JP5050684B2 - Photosensitive resin composition, method for forming silica-based coating, and apparatus and member provided with silica-based coating - Google Patents

Description

  The present invention relates to a photosensitive resin composition, a method for forming a silica-based film, and a semiconductor device, a flat display device, and an electronic device member including the silica-based film 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, an interlayer insulating film is formed by patterning a film formed by deposition or coating from a gas phase through a photoresist. When forming a fine pattern, vapor 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 desirable that the film has a low dielectric constant.

In order to meet these demands, for example, methods 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 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, ammonia having high volatility is generated, so that corrosion of the production apparatus has been a problem.

  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. there were.

  Accordingly, the present invention provides a photosensitive resin composition in which the formation of a silica-based coating that can be used as an interlayer insulating film is relatively easy, and the formed silica-based coating has excellent heat resistance and resolution, and uses the same. It aims at providing the formation method of a silica type coating film. 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.

  The photosensitive resin composition of the present invention comprises (a) component: a siloxane resin obtained by hydrolytic condensation of a first silane compound containing a compound represented by the following general formula (1), and (b) component: It contains a second silane compound having a hydrolyzable group, component (c): a solvent in which component (a) is dissolved, and component (d): naphthoquinonediazide sulfonic acid ester.

［式（１）中、Ｒ^１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 (1), R ¹ 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. ]

  According to such a photosensitive resin composition, since a siloxane resin is used, the process of converting an essential polysilazane structure into a polysiloxane structure can be omitted in the method described in Patent Document 1, so that silica can be relatively easily obtained. A system film can be formed.

  Furthermore, the silica-type film formed from this photosensitive resin composition is excellent in heat resistance and resolution. The reason why such an effect can be obtained by the silica-based film formed from the photosensitive resin composition of the present invention is not necessarily clear, but the present inventors consider as follows.

  That is, in the photosensitive resin composition of this invention, since the siloxane resin excellent in heat resistance is used, it is thought that the silica-type film formed is also excellent in heat resistance. Furthermore, since the compound represented by the general formula (1) has an acyloxy group that is highly soluble in an alkaline aqueous solution, the siloxane resin obtained by hydrolyzing it is also soluble in the alkaline aqueous solution. High nature. Therefore, since it becomes easy to dissolve the exposed portion with an alkaline aqueous solution during development after exposure when forming a silica-based film, the difference in solubility between the unexposed portion and the exposed portion in the alkaline aqueous solution increases. It is thought that the image quality is improved.

［式（２）中、Ｒ^２はＨ原子又は有機基を示し、Ｘは加水分解性基を示し、ｎは０〜３の整数を示し、ｎが２以下であるとき、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又は３であるとき、同一分子内の複数のＲ^２は同一でも異なっていてもよい。］ In the photosensitive resin composition of this invention, it is preferable that the said 2nd silane compound contains the silane compound represented by following General formula (2). Thereby, the adhesiveness with respect to the board | substrate of the silica type coating film formed from this photosensitive resin composition improves.

[In the formula (2), R ² represents an H atom or an organic group, X represents a hydrolyzable group, n represents an integer of 0 to 3, and when n is 2 or less, X in the above may be the same or different, and when n is 2 or 3, a plurality of R ² in the same molecule may be the same or different. ]

  In the photosensitive resin composition of this invention, it is preferable that the said 1st silane compound further contains the compound represented by following General formula (3). Thereby, the heat resistance of the silica-type film formed from this photosensitive resin composition further improves.

［式（３）中、Ｒ^３は有機基を示し、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 (3), R ³ represents an organic group, X represents a hydrolyzable group, and a plurality of X in the same molecule may be the same or different. ]

  The component (c) 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 application nonuniformity and repelling at the time of apply | coating this photosensitive resin composition on a board | substrate can be suppressed.

  The component (d) is preferably an ester of naphthoquinone diazide sulfonic acid and a monovalent or polyhydric alcohol, and the polyhydric alcohol is composed of ethylene glycol, propylene glycol, and polymers having a polymerization degree of 2 to 10. An alcohol selected from the group is preferred. Thereby, the transparency of the silica-type film formed from this photosensitive resin composition improves.

  The method for forming a silica-based coating according to the present invention includes a coating step of applying the photosensitive resin composition described above on a substrate and drying to obtain a coating, a first exposure step of exposing a predetermined portion of the coating, A removing step of removing the exposed predetermined portion of the film; and a heating step of heating the coating film from which the predetermined portion has been removed. According to such a forming method, since the above-described photosensitive resin composition is used, a silica-based film having excellent heat resistance and resolution can be obtained.

  Moreover, the formation method of the silica-type film of this invention is a 1st exposure process which exposes the predetermined part of a coating film which apply | coats the above-mentioned photosensitive resin composition on a board | substrate, and obtains a coating film by drying. A removing step for removing the exposed predetermined portion of the coating film; a second exposure step for exposing the coating film from which the predetermined portion has been removed; and a heating step for heating the coating film from which the predetermined portion has been removed. It may be. According to such a forming method, since the above-described photosensitive resin composition is used, a silica-based film having excellent heat resistance and resolution can be obtained. Furthermore, the component (d) 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 a silica-based coating formed from the above-described photosensitive resin composition as an interlayer insulating film, they exhibit excellent effects.

  In the present invention, it is relatively easy to form a silica-based film that can be used as an interlayer insulating film, and the formed silica-based film has heat resistance, crack resistance, resolution, insulating properties, low dielectric properties, and The photosensitive resin composition which is excellent in transparency by this, and the formation method of the silica type coating film using the same are provided. Furthermore, the present invention provides a semiconductor device, a flat display device, and a member for an electronic device provided with a silica-based film formed by the method.

  Hereinafter, preferred embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments. 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.

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: RI-monitor manufactured by Hitachi, Ltd., trade name “L-3000”
Integrator: GPC integrator manufactured by Hitachi, Ltd., trade 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 eluent: tetrahydrofuran (THF)
Measurement temperature: 23 ° C
Flow rate: 1.75 mL / min Measurement time: 45 minutes

(Photosensitive resin composition)
The photosensitive resin composition of this invention contains (a) component, (b) component, (c) component, and (d) component. Hereinafter, each component will be described.

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

［式（１）中、Ｒ^１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、各Ｘは同一でも異なっていてもよい。］

[In Formula (1), R ¹ represents an organic group, A represents a divalent organic group, and X represents a hydrolyzable group. Each X may be the same or different. ]

Examples of the organic group represented by R ¹ 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.

  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 C1-C7 linear divalent hydrocarbon group such as a methylene group, an ethylene group or a propylene group, a C3-7 group such as a cyclopentylene group or a cyclohexylene group. A cyclic divalent hydrocarbon group and a cyclic divalent hydrocarbon group having a norbornane skeleton are particularly preferred.

  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. In addition, as for the hydrolyzable group represented by X in the compounds represented by the general formulas (2) and (3) described later, the same groups as X in the compound represented by the general formula (1) are specific. Take as an example.

  Moreover, it is preferable that the said 1st silane compound further contains the compound represented by following General formula (3). Thereby, the heat resistance of the silica-type film obtained further improves.

［式（３）中、Ｒ^３は有機基を示し、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 (3), R ³ represents an organic group, X represents a hydrolyzable group, and a plurality of X in the same molecule may be the same or different. ]

Examples of the organic group represented by R ³ include an aliphatic hydrocarbon group and an aromatic hydrocarbon group. As the aliphatic hydrocarbon group, 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 methyl group, an ethyl group, a propyl group, a norbornyl group, and an adamantyl group are more preferable from the viewpoints of thermal stability and raw material availability.

  Moreover, as an aromatic hydrocarbon group, what is C6-C20 is preferable. Specific examples thereof include groups such as a phenyl group, a naphthyl group, an anthracenyl group, a phenanthrenyl group, and a pyrenyl group. Among these, a phenyl group and a naphthyl group are more preferable from the viewpoints of thermal stability and raw material availability.

  In addition, it is preferable that the content rate in case the said 1st silane compound contains the compound represented by the said General formula (3) is 10-90 mass% with respect to the whole said 1st silane compound. 30 to 80% by mass is more preferable.

  Furthermore, the first silane compound may contain a silane compound other than the compounds represented by the general formulas (1) and (3). As such a silane compound, for example, a compound represented by the following general formula (2) and n is 0 or 2 can be mentioned. In addition, the content rate of silane compounds other than the compound with which the said 1st silane compound is each represented by General formula (1) and (3) is 0-50 mass with respect to the said 1st silane compound whole. %.

  When hydrolyzing and condensing the first silane compound, one type of the compound represented by the general formula (1) may be used alone, or two or more types may be used in combination. Similarly, about the compound represented by General formula (3), 1 type may be used independently or 2 or more types may be used in combination.

Specific examples of the structure of a siloxane resin (silsesquioxane) obtained by hydrolytic condensation of a silane compound containing the compound represented by the above general formula (1) and the compound represented by the general formula (3) It is shown in the following general formula (4). In this specific example, a compound represented by one general formula (1) (R ¹ is a methyl group) and a compound represented by two general formulas (3) (R ² is a phenyl group, respectively) 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 (4), A represents a divalent organic group, a, b, and c represent the molar ratio (mol%) of the raw material corresponding to each site, respectively, a is 1 to 99, b 1 to 99, c is 1 to 99. However, the sum of a, b and c is 100.

  The hydrolysis condensation of the first silane compound described above 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 (1). 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 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 hydrolysis of an acyloxy group in 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.

  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 has a weight average molecular weight of preferably 500 to 1,000,000, more preferably 500 to 500,000 from the viewpoint of dissolution in a solvent, moldability, and the like. Is more preferable, 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.

  The blending ratio of the component (a) is 5 to 50% by mass with respect to the total solid content of the photosensitive resin composition from the viewpoint of solubility in a solvent, film thickness, moldability, solution stability, and the like. It is preferable that it is 7-40 mass%, it is further more preferable that it is 10-40 mass%, and it is especially preferable that it is 15-35 mass%. When the blending ratio is less than 5% by mass, the film formability of the silica-based film tends to be inferior, and when it exceeds 50% by mass, the stability of the solution tends to decrease.

  Since the photosensitive resin composition of this invention contains the above-mentioned (a) component, the silica-type film formed is excellent in heat resistance and resolution. Furthermore, in such a photosensitive resin composition, since the component (a) 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.

<(B) component>
The component (b) is a silane compound having a hydrolyzable group (second silane compound). This component is for improving the adhesion of the formed silica-based coating to the substrate.

  As the second silane compound, a conventionally known silane compound can be used. From the viewpoint of further improving the adhesion to the base of the silica-based film to be formed, a silane compound represented by the following general formula (2) is used. It is preferable to include.

［式（２）中、Ｒ^２はＨ原子又は有機基を示し、Ｘは加水分解性基を示し、ｎは０〜３の整数を示し、ｎが２以下であるとき、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又は３であるとき、同一分子内の複数のＲ^２は同一でも異なっていてもよい。］

[In the formula (2), R ² represents an H atom or an organic group, X represents a hydrolyzable group, n represents an integer of 0 to 3, and when n is 2 or less, X in the above may be the same or different, and when n is 2 or 3, a plurality of R ² in the same molecule may be the same or different. ]

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. Among these, a group having an amino group or an epoxy group and a methyl group are preferable from the viewpoint of adhesiveness.

  Examples of the compound (alkoxysilane) represented by the general formula (2) in which the hydrolyzable group represented by X is an alkoxy group include tetraalkoxysilane, trialkoxysilane, and diorganodialkoxysilane. .

  Examples of tetraalkoxysilane include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane, tetra-tert-butoxysilane, tetra Examples include phenoxysilane.

  Examples of trialkoxysilane include trimethoxysilane, triethoxysilane, tripropoxysilane, fluorotrimethoxysilane, fluorotriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, and methyltriisosilane. Propoxysilane, methyltri-n-butoxysilane, methyltriisobutoxysilane, methyltri-tert-butoxysilane, methyltriphenoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltri-n-propoxysilane, ethyltriisopropoxysilane Ethyltri-n-butoxysilane, ethyltriisobutoxysilane, ethyltri-tert-butoxysilane, ethyltriphenoxysilane, n-propyltrimethyl Xysilane, n-propyltriethoxysilane, n-propyltri-n-propoxysilane, n-propyltriisopropoxysilane, n-propyltri-n-butoxysilane, n-propyltriisobutoxysilane, n-propyltri- tert-butoxysilane, n-propyltriphenoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, isopropyltri-n-propoxysilane, isopropyltriisopropoxysilane, isopropyltri-n-butoxysilane, isopropyltriisobutoxysilane, Isopropyltri-tert-butoxysilane, isopropyltriphenoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, n-butyltri-n-propoxysilane n-butyltriisopropoxysilane, n-butyltri-n-butoxysilane, n-butyltriisobutoxysilane, n-butyltri-tert-butoxysilane, n-butyltriphenoxysilane, sec-butyltrimethoxysilane, sec- Butyltriethoxysilane, sec-butyltri-n-propoxysilane, sec-butyltriisopropoxysilane, sec-butyltri-n-butoxysilane, sec-butyltriisobutoxysilane, sec-butyltri-tert-butoxysilane, sec- Butyltriphenoxysilane, tert-butyltrimethoxysilane, tert-butyltriethoxysilane, tert-butyltri-n-propoxysilane, tert-butyltriisopropoxysilane, tert-butylto Ri-n-butoxysilane, tert-butyltriisobutoxysilane, tert-butyltri-tert-butoxysilane, tert-butyltriphenoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltri-n-propoxysilane, phenyl Triisopropoxysilane, phenyltri-n-butoxysilane, phenyltriisobutoxysilane, phenyltri-tert-butoxysilane, phenyltriphenoxysilane, trifluoromethyltrimethoxysilane, pentafluoroethyltrimethoxysilane, 3, 3, Examples include 3-trifluoropropyltrimethoxysilane and 3,3,3-trifluoropropyltriethoxysilane.

  Examples of the diorganodialkoxysilane include dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldi-n-propoxysilane, dimethyldiisopropoxysilane, dimethyldi-n-butoxysilane, dimethyldi-sec-butoxysilane, dimethyldi-tert- Butoxysilane, dimethyldiphenoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethyldi-n-propoxysilane, diethyldiisopropoxysilane, diethyldi-n-butoxysilane, diethyldi-sec-butoxysilane, diethyldi-tert-butoxysilane Diethyldiphenoxysilane, di-n-propyldimethoxysilane, di-n-propyldiethoxysilane, di-n-propyldi-n-propoxysilane, di-n Propyl diisopropoxy silane, di-n-propyl di-n-butoxy silane, di-n-propyl di-sec-butoxy silane, di-n-propyl di-tert-butoxy silane, di-n-propyl diphenoxy silane, diisopropyl dimethoxy Silane, diisopropyldiethoxysilane, diisopropyldi-n-propoxysilane, diisopropyldiisopropoxysilane, diisopropyldi-n-butoxysilane, diisopropyldi-sec-butoxysilane, diisopropyldi-tert-butoxysilane, diisopropyldiphenoxysilane, Di-n-butyldimethoxysilane, di-n-butyldiethoxysilane, di-n-butyldi-n-propoxysilane, di-n-butyldiisopropoxysilane, di-n-butyldi-n-butyl Xysilane, 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-butyldiisopropoxysilane, di-sec-butyldi-n-butoxysilane, di-sec-butyldi-sec-butoxysilane, di-sec-butyldi-tert -Butoxysilane, di-sec-butyldiphenoxysilane, di-tert-butyldimethoxysilane, di-tert-butyldiethoxysilane, di-tert-butyldi-n-propoxysilane, di-tert-butyldiisopropoxysilane Di-tert-butyldi-n-butoxy Silane, di-tert-butyldi-sec-butoxysilane, di-tert-butyldi-tert-butoxysilane, di-tert-butyldiphenoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldi-n-propoxysilane, Diphenyldiisopropoxysilane, diphenyldi-n-butoxysilane, diphenyldi-sec-butoxysilane, diphenyldi-tert-butoxysilane, diphenyldiphenoxysilane, bis (3,3,3-trifluoropropyl) dimethoxysilane, And methyl (3,3,3-trifluoropropyl) dimethoxysilane.

Examples of the compound represented by the general formula (2) in which X is an alkoxy group and R ² is an alkyl group having 1 to 20 carbon atoms include, for example, bis (trimethoxysilyl) methane in addition to the above-described compounds. Bis (triethoxysilyl) methane, bis (tri-n-propoxysilyl) methane, bis (triisopropoxysilyl) methane, bis (trimethoxysilyl) ethane, bis (triethoxysilyl) ethane, bis (tri-n -Propoxysilyl) ethane, bis (triisopropoxysilyl) ethane, bis (trimethoxysilyl) propane, bis (triethoxysilyl) propane, bis (tri-n-propoxysilyl) propane, bis (triisopropoxysilyl) propane And bissilylalkanes.

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

  Among these compounds represented by the general formula (2), tetraethoxysilane, 3-aminopropyltriethoxysilane and (3-glycidoxypropyl) methyldiethoxysilane are particularly preferable from the viewpoint of adhesiveness. preferable. From the same viewpoint, a compound in which n is 0 is preferable, and tetraalkoxysilane is particularly preferable.

  One type of the compound represented by the above general formula (2) may be used alone, or two or more types may be used in combination.

  The blending ratio of the component (b) is preferably in the range of 0.01 to 50% by mass, more preferably 0.05 to 35% by mass, and 0.1 to 25% by mass from the viewpoint of adhesiveness. More preferably. If the blending ratio is less than 0.01% by mass, the adhesion tends to be inferior, and if it exceeds 50% by mass, the stability of the photosensitive resin composition tends to decrease.

<(C) component>
The component (c) is a solvent in which the component (a) is dissolved. Specific examples thereof include aprotic solvents and protic solvents. These may be used individually by 1 type, or may be used in combination of 2 or more type.

  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, acetonyl acetone, 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 (c) can be appropriately selected according to the types of the component (a), the component (b), and the component (d). For example, when the component (d) 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 (c) 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 It can use 0.1-90 mass% with respect to the whole.

  As a method of adding the component (c) 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 (c) component later are mentioned.

<(D) component>
(D) 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 (d), 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, an ester of naphthoquinone diazide sulfonic acid and a monovalent or polyhydric alcohol is preferable from the viewpoint of compatibility with the component (a) and transparency of the formed silica-based coating. Examples of naphthoquinonediazide sulfonic acid include naphthoquinone-1,2-diazide-5-sulfonic acid, naphthoquinone-1,2-diazide-4-sulfonic acid, and derivatives thereof.

  As monovalent or polyhydric alcohols, those having 3 to 20 carbon atoms are preferred. When the monovalent or polyhydric alcohol has 1 or 2 carbon atoms, the obtained naphthoquinone diazide sulfonic acid ester is precipitated in the photosensitive resin composition, or the compatibility with the component (a) is low. Tend to. When the monovalent or polyhydric alcohol has more than 20, the proportion of the naphthoquinone diazide moiety in the naphthoquinone diazide sulfonic acid ester molecule is small, so that the photosensitivity 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, 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 alcohols such as ethylene glycol, propylene glycol, polyethylene glycol, and polypropylene glycol adducts.

  The above-mentioned naphthoquinone diazide sulfonic acid ester can be obtained by a conventionally known method. For example, it can be obtained by reacting a 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.

  The reaction solvent includes 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, and esters such as ethyl acetate and butyl acetate. Examples thereof include ether solvents, ether acetate solvents such as propylene glycol monomethyl ether acetate, ketone solvents such as acetone and isobutyl ketone, hexane, dimethyl sulfoxide and the like.

  The blending ratio of the component (d) is preferably 3 to 30% by mass and 5 to 25% by mass with respect to the entire solid content of the photosensitive resin composition from the viewpoint of photosensitive characteristics and the like. More preferably, it is further preferably 5 to 20% by mass. When the blending ratio of the component (d) is less than 5% by mass, the action of inhibiting dissolution in an alkaline developer is lowered, and the photosensitivity is lowered. Moreover, when the mixture ratio of (d) component exceeds 30 mass%, when forming a coating film, (d) component will precipitate and it exists in the tendency for a coating film to become non-uniform | heterogenous. Furthermore, in such a case, the concentration of the component (d) as a photosensitizer is high, light absorption occurs only near the surface of the coating film to be formed, and light during exposure does not reach the lower part of the coating film. The photosensitivity tends to decrease.

  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.

(Method for forming silica-based film)
The method for forming a silica-based coating according to the present invention includes a coating step of applying the photosensitive resin composition described above on a substrate and drying to obtain a coating, a first exposure step of exposing a predetermined portion of the coating, A removing step of removing the exposed predetermined portion of the film; and a heating step of heating the coating film from which the predetermined portion has been removed. Moreover, the formation method of the silica-type film of this invention is a 1st exposure process which exposes the predetermined part of a coating film which apply | coats the above-mentioned photosensitive resin composition on a board | substrate, and obtains a coating film by drying. A removing step for removing the exposed predetermined portion of the coating film; a second exposure step for exposing the coating film from which the predetermined portion has been removed; and a heating step for heating the coating film from which the predetermined portion has been removed. It may be. Hereinafter, each step will be described.

<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 the material of these substrates include organic polymers such as polyethylene terephthalate, polyethylene naphthalate, polyamide, polycarbonate, polyacryl, nylon, polyethersulfone, polyvinyl chloride, polypropylene, and triacetyl cellulose. A substrate in which the organic polymer or the like is in the form of a film can also 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 above-mentioned photosensitive resin composition is spin-coated on the substrate at 300 to 3000 rotations / minute, more preferably 400 to 2000 rotations / minute, to form a coating film. 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, for example, as follows. 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 number of rotations of spin coating or reducing 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 μm; 0.1 to 2 μm when used for a photoresist; preferably 1 to 50 μm 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 of the present invention can be suitably used for a silica-based film having a thickness of 0.5 to 3.0 μm, and is preferably used for a silica-based film having a thickness of 0.5 to 2.5 μm. And can be particularly suitably used for a silica-based film having a thickness of 1.0 to 2.5 μm.

  After the coating film is formed on the substrate as described above, the coating film is dried to remove the organic solvent in the coating film. A conventionally known method can be used for drying, for example, it can be dried using a hot plate. 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 of the coating film (hereinafter also referred to as “exposed portion”) is removed to obtain a coating film having a predetermined pattern. As a method of 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, and diamine. Secondary amines such as n-propylamine, tertiary amines such as triethylamine and methyldiethylamine, alcoholamines such as dimethylethanolamine and triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide A quaternary ammonium salt 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 preferable. It is use. In addition, an appropriate amount of a water-soluble organic solvent, for example, an alcohol such as methanol or ethanol, or a surfactant can be added to the developer. Furthermore, various organic solvents that dissolve the composition of the present invention 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 subjected to a rinsing process by washing with running water, for example.

<Second exposure step>
Further, if necessary, the entire surface of the coating film remaining after the removing step is exposed. Thereby, the component (c) having optical absorption in the visible light region is decomposed, and a compound having sufficiently small optical absorption in the visible light region is generated. 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 (c), 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., when 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. When the heating time is less than 2 minutes, the coating film tends not to be cured sufficiently. When the heating time exceeds 60 minutes, the heat input amount is 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 steps has sufficiently high heat resistance and high transparency even when heat treatment is performed at 350 ° C., for example, 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 past, 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 capacitor 10 shown in FIG. 1 includes a silicon wafer 1 (substrate) having diffusion regions 1A and 1B formed on the surface thereof, and a gate insulating film provided at a position between the diffusion regions 1A and 1B on the silicon wafer 1. 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 sequentially stacked from the silicon wafer 1 side. Interlayer insulating films 5 and 7 (insulating film).

  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 composition. The interlayer insulating films 5 and 7 are formed, for example, through a process of applying a photosensitive resin composition by a spin coating 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 so as 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 becomes a source electrode 36a and a drain electrode 36b in a state of being separated on the channel protective layer 35 is provided. A transparent conductive film 37a and a metal layer 38a are provided on the end 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 so that the drain electrode 36b, the pixel electrode 21, And a connection electrode 25 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, on a transparent insulating substrate 31 such as a glass substrate, 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. Form. 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 a sputtering method and patterned into a predetermined shape.

  Further, the above-described photosensitive resin composition to be the interlayer insulating film 39 is formed thereon with a film thickness of 2 μm, for example, by spin coating. The formed coating film is exposed through a mask and developed with an alkaline solution, whereby the 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, the pixel electrode 21 can be overlapped 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 above-described photosensitive resin composition that becomes the interlayer insulating film 39 has a relative dielectric constant of 3.0 to 3.8, which is higher than the relative dielectric constant of the inorganic film (the relative dielectric constant 8 of silicon nitride). The film thickness is low and 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. In addition, 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 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 full exposure processing after patterning. Thus, the resin clarification treatment can be performed not only optically but also chemically.

  In the exposure of the above-described photosensitive resin composition used as the interlayer insulating film 39 in this embodiment, a mercury lamp including bright lines of i-line (wavelength 365 nm), h-line (wavelength 405 nm) and g-line (wavelength 436 nm) is used. 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 contact hole processing accuracy and to suppress coloring caused by the photosensitive agent to a minimum. Moreover, you may use the short wavelength ultraviolet-ray from an excimer laser.

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

(Synthesis of 3-acetoxypropyltrimethoxysilane)
To a 1 L four-necked flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, 500 g of toluene, 250.0 g (1.258 mol) of 3-chloropropyltrimethoxylane and 129.6 g of potassium acetate (1. 321 mol) was added and stirred, and 5.84 g (0.0181 mol) of tetra n-butylammonium bromide was added and reacted at 90-100 ° C. for 2 hours. Next, the salt produced after cooling was suction filtered to obtain a yellow solution. Toluene in the resulting solution was distilled off under reduced pressure using an evaporator, and further distilled under reduced pressure, and 162.8 g (0.732 mol) of a colorless and transparent fraction having a distillation pressure of 80 to 81 ° C. at a reduced pressure of 0.4 kPa. Obtained. As a result of GC analysis of the obtained fraction, the GC purity was 99.0%. As a result of NMR and IR analysis, it was 3-acetoxypropyltrimethoxysilane.
The spectrum data of the obtained compound is shown below.
Infrared absorption spectrum (IR) data:
_{^{2841,2945cm -1 (-CH 3), 1740cm}} -1 (-COO -), 1086cm -1 (Si-O)
Nuclear magnetic resonance spectrum (NMR) data ( ¹ H-NMR solvent: CDCl ₃ ):
0.644-0.686ppm (dd, 2H, -CH _2- ), 1.703-1.779ppm (m, 2H, -CH _2- ), 2.045ppm (s, 3H, CH ₃ CO-), 3.575ppm (s, 9H, CH ₃ O-), 4.019-4.052 ppm (t, 2H, -COO-CH _2- ).

(Synthesis of siloxane resin)
Siloxane resin A: Synthesis of 3-acetoxypropylsilsesquioxane / phenylsilsesquioxane / methylsilsesquioxane copolymer (compound represented by the following formula (10); corresponding to the component (a));

（式（１０）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 the formula (10), 20, 50, 30 indicate the molar ratio of the raw materials corresponding to each part.)

  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 obtained by the above method, 30.0 g (0.151 mol) of phenyltrimethoxysilane and 12.4 g of methyltrimethoxysilane (0 0.0908 mol) in toluene was added dropwise at 20 to 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, it was found that no raw material remained. Next, toluene and water were added to the reaction solution for extraction, washed with an aqueous sodium hydrogen carbonate solution, and then washed with water until the solution became neutral. The organic layer was recovered and toluene was removed to obtain 34.6 g of the target siloxane resin A in the form of a viscous liquid. Furthermore, the obtained siloxane resin A was dissolved in propylene glycol monomethyl ether acetate to obtain a solution of siloxane resin A adjusted to have a solid content concentration of 50% by mass. Moreover, it was 1050 when the weight average molecular weight of the siloxane resin A was measured by GPC method.

  Siloxane resin B: 3-acetoxypropylsilsesquioxane / 2-norbornylsilsesquioxane / methylsilsesquioxane copolymer (compound represented by the following formula (5); equivalent to the component (a) above) ) Synthesis;

（式（５）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 (5), 20, 50 and 30 indicate the molar ratio of the raw materials corresponding to each part.)

  The purpose was the same as the synthesis method of the siloxane resin A except that 30.0 g (0.151 mol) of phenyltrimethoxysilane was changed to 39.0 g (0.151 mol) of 2-norbornyltriethoxysilane. Of siloxane resin B was obtained. Furthermore, the obtained siloxane resin B was dissolved in propylene glycol monomethyl ether acetate to obtain a solution of siloxane resin B adjusted so that the solid content concentration was 50% by mass. Moreover, it was 1020 when the weight average molecular weight of the siloxane resin B obtained by GPC method was measured.

  Siloxane resin C: 5-acetoxynorborna-2 (or 3) -yl) silsesquioxane / phenylsilsesquioxane / methylsilsesquioxane copolymer (compound represented by the following formula (20); Synthesis of (a) component);

（式（２０）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 the formula (20), 20, 50 and 30 indicate the molar ratio of the raw materials corresponding to each part.)

  Except for changing 13.5 g (0.0605 mol) of 3-acetoxypropyltrimethoxysilane to 39.0 g (0.151 mol) of (5-acetoxynorborna-2 (or 3) -yl) triethoxysilane, The target siloxane resin C38.7g was obtained by the same operation as the synthesis method of the siloxane resin A. Furthermore, the obtained siloxane resin C was dissolved in propylene glycol monomethyl ether acetate to obtain a solution of the siloxane resin C adjusted so that the solid content concentration was 50% by mass. Moreover, it was 1050 when the weight average molecular weight of the siloxane resin C was measured by GPC method.

  Siloxane resin D: Synthesis of 3-acetoxypropylsilsesquioxane / phenylsilsesquioxane copolymer (compound represented by the following formula (6); corresponding to the component (a));

（式（６）中、２０，８０は、それぞれ各部位に対応する原料のモル比を示す。）

(In the formula (6), 20, 80 indicate the molar ratio of the raw material corresponding to each part.)

  A 500 mL four-necked flask equipped with a stirrer, reflux condenser, dropping funnel and thermometer was charged with 38.4 g of methanol and 21.0 g of water, and 1.13 g (0.0189 mol) of acetic acid was added. Next, a methanol 19.2 g solution of 8.41 g (0.0378 mol) of 3-acetoxypropyltrimethoxysilane and 30.0 g (0.151 mol) of phenyltrimethoxysilane obtained by the above method was added to 20-30. It was dripped at ° 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, it was found that no raw material remained. Next, toluene was added for extraction, and after washing with an aqueous sodium hydrogen carbonate solution, the solution was washed with water until the solution became neutral. The organic layer was collected and toluene was removed to obtain 24.6 g of the target compound as a viscous liquid. Further, the obtained compound was dissolved in propylene glycol monomethyl ether acetate to obtain a solution adjusted to have a solid content concentration of 50% by mass. The weight average molecular weight measured by GPC method was 1100.

  Comparative siloxane resin A: Synthesis of phenylsilsesquioxane (compound represented by the following formula (7));

（ｎは整数を示す。）

(N represents an integer.)

  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, a toluene 27.9 g solution of phenyltrimethoxysilane 48.0 g (0.242 mol) was added dropwise at 20 to 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, it was found that no raw material remained. Next, toluene and water were added for extraction, and after washing with an aqueous sodium hydrogen carbonate solution, the solution was washed with water until the solution became neutral. The organic layer was collected and toluene was removed to obtain 34.6 g of the target comparative siloxane resin A in the form of a viscous liquid. Furthermore, the obtained comparative siloxane resin A was dissolved in propylene glycol monomethyl ether acetate to obtain a solution of comparative siloxane resin A adjusted to have a solid content concentration of 50% by mass. Moreover, it was 1000 when the weight average molecular weight of the comparison siloxane resin A obtained by GPC method was measured.

Synthesis of siloxane resin E;
A 2000 mL four-necked flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer was charged with a solution in which 317.9 g of tetraethoxysilane and 247.9 g of methyltriethoxysilane were dissolved in 1116.7 g of diethylene glycol dimethyl ether, 167.5 g of nitric acid adjusted to 0.644% by mass was added dropwise over 30 minutes with stirring. After the completion of the dropwise addition, the reaction was allowed to proceed for 3 hours, and then part of the generated ethanol and diethylene glycol dimethyl ether were distilled off in a warm bath under reduced pressure to obtain 740.0 g of a siloxane resin E solution having a solid content concentration of 25%. It was 870 when the weight average molecular weight of the siloxane resin E was measured by GPC method.

(Synthesis of naphthoquinone diazide sulfonate ester)
Synthesis of naphthoquinonediazide sulfonic acid ester A (corresponding to the above component (d));
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 further 1,2-diazonaphthoquinone-5--5 at room temperature (25 ° C.) conditions. 10.75 g of sulfonyl chloride, 4.05 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 filtered off. 300 g of methyl isobutyl ketone was added to the filtered solid and dissolved, and then washed twice with 50 g of ion-exchanged water, and the solvent of the organic layer was removed in a warm bath under reduced pressure to obtain 10.2 g of an oily compound. Got. This compound was dissolved in tetrahydrofuran to obtain 17.1 g of a solution of naphthoquinonediazide sulfonic acid ester A ester having a solid content concentration adjusted to 48% by mass.

Synthesis of naphthoquinonediazide sulfonic acid ester B (corresponding to component (d) 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. 75 g, 4.45 g of triethylamine and 0.5 g of dimethylaminopyridine were added, and the reaction was performed 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 an oily compound. 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 having a solid content concentration of 48%.

(Preparation of photosensitive resin composition)
[Example 1]
0.21 g of tetraethoxysilane and 0.31 g of naphthoquinone diazide sulfonate A solution were added to 4.2 g of the siloxane resin A, respectively, and stirred and dissolved at room temperature (25 ° C.) for 30 minutes. A functional resin composition was prepared.

[Example 2]
0.21 g of dimethyldiethoxysilane and 0.31 g of naphthoquinone diazide sulfonic acid ester A were added to 4.2 g of the siloxane resin A, respectively, and stirred and dissolved at room temperature for 30 minutes. A product was prepared.

[Example 3]
Example 0.22 g of (3-glycidoxypropyl) trimethoxysilane and 0.31 g of naphthoquinone diazide sulfonic acid ester A solution were added to 4.2 g of the siloxane resin A solution and stirred and dissolved at room temperature for 30 minutes. 3 photosensitive resin compositions were prepared.

[Example 4]
The photosensitive resin composition of Example 4 was prepared by adding 0.21 g of tetraethoxysilane and 0.31 g of naphthoquinone diazide sulfonate A solution to 4.2 g of the siloxane resin B, respectively, and stirring and dissolving at room temperature for 30 minutes. Was prepared.

[Example 5]
0.21 g of dimethyldiethoxysilane and 0.31 g of naphthoquinone diazide sulfonic acid ester B solution were added to 4.2 g of the siloxane resin B, respectively, and stirred and dissolved at room temperature for 30 minutes. Photosensitive resin composition of Example 5 A product was prepared.

[Example 6]
The photosensitive resin composition of Example 6 was prepared by adding 0.21 g of tetraethoxysilane and 0.31 g of naphthoquinone diazide sulfonate A solution to 4.2 g of the siloxane resin C, respectively, and stirring and dissolving at room temperature for 30 minutes. Was prepared.

[Example 7]
The photosensitive resin composition of Example 7 was prepared by adding 0.21 g of tetraethoxysilane and 0.31 g of naphthoquinone diazide sulfonic acid ester B solution to 4.2 g of the siloxane resin D, respectively, and stirring and dissolving at room temperature for 30 minutes. Was prepared.

[Comparative Example 1]
To 4.2 g of the comparative siloxane resin A, 3.6 g of the siloxane resin E solution and 0.44 g of the naphthoquinone diazide sulfonic acid ester A solution were respectively added and dissolved by stirring for 30 minutes at room temperature. A resin composition was prepared.

<Manufacture of silica-based coating>
The photosensitive resin compositions obtained in Examples 1 to 7 and Comparative Example 1 were filtered with a PTFE filter. This 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 3.0 μm. Then, it was made to dry at 150 degreeC for 2 minutes, and the solvent was removed. The obtained coating film was exposed at a dose of 30 mJ / cm ² using a PLA-600F projection exposure machine manufactured by Canon through a predetermined pattern mask. Subsequently, using a 2.38 mass% tetramethylammonium hydroxide aqueous solution, development processing was performed by a rocking immersion method at 25 ° C. for 2 minutes. 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 using a PLA-600F projection exposure machine manufactured by Canon at an exposure amount of 1000 mJ / cm ² . Subsequently, the pattern was finally cured in a quartz tube furnace in which the O ₂ concentration was controlled to be less than 1000 ppm over 350 ° C./30 minutes 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 composition of Examples 1-7 and Comparative Example 1.

[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 was observed using an electron microscope S-4200 (manufactured by Hitachi Instruments Service Co., Ltd.), and A was evaluated when a through hole pattern of 5 μm square was missing, and B was evaluated when it was not missing.

[Measurement of transmittance]
For a silica-based film coated on a glass substrate having no absorption in the visible light region, a transmittance of 300 nm to 800 nm was measured with a Hitachi UV3310 apparatus, and a value of 400 nm was defined as the transmittance.

[Evaluation of heat resistance]
The silica-based film formed on the silicon wafer was evaluated as A when the rate of decrease in film thickness after final curing with respect to the film thickness after removing the solvent was less than 10%, and B when it was 10% or more. The film thickness is a film thickness measured by an ellipsometer L116B manufactured by Gartner. Specifically, the film thickness is 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 the surface by the magnification of 10 times-100 times was confirmed 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 7 and Comparative Example 1 are shown in Table 1 below.

  From Table 1, according to the photosensitive resin composition of Examples 1-7, it is clear that the silica-type film excellent in resolution, heat resistance, crack tolerance, 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.

FIG. 1 is a schematic cross-sectional view showing an embodiment of an electronic component of the present invention. 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. 3 is a cross-sectional view taken along the line III-III ′ of the active matrix substrate of FIG.

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 (10)

(A) component: a siloxane resin obtained by hydrolytic condensation of a first silane compound containing a compound represented by the following general formula (1);
(B) component: a second silane compound having a hydrolyzable group;
(C) component: a solvent in which the component (a) is dissolved;
(D) component: naphthoquinone diazide sulfonic acid ester,
The photosensitive resin composition in which the component (d) is an ester of naphthoquinone diazide sulfonic acid and a monovalent or polyhydric alcohol .

[In formula (1), R ¹ 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 photosensitive resin composition of Claim 1 in which a said 2nd silane compound contains the silane compound represented by following General formula (2).

[In the formula (2), R ² represents an H atom or an organic group, X represents a hydrolyzable group, n represents an integer of 0 to 3, and when n is 2 or less, X in the above may be the same or different, and when n is 2 or 3, a plurality of R ² in the same molecule may be the same or different. ] The photosensitive resin composition of Claim 1 or 2 in which a said 1st silane compound further contains the compound represented by following General formula (3).

[In Formula (3), R ³ represents an organic group, X represents a hydrolyzable group, and a plurality of X in the same molecule may be the same or different. ]   The component (c) includes at least one solvent selected from the group consisting of an ether acetate solvent, an ether solvent, an ester solvent, an alcohol solvent, and a ketone solvent. The photosensitive resin composition of one term. The photosensitive resin as described in any one of Claims 1-4 whose said polyhydric alcohol is alcohol selected from the group which consists of ethylene glycol, propylene glycol, and those polymers with a polymerization degree 2-10. Composition. An application step of applying the photosensitive resin composition according to any one of claims 1 to 5 on a substrate and drying to obtain a coating film;
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 coating, comprising: An application step of applying the photosensitive resin composition according to any one of claims 1 to 5 on a substrate and drying to obtain a coating film;
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 coating, comprising: A semiconductor device comprising: a substrate; and a silica-based film formed on the substrate by the forming method according to claim 6 . A flat display device comprising: a substrate; and a silica-based film formed on the substrate by the forming method according to claim 6 . An electronic device member comprising: a substrate; and a silica-based film formed on the substrate by the forming method according to claim 6 .

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