having the above-described silica-based coating includes the memory cell capacitor shown in FIG. 1, and a specific example of the flat display device of the present invention having the above-described silica-based coating is illustrated in FIG. And a flat display device having an active matrix substrate shown in FIG.

  FIG. 1 is a schematic cross-sectional view showing a memory cell capacitor as one embodiment of an electronic component of the present invention. A memory cell capacitor 10 shown in FIG. 1 has a gate insulation provided at a position between a silicon wafer 1 (substrate) having diffusion regions 1A and 1B formed on the surface thereof and the diffusion regions 1A and 1B on the silicon wafer 1. The film 2B, the gate electrode 3 provided on the gate insulating film 2B, the counter electrode 8C provided above the gate electrode 3, and the gate electrode 3 and the counter electrode 8C are stacked in this order from the silicon wafer 1 side. Interlayer insulating films 5 and 7 (insulating coating).

  Over the diffusion region 1A, a sidewall oxide film 4A in contact with the sidewalls of the gate insulating film 2B and the gate electrode 3 is formed. On the diffusion region 1B, a sidewall oxide film 4B in contact with the sidewall of the gate insulating film 2B and the gate electrode 3 is formed. A field oxide film 2A for element isolation is formed between the silicon wafer 1 and the interlayer insulating film 5 on the opposite side of the diffusion region 1B from the gate insulating film 2B.

  The interlayer insulating film 5 is formed to cover the gate electrode 3, the silicon wafer 1, and the field oxide film 2A. The surface of the interlayer insulating film 5 opposite to the silicon wafer 1 is flattened. Interlayer insulating film 5 has a side wall located on diffusion region 1A, covers this side wall and diffusion region 1A, and covers part of the surface of interlayer insulating film 5 opposite to silicon wafer 1. An extending bit line 6 is formed. An interlayer insulating film 7 provided on the interlayer insulating film 5 is formed to extend so as to cover the bit line 6. The interlayer insulating film 5 and the interlayer insulating film 7 form a contact hole 5A in which the bit line 6 is embedded.

  The surface of the interlayer insulating film 7 opposite to the silicon wafer 1 is also planarized. A contact hole 7A penetrating the interlayer insulating film 5 and the interlayer insulating film 7 is formed at a position on the diffusion region 1B. A storage electrode 7A is embedded in the contact hole 7A, and the storage electrode 7A further extends so as to cover a portion around the contact hole 7A on the surface of the interlayer insulating film 7 opposite to the silicon wafer 1. . The counter electrode 8C is formed to cover the storage electrode 8A and the interlayer insulating film 7, and a capacitor insulating film 8B is interposed between the counter electrode 8C and the storage electrode 8A.

  The interlayer insulating films 5 and 7 are silica-based films formed from the above-described photosensitive resin film. The interlayer insulating films 5 and 7 are formed, for example, through a process of applying the above-described photosensitive resin composition by a spin coat method. Interlayer insulating films 5 and 7 may have the same composition or different compositions.

  FIG. 2 is a plan view showing the configuration of one pixel portion of the active matrix substrate in one embodiment of the flat display device of the present invention. In FIG. 2, the active matrix substrate 20 is provided with a plurality of pixel electrodes 21 in a matrix, and each gate for supplying scanning signals so as to pass through the periphery of the pixel electrodes 21 and to be orthogonal to each other. A wiring 22 and a source wiring 23 for supplying a display signal are provided. A part of the gate line 22 and the source line 23 overlaps the outer peripheral part of the pixel electrode 21. In addition, a TFT 24 as a switching element connected to the pixel electrode 21 is provided at the intersection of the gate line 22 and the source line 23. A gate wiring 22 is connected to the gate electrode 32 of the TFT 24, and the TFT 24 is driven and controlled by a signal input to the gate electrode. A source wiring 23 is connected to the source electrode of the TFT 24, and a data signal is input to the source electrode of the TFT 24. Further, the drain electrode of the TFT 24 is connected to the pixel electrode 21 via the connection electrode 25 and the contact hole 26, and an additional capacitance electrode (not shown) that is one electrode of the additional capacitance via the connection electrode 25. It is connected. The additional capacitor counter electrode 27, which is the other electrode of the additional capacitor, is connected to a common wiring.

  3 is a cross-sectional view taken along the line III-III ′ of the active matrix substrate of FIG. In FIG. 3, a gate electrode 32 connected to the gate wiring 22 is provided on a transparent insulating substrate 31, and a gate insulating film 33 is provided to cover the gate electrode 32. A semiconductor layer 34 is provided thereon so as to overlap with the gate electrode 32, and a channel protective layer 35 is provided on the central portion thereof. An n + Si layer that covers both ends of the channel protective layer 35 and a part of the semiconductor layer 34 and is separated on the channel protective layer 35 is provided as the source electrode 36a and the drain electrode 36b. A transparent conductive film 37a and a metal layer 38a are provided on the end portion of the source electrode 36a, which is one n + Si layer, to form a source wiring 23 having a two-layer structure. A transparent conductive film 37b and a metal layer 38b are provided on the end of the drain electrode 36b, which is the other n + Si layer, and the transparent conductive film 37b is extended to connect the drain electrode 36b and the pixel electrode 21. In addition, the connection electrode 25 is connected to an additional capacitance electrode (not shown) which is one electrode of the additional capacitance. Further, an interlayer insulating film 39 is provided so as to cover the TFT 24, the gate wiring 22, the source wiring 23, and the connection electrode 25. A transparent conductive film to be the pixel electrode 21 is provided on the interlayer insulating film 39, and is connected to the drain electrode 36 b of the TFT 24 by the connection electrode 25 through the contact hole 26 that penetrates the interlayer insulating film 39.

  The active matrix substrate of the present embodiment is configured as described above, and this active matrix substrate can be manufactured, for example, as follows.

  First, an n + Si layer to be a gate electrode 32, a gate insulating film 33, a semiconductor layer 34, a channel protective layer 35, a source electrode 36a and a drain electrode 36b is sequentially formed on a transparent insulating substrate 31 such as a glass substrate. To do. The manufacturing process so far can be performed in the same manner as in the conventional method for manufacturing an active matrix substrate.

  Next, the transparent conductive films 37a and 37b and the metal layers 38a and 38b constituting the source wiring 23 and the connection electrode 25 are sequentially formed by sputtering and patterned into a predetermined shape.

  Further, a coating film made of the above-described photosensitive resin composition to be the interlayer insulating film 39 is formed thereon by a spin coating method, and then dried under reduced pressure conditions to remove the solvent in the coating film, thereby remaining. A photosensitive resin film with a reduced amount of solvent is formed. Next, the photosensitive resin film is heat-treated to form a coating film having a thickness of, for example, 2 μm, and the formed coating film is exposed through a mask and developed with an alkaline solution, An interlayer insulating film 39 is formed. At this time, only the exposed portion is etched by the alkaline solution, and the contact hole 26 penetrating the interlayer insulating film 39 is formed.

  Thereafter, a transparent conductive film to be the pixel electrode 21 is formed by sputtering and patterned. As a result, the pixel electrode 21 is connected to the transparent conductive film 38 b connected to the drain electrode 36 b of the TFT 24 through the contact hole 26 penetrating the interlayer insulating film 39. In this way, the above-described active matrix substrate can be manufactured.

  Therefore, in the active matrix substrate obtained in this way, a thick interlayer insulating film 39 is formed between the gate wiring 22, the source wiring 23 and the TFT 24, and the pixel electrode 21. , 23 and the TFT 24 can be overlapped with each other and the surface thereof can be flattened. For this reason, when a configuration of a flat display device in which liquid crystal is interposed between the active matrix substrate and the counter substrate is used, the aperture ratio can be improved, and the electric field caused by each of the wirings 22 and 23 is caused by the pixel electrode 21. Disclination can be suppressed by shielding.

  In addition, the silica-based film formed of the above-described photosensitive resin film serving as the interlayer insulating film 39 has a relative dielectric constant of 3.0 to 3.8 and an inorganic film (silicon nitride relative dielectric constant 8). The relative dielectric constant is low, the transparency is high, and a thick film can be easily formed by a spin coating method. For this reason, the capacitance between the gate wiring 22 and the pixel electrode 21 and the capacitance between the source wiring 23 and the pixel electrode 21 can be lowered, and the time constant is lowered. 21 can further reduce the influence of the crosstalk and the like on the display by the capacitive component between the display 21 and the display, and a good and bright display can be obtained. Further, by performing patterning by exposure and alkali development, the tapered shape of the contact hole 26 can be improved, and the connection between the pixel electrode 21 and the connection electrode 25 (37b) can be improved. Furthermore, by using the above-described photosensitive resin composition, a thin film can be formed by using a spin coating method, so that a thin film having a thickness of several μm can be easily formed, and a photoresist process is not required for patterning. Therefore, it is advantageous in terms of productivity. Here, although the above-mentioned photosensitive resin composition used as the interlayer insulating film 39 is colored before coating, it can be made more transparent by performing an entire surface exposure process after patterning. Thus, the resin clarification treatment can be performed not only optically but also chemically.

  The exposure of the above-described photosensitive resin composition used as the interlayer insulating film 39 in the present embodiment is performed using a mercury lamp including bright lines of i-line (wavelength 365 nm), h-line (wavelength 405 nm), and g-line (wavelength 436 nm). It is common to use light rays. As the photosensitive resin composition, it is preferable to use a photosensitive resin composition having radiation sensitivity (absorption peak) to i-line having the highest energy (shortest wavelength) among these bright lines. It is possible to increase the processing accuracy of the contact hole and to suppress coloring due to the photosensitive agent to a minimum. Moreover, you may use the short wavelength ultraviolet-ray from an excimer laser.

  Hereinafter, specific examples according to the present invention will be described, but the present invention is not limited thereto.

[Synthesis of siloxane resin]
(Synthesis Example 1)
(1) Synthesis of siloxane resin A (corresponding to component (a) above) In a 2000 mL four-necked flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, 317.9 g of tetraethoxysilane and methyltriethoxysilane 247 Then, 167.5 g of nitric acid prepared to 0.644% by weight was added dropwise over 30 minutes with stirring to a solution obtained by dissolving 9.9 g in 1116.7 g of propylene glycol monomethyl ether acetate. After reacting for 3 hours after completion of the dropwise addition, a portion of the generated ethanol and propylene glycol monomethyl ether acetate was distilled off in a warm bath under reduced pressure to prepare a solution of siloxane resin A prepared to a solid content concentration of 25% by mass. 0 g was obtained. It was 870 when the weight average molecular weight of the siloxane resin A was measured by GPC method.

(Synthesis Example 2)
Siloxane resin B: Synthesis of 3-acetoxypropylsilsesquioxane / phenylsilsesquioxane / methylsilsesquioxane copolymer (compound represented by the following formula (4); corresponding to the component (d) above);

［式（４）中、２０，５０，３０は、それぞれ各部位に対応する原料のモル比を示す。］

[In Formula (4), 20, 50, and 30 show the molar ratio of the raw material corresponding to each site | part, respectively. ]

  To a 500 mL four-necked flask equipped with a stirrer, reflux condenser, dropping funnel and thermometer, 55.8 g of toluene and 35.7 g of water were charged, and 3.12 g (0.03 mol) of 35% hydrochloric acid was added. Next, 13.5 g (0.0605 mol) of 3-acetoxypropyltrimethoxysilane, 30.0 g (0.151 mol) of phenyltrimethoxysilane and 12.4 g (0.0908 mol) of methyltrimethoxysilane in toluene 27 .9 g solution was added dropwise at 20-30 ° C. After completion of dropping, the mixture was aged at the same temperature for 2 hours. As a result of analyzing the reaction solution at this time by GC (gas chromatograph), it was confirmed that no raw material remained. Next, toluene and water were added to the reaction solution to extract the product into an organic phase, which was washed with an aqueous sodium hydrogen carbonate solution and then washed with water until the solution became neutral. Thereafter, the organic phase was recovered, and toluene was removed to obtain 34.6 g of the target siloxane resin B in the form of a viscous liquid. Furthermore, the obtained siloxane resin B was dissolved in propylene glycol monomethyl ether acetate to obtain a solution of siloxane resin B prepared so that the solid content concentration was 50% by mass. Moreover, it was 1050 when the weight average molecular weight of the siloxane resin B was measured by GPC method.

(Synthesis of naphthoquinone diazide sulfonate ester)
Synthesis of naphthoquinone diazide sulfonic acid ester A (corresponding to component (c) above);
A 200 mL four-necked flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer was charged with 2.68 g of dipropylene glycol and 50 g of tetrahydrofuran, and 1,2-diazonaphthoquinone-5--5 at room temperature (25 ° C.). 10.75 g of sulfonyl chloride, 4.45 g of triethylamine and 0.5 g of dimethylaminopyridine were added, and the reaction was carried out at 50 ° C. for 4 hours. After completion of the reaction, the precipitated solid was separated by filtration, and the solvent was removed in a warm bath under reduced pressure. Thereafter, 50 g of methyl isobutyl ketone was added and dissolved, and then washed twice with 50 g of ion-exchanged water, and the solvent was concentrated in a warm bath under reduced pressure to obtain a naphtho prepared to have a solid content concentration of 48% by mass. 16.4 g of a quinonediazide sulfonate A solution was obtained.

Synthesis of naphthoquinonediazide sulfonic acid ester B (corresponding to component (c) above);
A 200 mL four-necked flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer was charged with 2.68 g of dipropylene glycol and 50 g of tetrahydrofuran, and 1,2-diazonaphthoquinone-5--5 at room temperature (25 ° C.). 10.75 g of sulfonyl chloride, 4.45 g of triethylamine and 0.5 g of dimethylaminopyridine were added, and the reaction was carried out at 50 ° C. for 4 hours. After completion of the reaction, the precipitated solid was separated by filtration, and the solvent was removed in a warm bath under reduced pressure. Thereafter, 50 g of methyl isobutyl ketone was added and dissolved, and then washed twice with 50 g of ion-exchanged water, and the solvent was removed in a warm bath under reduced pressure to obtain 10.2 g of oily naphthoquinone diazide sulfonate ester. . Among these, 7.3 g was charged into a container equipped with a stirrer, and 7.7 g of 3,4-dihydro-2H-pyran, 50 g of propylene glycol methyl ether acetate and 2.9 g of 5% HNO ₃ aqueous solution were added, and room temperature (25 ) For 72 hours. After completion of the reaction, 70 g of methyl isobutyl ketone was added, and further washed with 70 g of a 0.5% aqueous solution of tetramethylammonium hydroxide (TMAH), and then washed twice with 70 g of ion-exchanged water, and the organic layer was separated. . This solution was concentrated in a warm bath under reduced pressure to obtain 9.6 g of a solution of naphthoquinone diazide sulfonic acid ester B prepared so as to have a solid concentration of 48% by mass.

(Preparation of photosensitive resin composition and production of photosensitive resin film)
[Example 1]
To a 50 mL flask, 10.0 g of a siloxane resin A solution and 0.52 g of a naphthoquinone diazide sulfonic acid ester A solution were added and stirred at room temperature (24 ° C.) for 1 hour to prepare a photosensitive resin composition. The obtained photosensitive resin composition was spin-coated on a silicon wafer or glass substrate for 30 seconds at a rotational speed such that the film thickness after removal of the solvent was 2.0 μm, and then a vacuum dryer (manufactured by ELLY, The silica-based positive photosensitive resin film of Example 1 was prepared by drying at a reduced pressure of 20 mmHg and 30 ° C. for 10 minutes using a trade name “VOS-300VD”).

[Example 2]
To a 50 mL flask, 10.0 g of a solution of siloxane resin A and 0.52 g of a solution of naphthoquinone diazide sulfonic acid ester B were added and stirred at room temperature (24 ° C.) for 1 hour to prepare a photosensitive resin composition. A silica-based positive photosensitive resin film of Example 2 was produced using the obtained photosensitive resin composition, except that the degree of vacuum was 200 mmHg.

[Example 3]
To a 50 mL flask, add 5.0 g of siloxane resin A solution, 1.2 g of siloxane resin B solution and 0.18 g of naphthoquinone diazide sulfonate A solution, and stir at room temperature (24 ° C.) for 1 hour. A composition was prepared. Using the obtained photosensitive resin composition, the same operation as in Example 1 was performed to produce a silica-based positive photosensitive resin film of Example 3.

[Example 4]
To a 50 mL flask, add 5.0 g of siloxane resin A solution, 2.5 g of siloxane resin B solution and 0.32 g of naphthoquinone diazide sulfonic acid ester A solution, and stir at room temperature (24 ° C.) for 1 hour. A composition was prepared. Using the obtained photosensitive resin composition, the same operation as in Example 1 was performed to produce a silica-based positive photosensitive resin film of Example 4.

[Example 5]
To a 50 mL flask, add 10.0 g of siloxane resin A solution, 1.5 g of siloxane resin B solution and 0.68 g of naphthoquinone diazide sulfonate ester A solution, and stir at room temperature (24 ° C.) for 1 hour. A composition was prepared. Using the obtained photosensitive resin composition, the same operation as in Example 1 was performed to produce a silica-based positive photosensitive resin film of Example 5.

[Comparative Example 1]
To a 50 mL flask, 10.0 g of a siloxane resin A solution and 0.52 g of a naphthoquinone diazide sulfonic acid ester A solution were added and stirred at room temperature (24 ° C.) for 1 hour to prepare a photosensitive resin composition. The resulting photosensitive resin composition was spin-coated on a silicon wafer or glass substrate for 30 seconds at a rotational speed such that the film thickness after removal of the solvent was 2.0 μm. A conductive resin film was prepared.

[Comparative Example 2]
To a 50 mL flask, 10.0 g of a solution of siloxane resin A and 0.52 g of a solution of naphthoquinone diazide sulfonic acid ester B were added and stirred at room temperature (24 ° C.) for 1 hour to prepare a photosensitive resin composition. Using the obtained photosensitive resin composition, the same operation as in Comparative Example 1 was performed to produce a silica-based positive photosensitive resin film of Comparative Example 2.

[Comparative Example 3]
To a 50 mL flask is added 5.0 g of siloxane resin A solution, 1.2 g of siloxane resin B solution and 0.18 g of naphthoquinone diazide sulfonate A solution, and the mixture is stirred for 1 hour at room temperature (24 ° C.). A composition was prepared. Using the obtained photosensitive resin composition, the same operation as in Comparative Example 1 was performed to produce a silica-based positive photosensitive resin film in Comparative Example 3.

[Comparative Example 4]
To a 50 mL flask, add 5.0 g of siloxane resin A solution, 2.5 g of siloxane resin B solution and 0.32 g of naphthoquinone diazide sulfonic acid ester A solution, and stir at room temperature (24 ° C.) for 1 hour. A composition was prepared. Using the obtained photosensitive resin composition, the same operation as in Comparative Example 1 was performed to produce a silica-based positive photosensitive resin film of Comparative Example 4.

[Comparative Example 5]
To a 50 mL flask, add 10.0 g of siloxane resin A solution, 1.5 g of siloxane resin B solution and 0.68 g of naphthoquinone diazide sulfonate ester A solution, and stir at room temperature (24 ° C.) for 1 hour. A composition was prepared. Using the obtained photosensitive resin composition, the same operation as in Comparative Example 1 was performed to produce a silica-based positive photosensitive resin film of Comparative Example 5.

[Evaluation of solubility in unexposed areas]
Coating obtained by heat-treating the photosensitive resin film formed on the silicon wafer produced in Examples 1 to 5 and Comparative Examples 1 to 5 at 110 ° C., 120 ° C., and 130 ° C. for 150 seconds under normal pressure. The membrane was immersed in an aqueous solution of 2.38% by mass of tetramethylammonium hydroxide (hereinafter referred to as “TMAH”) at 25 ° C. for 60 seconds. However, when the coating film was dissolved within 60 seconds, the time when the coating film disappeared was defined as the immersion time. Subsequently, it rinsed with ion-exchange water, sprayed nitrogen gas, and dried the coating film. The unexposed area solubility was evaluated by a value calculated from the amount of decrease in film thickness (nm) before and after being immersed in a 2.38 mass% TMAH aqueous solution and the immersion time (seconds) (see the following formula). When the unexposed portion dissolution rate was less than 1 nm / second, the evaluation was A, when the dissolution rate was 1 nm / second or more to less than 100 nm / second, B, and when 100 nm / second or more, C was evaluated.
Unexposed part dissolution rate (nm / second) = Thickness reduction (nm) / Immersion time (second)

<Preparation of silica-based coating>
With respect to the coating film obtained by heat-treating the photosensitive resin film formed on the silicon wafer or glass substrate prepared in Examples 1 to 5 and Comparative Examples 1 to 5 at 120 ° C. for 150 seconds to remove the solvent. Then, exposure was performed at an exposure amount of 30 mJ / cm ² using a PLA-600F projection exposure machine manufactured by Canon Inc. through a predetermined pattern mask. Subsequently, using a 2.38 mass% TMAH aqueous solution, development processing was performed by a rocking immersion method at 25 ° C. for 1 minute. This was washed with running water with pure water and dried to form a pattern. Next, the entire surface of the pattern portion was exposed at an exposure amount of 1000 mJ / cm ² using a PLA-600F projection exposure machine manufactured by Canon Inc. Next, the pattern was finally cured at 350 ° C. for 30 minutes in a quartz tube furnace in which the O 2 concentration was controlled to be less than 1000 ppm to obtain a silica-based coating.

<Evaluation of coating>
By the above-mentioned method, film | membrane evaluation was performed with the following method with respect to the silica-type film formed from the photosensitive resin film of Examples 1-5 and Comparative Examples 1-5.

[Evaluation of resolution]
The evaluation of the resolution was made based on whether or not a 5 μm square through-hole pattern was missing from the silica-based film formed on the silicon wafer. That is, it is observed using an electron microscope S-4200 (manufactured by Hitachi Instrument Service Co., Ltd.), and when the through-hole pattern of 5 μm square of the exposed part is missing, A, when not missing, B, unexposed When the part dissolved and the pattern disappeared, it was evaluated as C.

[Measurement of transmittance]
About the silica-type film apply | coated on the glass substrate which does not absorb in a visible light area | region, the transmittance | permeability of wavelength 300nm -800nm was measured with Hitachi Ltd. UV3310 apparatus, and the value of wavelength 400nm was made into the transmittance | permeability.

[Evaluation of heat resistance]
The silica-based film formed on the silicon wafer was evaluated as A when the film thickness reduction rate after the final curing relative to the film thickness after removing the solvent was less than 10%, and as B when it was 10% or more. The film thickness is a film thickness measured with an ellipsometer L116B manufactured by Gartner, and is specifically a film thickness obtained from a phase difference caused by irradiation of a He—Ne laser on the film.

[Evaluation of crack resistance]
About the silica-type film formed on the silicon wafer, the presence or absence of the crack in a surface was confirmed with the magnification of 10-100 times with the metal microscope. Evaluation was made as A when no crack was generated and as B when a crack was observed.

<Evaluation results>
The evaluation results of the silica-based films formed from the photosensitive resin compositions of Examples 1 to 5 and Comparative Examples 1 to 5 are shown in Table 1 below.

  From the results shown in Table 1, according to the photosensitive resin films of Examples 1 to 5, the unexposed part dissolution rate has no temperature dependency when removing the solvent, has excellent process margins, and resolution. It is clear that a silica-based film having sufficiently high heat resistance, crack resistance and transparency can be obtained. In these examples, only the photosensitive resin composition from which a silica-based film having a high transmittance was obtained was shown, but it is also possible to provide a low transmittance according to the application.

It is a schematic cross section which shows one Embodiment of the electronic component of this invention. It is a top view which shows the structure of 1 pixel part of the active matrix substrate in one Embodiment of the flat display apparatus of this invention. FIG. 3 is a cross-sectional view taken along the line III-III ′ of the active matrix substrate of FIG. 2.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 1 ... Silicon wafer, 1A, 1B ... Diffusion region, 2A ... Field oxide film, 2B ... Gate insulating film, 3 ... Gate electrode, 4A, 4B ... Side wall oxide film, 5, 7 ... Interlayer insulating film, 5A, 7A ... Contact Hole 6, bit line 8 A storage electrode 8 B capacitor insulating film 8 C counter electrode 10 memory cell capacitor 21 pixel electrode 22 gate wiring 23 source wiring 24 TFT 25 Connection electrode, 26 ... contact hole, 31 ... transparent insulating substrate, 32 ... gate electrode, 36a ... source electrode, 36b ... drain electrode, 37a, 37b ... transparent conductive film, 38a, 38b ... metal layer, 39 ... interlayer insulating film .

Claims (9)

(A) component: a siloxane resin obtained by hydrolytic condensation of a silane compound containing a compound represented by the following general formula (1);
(B) component: a solvent in which the component (a) is dissolved;
(C) component: naphthoquinone diazide sulfonic acid ester,
A method for forming a photosensitive resin film, comprising: a step of applying a photosensitive resin composition containing a substrate onto a substrate and vacuum drying to form the photosensitive resin film.

[In Formula (1), R ¹ represents a group containing an H atom or F atom, or a B atom, N atom, Al atom, P atom, Si atom, Ge atom or Ti atom, or an organic group, and Represents a hydrolyzable group, n represents an integer of 0 to 2, a plurality of X in the same molecule may be the same or different, and when n is 2, a plurality of R ¹ in the same molecule is It may be the same or different. ] The photosensitive resin film according to claim 1, wherein the photosensitive resin composition further contains a siloxane resin obtained by hydrolytic condensation of the component (d): a compound represented by the following general formula (2). Method.

[In Formula (2), R ² represents an organic group, A represents a divalent organic group, X represents a hydrolyzable group, and a plurality of X in the same molecule may be the same or different. ]   3. The photosensitive composition according to claim 1, wherein the component (b) contains at least one solvent selected from the group consisting of ether acetate solvents, ether solvents, ester solvents, alcohol solvents, and ketone solvents. For forming a conductive resin film.   The formation method of the photosensitive resin film as described in any one of Claims 1-3 in which the said (c) component contains ester of monohydric or polyhydric alcohol, and a naphthoquinone diazide sulfonic acid. A heat treatment step of obtaining a coating film by further heat-treating the photosensitive resin film produced by the method for forming a photosensitive resin film according to any one of claims 1 to 4 at normal pressure,
A first exposure step of exposing a predetermined portion of the coating film;
Removing the exposed predetermined portion of the coating film; and
A heating step of heating the coating film from which the predetermined portion has been removed;
A method for forming a silica-based film having A heat treatment step of obtaining a coating film by further heat-treating the photosensitive resin film produced by the method for forming a photosensitive resin film according to any one of claims 1 to 4 at normal pressure,
A first exposure step of exposing a predetermined portion of the coating film;
Removing the exposed predetermined portion of the coating film; and
A second exposure step of exposing the coating film from which the predetermined portion has been removed;
A heating step of heating the coating film from which the predetermined portion has been removed;
A method for forming a silica-based film having   A semiconductor device comprising: a substrate; and a silica-based film formed on the substrate by the forming method according to claim 5.   A flat panel display device comprising: a substrate; and a silica-based film formed on the substrate by the forming method according to claim 5.   An electronic device member comprising: a substrate; and a silica-based film formed on the substrate by the forming method according to claim 5.

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