JP2011227159A - Photosensitive resin composition, forming method of silica based coating using the same, and device and member having silica based coating - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition which facilitates forming of silica based coating as an interlayer insulating film, is excellent in storage stability, is comparatively inexpensive, and is excellent in heat resistance, crack resistance, resolution, and transparency, to provide a forming method of the silica based coating using the photosensitive resin composition, and to provide a semiconductor device, a flat panel display and an electronic device member comprising the silica based coating.SOLUTION: A photosensitive resin composition comprises: a siloxane resin having a weight average molecular weight of 8000 to 300000 obtained through hydrolysis-condensation after mixing a first siloxane resin which is obtained by hydrolyzing and condensing a first silane compound containing a compound represented by general formula (1) and a second siloxane resin obtained by hydrolyzing and condensing a second silane compound containing a compound represented by general formula (2); a solvent; and a naphthoquinonediazidosulfonic ester.

Description

  The present invention relates to a photosensitive resin composition and a method for forming a silica-based coating using the same, a semiconductor device provided with the silica-based coating, a flat display device, and an electronic device member.

  In the manufacture of semiconductor devices and liquid crystal display devices, interlayer insulating films are used. In general, an interlayer insulating film is formed by patterning by being applied or deposited from a vapor phase and then etched through a photoresist. In the case of a fine pattern, gas phase etching is used for etching. However, vapor phase etching has a problem that the apparatus cost is high and the processing speed is slow, and development of a coating type photosensitive interlayer insulating film material for the purpose of reducing the process cost has been carried out. In particular, a liquid crystal display device requires a photosensitive interlayer insulating film material having positive photosensitive characteristics for insulation between a pixel electrode and a gate / drain wiring and for flattening a device.

  As a positive type photosensitive interlayer insulating film material, for example, Patent Document 1 discloses a photosensitive polysilazane resin composition containing polysilazane and a photoacid generator. Patent Document 2 discloses a composition composed of a siloxane resin and a photosensitive agent diazonaphthoquinone (DNQ). Further, Patent Document 3 discloses a composition comprising an acrylic resin and a photosensitizer diazonaphthoquinone.

JP 2000-181069 A JP 2009-211033 A Japanese Patent Laid-Open No. 2000-131844

  However, the photosensitive polysilazane resin composition described in Patent Document 1 has poor storage stability, and there is a tendency for the photosensitive properties to deteriorate or the molecular weight to change when stored for about one week at room temperature. Further, in the photosensitive siloxane resin composition described in Patent Document 2, storage stability is improved by adjusting the pH of the photosensitive siloxane resin composition, but it is not sufficient, and a catalyst is used during the synthesis of the siloxane resin. Since the acid contained in the product must be removed by washing the siloxane resin with water to adjust the pH, the process is complicated. Moreover, although the interlayer insulation film which consists of an acrylic resin composition of patent document 3 is transparent and stable, heat resistance is not enough at about 250 degreeC, and it applies it to the manufacturing process of a liquid crystal display device etc. It is difficult.

  Therefore, the present invention is relatively easy to form a silica-based film that can be used as an interlayer insulating film, and is excellent in storage stability, has a relatively low process cost, and the formed silica-based film is heat resistant. An object of the present invention is to provide a photosensitive resin composition excellent in crack resistance, resolution and transparency, and a method for forming a silica-based film using the same. Furthermore, an object of the present invention is to provide a semiconductor device, a flat display device, and a member for an electronic device provided with a silica-based film formed by a method for forming a silica-based film.

In order to achieve the above object, the present invention provides:
Component (a): a first siloxane resin obtained by hydrolytic condensation of a first silane compound containing a compound represented by the following general formula (1), and a compound represented by the following general formula (2) A third siloxane having a weight average molecular weight in the range of 8000 to 300,000 obtained by mixing with a second siloxane resin obtained by hydrolytic condensation of a second silane compound containing Resin,
(B) component: a solvent for dissolving the siloxane resin comprising the component (a),
(C) component: naphthoquinone diazide sulfonic acid ester,
The photosensitive resin composition containing is provided.

［一般式（１）中、Ｒ^１は１価の有機基を示し、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 General Formula (1), R ¹ represents a monovalent 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. May be. ]

［一般式（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。］
感光性樹脂組成物の構成成分として、シロキサン樹脂を用いているため、特許文献１に記載の方法では必須のポリシラザン構造をポリシロキサン構造に転化させる工程を省略することができることから、比較的容易にシリカ系被膜を形成することができる。

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

  Furthermore, the silica-type film formed from this photosensitive resin composition is excellent in crack resistance, 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 the present invention, since the first siloxane resin contained in the component (a) is excellent in flexibility, the occurrence of cracks during the heat treatment of the formed silica-based film is prevented. Therefore, it is excellent in crack resistance. Moreover, 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.

  According to the photosensitive resin composition of the present invention, by using two types of siloxane resins having different structures in combination, it is excellent in resolution and has a good pattern shape (small problems such as pattern dripping). A film can be formed.

  The photosensitive resin composition is sufficiently excellent in storage stability. Usually, a siloxane resin has a high molecular weight because silanol groups contained in the siloxane resin serve as crosslinking points, and dehydration condensation between the silanol groups is performed under an acid catalyst. The weight average molecular weight of the siloxane resin described in JP-A-2009-211033 (Patent Document 2) is about 1000, but if the weight average molecular weight is so small, the amount of silanol groups contained in the siloxane resin also increases. In addition, since the distance between the cross-linking points is close, dehydration condensation is easily performed, and the storage stability is deteriorated. On the other hand, since the molecular weight of the third siloxane resin of component (a) contained in the photosensitive resin composition of the present invention is 8000 to 300,000, the weight average molecular weight of the siloxane resin is relatively large, and the amount of silanol groups is small. Since it decreases, it is considered that the distance between the cross-linking points is increased and the storage stability is increased.

  The present invention also includes a step of obtaining a first siloxane resin by hydrolytic condensation of a first silane compound, a step of obtaining a second siloxane resin by hydrolytic condensation of a second silane compound, A third siloxane resin produced by mixing the siloxane resin and the second siloxane resin, hydrolyzing and condensing, and removing low boiling components such as alcohol and water produced by the hydrolytic condensation simultaneously with the hydrolytic condensation Is preferably used.

  The third siloxane resin of the component (a) contained in the photosensitive resin composition of the present invention can be obtained by mixing the first siloxane resin and the second siloxane resin and hydrolytic condensation. In some cases, the amount of the acid catalyst essential for the hydrolytic condensation is very small compared to the conventional case. This is because if a large amount of acid catalyst is present after hydrolysis condensation, silanol group hydrolysis condensation occurs during storage, and the storage stability of the photosensitive resin composition deteriorates.

  However, when the amount of the acid catalyst is small, the reactivity of the hydrolytic condensation of the silanol group contained in the siloxane resin is lowered. On the other hand, the hydrolysis condensation of the silanol group contained in the siloxane resin facilitates the reaction if the alcohol and water produced by the hydrolysis condensation are removed simultaneously with the hydrolysis condensation. Therefore, by performing the reaction while removing low-boiling components such as alcohol and water released from the siloxane resin by hydrolysis condensation, hydrolysis condensation can proceed while maintaining the reactivity of the silanol group, and a small amount of acid catalyst. Thus, a third siloxane resin can be obtained.

  On the other hand, the acid catalyst contained in the siloxane resin can be washed with water to reduce the acid catalyst in the photosensitive resin composition, and the storage stability can be improved (Patent Document 2: JP 2009-2111033 A). Operation is complicated and not suitable for mass production. On the other hand, according to the above-described method of the present invention, the above-described problem can be solved because washing with water is not necessary.

  In the present invention, a step of hydrolyzing and condensing the first silane compound to obtain a first siloxane resin, a step of hydrolyzing and condensing the second silane compound to obtain a second siloxane resin, and the first siloxane Production of third siloxane resin comprising a step of mixing a resin and a second siloxane resin, hydrolyzing and condensing low boiling components such as alcohol and water produced by the hydrolytic condensation at the same time as the hydrolytic condensation Provide a method. With such a method, the molecular weight of the siloxane resin is increased as described above, and the acid catalyst used can be reduced, so that the storage stability of the photosensitive resin composition is improved, and the siloxane resin is washed with water. Extra steps can be reduced.

In addition, the photosensitive resin composition of the present invention can exhibit good positive photosensitivity by containing an ester of phenols or alcohols and naphthoquinone diazide sulfonic acid as the component (c). Excellent developability can be obtained at the time of development after exposure for forming a film.
Furthermore, in the photosensitive resin composition of the present invention, the naphthoquinone diazide sulfonic acid ester as the component (c) is preferably an ester of naphthoquinone diazide sulfonic acid and a monovalent or polyhydric alcohol. More preferably, the polyhydric alcohol is an alcohol selected from the group consisting of ethylene glycol, propylene glycol, and polymers having a polymerization degree of 2 to 10.

  In the photosensitive resin composition of the present invention, the component (c) preferably contains an ester of phenols or alcohols having one or more aryl groups and naphthoquinone diazide sulfonic acid. Thereby, the photosensitive characteristic of the silica-type film formed from this photosensitive resin composition improves.

  In the photosensitive resin composition of the present invention, the component (b) comprises at least one solvent selected from the group consisting of ether acetate solvents, ether solvents, ester solvents, alcohol solvents, and ketone solvents. It is preferable to include. Thereby, the application nonuniformity and repelling at the time of apply | coating this photosensitive resin composition on a board | substrate can be suppressed.

  Moreover, in this invention, the manufacturing method of the photosensitive resin composition which has the process of mixing the 3rd siloxane resin, a naphthoquinone diazide sulfonate ester, and the solvent in which these melt | dissolve is provided.

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

  The present invention also includes a coating step of applying the photosensitive resin composition of the present invention described above on a substrate and drying to obtain a coating film, a first exposure step of exposing a predetermined portion of the coating film, and exposure of the coating film. A removal step of removing the predetermined portion, a second exposure step of exposing the coating film from which the predetermined portion has been removed, and a heating step of heating the coating film from which the predetermined portion has been removed. A forming method is provided. According to this forming method, since the above-mentioned photosensitive resin composition is used, a silica-based film having excellent heat resistance and resolution can be obtained. Furthermore, the component (c) having optical absorption in the visible light region is decomposed in the second exposure step, and a compound having sufficiently small optical absorption in the visible light region is generated. Therefore, the transparency of the resulting silica-based coating is improved.

  The present invention further provides a semiconductor device, a flat 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 of the present invention. Since these semiconductor devices, flat display devices, and electronic device members include the silica-based coating formed from the above-described photosensitive resin composition of the present invention as an interlayer insulating film, they exhibit excellent performance.

  According to the present invention, it is relatively easy to form a silica-based film that can be used as an interlayer insulating film, and it is excellent in storage stability, the process cost is relatively low, and the formed silica-based film is heat resistant. The photosensitive resin composition which is excellent in a property, crack tolerance, resolution, and transparency, and the formation method of a silica type coating film using the same can be provided. Moreover, according to this invention, it becomes possible to provide a semiconductor device, a flat display apparatus, and a member for electronic devices provided with the silica type film formed by the method of a silica type film.

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.

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

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

Here, the weight average molecular weight (Mw) can be measured using GPC under the following conditions, for example.
(conditions)
Sample: 10 μL
Standard polystyrene: Standard polystyrene manufactured by Tosoh Corporation (molecular weight: 190000, 17900, 9100, 2980, 578, 474, 370, 266)
Detector: 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, and (c) component. Hereinafter, each component will be described.

<(A) component>
The component (a) includes a compound represented by the following general formula (1), a first siloxane resin obtained by hydrolytic condensation of a first silane compound, and a compound represented by the following general formula (2) A third siloxane having a weight average molecular weight in the range of 8000 to 300,000 obtained by mixing with a second siloxane resin obtained by hydrolytic condensation of a second silane compound containing Resin.

［一般式（１）中、Ｒ^１は１価の有機基を示し、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 General Formula (1), R ¹ represents a monovalent organic group, A represents a divalent organic group, and X represents a hydrolyzable group. Each X may be the same or different. ]

［一般式（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 General 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, A plurality of X 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 general formula (1), examples of the monovalent 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 cycloheptyl group, a norbornyl group, and an adamantyl group. Among these, a linear hydrocarbon group having 1 to 5 carbon atoms such as a methyl group, an ethyl group, and a propyl group is more preferable, and a methyl group is particularly preferable from the viewpoint of availability of raw materials.

  In the general formula (1), 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.

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

［一般式（３）中、Ｒ^３は１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 General Formula (3), R ³ represents a monovalent organic group, X represents a hydrolyzable group, and a plurality of X in the same molecule may be the same or different. ]

In the general formula (3), examples of the monovalent 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 cycloheptyl 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.

Moreover, when hydrolyzing and condensing the compound represented by the general formula (3), the compound represented by the general formula (1) may be used alone or in combination of two or more. Good.
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.

The structure of the first siloxane resin (silsesquioxane) obtained by hydrolytic condensation of the silane compound containing the compound represented by the general formula (1) and the compound represented by the general formula (3). A specific example 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 ³ 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.

ここで、一般式（４）中、ａ、ｂ、ｃは、それぞれ各部位に対応する原料のモル比（モル％）を示し、ａは０．５〜９９、ｂは０．５〜９９、ｃは０．５〜９９である。ただし、ａ、ｂ及びｃの合計は１００である。また、一般式（４）中のＡは、２価の有機基を示す。

Here, in general formula (4), a, b, and c show the molar ratio (mol%) of the raw material corresponding to each part, respectively, a is 0.5-99, b is 0.5-99, c is 0.5-99. However, the sum of a, b and c is 100. Moreover, A in General formula (4) shows a bivalent organic group.

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. 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). When the amount used is less than 0.0001 mol, the reaction does not substantially proceed, and when it exceeds 1 mol, gelation tends to be promoted during hydrolysis condensation.

  In addition, when the above-mentioned catalyst is used in the hydrolytic condensation of the first siloxane resin, there is a possibility that the stability of the obtained photosensitive resin composition is deteriorated, or the corrosion of other materials is caused by including the catalyst. The impact may be a concern. The adverse effects such as these include, for example, the amount of the catalyst to be added is reduced as much as possible to proceed with the hydrolytic condensation, the catalyst is removed from the photosensitive resin composition after the hydrolytic condensation, or the catalyst is reacted with other compounds to form the catalyst. It can be solved by deactivating the function as. 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 water washing method, 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.

  The first siloxane resin thus obtained preferably has a weight average molecular weight of 500 to 100,000, more preferably 500 to 50,000, from the viewpoint of solubility in a solvent, moldability, and the like. More preferably, it is 500-10000, and it is especially preferable that it is 500-5000. If the weight average molecular weight is less than 500, the film-forming property of the silica-based film tends to be inferior. If the weight average molecular weight exceeds 100,000, the compatibility with the solvent tends to gradually decrease.

  During the hydrolysis and condensation, water and alcohol are by-produced, but can be removed during the hydrolysis and condensation of the third siloxane resin described later, or may be removed later.

  The second siloxane resin can be obtained by hydrolytic condensation of a silane compound containing the compound represented by the general formula (2). This component can improve the adhesion to the substrate of the silica-based film to be formed and the heat resistance and strength of the film. The component may be a conventionally known silane compound, but preferably contains a silane compound represented by the general formula (2) from the viewpoint of further improving the adhesion of the formed silica-based film to the substrate. .

In the general formula (2), examples of the organic group represented by R ² include 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.

  In the general formula (2), 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, diorgano Dialkoxysilane and the like.

  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.

In addition, examples of the compound in which X in the general formula (2) is an alkoxy group and R ² is an alkyl group having 1 to 20 carbon atoms include, for example, bis (trimethoxysilyl) methane, bis (Triethoxysilyl) methane, bis (tri-n-propoxysilyl) methane, bis (triisopropoxysilyl) methane, bis (trimethoxysilyl) ethane, bis (triethoxysilyl) ethane, bis (tri-n-propoxy) Silyl) ethane, bis (triisopropoxysilyl) ethane, bis (trimethoxysilyl) propane, bis (triethoxysilyl) propane, bis (tri-n-propoxysilyl) propane, bis (triisopropoxysilyl) propane, etc. Bissilylalkane is mentioned.

In the general formula (2), examples of the compound in which X is an alkoxy group and R ² is a group having an aromatic ring include, in addition to the above, bis (trimethoxysilyl) benzene, bis (triethoxysilyl) benzene, Examples thereof include bissilylbenzene such as bis (tri-n-propoxysilyl) benzene and bis (triisopropoxysilyl) benzene.

Examples of the compound in which X in the general formula (2) 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-aminopropyltrimethoxysilane N- (6-aminohexyl) aminopropyltrimethoxysilane, 3- (m-aminophenoxy) propyltrimethoxysilane, aminophenyltrimethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-aminopropyltriethoxysilane 3-aminopropyltrimethoxysilane, 6-azi Examples thereof include dosulfonylhexyltriethoxysilane.

In the general formula (2), examples of the compound 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) methyl Examples include diethoxysilane, (3-glycidoxypropyl) methyldimethoxysilane, and (3-glycidoxypropyl) trimethoxysilane.

  Among the compounds represented by the general formula (2) as described above, from the viewpoint of adhesiveness, tetraethoxysilane, 3-aminopropyltriethoxysilane, (3-glycidoxypropyl) methyltriethoxysilane, And dimethyldiethoxysilane is particularly preferable.

  One kind of the silane compound represented by the general formula (2) may be used alone, or two or more kinds may be used in combination.

  In addition, the hydrolytic condensation of the silane compound represented by the general formula (2) can be performed under the same conditions as the synthesis of the first siloxane resin described above, with respect to the amount of water required for hydrolysis, the type of acid catalyst, and the like. I can do it. About the addition amount of an acid catalyst, it is preferable that it is the range of 0.000001-1 mol with respect to 1 mol of compounds represented by General formula (2). When the amount used is less than 0.000001 mol, the reaction does not tend to proceed substantially, and when it exceeds 1 mol, gelation tends to be promoted during hydrolysis condensation. Further, after the hydrolysis condensation, the acid catalyst in the siloxane resin solution may or may not be removed. When the acid catalyst is not removed, the acid catalyst contained in the second siloxane resin can be used for hydrolysis condensation of the third siloxane resin described later. In this case, the acid catalyst is preferably used in an amount of 0.000001 to 0.005 mol.

  The second siloxane resin thus obtained preferably has a weight average molecular weight of 500 to 10,000, more preferably 500 to 5,000, from the viewpoint of solubility in a solvent, moldability, and the like. More preferably, it is -3000, and it is especially preferable that it is 500-2000. If this weight average molecular weight is less than 500, the film formability of the silica-based film tends to be inferior, and if this weight average molecular weight exceeds 10,000, the compatibility with the solvent tends to decrease.

  The first siloxane resin solution and the second siloxane resin solution are mixed in a solvent and hydrolyzed to form a third siloxane resin. At this time, the molecular weight of the siloxane resin is increased, the amount of silanol in the siloxane resin is decreased, and hydrolysis condensation is difficult to be performed. Moreover, the compatibility between siloxane resins is improved, and the applicability of the formed silica-based coating to the substrate is improved.

Furthermore, since the molecular weight of the siloxane resin increases, the dissolution rate with respect to the desired TMAH (tetramethylammonium hydroxide) alkaline aqueous solution concentration can be appropriately adjusted by adjusting the molecular weight.
In addition, if the third siloxane resins having different molecular weights are mixed, they can be controlled within a desired dissolution rate range. By this, since the dissolution rate of the unexposed part of the photosensitive resin composition and the dissolution rate of an exposed part can be adjusted, favorable resolution can be obtained.

  In the hydrolysis condensation of the third siloxane resin, the mixed solution of the first siloxane resin and the second siloxane resin is heated. The heat treatment method can be performed by a known method. Specifically, the container containing the mixed solution can be heat-treated in a warm bath or oil.

  The temperature for the heat treatment is preferably 70 to 200 ° C., and preferably 80 to 180 ° C. from the viewpoint of controlling the molecular weight, stability to the solution, and removal of low boiling components such as water and alcohol released from the siloxane resin. More preferably, it is 90-160 degreeC. If this heat treatment temperature is less than 70 ° C., a long time tends to be required to increase the molecular weight, and if it exceeds 200 ° C., the control of the molecular weight becomes difficult and gelation tends to occur.

  The hydrolysis condensation can be carried out under the same conditions as the synthesis of the first siloxane resin and the second siloxane resin described above with respect to the amount of water required for the hydrolysis condensation, the kind of the acid catalyst, and the like. The reaction can be carried out using the acid catalyst contained in the second siloxane resin as it is.

  At this time, by performing the reaction while removing low-boiling components such as alcohol and water desorbed from the siloxane resin by hydrolysis condensation, the hydrolysis condensation can proceed efficiently even if the addition amount of the acid catalyst is small. . The low boiling component may be removed from the siloxane resin solution by heating or the like at normal pressure, or may be removed while reducing the pressure.

  In addition, the blending ratio of the first siloxane resin and the second siloxane resin is 5 to 60% by mass on the basis of the solid content of the first siloxane resin from the viewpoint of heat resistance and stability to the solution. Is more preferable, 10 to 50% by mass is more preferable, 20 to 50% by mass is further preferable, and 30 to 50% by mass is particularly preferable. If the blending ratio is less than 5% by mass, the heat resistance tends to be inferior, and if it exceeds 60% by mass, the stability of the solution tends to decrease.

  In addition, the solution concentration when the first siloxane resin and the second siloxane resin are mixed is preferably 5 to 50% by mass based on the entire solid content of the siloxane resin from the viewpoint of controlling the molecular weight. More preferably, it is 10-40 mass%, and it is still more preferable that it is 20-30 mass%. If the blending ratio is less than 5% by mass, a long time tends to be required to increase the molecular weight, and if it exceeds 50% by mass, the molecular weight will increase in a short time and the control of the molecular weight tends to be difficult. is there.

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

  Examples of the aprotic solvent include acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-iso-propyl ketone, methyl-n-butyl ketone, methyl-iso-butyl ketone, methyl-n-pentyl ketone, methyl-n- Hexyl ketone, diethyl ketone, dipropyl ketone, di-iso-butyl ketone, trimethylnonanone, cyclohexanone, cyclopentanone, methylcyclohexanone, 2,4-pentanedione, 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 component (b) preferably contains at least one solvent selected from the group consisting of ether acetate solvents, ether solvents, ester solvents, alcohol solvents, and ketone solvents. Thereby, the application nonuniformity and repelling at the time of apply | coating this photosensitive resin composition on a board | substrate can be suppressed.

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

  Although the compounding quantity of such (b) component can be suitably adjusted according to the kind etc. of (a) component and (c) component, for example with respect to the whole solid content of the photosensitive resin composition, 0.1-90 mass% can be used.

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

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

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

  Examples of naphthoquinone diazide sulfonic acid esters include esters of naphthoquinone diazide sulfonic acid and phenols or alcohols. Among these, 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 resulting naphthoquinone diazide sulfonate is precipitated in the photosensitive resin composition, or the compatibility with the component (c) is low. Tend to. When the monovalent or polyhydric alcohol has more than 20 carbon atoms, 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 , 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, polyprolene glycol monomethyl ether with a polymerization degree of 1 to 10, polymerization degree 1 to 10 polyprolene glycol monoethyl ether, and polypropylene glycol monoalkyl ether having a polymerization degree of 1 to 10 whose alkyl group is propyl, isopropyl, butyl, isobutyl, tert-butyl, isoamyl, hexyl, cyclohexyl, etc. .

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

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

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

  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. And solvent solvents, ether acetate solvents such as propylene glycol monomethyl ether acetate, ketone solvents such as acetone and isobutyl ketone, hexane and dimethyl sulfoxide.

  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 blending ratio of the component (c) is preferably 1 to 30% by mass, and 3 to 25% by mass, based on the entire solid content of the photosensitive resin composition, from the viewpoint of photosensitive characteristics and the like. Is more preferable, and it is still more preferable that it is 3-20 mass%. When the blending ratio of the component (c) is 1% by mass or more, the dissolution inhibiting action in an alkaline developer is improved and the photosensitivity tends to be improved. Moreover, when the compounding ratio of (c) component is 30 mass% or less, when forming a coating film, (c) component cannot precipitate easily and it exists in the tendency for a coating film to become uniform. Further, in such a case, the concentration of the component (c) as the photosensitizer is not too high, and light absorption does not occur only in the vicinity of the surface of the formed coating film. There is a tendency that light at the time of exposure reaches and photosensitivity is improved.

  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 and other applications, 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 producing photosensitive resin composition)
It can be produced by a production method having a step of mixing the third siloxane resin, the naphthoquinone diazide sulfonate ester, and the solvent in which the third siloxane resin dissolves simultaneously or in any order.

(Method for forming silica-based film)
The method for forming a silica-based coating of the present invention includes a coating step of applying the above-described photosensitive resin composition of the present invention on a substrate and drying to obtain a coating, and a first exposure step of exposing a predetermined portion of the coating And a removing step for removing the exposed predetermined portion of the coating film, and a heating step for 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 spin coating rotations or increasing the number of coatings. Moreover, the film thickness of a coating film can be made thin by raising the rotation speed of a spin coat or reducing the frequency | count of application | coating.

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

  By adjusting the film thickness of the coating film as described above, the film thickness of the silica-based film that is the final product can be adjusted. The suitable film thickness of the silica-based coating varies depending on the intended use. For example, the thickness of the silica-based coating is 0.01 to 2 μm when used for an interlayer insulating film such as LSI; 2 to 40 μm when used for a passivation layer; 1 to 20 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 150 ° C, more preferably 70 to 140 ° C, and still more preferably 80 ° C to 130 ° C. If this drying temperature is less than 50 ° C., the organic solvent tends not to be sufficiently removed. In addition, when the drying temperature exceeds 150 ° C., the photosensitive agent in the film is decomposed to lower the transmittance, or the solubility in the developer is lowered due to the progress of curing of the coating film, resulting in lower exposure sensitivity and lower resolution. Tend to accompany.

<Decompression drying process>
Moreover, after forming a coating film on a board | substrate by an application | coating process, you may have a reduced pressure drying process before removing the solvent in a film | membrane with a hotplate etc. This reduced pressure drying has the effect of reducing the in-plane film thickness variation when the film is formed and the film thickness variation after development. The degree of vacuum in the vacuum drying step is preferably 150 Pa or less, more preferably 100 Pa or less, further preferably 50 Pa or less, and extremely preferably 20 Pa or less. Moreover, 0-100 degreeC is preferable, as for the temperature of vacuum drying, 10-50 degreeC is more preferable, and 20-30 degreeC is still more preferable. If the degree of vacuum is 150 Pa or more, removal of the solvent may not be sufficient. Further, when the temperature is 100 ° C. or higher, the in-plane film thickness variation becomes large, and when the temperature is 0 ° C. or lower, the solvent tends to be insufficiently removed.

<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 for removing the exposed portion of the coating film, a conventionally known method can be used. For example, a coating film having a predetermined pattern is obtained by removing the exposed portion by developing with a developer. be able to. Examples of the developer used here include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium oxalate, and aqueous ammonia, primary amines such as ethylamine and n-propylamine, diethylamine, 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 photosensitive resin 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 rinsed by running water cleaning, for example.

<Second exposure step>
Further, if necessary, the entire surface of the coating film remaining after the removing step is exposed. 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 cell capacitor 10 shown in FIG. 1 has a gate insulation provided at a position between a silicon wafer 1 (substrate) having diffusion regions 1A and 1B formed on the surface thereof and the diffusion regions 1A and 1B on the silicon wafer 1. The film 2B, the gate electrode 3 provided on the gate insulating film 2B, the counter electrode 8C provided above the gate electrode 3, and the gate electrode 3 and the counter electrode 8C are stacked in this order from the silicon wafer 1 side. Interlayer insulating films 5 and 7 (insulating coating).

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

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

  The surface of the interlayer insulating film 7 opposite to the silicon wafer 1 is also planarized. A contact hole 7A penetrating the interlayer insulating film 5 and the interlayer insulating film 7 is formed at a position on the diffusion region 1B. A storage electrode 8A is embedded in the contact hole 7A, and the storage electrode 8A further extends 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 the source electrode 36a and the 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 to connect the drain electrode 36b and the pixel electrode 21. In addition, the connection electrode 25 is connected to an additional capacitance electrode (not shown) which is one electrode of the additional capacitance. Further, an interlayer insulating film 39 is provided so as to cover the TFT 24, the gate wiring 22, the source wiring 23, and the connection electrode 25. A transparent conductive film to be the pixel electrode 21 is provided on the interlayer insulating film 39, and is connected to the drain electrode 36 b of the TFT 24 by the connection electrode 25 through the contact hole 26 that penetrates the interlayer insulating film 39.

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

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

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

  Further, 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, which becomes the interlayer insulating film 39, has a relative dielectric constant of 3.0 to 3.8, compared to the relative dielectric constant of the inorganic film (the relative dielectric constant of silicon nitride 8) 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. Further, by performing patterning by exposure and alkali development, the tapered shape of the contact hole 26 can be improved, and the connection between the pixel electrode 21 and the connection electrode (transparent conductive film) 37b can be improved. Furthermore, by using the above-described photosensitive resin composition, a thin film can be formed by using a spin coating method, so that a thin film having a thickness of several μm can be easily formed, and a photoresist process is not required for patterning. Therefore, it is advantageous in terms of productivity. Here, although the above-mentioned photosensitive resin composition used as the interlayer insulating film 39 is colored before coating, it can be made more transparent by performing an entire surface exposure process after patterning. Thus, the resin clarification treatment can be performed not only optically but also chemically.

  The exposure of the above-described photosensitive resin composition used as the interlayer insulating film 39 in the present embodiment is performed using a mercury lamp including bright lines of i-line (wavelength 365 nm), h-line (wavelength 405 nm), and g-line (wavelength 436 nm). It is common to use light rays. As the photosensitive resin composition, it is preferable to use a photosensitive resin composition having radiation sensitivity (absorption peak) to i-line having the highest energy (shortest wavelength) among these bright lines. It is possible to increase the 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.

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

(Synthesis of first siloxane resin)
(Synthesis Example 1) Synthesis of first siloxane resin A ′: (compound represented by the following formula (10); corresponding to the above general formula (1))

［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 Formula (10), 20, 50, and 30 show the molar ratio of the raw material corresponding to each site | part, respectively. ]

To a 500 mL four-necked flask equipped with a stirrer, reflux condenser, dropping funnel and thermometer, 55.8 g of toluene and 35.7 g of water were charged, and 3.12 g (0.03 mol) of 35% hydrochloric acid was added. Next, 13.5 g (0.0605 mol) of 3-acetoxypropyltrimethoxysilane, 30.0 g (0.151 mol) of phenyltrimethoxysilane and 12.4 g (0.0908 mol) of methyltrimethoxysilane in toluene 27 .9 g solution was added dropwise at 20-30 ° C. After completion of dropping, the mixture was aged at the same temperature for 2 hours. As a result of analyzing the reaction solution at this time by GC (gas chromatography), it was confirmed that no raw material remained. Next, toluene and water were added to the reaction solution to extract the product into an organic phase, which was washed with an aqueous sodium hydrogen carbonate solution and then washed with water until the solution became neutral. Thereafter, the organic phase was recovered, and toluene was removed to obtain 34.6 g of a viscous liquid siloxane resin. Furthermore, the obtained siloxane resin was dissolved in propylene glycol monomethyl ether acetate to obtain a siloxane resin solution adjusted to have a solid content concentration of 50% by mass.
The above siloxane resin and 69.2 g of methyl isobutyl ketone were charged into a 300 mL separatory funnel to make the solution uniform, and then extracted by adding 17.3 g of ion-exchanged water. After washing with water three times, the pH of the aqueous phase became 7.0, and the organic phase was recovered and concentrated to obtain 69.2 g of the target siloxane resin A in the form of a viscous liquid. Moreover, it was 1050 when the weight average molecular weight of the siloxane resin A was measured by GPC method.

(Synthesis Example 2) Synthesis of first siloxane resin B (compound represented by the following formula (5); corresponding to the above general formula (1))

［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 show the molar ratio of the raw material corresponding to each site | part, respectively. ]

  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. 78.4 g of the first siloxane resin B solution adjusted to 50% by mass was obtained. Moreover, it was 1020 when the weight average molecular weight of the siloxane resin B was measured by GPC method.

(Synthesis Example 3) Synthesis of first siloxane resin C (compound represented by the following formula (20); corresponding to the above general formula (1))

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

  Except for changing 13.5 g (0.0605 mol) of 3-acetoxypropyltrimethoxysilane to 39.0 g (0.0605 mol) of (5-acetoxynorborna-2 (or 3) -yl) triethoxysilane, 78.4 g of the 1st siloxane resin C solution adjusted to the target 50 mass% by operation similar to the synthesis | combining method of the said siloxane resin A was obtained. Moreover, it was 1050 when the weight average molecular weight of the siloxane resin C was measured by GPC method.

(Synthesis of second siloxane resin)
(Synthesis Example 4) Synthesis of Second Siloxane Resin D: Synthesis of Compound Represented by General Formula (6) below; Corresponding to General Formula (2) above

  In a 1000 mL four-necked flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, 131.5 g of tetraethoxysilane, 169.0 g of methyltriethoxysilane and 46.9 g of diethoxydimethylsilane were added to propylene glycol monomethyl ether acetate 123. A solution dissolved in 0.5 g was charged, and an aqueous nitric acid solution in which 0.04 g of 60% nitric acid was dissolved in 97.2 g of ion-exchanged water was added dropwise over 60 minutes with stirring. After completion of the dropwise addition, the mixture was reacted for 3 hours to obtain 568.2 g of a siloxane resin D solution having a solid content concentration of 20%. Moreover, it was 1200 when the weight average molecular weight of the siloxane resin D was measured by GPC method.

(Synthesis Example 5) Synthesis of second comparative siloxane resin E: Synthesis of compound represented by general formula (6) above; equivalent to general formula (2) above

  In a 1000 mL four-necked flask equipped with a stirrer, a reflux condenser, a dropping funnel, and a thermometer, 189.3 g of tetraethoxysilane, 243.3 g of methyltriethoxysilane, and 67.6 g of diethoxydimethylsilane were mixed with propylene glycol monomethyl ether acetate 258. A solution dissolved in .9 g was charged, and 140.9 g of a 0.6441% nitric acid aqueous solution was added dropwise over 60 minutes with stirring. After completion of the dropwise addition, the mixture was reacted for 3 hours to obtain 897.3 g of a solution. The low-boiling component was further distilled off from this solution with an evaporator, and after completion of the distillation, the weight of the solution was 464.0 g. To this solution, 253.8 g of propylene glycol monomethyl ether acetate was further added to obtain 717.8 g of a second comparative siloxane resin solution adjusted to 25% by mass. Moreover, it was 1250 when the weight average molecular weight of the siloxane resin E was measured by GPC method.

(Synthesis of third siloxane resin)
(Synthesis Example 6) Synthesis of third siloxane resin F (equivalent to hydrolytic condensation treatment third siloxane resin)

A 300 mL four-necked flask equipped with a stirrer, a reflux condenser, and a thermometer was charged with 37.5 g of siloxane resin A, 85.2 g of siloxane resin D, and 33.5 g of propylene glycol monomethyl ether acetate at room temperature (25 ° C. ). Thereafter, heat treatment was performed in an oil bath for 7 hours under the condition that the temperature of the mixed solution was 150 ° C. Low boiling components were distilled off at normal pressure. After the completion of the reaction, 44.8 g of propylene glycol monomethyl ether acetate was added and the mixture was allowed to stand at room temperature and cooled to obtain 144.9 g of a siloxane resin solution F adjusted to 25% by mass.
It was 10860 when the weight average molecular weight of the obtained siloxane resin F was measured. Further, this solution was applied on a silicon wafer substrate at 1100 revolutions for 30 seconds and the solvent was removed at a temperature of 120 ° C. The dissolution rate in 2.38% TMAH was 5.3 nm / sec.

  (Synthesis Example 7) Synthesis of the third siloxane resin G (the composition ratio of the siloxane resins A and D of Synthesis Example 6 was changed)

A 300 mL four-necked flask equipped with a stirrer, a reflux condenser and a thermometer was charged with 30.0 g of siloxane resin A, 159.1 g of siloxane resin D, and 43.3 g of propylene glycol monomethyl ether acetate and dissolved at room temperature. . Thereafter, heat treatment was performed in an oil bath for 8 hours under the condition that the temperature of the mixed solution was 150 ° C. Low boiling components were distilled off at normal pressure. After completion of the reaction, 87.0 g of propylene glycol monomethyl ether acetate was added and the mixture was allowed to stand at room temperature and cooled to obtain 185.5 g of a siloxane resin solution G adjusted to 25% by mass.
It was 12330 when the weight average molecular weight of the obtained siloxane resin G was measured. Also, the dissolution rate of 2.38% TMAH (tetramethylammonium hydroxide) in a film obtained by applying this solution onto a silicon wafer substrate at 1100 rpm for 30 seconds and removing the solvent at a temperature of 120 ° C. was 4. It was 7 nm / sec.

(Synthesis Example 8) Synthesis of the third siloxane resin H (the siloxane resin A of Synthesis Example 6 was changed to B)

Synthesis was performed in the same manner as in Synthesis Example 6 except that 37.5 g of siloxane resin A was changed to 37.5 g of siloxane resin B, to obtain 142.7 g of siloxane resin H adjusted to 25% by mass.
It was 11580 when the weight average molecular weight of the obtained siloxane resin H was measured. Further, this solution was applied on a silicon wafer substrate at 1100 revolutions for 30 seconds, and the dissolution rate of the film from which the solvent was removed at a temperature of 115 ° C. in 2.38% TMAH was 9.7 nm / sec.

(Synthesis Example 9) Synthesis of Siloxane Resin I (Replacement of Siloxane Tree A in Synthesis Example 6 to C)

Synthesis was performed in the same manner as in Synthesis Example 6 except that 37.5 g of siloxane resin A was changed to 37.5 g of siloxane resin C, to obtain 143.3 g of siloxane resin solution I adjusted to 25% by mass.
The weight average molecular weight of the obtained siloxane resin I was measured and found to be 10930. Further, this solution was applied on a silicon wafer substrate at 1100 revolutions for 30 seconds and the solvent was removed at a temperature of 115 ° C. The dissolution rate in 2.38% TMAH was 12.6 nm / sec.

(Synthesis Example 10) Synthesis of Comparative Siloxane Resin J (Low Boiling Component Not Removed during Synthesis of Siloxane Resin D)

  In a 300 mL four-necked flask equipped with a stirrer, reflux condenser, dropping funnel and thermometer, 67.5 g of siloxane resin A and 126.3 g of comparative siloxane resin D, 27.0 g of 10% nitric acid, and 97.9 g of propylene glycol monomethyl ether acetate were added. The mixture was heated and stirred at 95 ° C. for 5 hours. Next, methyl isobutyl ketone and water were added to the reaction solution for extraction, and then the organic phase was recovered, and methyl isobutyl ketone was removed to obtain 324.8 g of a viscous liquid siloxane resin. Further, the obtained siloxane resin was dissolved in propylene glycol monomethyl ether acetate to obtain a solution of comparative siloxane resin J adjusted to have a solid content concentration of 25% by mass. Moreover, it was 6800 when the weight average molecular weight of the siloxane resin J was measured by GPC method. The solution was applied on a silicon wafer substrate at 1100 revolutions for 30 seconds, and the solvent was removed at a temperature of 115 ° C. The dissolution rate in 2.38% TMAH was 11.7 nm / sec.

(Synthesis Example 11) Synthesis of Comparative Siloxane Resin K (with Low Molecular Weight of Siloxane Resin F)

  A 2000 mL four-necked flask equipped with a stirrer, a reflux condenser and a thermometer was charged with 50.0 g of siloxane resin A, 113.6 siloxane resin B: 113.6, and 44.7 g of propylene glycol monomethyl ether acetate and dissolved at room temperature. . Thereafter, heat treatment was performed in an oil bath for 4 hours under the condition that the temperature of the mixed solution was 150 ° C. Low boiling components were distilled off at normal pressure. After completion of the reaction, 59.8 g of propylene glycol monomethyl ether acetate was added, and the mixture was allowed to stand at room temperature and cooled to obtain 168.4 g of 25 mass% heat-treated siloxane resin K. Moreover, it was 6450 when the weight average molecular weight of the siloxane resin K was measured by GPC method. The solution was applied on a silicon wafer substrate at 1100 rpm for 30 seconds, and the solvent was removed at a temperature of 115 ° C. The dissolution rate in 2.38% TMAH was 58.9 nm / sec.

Synthesis Example 12 Synthesis of Comparative Siloxane Resin L (Increased Molecular Weight of Siloxane Resin D)

  A 100 mL four-necked flask equipped with a stirrer, a reflux condenser and a thermometer was charged with 56.8 g of siloxane resin D and 16.3 g of propylene glycol monomethyl ether acetate and dissolved at room temperature. Thereafter, heat treatment was performed in an oil bath for 20 hours under the condition that the temperature of the mixed solution was 130 ° C. Low boiling components were distilled off at normal pressure. After completion of the reaction, 10.9 g of propylene glycol monomethyl ether acetate was added, and the mixture was allowed to stand at room temperature and cooled to obtain 47.1 g of siloxane resin L adjusted to 25% by mass. Moreover, it was 25200 when the weight average molecular weight of the siloxane resin L was measured by GPC method. This solution was applied on a silicon wafer substrate at 1100 revolutions for 30 seconds, and the dissolution rate of the film from which the solvent was removed at 120 ° C. in 2.38% TMAH was 11.2 nm / sec.

(Synthesis of naphthoquinone diazide sulfonate ester)
(Synthesis Example 13) Synthesis of naphthoquinone diazide sulfonate A (corresponding to component (c) above)

  In a 1000 mL four-necked flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, 21.23 g of TrisP-PA (trade name, manufactured by Honshu Chemical Industry Co., Ltd., trisphenol novolak) under a dry nitrogen stream 0.05 mol) and 37.62 g (0.14 mol) of 5-naphthoquinone diazide sulfonyl chloride were dissolved in 450 g of 1,4-dioxane and brought to room temperature (25 ° C.). Here, 15.58 g (0.154 mol) of triethylamine mixed with 50 g of 1,4-dioxane was added dropwise so that the temperature in the system would not be 35 ° C. or higher. After completion of dropping, the mixture was stirred at 30 ° C. for 2 hours. The triethylamine salt was filtered and the filtrate was poured into water. Thereafter, the deposited precipitate was collected by filtration. This precipitate was dried with a vacuum dryer to obtain 48.36 g of a solid (naphthoquinone diazide sulfonate A).

(Synthesis Example 14) Synthesis of naphthoquinone diazide sulfonate ester B (corresponding to component (c) above)

  A 200 mL four-necked flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer was charged with 5.41 g of m-cresol and 50 g of tetrahydrofuran, and further 1,2-diazonaphthoquinone-5--5 at room temperature (25 ° C.). 13.43 g of sulfonyl chloride and 5.06 g of triethylamine were added, and the reaction was performed at room temperature (25 ° C.) for 4 hours. After completion of the reaction, the precipitated solid was filtered off. After adding 300 g of methyl isobutyl ketone to the solid matter separated by filtration and washing it with ion-exchanged water 50 g twice, the solvent was removed in a warm bath under reduced pressure to remove a solid substance (naphthoquinone diazide sulfonate B ) 14.7 g was obtained.

[Preparation of photosensitive resin composition]
Example 1
0.2 g of naphthoquinone diazide sulfonic acid ester A was added to 5.0 g of siloxane resin F solution (solid content: 1.25 g), and the mixture was stirred and dissolved at room temperature (25 ° C.) for 30 minutes. Photosensitive resin composition of Example 1 A product was prepared.

(Example 2)
0.2 g of naphthoquinone diazide sulfonic acid ester B was added to 5.0 g of siloxane resin F solution (solid content: 1.25 g), and the mixture was stirred and dissolved at room temperature (25 ° C.) for 30 minutes. Photosensitive resin composition of Example 2 A product was prepared.

(Example 3)
Add naphthoquinone diazide sulfonate A 0.15 g and naphthoquinone diazide sulfonate B 0.05 g to 5.0 g (solid content 1.25 g) of siloxane resin F, respectively, and stir and dissolve at room temperature (25 ° C.) for 30 minutes. A photosensitive resin composition of Example 3 was prepared.

Example 4
0.2 g of naphthoquinone diazide sulfonic acid ester A was added to 5.0 g of siloxane resin G solution (solid content: 1.25 g), and the mixture was stirred and dissolved at room temperature (25 ° C.) for 30 minutes. Photosensitive resin composition of Example 4 A product was prepared.

(Example 5)
0.2 g of naphthoquinone diazide sulfonic acid ester A was added to 5.0 g of siloxane resin H solution (solid content: 1.25 g), and the mixture was stirred and dissolved at room temperature (25 ° C.) for 30 minutes. Photosensitive resin composition of Example 5 A product was prepared.

(Example 6)
0.2 g of naphthoquinone diazide sulfonic acid ester A is added to 5.0 g of siloxane resin I solution (solid content: 1.25 g), and the mixture is stirred and dissolved at room temperature (25 ° C.) for 30 minutes. A product was prepared.

(Example 7)
To 3.5 g of the siloxane resin F (solid content 0.88 g), 1.5 g of the siloxane resin H solution (solid content 0.27 g) and 0.2 g of the naphthoquinone diazide sulfonic acid ester B solution were added, respectively. The mixture was stirred and dissolved at 25 ° C. for 30 minutes to prepare a photosensitive resin composition of Example 7.

(Example 8)
To a solution of 3.5 g of siloxane resin F (solid content of 0.88 g), 1.5 g of solution of siloxane resin I (solid content of 0.27 g) and 0.2 g of solution of naphthoquinone diazide sulfonic acid ester B were added. The mixture was stirred and dissolved at 25 ° C. for 30 minutes to prepare a photosensitive resin composition of Example 8.

(Comparative Example 1)
0.2 g of naphthoquinone diazide sulfonic acid ester A solution was added to 5.0 g of siloxane resin J solution (solid content: 1.25 g), and the mixture was stirred and dissolved at room temperature (25 ° C.) for 30 minutes. A functional resin composition was prepared.

(Comparative Example 2)
0.2 g of naphthoquinone diazide sulfonate A solution was added to 5.0 g of siloxane resin K solution (solid content: 1.25 g), respectively, and dissolved by stirring at room temperature (25 ° C.) for 30 minutes. Comparative Example 2 A photosensitive resin composition was prepared.

(Comparative Example 3)
0.2 g of naphthoquinone diazide sulfonic acid ester B solution was added to 5.0 g of siloxane resin L solution (solid content: 1.25 g), and the mixture was stirred and dissolved at room temperature (25 ° C.) for 30 minutes. A photosensitive resin composition was prepared.

  The composition (unit: g) of the photosensitive resin composition of each example and comparative example is shown in Table 1 below.

<Manufacture of silica-based coating>
The photosensitive resin compositions obtained in Examples 1 to 8 and Comparative Examples 1 to 3 were filtered with a PTFE (polytetrafluoroethylene) 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 2.0 μm. Then, it was made to dry at 90 to 120 degreeC for 2 minutes, and the solvent was removed. The obtained coating film was exposed through a predetermined pattern mask using a PLA-600F projection exposure machine manufactured by Canon Inc. with an exposure amount of 50 mJ / cm ² . Subsequently, using a 2.38 mass% TMAH (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 Inc. at an exposure amount of 1000 mJ / cm ² . Next, the pattern was finally cured at 350 ° C. for 30 minutes in a quartz tube furnace in which the O ₂ concentration was controlled to be less than 1000 ppm to obtain a silica-based coating.

<Evaluation of coating>
By the above-mentioned method, film | membrane evaluation was performed with the following method with respect to the silica-type film formed from the photosensitive resin composition of Examples 1-8 and Comparative Examples 1-3.

[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 Sokki Service Co., Ltd.), and “A” was evaluated when a 5 μm square through hole pattern was missing, and “B” was evaluated when it was not missing.

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

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

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

[Evaluation of temperature dependence]
With respect to the silica-based film formed on the silicon wafer, the resolution was confirmed when the temperature of the solvent removal step by a hot plate after spin coating was increased by 5 ° C. When using an electron microscope S-4200 (manufactured by Hitachi Sokki Service Co., Ltd.), if the through hole pattern of 5 μm square is missing, A, if it is almost missing but a little undissolved residue is observed B The case where it was not missing was evaluated as C.

[Storage stability evaluation]
The photosensitive resin compositions produced in Examples 1 to 8 and Comparative Examples 1 to 3 were stored for 3 weeks in a clean room at 24 ° C. and a relative humidity of 50%. Using the photosensitive resin composition after storage, a silica-based film is formed on a silicon wafer by the same method as described above, and the film thickness of the siloxane resin film is measured with an optical film thickness meter, and then 2.38. Immersion development was carried out with a mass% tetramethylammonium hydroxide aqueous solution, the dissolution time of the siloxane resin film at that time was measured, and the dissolution rate of the siloxane resin film was measured and evaluated. The case where the variation from the initial dissolution rate value was within 10% was evaluated as A, 10-20% as B, 20-30% as C, and 30% or more as D.

<Evaluation results>
The evaluation results of the silica-based films formed from the photosensitive resin compositions of Examples 1 to 8 and Comparative Examples 1 to 3 are shown in Table 1 below.

  From Table 1, the silica-based film formed from the photosensitive resin compositions of Examples 1 to 8 has very high storage stability and is excellent in resolution, transmittance, heat resistance and crack resistance. it is obvious. On the other hand, it was found that the silica-based films formed from the photosensitive resin compositions of Comparative Examples 1 to 3 had poor storage stability and the dissolution rate fluctuated by 20% or more from the initial value. Moreover, the crack generate | occur | produced about the comparative example 3 which does not contain the 1st siloxane resin shown by General formula (1).

  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, 8A ... storage electrode, 8B ... capacitor insulating film, 8C ... counter electrode, 10 ... memory cell capacitor, 20 ... active matrix substrate, 21 ... pixel electrode, 22 ... gate wiring, 23 ... source wiring, 24 ... TFT, 25 ... connection electrode, 26 ... contact hole, 27 ... additional capacitor counter electrode, 31 ... transparent insulating substrate, 32 ... gate electrode, 33 ... gate insulating film, 34 ... semiconductor layer, 35 ... channel protective layer, 36a ... Source electrode, 36b ... Drain electrode, 37a, 37b ... Transparent conductive film, 38a, 38b ... Metal layer, 39 ... Interlayer insulating film.

Claims (10)

Component (a): a first siloxane resin obtained by hydrolytic condensation of a first silane compound containing a compound represented by the following general formula (1), and a compound represented by the following general formula (2) A third siloxane having a weight average molecular weight in the range of 8000 to 300,000 obtained by mixing with a second siloxane resin obtained by hydrolytic condensation of a second silane compound containing Resin,
(B) component: a solvent for dissolving the siloxane resin comprising the component (a),
(C) component: naphthoquinone diazide sulfonic acid ester,
Containing a photosensitive resin composition.

[In General Formula (1), R ¹ represents a monovalent 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. May be. ]

[In General 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, A plurality of X 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. ]   Hydrolyzing and condensing the first silane compound to obtain a first siloxane resin, hydrolyzing and condensing the second silane compound to obtain a second siloxane resin, the first siloxane resin and the second A third siloxane resin produced by mixing and hydrolyzing and condensing the siloxane resin of the product and removing low boiling components such as alcohol and water produced by the hydrolytic condensation simultaneously with the hydrolytic condensation is used. The photosensitive resin composition as described.   The photosensitive resin composition of Claim 1 or Claim 2 whose naphthoquinone diazide sulfonic acid ester of said (c) component is ester of naphthoquinone diazide sulfonic acid and monohydric or polyhydric alcohol.   The photosensitive resin composition according to claim 4, wherein the polyhydric alcohol is an alcohol selected from the group consisting of ethylene glycol, propylene glycol, and polymers having a polymerization degree of 2 to 10.   The component (b) contains at least one solvent selected from the group consisting of ether acetate solvents, ether solvents, ester solvents, alcohol solvents and ketone solvents. The photosensitive resin composition as described in 2. An application step of applying the photosensitive resin composition according to claim 1 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 film having An application step of applying the photosensitive resin composition according to claim 1 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 film having   A semiconductor device comprising a substrate and a silica-based coating formed on the substrate by the method for forming a silica-based coating according to claim 6.   A flat display device comprising a substrate and a silica-based film formed on the substrate by the method for forming a silica-based film according to claim 6.   An electronic device member comprising a substrate and a silica-based film formed on the substrate by the method for forming a silica-based film according to claim 6 or 7.

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