JP2011257611A - Photosensitive resin composition, method for forming silica-based coating film, and electronic component - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition excellent in long-term stability when the composition is left to stand at room temperature, and allowing pattern formation with high accuracy even when exposure luminous energy is low.SOLUTION: The photosensitive resin composition contains: a siloxane resin having a weight average molecular weight of 5000 or more, obtained by hydrolyzing and condensing a siloxane compound containing a compound expressed by a general formula (1); at least one kind selected from a group consisting of a photoacid generator and a photobase generator; and a solvent that can dissolve the above siloxane resin. In the formula (1), Rrepresents a hydrogen atom or a F atom, or a group containing an atom of B, N, Al, P, Si, Ge or Ti, or an organic group having 1 to 20 carbon atoms; X represents a hydrolyzable group; n represents an integer of 0 to 2; 4-n of X may be identical or different from one another; and when n is 2, two of Rmay be identical or different from each other.

Description

  The present invention relates to a photosensitive resin composition, a method for forming a silica-based film, and an electronic component.

Conventionally, as an insulating film used for LSIs and displays, etc., it is excellent in heat resistance, electrical reliability, etc., so that it is an SiO ₂ film formed by a CVD method and an organic SOG (Spin On Glass) formed by a coating method. Membranes and inorganic SOG membranes are frequently used. However, it is impossible to directly form wiring trenches and via holes in conventional insulating films, and usually after patterning a photoresist on the insulating film, a dry etching process using plasma or a wet etching process using chemicals is performed. Next, a pattern is formed through a resist removal process and a cleaning process. On the other hand, if photosensitive properties are imparted to an insulating film material having excellent heat resistance, electrical reliability, transparency, etc., the resist material that is essential in the above process becomes unnecessary, and plasma dry etching treatment or chemical solution It is possible to omit the wet etching process, the resist removal process and the cleaning process.

  In recent years, photosensitive polysiloxane materials excellent in heat resistance, electrical reliability, transparency, and the like have been proposed. For example, Patent Document 1 and Patent Document 2 disclose a photosensitive resin composition comprising an alkali-soluble siloxane polymer from which water and a catalyst have been removed, a photoacid generator, and a solvent. Patent Documents 3 and 4 disclose photosensitive polysilazane compositions containing polysilazane and a photoacid generator.

Japanese Patent Laid-Open No. 6-148895 Japanese Patent Laid-Open No. 10-246960 JP 2000-181069 A Japanese Patent Laid-Open No. 2002-7502

  The present inventors have studied in detail the patterning using the insulating film material provided with such conventional photosensitive characteristics. As a result, for example, when a photosensitive resin composition comprising an alkali-soluble siloxane polymer from which water and catalyst have been removed, a photoacid generator, and a solvent as disclosed in Patent Document 1 and Patent Document 2 is used, both of them are used in a large amount. It was revealed that the exposure amount was required and the mass productivity was not excellent. Further, when a photosensitive polysilazane composition containing polysilazane and a photoacid generator disclosed in Patent Document 3 and Patent Document 4 is used, the exposure amount is small, but it is immersed in pure water after exposure or requires a humidification treatment. It has become clear that the process becomes complicated and it is difficult to obtain high pattern accuracy.

  Furthermore, it is clear that conventional photosensitive resin compositions as disclosed in Patent Documents 1 to 4 have poor stability at room temperature for a long time, so that sensitivity and resolution are likely to change, and mass productivity is poor. It became.

  The present invention has been made in view of such circumstances, and is excellent in long-term room temperature storage stability, and further, a photosensitive resin composition capable of forming a pattern with high accuracy even when the exposure amount is relatively small, and curing with high pattern accuracy. It is an object of the present invention to provide a method for forming a silica-based film from which a product can be obtained, and an electronic component using the photosensitive resin composition or method described above.

  As a result of extensive research, the present inventors have found that a photosensitive resin composition containing a specific component and a pattern forming method can solve various conventional problems, and complete the present invention. It came.

［式中、Ｒ^１は、Ｈ原子若しくはＦ原子、又はＢ原子、Ｎ原子、Ａｌ原子、Ｐ原子、Ｓｉ原子、Ｇｅ原子若しくはＴｉ原子を含む基、又は炭素数１〜２０の有機基を示し、Ｘは加水分解性基を示し、ｎは０〜２の整数を示し、４−ｎ個のＸは同一でも異なっていてもよく、ｎが２のとき、２個のＲ^１は同一でも異なっていてもよい。］ That is, the present invention comprises a siloxane resin having a weight average molecular weight of 5000 or more obtained by hydrolytic condensation of a siloxane compound containing a compound represented by the following general formula (1), a photoacid generator and a photobase generator. Provided is a photosensitive resin composition containing at least one selected from the group and a solvent capable of dissolving the siloxane resin.

[Wherein R ¹ represents an H atom or F atom, or a group containing a B atom, N atom, Al atom, P atom, Si atom, Ge atom or Ti atom, or an organic group having 1 to 20 carbon atoms. , X represents a hydrolyzable group, n represents an integer of 0 to 2, 4-n X may be the same or different, and when n is 2, two R ¹ are the same or different It may be. ]

  According to the photosensitive resin composition of the present invention, since the specific siloxane resin is used, the highly reactive SiOH group concentration can be reduced. As a result, the photosensitive property is excellent in long-term room temperature stability. It can be a resin solution. In addition, the siloxane resin according to the present invention can form a silica-based film having excellent insulating properties, low dielectric properties, heat resistance, and transparency.

  In addition, since the photosensitive resin composition of the present invention contains at least one selected from the group consisting of a photoacid generator and a photobase generator, it exhibits negative photosensitivity excellent in transparency and resolution. In addition, it is possible to obtain excellent developability at the time of development after exposure when forming a silica-based film.

  In the photosensitive resin composition of the present invention, the solvent is at least one solvent selected from the group consisting of ether acetate solvents, ether solvents, acetate solvents, alcohol solvents, and ketone solvents. It is preferable to include. By using such a solvent, the compatibility between the siloxane resin and the solvent can be increased, and a coating film with excellent in-plane uniformity can be formed with a small film thickness on the coating film surface.

  Moreover, it is preferable that the photosensitive resin composition of this invention further contains a hardening acceleration | stimulation catalyst. When the photosensitive resin composition contains a curing accelerating catalyst, the condensation reaction of SiOH groups present in the siloxane resin can be promoted, so that the resolution during development is improved and the insulation during curing is excellent. A silica-based film can be obtained.

  In addition, the present invention provides the above-described photosensitive resin composition of the present invention on a substrate to form a film, removes the solvent contained in the film, and heats the film after exposure and exposure through a pattern mask. Provided is a method for forming a silica-based film, which is developed to remove the unexposed film and heat-treat the remaining film to obtain a silica-based film having a pattern.

  According to the method for forming a silica-based film of the present invention, since the photosensitive resin composition of the present invention is used, the silica-based film having excellent in-plane film thickness uniformity, resolution, insulation, and transparency. Can be obtained. In addition, the photoacid generator or photobase generator contained in the photosensitive resin composition is photodegraded, and the resulting acid or base further accelerates the condensation reaction between silanol groups in the silica coating, so that the resulting silica type The heat resistance and mechanical strength of the coating are improved.

  The present invention further provides an electronic component comprising a substrate and a silica-based film having a pattern formed on the substrate by the above method.

  Since the electronic component of the present invention includes the silica-based film formed by the above method using the photosensitive resin composition of the present invention, the electronic component has excellent performance.

As described above, according to the present invention, it is easy to form a silica-based film having a pattern that can be used as an insulating film, and the formed silica-based film has a coating property, resolution, insulating properties, low A photosensitive resin composition having excellent dielectric properties, heat resistance, transparency, and mechanical properties, and a method for forming a silica-based film using the same can be provided.
Furthermore, this invention can provide an electronic component provided with the silica-type film which has the pattern formed by the formation method of the said silica-type film.

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

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

Here, the weight average molecular weight (Mw) can be measured using GPC under the following conditions, for example.
(conditions)
Sample: 5 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: 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

［式中、Ｒ^１は、Ｈ原子若しくはＦ原子、又はＢ原子、Ｎ原子、Ａｌ原子、Ｐ原子、Ｓｉ原子、Ｇｅ原子若しくはＴｉ原子を含む基、又は炭素数１〜２０の有機基を示し、Ｘは加水分解性基を示し、ｎは０〜２の整数を示し、４−ｎ個のＸは同一でも異なっていてもよく、ｎが２のとき、２個のＲ^１は同一でも異なっていてもよい。］
（ｂ）成分：光酸発生剤及び光塩基発生剤からなる群より選択される少なくとも１種
（ｃ）成分：上記シロキサン樹脂を溶解可能な溶媒。
以下、（ａ）成分、（ｂ）成分、（ｃ）成分のそれぞれにについて詳述する。 [Photosensitive resin composition]
The photosensitive resin composition which concerns on this embodiment contains the following (a)-(c) component.
(A) Component: Siloxane resin having a weight average molecular weight of 5000 or more obtained by hydrolytic condensation of a siloxane compound containing a compound represented by the following general formula (1)

[Wherein R ¹ represents an H atom or F atom, or a group containing a B atom, N atom, Al atom, P atom, Si atom, Ge atom or Ti atom, or an organic group having 1 to 20 carbon atoms. , X represents a hydrolyzable group, n represents an integer of 0 to 2, 4-n X may be the same or different, and when n is 2, two R ¹ are the same or different It may be. ]
(B) Component: At least one component (c) selected from the group consisting of a photoacid generator and a photobase generator: A solvent capable of dissolving the siloxane resin.
Hereinafter, each of the component (a), the component (b), and the component (c) will be described in detail.

<(A) component>
The component (a) is a siloxane resin having a weight average molecular weight of 5000 or more obtained by hydrolytic condensation of a silane compound containing the compound represented by the general formula (1). The siloxane resin preferably has an OH group at the terminal or side chain of the resin. This is because the hydrolysis condensation reaction for curing the photosensitive resin composition further proceeds.

Among the atoms or groups represented by R ¹ in the general formula (1), examples of the organic group having 1 to 20 carbon atoms include an aliphatic hydrocarbon group (aliphatic chain hydrocarbon group, aliphatic cyclic carbonization). A hydrogen group and a hydrocarbon group to which these are linked, the same applies hereinafter), an aromatic hydrocarbon group, a group in which an aliphatic hydrocarbon group and an aromatic hydrocarbon group are linked, and the like. Among these, a linear, branched or cyclic aliphatic hydrocarbon group having 1 to 20 carbon atoms is preferable. Specific examples of the linear aliphatic hydrocarbon group having 1 to 20 carbon atoms include groups such as a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and an n-pentyl group. Specific examples of the branched aliphatic hydrocarbon group include groups such as isopropyl group and isobutyl group. Specific examples of the cyclic aliphatic hydrocarbon group include groups such as a cyclopentyl group, a cyclohexyl group, a cycloheptylene group, a norbornyl group, and an adamantyl group. Among these, a linear aliphatic hydrocarbon group having 1 to 5 carbon atoms such as a methyl group, an ethyl group, and an n-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, a divalent aliphatic hydrocarbon group, an aromatic hydrocarbon group, and an aliphatic hydrocarbon group. And divalent groups linked to each other. 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 cyclopentylene group or a cyclohexylene group such as a C3-C3 group. 7 cyclic divalent hydrocarbon groups and cyclic divalent hydrocarbon groups 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.

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

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

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

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

In addition, the compound of the general formula (1) in which R ¹ is an organic group having 1 to 20 carbon atoms, and other compounds than the above include, for example, bis (trimethoxysilyl) methane, bis (triethoxysilyl) methane, bis (Tri-n-propoxysilyl) methane, bis (tri-iso-propoxysilyl) methane, bis (trimethoxysilyl) ethane, bis (triethoxysilyl) ethane, bis (tri-n-propoxysilyl) ethane, bis ( Tri-iso-propoxysilyl) ethane, bis (trimethoxysilyl) propane, bis (triethoxysilyl) propane, bis (tri-n-propoxysilyl) propane, bis (tri-iso-propoxysilyl) propane, bis (tri Methoxysilyl) benzene, bis (triethoxysilyl) benzene, bis (tri-n-pro Examples thereof include bissilylalkanes such as (poxysilyl) benzene and bis (tri-iso-propoxysilyl) benzene, and bissilylbenzene.

  Moreover, as a compound (halogenated silane) of General formula (1) whose hydrolyzable group X is a halogen atom (halogen group), the alkoxy group in each alkoxysilane molecule mentioned above is substituted with a halogen atom, for example. And the like. Furthermore, examples of the compound (acetoxysilane) of the general formula (1) in which the hydrolyzable group X is an acetoxy group include those in which the alkoxy group in each alkoxysilane molecule described above is substituted with an acetoxy group. It is done. Furthermore, examples of the compound (isocyanate silane) of the general formula (1) in which the hydrolyzable group X is an isocyanate group include those in which the alkoxy group in each alkoxysilane molecule described above is substituted with an isocyanate group. Can be mentioned. Furthermore, examples of the compound (hydroxysilane) of the general formula (1) in which the hydrolyzable group X is a hydroxyl group include those in which the alkoxy group in each alkoxysilane molecule described above is substituted with a hydroxyl group. Can be mentioned.

  The compound represented by General formula (1) is used individually by 1 type or in combination of 2 or more types.

  Further, a resin obtained by hydrolytic condensation of a partial condensate such as a multimer of the compound represented by the general formula (1), a partial condensate such as a multimer of the compound represented by the general formula (1) and the general Resin obtained by hydrolytic condensation of the compound represented by formula (1), resin obtained by hydrolytic condensation of the compound represented by general formula (1) and other compounds, general formula (1) It is also possible to use a resin obtained by hydrolytic condensation of a partial condensate such as a multimer of the compound represented by general formula (1) and another compound.

  Examples of partial condensates such as multimers of the compound represented by the general formula (1) include hexamethoxydisiloxane, hexaethoxydisiloxane, hexa-n-propoxydisiloxane, hexa-iso-propoxydisiloxane, and the like. Examples include hexaalkoxydisiloxane, trisiloxane having advanced partial condensation, tetrasiloxane, and oligosiloxane.

  Examples of the “other compounds” include compounds having a polymerizable double bond or triple bond. Examples of the compound having a polymerizable double bond include ethylene, propylene, isobutene, butadiene, isoprene, vinyl chloride, vinyl acetate, vinyl propionate, vinyl caproate, vinyl stearate, methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether. , Acrylonitrile, styrene, methacrylic acid, methyl methacrylate, ethyl methacrylate, methacrylate-n-propyl, methacrylate-iso-propyl, methacrylate-n-butyl, acrylic acid, methyl acrylate, ethyl acrylate, acrylic acid Examples thereof include phenyl, vinylpyridine, vinylimidazole, acrylamide, allylbenzene, diallylbenzene and the like, and those obtained by partial condensation of these compounds. Examples of the compound having a triple bond include acetylene and ethynylbenzene.

  The resins thus obtained are used alone or in combination of two or more.

  The amount of water used when hydrolyzing and condensing the silane compound containing the compound represented by the general formula (1) is 0.1 to 1000 mol per mole of the compound represented by the general formula (1). Preferably, it is 0.5-100 mol. If the amount of water is less than 0.1 mol, the hydrolysis-condensation reaction tends not to proceed sufficiently, and if the amount of water exceeds 1000 mol, gelation tends to occur during hydrolysis or condensation.

  Moreover, it is also preferable to use a catalyst in the hydrolysis condensation of the compound represented by the general formula (1). Examples of such a catalyst include an acid catalyst, an alkali catalyst, and a metal chelate compound.

  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- Examples thereof include toluenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, trifluoroethanesulfonic acid, and the like. 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.

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

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

  In the hydrolytic condensation of the compound represented by the general formula (1), it is preferable to carry out hydrolysis using such a catalyst. However, when the stability of the composition is deteriorated or the catalyst is contained, corrosion to other materials, etc. In some cases, the impact of In such a case, for example, after the hydrolysis, the catalyst may be removed from the composition, or may be reacted with another compound to deactivate the function as a catalyst. There is no particular limitation on the method of removing or reacting, but it may be removed using distillation, ion chromatography column or the like. Moreover, the hydrolyzate obtained from the compound represented by the general formula (1) may be taken out of the composition by reprecipitation or the like. In addition, as a method of deactivating the function as a catalyst by reaction, for example, when the catalyst is an alkali catalyst, a method of adding an acid catalyst and neutralizing it by an acid-base reaction or bringing the pH to the acidic side can be mentioned. It is done.

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

  Furthermore, since the alcohol by-produced by this hydrolysis is a protic solvent, it is preferably removed using an evaporator or the like.

  The resin thus obtained preferably has a weight average molecular weight of 5,000 to 100,000, preferably 5,000 to 50,000, from the viewpoints of solubility in a solvent, mechanical properties, moldability, room temperature storage stability, and the like. More preferably, it is further preferably 5000 to 30000, particularly preferably 6000 to 20000, and most preferably 6000 to 15000. If the weight average molecular weight is less than 5,000, the room temperature storage stability of the solution tends to be inferior. If the weight average molecular weight exceeds 100,000, the compatibility with the solvent tends to decrease.

When adhesion to the substrate and mechanical strength are required, H atom, F atom, B atom, N atom, Al atom, P atom, Si atom, Ge atom with respect to 1 mol of Si atom in the general formula (1) , The total content of at least one atom selected from the group consisting of Ti atoms and C atoms (this is the total number (M) of specific bonding atoms (R ¹ in the general formula (1)). 1.3-0.2 mol, more preferably 1.0-0.2 mol, particularly preferably 0.90-0.2 mol, 0.8-0. Very preferably 2 moles. If it does in this way, the adhesiveness to the other film | membrane (layer) of hardened | cured material and the fall of mechanical strength can be suppressed.

  When the total number (M) of the specific bonding atoms is less than 0.20, the dielectric properties tend to be inferior when the cured product is used as an insulating film. There is a tendency that the adhesiveness to the film (layer), mechanical strength, etc. are inferior. Further, among the above-mentioned specific bonding atoms, at least one kind selected from the group consisting of H atom, F atom, N atom, Si atom, Ti atom and C atom in terms of film formability of the cured product. It is preferable that an atom is included, and among them, in terms of dielectric properties and mechanical strength, at least one atom selected from the group consisting of H atom, F atom, N atom, Si atom and C atom is included. Is more preferable.

In addition, the total number (M) of a specific bond atom can be calculated | required from the preparation amount of siloxane resin, for example, following formula (A):
M = (M1 + (M2 / 2) + (M3 / 3)) / Msi (A)
It can be calculated using the relationship represented by In the formula, M1 represents the total number of atoms bonded to a single (only one) Si atom among specific bond atoms, and M2 is bonded to two silicon atoms among the specific bond atoms. M3 represents the total number of atoms bonded to three of the specific bonding atoms, and Msi represents the total number of Si atoms.

  Such siloxane resins are used alone or in combination of two or more. As a method of combining two or more types of siloxane resins, for example, a method of combining two or more types of siloxane resins having different weight average molecular weights, or two or more types of siloxane resins obtained by hydrolytic condensation using different compounds as essential components The method of combining, etc. are mentioned.

<(B) component>
The component (b) is at least one selected from the group consisting of a photoacid generator and a photobase generator, and the component (a) can be photocured (hydrolytic polycondensation) by irradiation with radiation. Defined as a compound capable of releasing an acidic or basic active substance.

  Examples of the photoacid generator include diarylsulfonium salts, triarylsulfonium salts, dialkylphenacylsulfonium salts, diaryliodonium salts, aryldiazonium salts, aromatic tetracarboxylic acid esters, aromatic sulfonic acid esters, nitrobenzyl esters, oximes. Examples include sulfonic acid esters, aromatic N-oxyimide sulfonates, aromatic sulfamides, haloalkyl group-containing hydrocarbon compounds, haloalkyl group-containing heterocyclic compounds, and naphthoquinone diazide-4-sulfonic acid esters. These are used singly or in combination of two or more. It can also be used in combination with other sensitizers.

  Examples of the photobase generator include compounds represented by the following general formulas (2) to (5), nonionic photobase generators such as nifedipines, cobalt amine complexes, the following general formula (6), Examples thereof include ionic photobase generators such as quaternary ammonium salts represented by the following general formula (7). These may be used alone or in combination of two or more. It can also be used in combination with other sensitizers.

(R ² —OCO—NH) _m —R ³ (2)
Here, in the formula, R ² represents a monovalent organic group having 1 to 30 carbon atoms, may include an aromatic ring having a methoxy group or a nitro group in the side chain, and R ³ represents 1 to 1 carbon atoms. 20 represents a 1-4 valent organic group, and m is an integer of 1-4.

^{(R 4 R 5 C = N} -OCO) m -R 3 ... (3)
Here, in the formula, R ³ and m are the same as those in the general formula (2), and R ⁴ and R ⁵ each independently represent a monovalent organic group having 1 to 30 carbon atoms, and are bonded to each other. An annular structure may be formed.

R ² —OCO—NR ⁶ R ⁷ (4)
Here, in the formula, R ² has the same meaning as that in the general formula (2), and R ⁶ and R ⁷ each independently represent a monovalent organic group having 1 to 30 carbon atoms and are bonded to each other to form a ring. A structure may be formed, and one of them may be a hydrogen atom.

R ⁸ —CO—R ⁹ —NR ⁶ R ⁷ (5)
Here, in the formula, R ⁶ and R ⁷ have the same meanings as those in the general formula (4), R ⁸ represents a monovalent organic group having 1 to 30 carbon atoms, and an alkoxy group or nitro group is present in the side chain. An aromatic ring having an amino group, an alkyl-substituted amino group or an alkylthio group, R ⁹ represents a divalent organic group having 1 to 30 carbon atoms.

ここで、式中、Ｒ^１０は炭素数１〜３０の１価の有機基を示し、Ｒ^１１及びＲ^１２は各々独立に炭素数１〜３０の１価の有機基又は水素原子を示し、Ｘ^１は、下記一般式（６Ａ）、（６Ｂ）、（６Ｃ）、（６Ｄ）、（６Ｅ）及び（６Ｆ）（以下、「（６Ａ）〜（６Ｆ）」のように表記する。）のいずれかで表される１価の基を示し、Ｚ⁻はアンモニウム塩の対イオンを示し、ｔは１〜３の整数であり、ｐ及びｑは０〜２の整数であり、ｔ＋ｐ＋ｑ＝３である。

Here, in the formula, R ¹⁰ represents a monovalent organic group having 1 to 30 carbon atoms, R ¹¹ and R ¹² each independently represents a monovalent organic group having 1 to 30 carbon atoms or a hydrogen atom, and X ¹ is any ^one of the following general formulas (6A), (6B), (6C), (6D), (6E) and (6F) (hereinafter referred to as “(6A) to (6F)”). Z ⁻ represents a counter ion of an ammonium salt, t is an integer of 1 to 3, p and q are integers of 0 to 2, and t + p + q = 3 .

ここで、式中、Ｒ^１３、Ｒ^１４、Ｒ^１５及びＲ^１６は各々独立に炭素数１〜３０の１価の有機基を示し、Ｒ^１７、Ｒ^１８及びＲ^１９は各々独立に炭素数１〜３０の２価の有機基又は単結合を示し、Ｒ^２０及びＲ^２１は各々独立に炭素数１〜３０の３価の有機基を示す。

Here, in the formula, R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ each independently represent a monovalent organic group having 1 to 30 carbon atoms, and R ¹⁷ , R ¹⁸ and R ¹⁹ each independently represent 1 carbon atom. Represents a divalent organic group or single bond of ˜30, and R ²⁰ and R ²¹ each independently represents a trivalent organic group having 1 to 30 carbon atoms.

ここで、式中、Ｒ^１０、Ｒ^１１及びＲ^１２、Ｚ⁻、ｔ、ｐ及びｑは上記一般式（６）におけるものと同様であり、Ｘ^２は下記一般式（７Ａ）〜（７Ｄ）のいずれかで表される２価の基を示す。

Here, in the formula, R ¹⁰ , R ¹¹ and R ¹² , Z ⁻ , t, p and q are the same as those in the above general formula (6), and X ² is the following general formula (7A) to (7D). The bivalent group represented by either of these is shown.

ここで、式中、Ｒ^１３、Ｒ^１４、Ｒ^１５、Ｒ^１６、Ｒ^１７、Ｒ^１８、Ｒ^１９、Ｒ^２０及びＲ^２１は、上記一般式（６Ａ）〜（６Ｆ）におけるものと同義である。

Here, in formula, R <^13> , R <^14> , R <^15> , R <^16> , R <^17> , R <^18> , R <^19> , R < ²⁰ > and R < ²¹ > are synonymous with those in the above general formulas (6A) to (6F). .

  The amount of component (b) used is not particularly limited, but depends on the sensitivity and efficiency of the photoacid generator or photobase generator used, the light source used, the desired thickness of the cured product, etc. The range is wide. Specifically, the use amount of the component (b) is preferably 0.0001 to 50% by weight, and is 0.001 to 20% by weight with respect to the total amount of the component (a) in the radiation curable composition. More preferably, it is 0.01 to 10% by weight. If the amount used is less than 0.0001% by weight, the photocurability tends to be reduced or a large amount of exposure tends to be required for curing. If the amount used exceeds 50% by weight, the stability of the composition and the film formability are increased. Etc. tend to be inferior, and the electrical properties and process compatibility of the cured product tend to be reduced.

  Moreover, you may use a photosensitizer together with the photo-acid generator or photobase generator mentioned above. By using a photosensitizer, radiation energy rays can be efficiently absorbed, and the sensitivity of the photoacid generator or photobase generator can be improved. Examples of the photosensitizer include anthracene derivatives, perylene derivatives, anthraquinone derivatives, thioxanthone derivatives, and coumarins.

  In order to improve the storage stability, when storing the photosensitive resin composition, for example, it is preferable to store at a temperature of 5 ° C. or lower. The lower limit of this temperature is preferably equal to or higher than the freezing point of the solvent in the photosensitive resin composition, and is preferably −50 ° C.

<(C) component>
The component (c) is a solvent capable of dissolving the component (a), and examples thereof include an aprotic solvent and a protic solvent, and it is preferable to contain an aprotic solvent. The inventors presume that an aprotic solvent is effective in reducing the exposure dose and improving the pattern accuracy.

  A protic solvent typified by alcohol has a hydrogen atom bonded to an oxygen atom having a large electronegativity. For this purpose, protic solvent molecules solvate by forming hydrogen bonds with nucleophiles and the like. That is, since the protic solvent solvates with the siloxane resin obtained by hydrolyzing the compound represented by the general formula (1), in order for the siloxane resin to condense, this solvent molecule must be removed. It is considered that there is a tendency to inhibit the curing at the same time.

  On the other hand, an aprotic solvent is a solvent that does not have a hydrogen atom on an element having a large electronegativity, and is considered to have a smaller factor of reaction inhibition than a protic solvent. Therefore, the curing reaction proceeds with the generation of the acidic active substance and the basic active substance in the exposed portion, and the pattern accuracy is unlikely to decrease due to the diffusion of acid or base, and the pattern accuracy tends to be improved. This is different from the mechanism of improving the pattern accuracy by deactivating (neutralizing) the acid generated by the conventional acid diffusion control agent. Thereby, when the aprotic solvent is contained in the component (c), it is considered that the effects of improving the pattern accuracy and reducing the exposure amount are more effectively exhibited.

  Examples of the aprotic solvent contained in the component (c) include acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-iso-propyl ketone, methyl-n-butyl ketone, methyl-iso-butyl ketone, and methyl-n-. Pentyl ketone, methyl-n-hexyl ketone, diethyl ketone, dipropyl ketone, di-iso-butyl ketone, trimethylnonanone, cyclohexanone, cyclopentanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone, γ-butyrolactone Ketone solvents such as γ-valerolactone; diethyl ether, methyl ethyl ether, methyl-n-di-n-propyl ether, di-iso-propyl ether, tetrahydrofuran, methyltetrahydrofuran, dioxane, dimethyl Ludioxane, 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, triethyl N-butyl 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, dipropylene glycol Dimethyl ether, dipropylene glycol 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, tetrapropylene glycol dimethyl ether, tetrapropylene glycol Diethyl ether, tetradipropylene 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 Ether solvents such as methyl acetate, ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-acetate Methoxybutyl, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methyl cyclohexyl acetate, nonyl acetate, methyl acetoacetate, ethyl acetoacetate, diethylene acetate Recall monomethyl ether, acetic acid diethylene glycol monoethyl ether, acetic acid diethylene glycol mono-n-butyl ether, acetic acid dipropylene glycol monomethyl ether, acetic acid dipropylene glycol monoethyl ether, diacetic acid glycol, acetic acid methoxytriglycol, acetic acid ethyl ethyl, propionic acid n- Ester solvents such as butyl, i-amyl propionate, 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, Ether acetate solvents such as ethylene glycol-n-butyl 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-ethylpyrrolidinone, N-propylpyrrolidinone, N-butylpyrrolidinone, N-hexylpyrrolidinone, N-cyclohexylpyrrolidinone, N, N-dimethylformamide, N, N-dimethylacetamide, N, N-dimethylsulfoxide, etc. In-plane film thickness uniformity during coating, sensitivity and pattern accuracy during pattern formation, and cured product From the viewpoint of mechanical strength, ether solvents, ester solvents, ether acetate solvents and ketone solvents are preferred. Moreover, it is preferable that it is a solvent which does not have a nitrogen atom.

  Among these, an ether acetate solvent, an ether solvent, and a ketone solvent are preferable, an ether acetate solvent and an ether solvent are more preferable, and an ether acetate solvent is particularly preferable. These are used singly or in combination of two or more.

  The proportion of the aprotic solvent used is preferably 50% by weight or more in the total solvent, more preferably 70% by weight or more, particularly preferably 90% by weight or more, and 95% by weight or more. It is very preferable. If the use ratio is small, the exposed area tends not to be cured sufficiently when the exposure amount is small. Alternatively, if the use ratio is small, heat treatment at a higher temperature is required for sufficient curing, and the generated acid or base tends to diffuse, and the pattern accuracy tends to deteriorate.

  (C) Although the method using a component is not specifically limited, For example, (a) The method used as a solvent at the time of preparing a component, (a) The method of adding after preparing a component, The method of performing solvent exchange, (a) There is a method of taking out the components by evaporating the solvent and adding (c) a solvent.

  The amount of this solvent (the total of the aprotic solvent and the protic solvent) is preferably such that the concentration of the component (a) (siloxane resin) is 3 to 60% by weight. If the amount of the solvent is excessive and the concentration of the component (a) is less than 3% by weight, it tends to be difficult to form a cured product having a desired film thickness. The amount of the solvent is too small and the concentration of the component (a) is 60% by weight. When it exceeds%, the film formability of the cured product is deteriorated and the stability of the composition itself tends to be lowered.

<(D) component>
The photosensitive resin composition according to the present embodiment can further contain a curing accelerating catalyst as the component (d) in addition to the components (a) to (c). Here, when the curing accelerating catalyst is added to the photosensitive resin composition, the condensation reaction is accelerated, and the effect of reducing the amount of photoacid generator or the amount of photobase generator, the effect of reducing the exposure amount, or the PEB It is considered that a temperature lowering effect can be expected. This curing accelerating catalyst is different from a normal photoacid generator or photobase generator that generates an active substance by the light of component (b). Therefore, although an onium salt can be used as the component (d), the onium salt is usually distinguished from an onium salt used as a photoacid generator or a photobase generator. However, any material that has both photoacid generation ability or photobase generation ability and curing acceleration catalytic ability can be used.

  It is considered that the curing accelerating catalyst which is the component (d) is a unique one which does not show a catalytic action in a solution and shows activity in a coated film. In the exposed area, the condensation reaction by the curing accelerating catalyst, that is, the curing reaction proceeds with the generation of the acidic active substance or basic active substance, so the pattern accuracy is less likely to deteriorate due to diffusion of acid or base, that is, the pattern accuracy is further improved. It is estimated that.

  Means for examining the curing acceleration catalytic ability of the curing acceleration catalyst are shown in 1-4 below.

1. A composition comprising the component (a) and the component (c) is prepared.
2. The composition prepared in 1 above is applied to a silicon wafer so that the film thickness after baking is 1.0 ± 0.1 μm, and the film is baked at a predetermined temperature for 30 seconds to measure the film thickness.
3. The silicon wafer on which the film is formed is immersed in a 2.38 wt% tetramethylammonium hydroxide (TMAH) aqueous solution at 23 ± 2 ° C. for 30 seconds, and the film thickness of the film after rinsing and drying is observed. At this time, the minimum temperature at the time of baking at which the change in film thickness before and after immersion in the TMAH aqueous solution is within 20% is defined as the insoluble temperature.
4). In the composition prepared in 1 above, 0.01% by weight of the compound whose curing acceleration catalytic ability is to be confirmed is added to the total amount of the component (a) to obtain a composition. Determine the insoluble temperature. If the insolubility temperature is lowered by adding a compound for which curing acceleration catalytic ability is desired, the compound has curing acceleration catalytic ability.

  As the curing accelerating catalyst as component (d), an onium salt is preferable from the viewpoint of improving the electrical characteristics and mechanical strength of the resulting cured product and further improving the stability of the composition, and a quaternary ammonium salt. It is more preferable that

  Examples of other curing accelerating catalysts include alkali metals such as sodium hydroxide, sodium chloride, potassium hydroxide, and potassium chloride. These are used alone or in combination of two or more. However, when using these curing accelerating catalysts, it is preferable to use an onium salt in combination.

  More specifically, as the onium salt, ammonium hydroxide, ammonium fluoride, ammonium chloride, ammonium bromide, ammonium iodide, ammonium phosphate salt, ammonium nitrate salt, ammonium borate salt, ammonium sulfate salt, ammonium formate salt, maleic acid Ammonium salt, ammonium fumarate, ammonium phthalate, ammonium malonate, ammonium succinate, ammonium tartrate, ammonium malate, ammonium lactate, ammonium citrate, ammonium acetate, ammonium propionate, Ammonium butanoate, ammonium pentanoate, ammonium hexanoate, ammonium heptanoate, ammonium octanoate, ammonium nonanoate Salt, ammonium decanoate, ammonium oxalate, ammonium adipate, ammonium sebacate, ammonium butyrate, ammonium oleate, ammonium stearate, ammonium linoleate, ammonium linoleate, ammonium salicylate Benzene sulfonic acid ammonium salt, benzoic acid ammonium salt, p-aminobenzoic acid ammonium salt, p-toluenesulfonic acid ammonium salt, methanesulfonic acid ammonium salt, trifluoromethanesulfonic acid ammonium salt, trifluoroethanesulfonic acid ammonium salt, etc. The ammonium salt compound of these is mentioned.

  In these onium salt compounds, ammonium salts such as tetramethylammonium nitrate, tetramethylammonium acetate, tetramethylammonium propionate, tetramethylammonium maleate, and tetramethylammonium sulfate are used from the viewpoint of accelerating the curing of the cured product. Is preferred.

  These are used singly or in combination of two or more.

  The amount of component (d) used is preferably 0.0001 to 5% by weight, more preferably 0.0001 to 1% by weight, based on the total amount of component (a) in the photosensitive resin composition. preferable. If the amount used is less than 0.0001% by weight, a large amount of exposure tends to be required for curing. When the amount used exceeds 5% by weight, the stability of the composition and the film formability tend to be inferior, and the electrical properties and process suitability of the cured product tend to be lowered.

  Moreover, from the viewpoint of sensitivity and stability, the amount of the curing accelerating catalyst that is component (d) is 0.0001 to 5.0% by weight based on the total amount of component (a) in the photosensitive resin composition. It is preferable that it is 0.001-2.0 weight%, and it is especially preferable that it is 0.01-1.0 weight%.

  In addition, an onium salt can be added so that it may become a desired density | concentration, after melt | dissolving or diluting in water or a solvent as needed. Further, the timing of addition is not particularly limited, and examples include the time when the component (a) is hydrolyzed, during the hydrolysis, at the end of the reaction, before and after the solvent is distilled off, and when the acid generator is added.

<Other ingredients>
Moreover, the photosensitive resin composition which concerns on this embodiment may further contain a pigment | dye. When the photosensitive resin composition contains a pigment, for example, an effect of adjusting sensitivity, an effect of suppressing a standing wave effect, and the like are obtained.

  In addition, the photosensitive resin composition according to the present embodiment has a thermal decomposability such as a surfactant, a silane coupling agent, a thickener, an inorganic filler, and polypropylene glycol as long as the object and effect of the present invention are not impaired. You may further contain a compound, a volatile compound, etc. The thermally decomposable compound and the volatile compound are preferably decomposed or volatilized by heat (preferably 250 to 500 ° C.) and can form voids. Moreover, you may provide void | hole formation ability to the siloxane resin which is (a) component.

  In addition, when using the photosensitive resin composition for an electronic component, it is desirable not to contain an alkali metal or an alkaline earth metal, and even if it is included, the metal ion concentration in the composition may be 1000 ppm or less. Preferably, it is 1 ppm or less. When these metal ion concentrations exceed 1000 ppm, the metal ions easily flow into electronic components such as semiconductor elements having a cured product obtained from the composition, which may adversely affect the device performance itself. Therefore, it is effective to remove alkali metal or alkaline earth metal from the composition using an ion exchange filter or the like, if necessary. However, when used for optical waveguides, other uses, etc., this is not limited as long as the purpose is not impaired.

  Next, a method for forming a cured product patterned on a substrate using the photosensitive resin composition according to the present embodiment will be described by taking a spin coat method generally excellent in film formability and film uniformity as an example. However, the cured product forming method is not limited to the spin coating method. Further, the substrate may be one having a flat surface or one having electrodes or the like and having irregularities.

  First, the photosensitive resin composition is spin-coated on a substrate such as a silicon wafer or a glass substrate, preferably at 500 to 5000 revolutions / minute, more preferably 500 to 3000 revolutions / minute, to form a film. If the rotational speed is less than 500 revolutions / minute, the film uniformity tends to deteriorate, and if it exceeds 5000 revolutions / minute, the film formability may deteriorate.

  The film thickness of the cured product varies depending on the intended use. For example, the film thickness when used for an interlayer insulating film such as LSI is preferably 0.01 to 2 μm, and the film thickness when used for a passivation layer is 2 to 2 μm. It is preferable that it is 40 micrometers. The film thickness when used for liquid crystal is preferably 0.1 to 20 μm, the film thickness when used for a photoresist is preferably 0.1 to 2 μm, and the film when used for an optical waveguide The thickness is preferably 1 to 50 μm. Usually, this film thickness is generally preferably from 0.01 to 10 μm, more preferably from 0.01 to 5 μm, still more preferably from 0.01 to 3 μm, and preferably from 0.01 to 2 μm. Is particularly preferable, and it is very preferably 0.1 to 2 μm. In order to adjust the film thickness of the cured product, for example, the concentration of the component (a) in the composition may be adjusted. When using the spin coating method, the film thickness can be adjusted by adjusting the number of rotations and the number of coatings. When the film thickness is controlled by adjusting the concentration of the component (a), for example, when the film thickness is increased, the concentration of the component (a) is increased, and when the film thickness is decreased, the component (a) It can be controlled by lowering the concentration of. In addition, when adjusting the film thickness using the spin coating method, for example, when increasing the film thickness, the rotation speed is decreased or the number of coatings is increased, and when the film thickness is decreased, the rotation speed is decreased. It can be adjusted by raising or reducing the number of times of application.

  Next, the solvent in the coating is dried by a hot plate or the like preferably at 50 to 200 ° C., more preferably at 70 to 150 ° C., but the drying temperature is set so that the coating dissolves under various conditions during subsequent development. It needs to be adjusted. If the drying temperature is less than 50 ° C., the solvent tends not to be sufficiently dried. If the drying temperature exceeds 200 ° C., the solvent does not dissolve during development and a pattern may not be formed.

Next, radiation is exposed through a mask having a desired pattern. Preferably this dose is 5~5000mJ / cm ^2, more preferably 5~1000mJ / cm ^2, particularly preferably from 5~500mJ / cm ^2, is 5 to 100 mJ / cm ² It is very preferable. The exposure amount may become difficult to control by the light source is less than ^{5mJ / cm 2, 5000mJ / cm} 2 greater than the exposure time becomes long, there is a tendency that the productivity is deteriorated. In addition, the exposure amount of the conventional general siloxane type photosensitive resin composition is about 500-5000 mJ / cm < ² >.

  For example, visible light, ultraviolet light, infrared light, X-rays, α-rays, β-rays, γ-rays and the like can be used as the radiation in this case, and ultraviolet rays are particularly preferable. Examples of the ultraviolet ray generation source include an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, and an excimer lamp.

  Although the unexposed area is sufficiently soluble in the developer, an acidic active substance or a basic active substance is generated in the exposed area, causing a hydrolysis condensation reaction, resulting in a decrease in solubility in the developer. Thereby, a pattern is formed.

  Next, heating (post-exposure baking: PEB) is performed after exposure. This heating is to heat the film with a hot plate or the like, but it is preferable to heat in a temperature range where the solubility of the unexposed portion in the developer does not decrease. This temperature is preferably 50 to 200 ° C, more preferably 70 to 150 ° C, and particularly preferably 70 to 110 ° C. In general, when the temperature is high, the generated acid is likely to diffuse, so this temperature should be low.

  For removal of unexposed portions of the photosensitive resin composition, that is, development, for example, a developer such as an alkaline aqueous solution can be used. Examples of the alkaline aqueous solution include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and ammonia; primary amines such as ethylamine and n-propylamine; diethylamine and di-n. -Secondary amines such as propylamine; tertiary amines such as triethylamine and methyldiethylamine; alcohol amines such as dimethylethanolamine and triethanolamine; tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide and the like And quaternary ammonium salts. In addition, an aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent or a surfactant to these alkaline aqueous solutions can also be suitably used. Since the electronic component dislikes alkali metal contamination, a tetramethylammonium hydroxide aqueous solution is preferable as the developer.

A suitable development time depends on the film thickness and the solvent, but is preferably 5 seconds to 5 minutes, more preferably 30 seconds to 3 minutes, and particularly preferably 30 seconds to 1 minute.
If the development time is less than 5 seconds, it may be difficult to control the time on the entire surface of the wafer or substrate, and if it exceeds 5 minutes, the productivity tends to deteriorate. The processing temperature during development is generally 20-30 ° C. As the developing method, for example, methods such as spraying, paddle, dipping, and ultrasonic waves are possible. Next, the pattern formed by development can be rinsed with distilled water or the like, if necessary.

  In the present embodiment, the cured product patterned by the above method can be used as it is as a resist mask.

In the present embodiment, when the cured product patterned by the above method is left as an interlayer insulating film, a cladding layer, etc., for example, the coating is baked at a heating temperature of 100 to 500 ° C. to perform final curing. preferable. This final curing is preferably performed in the air or under reduced pressure in an inert atmosphere such as N ₂ , Ar, or He, but there is no particular limitation as long as the characteristics required for the intended use are satisfied. If the heating temperature is less than 100 ° C, sufficient curing tends to be not achieved, and electrical insulation tends to be inferior. If the heating temperature exceeds 500 ° C, the material used for the lower layer may be deteriorated.

  The heating time for final curing is preferably 2 to 240 minutes, and more preferably 2 to 120 minutes. If this heating time exceeds 240 minutes, it may not be suitable for mass production. Examples of the heating apparatus include a furnace such as a quartz tube furnace, a heat treatment apparatus such as a hot plate and rapid thermal annealing (RTA).

  Examples of the electronic component having such a cured product include devices having an insulating film such as a semiconductor element and a multilayer wiring board. Specifically, in a semiconductor element, it can be used as a surface protective film (passivation film), a buffer coat film, an interlayer insulating film, and the like. On the other hand, in a multilayer wiring board, it can be suitably used as an interlayer insulating film.

  As semiconductor elements, for example, individual semiconductors such as diodes, transistors, compound semiconductors, thermistors, varistors, thyristors, DRAMs (dynamic random access memories), SRAMs (static random access memories), EPROMs (erasables) Programmable read-only memory (ROM), mask ROM (mask read-only memory), EEPROM (electrically erasable programmable read-only memory), memory elements such as flash memory, microprocessor, DSP, ASIC, etc. Theoretical circuit elements, integrated circuit elements such as compound semiconductors represented by MMIC (monolithic microwave integrated circuit), hybrid integrated circuits (hybrid IC), light emitting diodes De, and the like photoelectric conversion element such as a charge coupled device. Examples of the multilayer wiring board include a high-density wiring board such as MCM.

  Moreover, although it can be used also as uses, such as a component for liquid crystals, an optical waveguide, a photoresist, a use application is not this limitation.

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

  In the following examples, the photosensitive resin composition is used until the development step of the photosensitive resin composition is completed so that the photoacid generator or photobase generator is not excited. Working in an environment that does not include the photosensitive wavelength of the sensitizer and sensitizer.

Example 1
In a solution prepared by dissolving 106.8 g of tetraethoxysilane, 183.8 g of methyltriethoxysilane, and 4.2 g of tetramethylammonium nitrate aqueous solution (pH 3.6) prepared in 2.38 wt% in 635.2 g of diethylene glycol dimethyl ether, An aqueous nitric acid solution prepared by diluting 0.9 g of 60% nitric acid with 69.1 g of ion-exchanged water was added dropwise over 30 minutes with stirring. After reacting for 3 hours after completion of the dropwise addition, a portion of the ethanol and diethylene glycol dimethyl ether produced were distilled off in a warm bath under reduced pressure, and further heated in a warm bath at 90 ° C. for 10 hours to obtain 482.2 g of polysiloxane solution. Obtained. To this, 17.8 g of diethylene glycol dimethyl ether was added to obtain a polysiloxane solution for a photosensitive resin composition. It was 8450 when the weight average molecular weight of polysiloxane was measured by GPC method.
A photoacid generator (PAI-101, manufactured by Midori Chemical Co., Ltd.) 0.1 g was blended with 10.0 g of this polysiloxane solution for a photosensitive resin composition to prepare a photosensitive resin composition. In addition, the usage-amount of (a) component is 20.0 weight% with respect to the photosensitive resin composition total amount, and the usage-amount of (b) component is 1.0 weight% with respect to the photosensitive resin composition total amount. Yes, the amount of component (d) used was 0.02% by weight based on the total amount of the photosensitive resin composition.

2 mL of the above photosensitive resin composition is dropped on the center of a 5-inch silicon wafer, and a coating film is produced on the wafer by spin coating (rotating for 30 seconds at 700 rpm), and then applied to an 80 ° C. hot plate Dry for 30 seconds above. Thereafter, the dried coating film is irradiated with ultraviolet light of 200 mJ / cm ² with an exposure machine (PLA-600F, manufactured by Canon Inc.) through a negative mask having a line pattern with a minimum line width of 10 μm. did. The wafer with the exposed coating film is heated on a hot plate at 100 ° C. for 60 seconds, allowed to cool naturally until the wafer reaches room temperature, and then developed with a 2.38 wt% tetramethylammonium hydroxide (TMAH) aqueous solution. The unexposed part was dissolved by immersing in the solution for 60 seconds. Thereafter, the wafer was washed with water and spin-dried. Then, using a furnace body, the spin-dried wafer was heated at 350 ° C. for 30 minutes in a nitrogen atmosphere to obtain a cured photosensitive resin on the wafer. When the pattern shape of the cured product of the photosensitive resin was observed from above with an optical microscope and the cross-sectional shape was observed with an SEM, it was found that the line was formed with high accuracy and the pattern accuracy was 10 μm.

  Further, a pattern film is formed on the photosensitive resin composition that has been left in a clean room environment (room temperature 24 ° C., humidity 40%) for one week by the same operation as the above-described forming method, and a cured product of the photosensitive resin. As a result, it was found that there was no change from the pattern shape one week ago, and the pattern accuracy was 10 μm.

(Example 2)
A solution prepared by dissolving 106.8 g of tetraethoxysilane, 183.8 g of methyltriethoxysilane and 21.0 g of a tetramethylammonium nitrate aqueous solution (pH 3.6) prepared in 2.38% by weight in 618.4 g of propylene glycol methyl ether acetate. A nitric acid aqueous solution in which 0.9 g of 60% nitric acid was diluted with 69.1 g of ion-exchanged water was added dropwise over 30 minutes with stirring. After the completion of the dropwise addition, the reaction was allowed to proceed for 3 hours, and then a portion of the produced ethanol and propylene glycol methyl ether acetate was distilled off in a warm bath under reduced pressure. .3 g was obtained. To this was added 34.7 g of propylene glycol methyl ether acetate to obtain a polysiloxane solution for a photosensitive resin composition. It was 8000 when the weight average molecular weight of polysiloxane was measured by GPC method.
A photoacid generator (PAI-101, manufactured by Midori Chemical Co., Ltd.) (0.04 g) was blended with 10.0 g of the polysiloxane solution for the photosensitive resin composition to prepare a photosensitive resin composition. In addition, the usage-amount of (a) component is 20.0 weight% with respect to the photosensitive resin composition total amount, and the usage-amount of (b) component is 0.4 weight% with respect to the photosensitive resin composition total amount. The amount of component (d) used was 0.1% by weight based on the total amount of the photosensitive resin composition.

2 mL of the photosensitive resin composition is dropped on the center of a 6-inch silicon wafer, and a coating film is formed on the wafer by spin coating (rotating for 30 seconds at 700 rotations / minute). Dry for 60 seconds above. Thereafter, the dried coating film was exposed to ultraviolet light of 75 mJ / cm ² with an exposure machine (FPA-3000 iW, manufactured by Canon Inc.) through a negative mask having a line pattern with a minimum line width of 2 μm. Irradiated. The wafer with the exposed coating film was heated on a hot plate at 100 ° C. for 60 seconds, allowed to cool naturally until the wafer reached room temperature, and then 2.38 weight by a coater / developer (Mark 7, Tokyo Electron). The wafer was immersed for 30 seconds in a developer composed of an aqueous solution of% tetramethylammonium hydroxide (TMAH) and subjected to paddle development to dissolve unexposed portions. Thereafter, the wafer was washed with water and spin-dried. Then, using a furnace body, the spin-dried wafer was heated at 350 ° C. for 30 minutes in a nitrogen atmosphere to obtain a radiation cured product on the wafer. When the pattern shape of the radiation cured product was observed from above with an optical microscope and the cross-sectional shape was observed with an SEM, it was found that the line was formed with high accuracy and the pattern accuracy was 2 μm.

  Further, as in Example 1, the pattern shape of the cured product of the photosensitive resin composition that had been left in a clean room environment (room temperature 24 ° C., humidity 40%) for 1 week was confirmed. It was found that there was no change in shape and pattern accuracy was 2 μm.

(Example 3)
A photobase generator (NBC-101, manufactured by Midori Chemical Co., Ltd.) (0.040 g) was blended with 10.0 g of the polysiloxane solution for a photosensitive resin composition obtained in Example 2 to prepare a photosensitive resin composition. In addition, the usage-amount of (a) component is 20 weight% with respect to the photosensitive resin composition total amount, The usage-amount of (b) component is 0.4 weight% with respect to the radiation-curable composition total amount, The amount of component (d) used was 0.1% by weight based on the total amount of the radiation curable composition.

2 mL of the photosensitive resin composition is dropped on the center of a 6-inch silicon wafer, and a coating film is formed on the wafer by spin coating (rotating for 30 seconds at 700 rotations / minute). Dry for 60 seconds above. Thereafter, the dried coating film was exposed to ultraviolet light of 75 mJ / cm ² with an exposure machine (FPA-3000 iW, manufactured by Canon Inc.) through a negative mask having a line pattern with a minimum line width of 2 μm. Irradiated. The wafer with the exposed coating film was heated on a hot plate at 100 ° C. for 60 seconds, allowed to cool naturally until the wafer reached room temperature, and then 2.38 weight by a coater / developer (Mark 7, Tokyo Electron). The wafer was immersed for 30 seconds in a developer composed of an aqueous solution of% tetramethylammonium hydroxide (TMAH) and subjected to paddle development to dissolve unexposed portions. Thereafter, the wafer was washed with water and spin-dried. Then, using a furnace body, the spin-dried wafer was heated at 350 ° C. for 30 minutes in a nitrogen atmosphere to obtain a radiation cured product on the wafer. When the pattern shape of the radiation cured product was observed from above with an optical microscope and the cross-sectional shape was observed with an SEM, it was found that the line was formed with high accuracy and the pattern accuracy was 2 μm.

  Further, as in Example 1, the pattern shape of the cured product of the photosensitive resin composition that had been left in a clean room environment (room temperature 24 ° C., humidity 40%) for 1 week was confirmed. It was found that there was no change in shape and pattern accuracy was 2 μm.

(Comparative Example 1)
Nitric acid obtained by diluting 0.9 g of 60% nitric acid with 69.1 g of ion-exchanged water in a solution prepared by dissolving 106.8 g of tetraethoxysilane and 183.8 g of methyltriethoxysilane in 639.4 g of propylene glycol methyl ether The aqueous solution was added dropwise over 30 minutes with stirring. After the completion of the dropwise addition, the reaction was allowed to proceed for 3 hours, and then part of the produced ethanol and propylene glycol methyl ether acetate was distilled off in a warm bath under reduced pressure to obtain 478.3 g of a polysiloxane solution. To this was added 21.7 g of propylene glycol methyl ether acetate to obtain a polysiloxane solution for a photosensitive resin composition. It was 870 when the weight average molecular weight of polysiloxane was measured by GPC method.
A photoacid generator (PAI-101, manufactured by Midori Chemical Co., Ltd.) 0.1 g was blended with 10.0 g of this polysiloxane solution for a photosensitive resin composition to prepare a photosensitive resin composition. In addition, the usage-amount of (a) component is 20.0 weight% with respect to the photosensitive resin composition total amount, and the usage-amount of (b) component is 1.0 weight% with respect to the photosensitive resin composition total amount. there were.

2 mL of the photosensitive resin composition is dropped on the center of a 5-inch silicon wafer, and a coating film is formed on the wafer by spin coating (rotating for 30 seconds at 700 rotations / minute). Dry for 60 seconds above. Thereafter, the dried coating film is irradiated with ultraviolet light of 200 mJ / cm ² with an exposure machine (PLA-600F, manufactured by Canon Inc.) through a negative mask having a line pattern with a minimum line width of 10 μm. did. The wafer with the exposed coating film is heated on a hot plate at 100 ° C. for 60 seconds, allowed to cool naturally until the wafer reaches room temperature, and then developed with a 2.38 wt% tetramethylammonium hydroxide (TMAH) aqueous solution. The wafer was immersed in the solution for 30 seconds to dissolve the unexposed portion. Then, when the wafer was washed with water and spin-dried, the coating film was completely dissolved, and no pattern formation was observed.

(Comparative Example 2)
Development was performed in the same manner as in Comparative Example 1 except that the exposure of ultraviolet light 200 mJ / cm ² was changed to 1000 mJ / cm ² of ultraviolet light. After development, the wafer was washed with water and spin dried. Then, using the furnace body, the spin-dried wafer was heated at 350 ° C. for 30 minutes in a nitrogen atmosphere to obtain a cured photosensitive resin on the wafer. When the pattern shape of the cured photosensitive resin was observed from above with an optical microscope and the cross-sectional shape was observed with an SEM, a line with a width of 10 μm was formed, but the shape was not good.
Furthermore, when the photosensitive resin composition was left to stand for 1 week in a clean room environment (room temperature 24 ° C., humidity 40%) to form a pattern film by the same operation as the above-described formation method, The coating film was dissolved and no pattern formation was observed.

(Comparative Example 3)
0.1 g of a photobase generator (NBC-101, manufactured by Midori Chemical Co., Ltd.) was blended with 10.0 g of the polysiloxane solution for a photosensitive resin composition obtained in Comparative Example 1 to prepare a photosensitive resin composition. In addition, the usage-amount of (a) component was 20 weight% with respect to the photosensitive resin composition total amount, and the usage-amount of (b) component was 1.0 weight% with respect to the photosensitive resin composition total amount. .

Pattern formation and curing were performed in the same manner as in Comparative Example 1 to obtain a cured photosensitive resin on the wafer. When the pattern shape of the cured photosensitive resin was observed from above with an optical microscope and the cross-sectional shape was observed with an SEM, a line with a width of 10 μm was formed, but the shape was not good.
Furthermore, when the photosensitive resin composition was left to stand for 1 week in a clean room environment (room temperature 24 ° C., humidity 40%) to form a pattern film by the same operation as the above-described formation method, The coating film was dissolved and no pattern formation was observed.

  The results are shown in Table 1 for Examples 1 to 3 and Comparative Examples 1 to 3.

  Even if the exposure amount is relatively small, a cured product having excellent pattern accuracy can be obtained by the photosensitive resin composition having excellent room temperature storage stability and the method for forming a silica-based film having a pattern. Therefore, the present invention is useful for electronic components.

Claims (6)

A siloxane resin having a weight average molecular weight of 5000 or more obtained by hydrolytic condensation of a siloxane compound containing a compound represented by the following general formula (1):
At least one selected from the group consisting of a photoacid generator and a photobase generator;
A solvent capable of dissolving the siloxane resin;
Containing a photosensitive resin composition.

[Wherein R ¹ represents an H atom or F atom, or a group containing a B atom, N atom, Al atom, P atom, Si atom, Ge atom or Ti atom, or an organic group having 1 to 20 carbon atoms. , X represents a hydrolyzable group, n represents an integer of 0 to 2, 4-n X may be the same or different, and when n is 2, two R ¹ are the same or different It may be. ]   The photosensitive resin composition according to claim 1, wherein the solvent contains at least one solvent selected from the group consisting of an ether acetate solvent, an ether solvent, an acetate solvent, an alcohol solvent, and a ketone solvent.   The photosensitive resin composition of Claim 1 or 2 which further contains a hardening acceleration catalyst.   The photosensitive resin composition according to claim 3, wherein the onium salt is an ammonium salt.   A photosensitive resin composition according to any one of claims 1 to 4 is applied onto a substrate to form a film, the solvent contained in the film is removed, and the film is exposed to light through a pattern mask. A method for forming a silica-based coating, which comprises heating and developing after exposure to remove the unexposed portion of the coating and heat-treating the remaining coating to obtain a silica-based coating having a pattern. A substrate,
A silica-based coating film having a pattern formed on the substrate by the method according to claim 5;
With electronic components.