JP2012242483A - Silica-based photosensitive resin composition, method for forming silica-based insulating coating film having pattern, and electronic component having the coating film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silica-based photosensitive resin composition having excellent long-term storage stability at room temperature (20 to 25°C) and high sensitivity and allowing pattern formation with high accuracy, to provide a method for forming a silica-based insulating coating film for obtaining a cured product with high pattern accuracy by using the composition, and to provide electronic components using the composition.SOLUTION: The silica-based photosensitive resin composition includes the following components as essential components: (a) a siloxane resin obtained by hydrolyzing and condensing a compound expressed by a general formula (1); (b) at least one kind selected from the group consisting of a photoacid generator or a photobase generator; (c) an organic solvent that can dissolve the component (a); and (d) an onium salt.

Description

  The present invention relates to a silica-based photosensitive resin composition, a method for forming a silica-based insulating film having a pattern, and an electronic component including the same.

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. 06-148895 Japanese Patent Laid-Open No. 10-246960 JP 2000-181069 A Japanese Patent Laid-Open No. 2002-075022

However, the present inventors have studied in detail the patterning using such a conventional insulating film material provided with photosensitive characteristics. For example, the water disclosed in Patent Document 1 and Patent Document 2 is used. When a photosensitive resin composition comprising an alkali-soluble siloxane polymer from which the catalyst has been removed, a photoacid generator, and a solvent is used, it is clear that both require a large amount of exposure and are not excellent in mass productivity. . Moreover, when the photosensitive polysilazane composition containing the polysilazane and the photoacid generator disclosed in Patent Document 3 and Patent Document 4 is used, the exposure amount is small, but the treatment immersed in pure water after the exposure or the humidification treatment is performed. It has become clear that the process becomes complicated, such as necessary, and that it is difficult to obtain high pattern accuracy.
It has also been clarified that these photosensitive resin compositions have a low long-term storage stability at room temperature because sensitivity and resolution are likely to change, and are poor in mass productivity.

  The present invention has been made in view of such circumstances, and is excellent in long-term room temperature (20 to 25 ° C.) storage stability, a silica-based photosensitive resin composition that can form a pattern with high sensitivity and accuracy, and pattern accuracy. The present invention provides a method for forming a silica-based insulating coating that can provide a highly cured product and an electronic component using the same.

  As a result of intensive studies, the present inventors have found that a silica-based photosensitive resin composition containing a specific component and a pattern forming method can solve various conventional problems and complete the present invention. It came to do.

That is, the present invention
(A) component: a siloxane resin obtained by hydrolytic condensation of a compound represented by the following general formula (1),
(B) component: at least one selected from the group consisting of a photoacid generator or a photobase generator;
(C) component: an organic solvent capable of dissolving the component (a),
(D) Component: A silica-based photosensitive resin composition containing an onium salt as an essential component.

［一般式（１）中、Ｒ^１は、Ｈ原子若しくはＦ原子、又はＢ原子、Ｎ原子、Ａｌ原子、Ｐ原子、Ｓｉ原子、Ｇｅ原子若しくはＴｉ原子を含む基、又は炭素数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、ｎが２のとき、各Ｒ^１は同一でも異なっていてもよく、ｎが０〜２のとき、各Ｘは同一でも異なっていてもよい。］

[In General Formula (1), R ¹ is an H atom or an F atom, or a group containing a B atom, an N atom, an Al atom, a P atom, a Si atom, a Ge atom, or a Ti atom, or a group having 1 to 20 carbon atoms. Represents an organic group, X represents a hydrolyzable group, n represents an integer of 0 to 2, and when n is 2, each R ¹ may be the same or different, and when n is 0 to 2, Each X may be the same or different. ]

  According to the silica-based photosensitive resin composition used in the present invention, since the specific siloxane resin is used as the component (a), the highly reactive silanol (SiOH) group concentration can be reduced. As a result, a photosensitive resin solution having excellent long-term room temperature storage stability can be obtained. Moreover, the siloxane resin can form a silica-based film having excellent insulating properties, low dielectric properties, heat resistance, and transparency.

  Moreover, since the silica-type photosensitive resin composition used for this invention contains at least 1 sort (s) selected from the group which consists of a photo-acid generator and a photobase generator as (b) component, transparency and resolution Can exhibit negative photosensitivity, and excellent developability at the time of development after exposure in forming a silica-based film.

  Moreover, the silica type photosensitive resin composition of this invention contains the organic solvent which can melt | dissolve (a) component as (c) component. At this time, if one or more solvents selected from the group consisting of ether acetate solvents, ether solvents, acetate solvents, alcohol solvents, and ketone solvents are included, the compatibility with the siloxane resin is high, and the coating surface Thus, a coating film having excellent in-plane uniformity with a film thickness with little unevenness can be formed.

  Further, since the silica-based photosensitive resin composition used in the present invention contains an onium salt as the component (d), the condensation reaction of silanol groups present in the siloxane resin can be promoted, and the resolution during development is improved. Can be improved, and after curing, a silica-based film having excellent insulating properties can be formed.

  The silica-based photosensitive resin composition of the present invention is a catalyst in which the catalyst used in the hydrolytic condensation of the compound represented by the general formula (1) is selected from an acid catalyst, an alkali catalyst, and a metal chelate compound. And the content thereof is 0.0000005 to 0.00001 mol with respect to 1 mol of the total amount of X of the compound represented by the general formula (1), so that the room temperature of the silica-based photosensitive resin composition solution is During the standing, hydrolysis condensation of the siloxane resin can be suppressed, and a silica-based photosensitive resin composition solution excellent in long-term room temperature storage stability can be obtained. In addition, since the amount of catalyst used for hydrolysis and condensation is reduced compared to conventional methods, a relatively large amount of hydrolyzable groups remain in the siloxane resin, resulting in high sensitivity of the silica-based photosensitive resin composition. Can be

  Further, the present invention provides a silica-based photosensitive resin composition by coating the silica-based photosensitive resin composition of the present invention described above on a substrate to form a coating film, removing an organic solvent contained in the coating film. After forming the layer, the film of the silica-based photosensitive resin composition layer is subjected to exposure / post-exposure heating / development through a pattern mask to remove the unexposed film, and then the remaining film is heat-treated. A method for forming a silica-based insulating coating having a pattern is provided. According to this forming method, since the above-mentioned silica-based photosensitive resin composition is used, a silica-based film having excellent in-plane film thickness uniformity, resolution, insulation, and transparency can be obtained.

  The present invention further provides an electronic component comprising a silica-based insulating coating having a pattern formed by the method for forming a silica-based insulating coating having the above pattern. These electronic components have excellent performance because they are provided with a silica-based film formed from the above-described silica-based photosensitive resin composition as an insulating film.

The present invention makes it 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 coating properties, resolution, insulating properties, heat resistance, transparency, and storage. A photosensitive resin composition excellent in stability, mass productivity, 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

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

<(A) component>
The component (a) is a siloxane resin obtained by hydrolytic condensation of the compound represented by the general formula (1). The siloxane resin preferably has a hydroxyl (OH) group at the terminal or side chain of the resin. This is for imparting alkali solubility to the unexposed area when a film formed using the silica-based photosensitive resin composition is developed after exposure. In addition, after exposure, a part of the hydroxyl group of the exposed portion undergoes a condensation reaction with the component (b), so that the alkali-soluble contrast with respect to the unexposed portion can be improved. The condensation reaction is more likely to proceed.

In general formula (1), R ¹ is 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 compound having 1 to 20 carbon atoms. Indicates a group.
(A) Selected from the group consisting of H atom, F atom, B atom, N atom, Al atom, P atom, Si atom, Ge atom, Ti atom, and C atom with respect to 1 mol of Si atom in the component siloxane resin The total content of the at least one kind of atoms is preferably 0.65 mol or less. In other words, the total number of the above atoms bonded to one Si atom in the siloxane resin molecule is preferably 0.65 or less. By so doing, a decrease in the adhesiveness and mechanical strength of the silica-based coating is suppressed.
In the general formula (1), examples of the organic group having 1 to 20 carbon atoms represented by R ¹ include an aliphatic hydrocarbon group and an aromatic hydrocarbon group. Among these, a linear, branched or cyclic aliphatic hydrocarbon group having 1 to 20 carbon atoms is preferable. Specific examples of the linear aliphatic hydrocarbon group having 1 to 20 carbon atoms include groups such as a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and an n-pentyl group. Specific examples of the branched aliphatic hydrocarbon group include groups such as isopropyl group and isobutyl group. Specific examples of the cyclic aliphatic hydrocarbon group include groups such as a cyclopentyl group, a cyclohexyl group, a cycloheptylene group, a norbornyl group, and an adamantyl group. Specific examples of the aromatic hydrocarbon group include unsubstituted and substituted groups such as benzene, toluene, xylene, ethylbenzene, cumene, styrene, naphthalene, anthracene, and phenanthrene. 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 general formula (1), as R ¹ , two are bonded to a silicon (Si) atom to form a ring structure, or one is bonded to a silicon (Si) atom and the other is bonded to another silicon atom. As the divalent organic group represented by R ^{1 in} which is bonded to a silicon (Si) atom and the other is bonded to a monovalent R ¹ , for example, a divalent aromatic hydrocarbon group and a divalent aliphatic hydrocarbon group Is mentioned. 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 viewpoints of solution stability and coatability of the silica-based photosensitive resin composition.

  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, 3-acetoxypropyltrimethoxysilane, 3-acetoxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-glycidoxypropyltrimethoxy Examples include silane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane.

  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.

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

  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 compound represented by the general formula (1) is preferably 0.1 to 1000 mol, more preferably 1 mol per mol of the compound represented by the general formula (1). Is 0.5 to 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 preferable to use a catalyst in the hydrolysis condensation of the compound represented by the general formula (1). Examples of such a catalyst include a catalyst selected from 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 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 hydrolysis-condensation product obtained from the compound represented by General formula (1) may be taken out from a composition by reprecipitation etc. 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 0.0000005 to 0.00001 mol, more preferably 0.0000008 to 0, based on 1 mol of the total amount of X of the compound represented by the general formula (1). 0.00000 mol, particularly preferably 0.000001 to 0.000005 mol.
If the amount used is less than 0.0000005 mol, the reaction does not substantially proceed, and if it exceeds 0.00001 mol, gelation tends to be promoted during hydrolysis condensation. By performing hydrolysis condensation using a small amount of catalyst in this way, the amount of catalyst in the silica-based photosensitive resin composition can be reduced, and hydrolysis condensation of the siloxane resin during storage of the solution can be suppressed. Therefore, a silica-based photosensitive resin composition having excellent long-term storage stability can be obtained.

  Further, in the present invention, the effect of improving the sensitivity of the resulting silica-based photosensitive resin composition can be obtained by synthesizing a siloxane resin by performing hydrolysis condensation using a relatively small amount of catalyst. The reason why this effect is obtained is not always clear. A possible reason is that the proportion of unreacted hydrolyzable groups in the siloxane resin increases by hydrolytic condensation with a small amount of catalyst, and the crosslinking in the siloxane resin when a silica-based photosensitive resin composition is obtained. It is speculated that the sensitivity may be increased because the number of sites increases.

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

  The siloxane resin thus obtained preferably has a weight average molecular weight of 2000 to 100,000 from the viewpoints of solubility in a solvent, mechanical properties, moldability, resolution, room temperature storage stability, and the like. It is more preferable that it is -50000, it is still more preferable that it is 3000-30000, and it is especially preferable that it is 3500-20000. If this weight average molecular weight is less than 2000, the room temperature stability of the solution tends to be inferior, and if this weight average molecular weight exceeds 100,000, the compatibility with the solvent tends to decrease.

<(B) component>
The component (b) is a photoacid generator or photobase generator, and releases an acidic active substance or basic active substance capable of photocuring (hydrolytic polycondensation) of the component (a) when irradiated with radiation. Is defined as a compound that can.

  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 general formula (2), 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 is A 1 to tetravalent organic group having 1 to 20 carbon atoms is shown, and m is an integer of 1 to 4.

^{(R 4 R 5 C = N} -OCO) m -R 3 ··· (3)
Here, in the general formula (3), 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. , May be bonded together to form a ring structure.

R ² —OCO—NR ⁶ R ⁷ (4)
Here, in General Formula (4), R ² has the same meaning as in General Formula (2), R ⁶ and R ⁷ each independently represent a monovalent organic group having 1 to 30 carbon atoms, and They may combine to form a cyclic structure, and either one may be a hydrogen atom.

R ⁸ —CO—R ⁹ —NR ⁶ R ⁷ (5)
Here, in the general formula (5), 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 alkoxy in the side chain. An aromatic ring having a group, a nitro group, an amino group, an alkyl-substituted amino group or an alkylthio group may be contained, and R ⁹ represents a divalent organic group having 1 to 30 carbon atoms.

ここで、一般式（６）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 General Formula (6), R ¹⁰ represents a monovalent organic group having 1 to 30 carbon atoms, and R ¹¹ and R ¹² are each independently a monovalent organic group having 1 to 30 carbon atoms or a hydrogen atom. X ¹ is represented by the following general formulas (6A), (6B), (6C), (6D), (6E) and (6F) (hereinafter referred to as “(6A) to (6F)”) ) Represents a monovalent group, 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、一般式（７）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 general formula (7), R ¹⁰ , R ¹¹ and R ¹² , Z ⁻ , t, p and q are the same as those in the general formula (6), and X ² is the following general formula (7A). The bivalent group represented by any of-(7D) 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, it is preferable that the usage-amount of (b) component is 0.0001-50 mass% with respect to the total mass of (a) component in a radiation-curable composition, and 0.001-20 mass%. It is more preferable that it is 0.01-10 mass%. If the amount used is less than 0.0001% by mass, the photocurability tends to be reduced, or a large amount of exposure is required to cure, and if it exceeds 50% by mass, 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 addition, when preserve | saving a silica type photosensitive resin composition, you may preserve | save at room temperature, but it is more preferable to preserve | save at the temperature of 5 degrees C or less, for example, in order to improve storage stability. The lower limit of this temperature is preferably not less than the freezing point of the solvent in the silica-based photosensitive resin composition, and preferably not less than −50 ° C.

<(C) component>
The component (c) is an organic 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-propyl ether, di-iso-propyl ether, tetrahydrofuran, methyltetrahydrofuran, dioxane, dimethyldioxy Sun, 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 methyl mono-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, etc. Ether solvents; 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-methoxybutyl acetate , Methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methyl cyclohexyl acetate, nonyl acetate, methyl acetoacetate, ethyl acetoacetate, diethyleneglycol acetate Monomethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, glycol diacetate, methoxytriglycol acetate, ethyl propionate, n-butyl propionate Ester solvents such as 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, diethyl Ether acetate solvents such as 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-methyl Examples include pyrrolidinone, N-ethylpyrrolidinone, N-propylpyrrolidinone, N-butylpyrrolidinone, N-hexylpyrrolidinone, N-cyclohexylpyrrolidinone, N, N-dimethylformamide, N, N-dimethylacetamide, N, N-dimethylsulfoxide and the like. In-plane film thickness uniformity during coating, sensitivity and pattern accuracy during pattern formation, and the mechanical strength of the cured product From the viewpoint, 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, the inventors believe that the ether acetate solvent is preferred first, the ether solvent is preferred second, and the ketone solvent is preferred third. These are used singly or in combination of two or more.

  The use ratio of the aprotic solvent is preferably 50% by mass or more, more preferably 70% by mass or more, particularly preferably 90% by mass or more, and 95% by mass or more in the total solvent. 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 the organic 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 mass. If the amount of the solvent is excessive and the concentration of the component (a) is less than 3% by mass, it tends to be difficult to form a cured product having a desired film thickness, and the amount of the solvent is excessive and the concentration of the component (a) is 60% by mass. When it exceeds%, the film formability of the cured product is deteriorated and the stability of the composition itself tends to be lowered.

  As the curing accelerating catalyst which is component (d), an onium salt is used as an essential component. Other compounds include, for example, alkali metals such as sodium hydroxide, sodium chloride, potassium hydroxide, potassium chloride and the like, and these are used alone or in combination of two or more.

  From the viewpoint that the electrical properties and mechanical strength of the resulting cured product can be improved, and further the stability of the composition can be improved, it is more preferable to use a quaternary ammonium salt as the onium salt.

  Examples of these onium salt compounds include ammonium hydroxide, ammonium fluoride, ammonium chloride, ammonium bromide, ammonium iodide, ammonium phosphate, ammonium nitrate, ammonium borate, ammonium sulfate, ammonium formate, and ammonium maleate. , Ammonium fumarate, ammonium phthalate, ammonium malonate, ammonium succinate, ammonium tartrate, ammonium malate, ammonium lactate, ammonium citrate, ammonium acetate, ammonium propionate, butanoic acid Ammonium salt, ammonium pentanoate, ammonium hexanoate, ammonium heptanoate, ammonium octanoate, ammonium nonanoate Nium salt, ammonium decanoate, ammonium oxalate, ammonium adipate, ammonium sebacate, ammonium butyrate, ammonium oleate, ammonium stearate, ammonium linoleate, ammonium linolenate, 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.

  Moreover, it is preferable that the usage-amount of (d) component is 0.0001-5 mass% with respect to the total amount of (a) component in a silica type photosensitive resin composition, and is 0.0001-1 mass%. More preferably. If the amount used is less than 0.0001% by mass, a large amount of exposure tends to be required for curing. When the amount used exceeds 5% by mass, 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.

  These onium salts can be added to a desired concentration after being dissolved or diluted in water or a solvent as necessary. 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, you may add a pigment | dye to the silica type photosensitive resin composition of this invention. By adding the dye, for example, an effect of adjusting sensitivity, an effect of suppressing the standing wave effect, and the like can be obtained.

  Further, a surfactant, a silane coupling agent, a thickener, an inorganic filler, a thermally decomposable compound such as polypropylene glycol, and a volatile compound may be added as long as the purpose and effect of the present invention are not impaired. Good. 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 a silica type 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 contained, those metal ion concentrations in the composition are 1000 ppm or less. It is preferably 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.

  A method of forming a cured product patterned on a substrate using such a silica-based photosensitive resin composition of the present invention will be described by taking a spin coating 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 silica-based 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 from 0.01 to 2 μm. Particularly preferred is 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 organic solvent in the film 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 film dissolves under various conditions at the subsequent development. Need to be adjusted. If the drying temperature is less than 50 ° C., the organic solvent tends not to be sufficiently dried. If the drying temperature exceeds 200 ° C., the organic solvent does not dissolve during development and a pattern may not be formed.

Next, radiation is exposed through a mask having a desired pattern (pattern mask). Preferably this dose is 5~5000mJ / cm ^2, more preferably 5~1000mJ / cm ^2, it is highly preferably 5~500mJ / cm ^2. 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.

  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 the unexposed portion of the silica-based 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; four amines such as tetramethylammonium hydroxide (TMAH) and tetraethylammonium hydroxide A grade ammonium salt etc. are mentioned. 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.

  Although suitable development time depends on the film thickness and the solvent, it 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.

  The cured product patterned according to the present invention can be used as it is as a resist mask.

When the cured product patterned according to the present invention is left as an interlayer insulating film, a clad layer, etc., for example, it is preferable to perform final curing by baking the coating at a heating temperature of 100 to 500 ° C. This final curing is preferably performed under an inert atmosphere such as N ₂ , Ar, or He, in the air, or under reduced pressure, but is not particularly limited 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. Moreover, as a multilayer wiring board, high density wiring boards, such as MCM (multichip module), etc. are mentioned, for example.

  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 this example, the silica-based photosensitive resin composition is used until the development step of the silica-based photosensitive resin composition is completed so that the photoacid generator or the photobase generator is not excited. The work was carried out in an environment that did not include the photosensitizing wavelength of the photobase generator and sensitizer.

Example 1
23.8 g of tetraethoxysilane, 40.9 g of methyltriethoxysilane, 4.0 g of 3-acetoxypropyltrimethoxysilane, and tetramethylammonium nitrate aqueous solution (pH 3.6) prepared as 2.38% by mass as an onium salt. An aqueous solution of nitric acid obtained by diluting 0.007 g of 0.6 mass% nitric acid with 16.2 g of ion-exchanged water was dropped into a solution obtained by dissolving 1 g of propylene glycol monomethyl ether acetate in 15.1 g over 30 minutes with stirring. . After completion of the dropwise addition, the mixture was reacted in a 70 ° C. warm bath for 2 hours, and then ethanol and propylene glycol monomethyl ether acetate produced in the warm bath were distilled off under reduced pressure, followed by heating in a 90 ° C. warm bath for 2 hours. As a result, 81.5 g of a polysiloxane solution was obtained. To this, 71.3 g of propylene glycol monomethyl ether acetate was added to obtain a polysiloxane solution. The weight average molecular weight of the polysiloxane measured by GPC method was 4500.
A photoacid generator (PAI-101, manufactured by Midori Chemical Co., Ltd., α- (p-tolylsulfonyloxyimino) -4-methoxyphenylacetonitrile) was added to 10.0 g of this polysiloxane solution for silica-based photosensitive resin composition. 1 g was blended to prepare a photosensitive resin composition.

About 2 mL of the above-mentioned silica-based photosensitive resin composition is dropped on the center of a 5-inch silicon wafer, and a coating film is produced on the wafer by a spin coating method (rotating for 30 seconds at 1000 rpm). For 30 seconds on a hot plate. Then, ultraviolet light is applied to the dried coating film through 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 at 20 mJ / cm ^2. Irradiated. The wafer provided 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 developed with an aqueous 2.38 mass% tetramethylammonium hydroxide (TMAH) 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 the furnace body, the spin-dried wafer was heated at 350 ° C. for 30 minutes in a nitrogen atmosphere to obtain a cured product of the silica-based photosensitive resin composition layer on the wafer. When the pattern shape of the cured product of the silica-based 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, the above-mentioned silica-based photosensitive resin composition that has been left in a clean room environment (24 ° C., humidity 40% RH) for 1 week is formed into a pattern film by the same operation as the above-described forming method. When the pattern shape of the cured product was confirmed, 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 silica-based polysiloxane solution was obtained in the same manner as in Example 1 except that 0.126 g of 0.6% by mass nitric acid was used as nitric acid. It was 6000 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 the polysiloxane solution for silica-based photosensitive resin composition to prepare a silica-based photosensitive resin composition.

A cured product of the silica-based photosensitive resin composition was obtained on the wafer in the same manner as in Example 1 except that 60 mJ / cm ^{2 was} irradiated with ultraviolet light, and the pattern shape of the cured product of the silica-based photosensitive resin composition layer was measured with an optical microscope. As a result of observing from above and observing the cross-sectional shape by SEM, it was found that the line was formed with high accuracy and the pattern accuracy was 10 μm.

  Further, the silica-based photosensitive resin composition, which was allowed to stand in a clean room environment (24 ° C., humidity 40% RH) for 1 week, was subjected to the same operation as the above-described forming method to form a pattern film. When the pattern shape of the cured product of the resin layer was confirmed, it was found that there was no change from the pattern shape one week ago, and the pattern accuracy was 10 μm.

(Example 3)
A solution prepared by dissolving 48.1 g of tetraethoxysilane, 82.7 g of methyltriethoxysilane, and 0.2 g of tetramethylammonium nitrate aqueous solution (pH 3.6) prepared to 2.38% by mass in 286.6 g of propylene glycol monomethyl ether acetate. A nitric acid aqueous solution in which 0.013 g of 0.6 mass% nitric acid was diluted with 31.2 g of ion-exchanged water was added dropwise over 30 minutes with stirring. After reacting at room temperature (24 ° C) for 2 hours, ethanol and a part of propylene glycol monomethyl ether acetate were distilled off in a warm bath under reduced pressure, and further heated in a warm bath at 90 ° C for 2 hours. 153.1 g of siloxane solution was obtained. To this was added 82.5 g of propylene glycol monomethyl ether acetate to obtain a polysiloxane solution. The weight average molecular weight of the polysiloxane measured by GPC method was 7800.
A photoacid generator (PAI-101, manufactured by Midori Chemical Co., Ltd.) 0.1 g was blended with 10.0 g of the polysiloxane solution for silica-based photosensitive resin composition to prepare a silica-based photosensitive resin composition.

A cured product of the silica-based photosensitive resin composition layer was obtained on the wafer in the same manner as in Example 1 except that ultraviolet light was irradiated at 100 mJ / cm ² . Then, when the pattern shape of the cured product of the silica-based photosensitive resin composition layer was observed from above with an optical microscope and the cross-sectional shape was observed with an SEM, the line was formed with high accuracy and the pattern accuracy was 10 μm. I understood.

  Further, the silica-based photosensitive resin composition, which was allowed to stand in a clean room environment (24 ° C., humidity 40% RH) for 1 week, was subjected to the same operation as the above-described forming method to form a pattern film. When the pattern shape of the cured product of the resin composition layer was confirmed, it was found that there was no change from the pattern shape one week ago, and the pattern accuracy was 10 μm.

Example 4
To 10.0 g of the polysiloxane solution for silica-based photosensitive resin composition obtained in Example 3, 0.1 g of a photobase generator (NBC-101, manufactured by Midori Chemical Co., Ltd., 2-nitrobenzyl cyclohexyl carbamate) was blended. A silica-based photosensitive resin composition was prepared.

  As in Example 1, a cured product of the silica-based photosensitive resin composition layer was obtained on the wafer, the pattern shape of the cured product of the silica-based photosensitive resin composition layer was observed from above with an optical microscope, and a cross section by SEM When the shape was observed, it was found that the line was formed with high accuracy and the pattern accuracy was 10 μm.

  Further, the above-mentioned silica-based photosensitive resin composition that has been left in a clean room environment (24 ° C., humidity 40% RH) for 1 week is formed into a pattern film by the same operation as the above-described forming method. When the pattern shape of hardened | cured material was confirmed, it turned out that there is no change with the pattern shape of one week ago, and a silica type | system | group pattern precision is 10 micrometers.

(Comparative Example 1)
In a solution prepared by dissolving 34.2 g of tetraethoxysilane and 58.8 g of methyltriethoxysilane in 203.8 g of propylene glycol methyl ether, 0.576 g of 60 mass% nitric acid was diluted with 22.2 g of ion-exchanged water. An aqueous nitric acid solution was added dropwise over 30 minutes with stirring. After the completion of the dropwise addition, the reaction was allowed to proceed for 2 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 125.6 g of a polysiloxane solution. To this was added 34.4 g of propylene glycol methyl ether acetate to obtain a polysiloxane solution for a silica-based photosensitive resin composition. It was 840 when the weight average molecular weight of polysiloxane was measured by GPC method.

Further, similarly to Example 1, ultraviolet light was irradiated at 500 mJ / cm ² with an exposure machine (PLA-600F, manufactured by Canon Inc.) through a negative mask having a line pattern having a minimum line width of 10 μm. The wafer provided 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 developed with an aqueous 2.38 mass% tetramethylammonium hydroxide (TMAH) solution. The unexposed part was dissolved by immersing in the solution for 60 seconds. Thereafter, the wafer was washed with water and spin-dried. As a result, the coating film was completely dissolved, and no pattern formation was observed.

(Comparative Example 2)
0.040 g of a photobase generator (NBC-101, manufactured by Midori Chemical Co., Ltd.) is mixed with 10.0 g of the polysiloxane solution for silica-based photosensitive resin composition of Comparative Example 1 to prepare a silica-based photosensitive resin composition. did.
Using this silica-based photosensitive resin solution, development was performed in the same manner as in Example 1, and the wafer was washed with water and spin-dried. As a result, the coating film was completely dissolved, pattern formation was not observed, and the insulating film characteristics were improved. It could not be measured.

(Comparative Example 3)
A nitric acid aqueous solution in which 0.542 g of 60 mass% nitric acid is diluted with 31.2 g of ion-exchanged water in a solution of 48.1 g of tetraethoxysilane and 82.7 g of methyltriethoxysilane dissolved in 286.6 g of propylene glycol monomethyl ether Was added dropwise over 30 minutes with stirring. After reacting at room temperature for 2 hours, a portion of the produced ethanol and propylene glycol monomethyl ether acetate was distilled off in a warm bath under reduced pressure, and further heated in a warm bath at 70 ° C. for 4 hours to obtain a polysiloxane solution 153. 1 g was obtained.
To this was added 82.5 g of propylene glycol monomethyl ether acetate to obtain a polysiloxane solution. It was 6400 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 the polysiloxane solution for silica-based photosensitive resin composition to prepare a silica-based photosensitive resin composition.

A cured product of the silica-based photosensitive resin composition layer was obtained on the wafer in the same manner as in Example 1 except that ultraviolet light was irradiated at 500 mJ / cm ² . When the pattern shape of the cured product of the silica-based photosensitive resin composition was observed from above with an optical microscope and the cross-sectional shape was observed with an SEM, the line was formed with high accuracy and the pattern accuracy was 10 μm. I understood.
However, when the above-mentioned silica-based photosensitive resin composition that was allowed to stand for 1 week in a clean room environment (24 ° C., humidity 40% RH) was subjected to the same operation as the above-described formation method, a pattern film was developed. The coating film dissolved therein, and no pattern formation was observed.

  A result is shown in Table 1 about the above Examples 1-4 and Comparative Examples 1-3.

ＰＢ：ポストベーキング（後加熱）
ＰＥＢ：ポストエクスプロージャベイク（露光後の加熱）

PB: Post baking (post heating)
PEB: Post-exposure bake (heating after exposure)

  (D) Comparative Examples 1-3 which do not mix | blend the onium salt of a component cannot form a pattern even if it makes an exposure amount high, or is inferior to storage stability. In contrast, Examples 1 to 3, in which an onium salt was blended in advance, can form a pattern with high sensitivity and accuracy even when the exposure amount is low, and are excellent in storage stability.

  By the method of forming the silica-based photosensitive resin composition of the present invention and a silica-based film having a pattern, coating properties, resolution, insulating properties, low dielectric properties, heat resistance, transparency, mechanical properties, and room temperature storage stability It is possible to obtain an excellent cured product. Therefore, the present invention is useful for electronic components.

Claims (4)

(A) component: a siloxane resin obtained by hydrolytic condensation of a compound represented by the following general formula (1),
(B) component: at least one selected from the group consisting of a photoacid generator or a photobase generator;
(C) component: an organic solvent capable of dissolving the component (a),
(D) Component: A silica-based photosensitive resin composition containing an onium salt.

[In General Formula (1), R ¹ is an H atom or an F atom, or a group containing a B atom, an N atom, an Al atom, a P atom, a Si atom, a Ge atom, or a Ti atom, or a group having 1 to 20 carbon atoms. Represents an organic group, X represents a hydrolyzable group, n represents an integer of 0 to 2, and when n is 2, each R ¹ may be the same or different, and when n is 0 to 2, Each X may be the same or different. ]   The catalyst used in the hydrolytic condensation of the compound represented by the general formula (1) is a catalyst selected from an acid catalyst, an alkali catalyst, and a metal chelate compound, and the content thereof is the general formula (1). The silica-based photosensitive resin composition according to claim 1, wherein the amount is 0.0000005 to 0.00001 mol with respect to 1 mol of the total amount of X of the compound represented by formula (1).   A silica-based photosensitive resin composition layer according to claim 1 or 2 is coated on a substrate to form a coating film, an organic solvent contained in the coating film is removed, and a silica-based photosensitive resin composition layer is formed. After the film is formed, the film of the silica-based photosensitive resin composition layer is subjected to exposure / post-exposure heating / development through a pattern mask to remove the unexposed film, and then the remaining film is heat-treated. A method for forming a silica-based insulating coating having:   An electronic component comprising a silica-based insulating film having a pattern formed by the method according to claim 3.