JP4655633B2 - Radiation curable composition, storage method thereof, cured film forming method, pattern forming method, pattern using method, electronic component and optical waveguide - Google Patents

Description

  The present invention relates to a radiation curable composition, a storage method thereof, a cured film forming method, a pattern forming method, a pattern using method, an electronic component, and an optical waveguide.

Conventionally, as an insulating film used for LSI, PDP, 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, radiation curable polysiloxane materials having excellent 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. Furthermore, Patent Document 5 discloses a radiation curable composition comprising a hydrolyzable silane compound, a photoacid generator and an acid diffusion controller.
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 JP 2001-288364 A

  However, the present inventors have studied in detail the patterning using such an insulating film material imparted with photosensitive characteristics as described above. For example, Patent Documents 1 and 2 disclose the patterning. When using a photosensitive resin composition comprising an alkali-soluble siloxane polymer from which water and catalyst have been removed, a photoacid generator, and a solvent, both require a large amount of exposure for curing and are not excellent in mass productivity. Became clear. Further, when a photosensitive polysilazane composition containing polysilazane and a photoacid generator disclosed in Patent Document 3 and Patent Document 4 is used, the composition is cured with a small exposure amount, but is immersed in pure water after exposure or is subjected to a humidification treatment. It has become clear that the process becomes complicated, for example, requiring high pattern accuracy, making it difficult to obtain high pattern accuracy. On the other hand, when a radiation curable composition comprising a hydrolyzable silane compound, a photoacid generator and an acid diffusion control agent disclosed in Patent Document 5 is used, the acid diffusion control agent suppresses the diffusion of acid generated by radiation. As a result, the pattern accuracy of the silane compound can be increased. However, since the acid diffusion controlling agent deactivates (neutralizes) the acid, when the amount of the photoacid generator is small or when the exposure amount is small, the curability is lowered and the pattern accuracy may be lowered. On the other hand, it became clear that pursuing improved pattern accuracy resulted in an increase in exposure and was not suitable for mass production.

  The present invention has been made in view of such circumstances, and a radiation curable composition capable of obtaining a cured product having excellent pattern accuracy even when the exposure amount is relatively small, a storage method thereof, a cured film forming method, and pattern formation. In addition to providing a method, a pattern using method, an electronic component, and an optical waveguide using the method are provided.

  When forming a pattern by generating an acid by radiation, in the conventional technique, the generated acid is deactivated by an acid diffusion control agent in order to improve pattern accuracy. If it carries out like this, it will be necessary to increase an exposure amount in order to generate | occur | produce an extra acid for the part which deactivated, and it is difficult to improve a pattern precision and reduction of an exposure amount simultaneously.

  In order to suppress acid diffusion, instead of deactivating the acid with an acid diffusion controller, the amount of generated acid is reduced by reducing the exposure amount, and the post-exposure baking (PEB) process temperature after exposure is lowered. Means such as causing the PEB or not performing PEB are also conceivable. Conventionally, however, the idea underlying such means has not been recognized. Also, no radiation curable composition suitable for such means is found. A radiation-curable composition suitable for such means can form a pattern with high accuracy without using an acid diffusion controller. However, when patterning using a conventional radiation curable composition, curing does not proceed sufficiently if the amount of acid generated is reduced. Moreover, unless the temperature of the post-exposure bake (PEB) process after exposure is lowered or PEB is not performed, curing of the exposed portion does not proceed in the same manner. As a result, it becomes difficult to form a pattern with high accuracy.

  On the other hand, when a radiation curable composition containing a large amount of water is stored for 7 days in an air atmosphere at, for example, 7 ° C. and then used to form a pattern, it is difficult to form a pattern with high accuracy. It became clear that Thus, the radiation-curable composition containing a large amount of water tends to have insufficient storage stability.

  As a result of intensive studies, the present inventors have found that a radiation curable composition containing a specific component, a cured film forming method, and a pattern forming method can solve various conventional problems. The invention has been completed.

  The present invention comprises (a) component: siloxane resin, (b) component: photoacid generator or photobase generator, (c) component: solvent capable of dissolving (a) component, and (d) component: curing acceleration. A radiation curable composition comprising a catalyst, wherein the radiation curable composition has a water content of 2% by mass or less in the radiation curable composition.

  Such a radiation curable composition can form a cured product having sufficiently high pattern accuracy even when the exposure amount is relatively small. In addition, this radiation curable composition can form a sufficiently accurate pattern even after being stored for a long time.

In the present invention, the siloxane resin is represented by the following general formula (1);
R ¹ _n SiX _4-n (1)
(In the formula, R ¹ represents an H atom or F atom, or a group containing 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, and when n is 2, each R ¹ may be the same or different, and when n is 0 to 2, each X is the same But it may be different.)
The said radiation-curable composition containing resin obtained by hydrolytic condensation of the compound represented by these is provided.

  The present invention provides the above radiation curable composition, wherein the curing accelerating catalyst is an onium salt. An onium salt is preferable from the viewpoint of improving the electrical properties and mechanical strength of the resulting cured product, and further improving the stability of the composition.

  The present invention provides the radiation curable composition, wherein the curing accelerating catalyst is a quaternary ammonium salt. By using a quaternary ammonium salt as an effect promoting catalyst, the effect of improving the electrical characteristics and mechanical strength and the effect of improving the stability of the composition are more effectively exhibited.

  This invention has the process of apply | coating the said radiation-curable composition on a board | substrate, drying and obtaining a coating film, the process of exposing the coating film, and hardening which does not heat a coating film after the process of exposing A film forming method is provided. According to this method, acid diffusion due to heating and an increase in production cost are sufficiently suppressed, and the pattern accuracy of the obtained cured film is sufficiently excellent.

  The present invention comprises a step of applying the radiation curable composition on a substrate and drying to obtain a coating film, a step of exposing the coating film, and a step of heating the coating film after the exposing step. A film forming method is provided.

  This invention provides the said cured film formation method which heats a coating film to 70-110 degreeC in the process of heating mentioned above. Thereby, the spreading | diffusion of the acid at the time of a heating can be suppressed more.

This invention provides the said pattern formation method which exposes a coating film by irradiation of the light of the light quantity of 5.0-100mJ / cm < ² > in the process of exposing mentioned above. By setting the amount of light within the above range, exposure control is facilitated and production efficiency tends to be improved.

  The present invention includes a step of applying the radiation curable composition on a substrate and drying to obtain a coating film, a step of exposing the coating film through a mask, and an unexposed portion of the coating film after the exposing step. A pattern forming method in which the coating film is not heated after the exposing step. According to this method, acid diffusion due to heating and an increase in production cost are sufficiently suppressed, and the pattern accuracy of the obtained cured film is sufficiently excellent. Note that “heating” here refers to heating in a stage prior to the removal step, and may be heated after the removal step.

  The present invention includes a step of applying the radiation curable composition on a substrate and drying to obtain a coating film, a step of exposing the coating film through a mask, and a step of heating the coating film after the exposure step. And a step of removing an unexposed portion of the coating film by development after the heating step.

  This invention provides the said pattern formation method which heats a coating film to 70-110 degreeC in the process of heating mentioned above. Thereby, the spreading | diffusion of the acid at the time of a heating can be suppressed more.

This invention provides the said pattern formation method which exposes a coating film by irradiation of the light of the light quantity of 5.0-100mJ / cm < ² > in the process of exposing mentioned above. By setting the amount of light within the above range, exposure control is facilitated and production efficiency tends to be improved.

  The present invention provides the pattern forming method using a tetramethylammonium hydroxide aqueous solution as a developer in the removing step. Thereby, the contamination by the alkali metal of the electronic component at the time of image development can fully be suppressed.

  The present invention provides a pattern use method using a pattern formed by the pattern forming method as a resist mask.

  The present invention provides an electronic component having a pattern formed by the pattern forming method.

  The present invention provides an optical waveguide provided with a pattern formed by the pattern forming method.

  According to the radiation curable composition having such a component structure, the cured film forming method and pattern forming method using the radiation curable composition, and the storage method of the radiation curable composition, the exposure amount is relatively small. However, the hardened | cured material excellent in pattern precision can be formed, and the conventional trouble that a small exposure amount and the outstanding pattern precision cannot be made compatible can be solved.

  In the present invention, the details of the mechanism that provides such an effect that has not been obtained in the past are still unclear. However, the present inventors, for example, do not need to use an acid diffusion control agent that suppresses diffusion of the generated acid, or further include a curing accelerating catalyst as an additive. It is estimated that a sufficiently excellent pattern accuracy can be secured even if the reduction is achieved.

  The improvement in pattern accuracy is presumed to be caused by the fact that the curing reaction of the radiation curable composition occurs prior to the diffusion of the acid or base when a curing accelerating catalyst is used as an additive. Such a mechanism is different from the conventional mechanism in which the pattern accuracy is improved by deactivating (neutralizing) the acid generated by the acid diffusion controller. In the present invention, it is considered that it is possible to achieve both improvement in pattern accuracy and reduction in exposure based on the above-described mechanism different from the conventional one.

  According to the radiation curable composition, the storage method, the cured film forming method, and the pattern forming method of the present invention, a cured product having excellent pattern accuracy can be obtained even when the exposure amount is relatively small. Therefore, the present invention is useful for a pattern use method, an electronic component, and an optical waveguide.

  Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings as necessary. In the drawings, the same elements are denoted by the same reference numerals, and redundant description is omitted. Further, the positional relationship such as up, down, left and right is based on the positional relationship shown in the drawings unless otherwise specified. Further, the dimensional ratios in the drawings are not limited to the illustrated ratios.

<(A) component>
The component (a) is a siloxane resin, and a known one can be used, but it is preferable to have an OH group at the end or side chain of the resin. This is because the hydrolysis condensation reaction for curing the radiation curable composition further proceeds.

  The siloxane resin preferably has a weight average molecular weight (Mw) of 500 to 1,000,000, more preferably 500 to 500,000 from the viewpoints of solubility in a solvent, mechanical properties, moldability, and the like. More preferably, it is 100,000, particularly preferably 500-10000, and most preferably 500-5000. If this weight average molecular weight is less than 500, the film formability of the cured product tends to be inferior. If this weight average molecular weight exceeds 1,000,000, the compatibility with the solvent tends to decrease. In the present specification, the weight average molecular weight is measured by gel permeation chromatography (hereinafter referred to as “GPC”) and converted using a standard polystyrene calibration curve.

The weight average molecular weight (Mw) can be measured, for example, by GPC under the following conditions.
Sample: radiation curable composition (10 μL)
Standard polystyrene: Standard polystyrene manufactured by Tosoh Corporation (molecular weight: 190,000, 17900, 9100, 2980, 578, 474, 370, 266)
Detector: RI-monitor manufactured by Hitachi, Ltd., trade name “L-3000”
Integrator: GPC integrator manufactured by Hitachi, Ltd., trade name “D-2200”
Pump: manufactured by Hitachi, Ltd., trade name “L-6000”
Degassing apparatus: Showa Denko Co., Ltd., trade name “Shodex DEGAS”
Column: manufactured by Hitachi Chemical Co., Ltd., trade names “GL-R440”, “GL-R430”, “GL-R420” connected in this order. Eluent: Tetrahydrofuran (THF)
Measurement temperature: 23 ° C
Flow rate: 1.75 mL / min Measurement time: 45 minutes

As preferable siloxane resin, for example, the following general formula (1);
R ¹ _n SiX _4-n (1)
And a resin obtained by hydrolysis and condensation using the compound represented by formula (I) as an essential component. Here, in the formula, R ¹ is an H atom or 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 an organic compound having 1 to 20 carbon atoms. 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, X may be the same or different.

  Examples of the hydrolyzable group X include an alkoxy group, an aryloxy group, a halogen atom, an acetoxy group, an isocyanate group, and a hydroxyl group. Among these, an alkoxy group or an aryloxy group is preferable from the viewpoint of liquid stability of the composition itself, coating properties, and the like, and an alkoxy group is more preferable.

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

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

  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, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltri-n-propoxysilane, ethyltri-iso-propoxysilane, ethyltri N-butoxysilane, ethyltri-iso-butoxysilane, ethyltri-tert-butoxysilane, n-propyltrimethoxysilane, n-propyltrie Xysilane, n-propyltri-n-propoxysilane, n-propyltri-iso-propoxysilane, n-propyltri-n-butoxysilane, n-propyltri-iso-butoxysilane, n-propyltri-tert-butoxy Silane, iso-propyltrimethoxysilane, iso-propyltriethoxysilane, iso-propyltri-n-propoxysilane, iso-propyltri-iso-propoxysilane, iso-propyltri-n-butoxysilane, iso-propyltri -Iso-butoxysilane, iso-propyltri-tert-butoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, n-butyltri-n-propoxysilane, n-butyltri-iso-propoxysilane, n- Tiltly-n-butoxysilane, n-butyltri-iso-butoxysilane, n-butyltri-tert-butoxysilane, sec-butyltrimethoxysilane, sec-butyltriethoxysilane, sec-butyltri-n-propoxysilane, sec- Butyltri-iso-propoxysilane, sec-butyltri-n-butoxysilane, sec-butyltri-iso-butoxysilane, sec-butyltri-tert-butoxysilane, t-butyltrimethoxysilane, t-butyltriethoxysilane, t- Butyltri-n-propoxysilane, t-butyltri-iso-propoxysilane, t-butyltri-n-butoxysilane, t-butyltri-iso-butoxysilane, t-butyltri-tert-butoxysilane, phenyl Limethoxysilane, phenyltriethoxysilane, phenyltri-n-propoxysilane, phenyltri-iso-propoxysilane, phenyltri-n-butoxysilane, phenyltri-iso-butoxysilane, phenyltri-tert-butoxysilane, tri Examples include fluoromethyltrimethoxysilane, pentafluoroethyltrimethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, and 3,3,3-trifluoropropyltriethoxysilane.

  Examples of dialkoxysilane include methyldimethoxysilane, methyldiethoxysilane, methyldi-n-propoxysilane, methyldi-iso-propoxysilane, methyldi-n-butoxysilane, methyldi-sec-butoxysilane, and methyldi-tert-butoxy. Silane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldi-n-propoxysilane, dimethyldi-iso-propoxysilane, dimethyldi-n-butoxysilane, dimethyldi-sec-butoxysilane, dimethyldi-tert-butoxysilane, diethyldimethoxysilane, Diethyldiethoxysilane, diethyldi-n-propoxysilane, diethyldi-iso-propoxysilane, diethyldi-n-butoxysilane, diethyldi-sec-butoxy Lan, diethyldi-tert-butoxysilane, di-n-propyldimethoxysilane, di-n-propyldiethoxysilane, di-n-propyldi-n-propoxysilane, di-n-propyldi-iso-propoxysilane, di- n-propyldi-n-butoxysilane, di-n-propyldi-sec-butoxysilane, di-n-propyldi-tert-butoxysilane, di-iso-propyldimethoxysilane, di-iso-propyldiethoxysilane, di- iso-propyldi-n-propoxysilane, di-iso-propyldi-iso-propoxysilane, di-iso-propyldi-n-butoxysilane, di-iso-propyldi-sec-butoxysilane, di-iso-propyldi-tert- Butoxysilane, di-n-butyldimeth Sisilane, di-n-butyldiethoxysilane, di-n-butyldi-n-propoxysilane, di-n-butyldi-iso-propoxysilane, di-n-butyldi-n-butoxysilane, di-n-butyldi- sec-butoxysilane, di-n-butyldi-tert-butoxysilane, di-sec-butyldimethoxysilane, di-sec-butyldiethoxysilane, di-sec-butyldi-n-propoxysilane, di-sec-butyldi- iso-propoxysilane, di-sec-butyldi-n-butoxysilane, di-sec-butyldi-sec-butoxysilane, di-sec-butyldi-tert-butoxysilane, di-tert-butyldimethoxysilane, di-tert- Butyldiethoxysilane, di-tert-butyldi-n-propoxy Orchid, di-tert-butyldi-iso-propoxysilane, di-tert-butyldi-n-butoxysilane, di-tert-butyldi-sec-butoxysilane, di-tert-butyldi-tert-butoxysilane, diphenyldimethoxysilane, Diphenyldiethoxysilane, diphenyldi-n-propoxysilane, diphenyldi-iso-propoxysilane, diphenyldi-n-butoxysilane, diphenyldi-sec-butoxysilane, diphenyldi-tert-butoxysilane, bis (3,3 , 3-trifluoropropyl) dimethoxysilane, methyl (3,3,3-trifluoropropyl) dimethoxysilane and the like.

  Examples of the compound (aryloxysilane) of the general formula (1) in which the hydrolyzable group X is an aryloxy group include, for example, tetraaryloxysilane, triaryloxysilane, diaryloxysilane, etc., which may be substituted, respectively. Is mentioned.

  Examples of tetraaryloxysilane include tetraphenoxysilane.

  Examples of the triaryloxysilane include triphenoxysilane, methyltriphenoxysilane, ethyltriphenoxysilane, n-propyltriphenoxysilane, iso-propyltriphenoxysilane, sec-butyltriphenoxysilane, and t-butyltriphenoxysilane. And phenyltriphenoxysilane.

  Diaryloxysilanes include dimethyldiphenoxysilane, diethyldiphenoxysilane, di-n-propyldiphenoxysilane, di-iso-propyldiphenoxysilane, di-n-butyldiphenoxysilane, di-sec-butyldiphenoxy. Silane, di-tert-butyldiphenoxysilane, diphenyldiphenoxysilane and the like can be mentioned.

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.

Examples of the compound represented by the general formula (1) in which R ¹ is a group containing a Si atom include hexaalkoxydisilanes such as hexamethoxydisilane, hexaethoxydisilane, hexa-n-propoxydisilane, and hexa-iso-propoxydisilane. 1,2-dimethyltetramethoxydisilane, 1,2-dimethyltetraethoxydisilane, 1,2-dimethyltetrapropoxydisilane and other dialkyltetraalkoxydisilanes.

  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.

  Thus, the resin obtained can be used individually by 1 type or in combination of 2 or more types.

  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 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, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid , Nonanoic acid, decanoic acid, oxalic acid, adipic acid, sebacic acid, butyric acid, oleic acid, stearic acid, linoleic acid, linolenic acid, salicylic acid, benzenesulfonic acid, benzoic acid, p-aminobenzoic acid, p-toluenesulfonic acid Methanesulfonic acid, trifluoromethanesulfonic acid, trifluoroethanesulfonic acid and the like. 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, dimethylamine, diethylamine, dipropylamine, dibutylamine, dipentylamine , Dihexylamine, dicyclopentylamine Dicyclohexylamine, trimethylamine, triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, tri cyclopentylamine, tri cyclohexylamine, and the like. These are used singly or in combination of two or more.

  The metal chelate compound is not particularly limited as long as it has a metal and a polydentate ligand, and may further have an organic group. Examples of the metal in the metal chelate compound include titanium, zirconium, aluminum and the like. Examples of the multidentate ligand include acetylacetonato ion and ethyl acetoacetate. Examples of the organic group include alkoxy groups such as a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, a sec-butoxy group, and a tert-butoxy group. Specific examples of metal chelate compounds include trimethoxy (acetylacetonato) titanium, triethoxy (acetylacetonato) titanium, tri-n-propoxy (acetylacetonato) titanium, tri-iso-propoxy (acetylacetonato) titanium, tri -N-butoxy (acetylacetonato) titanium, tri-sec-butoxy (acetylacetonato) titanium, tri-tert-butoxy (acetylacetonato) titanium, dimethoxybis (acetylacetonato) titanium, diethoxybis (acetylacetonato) Titanium, di-n-propoxybis (acetylacetonato) titanium, diiso-propoxybis (acetylacetonato) titanium, di-n-butoxybis (acetylacetonato) titanium, disec-butoxybis (acetylacetonato) tita , Di-tert-butoxybis (acetylacetonato) titanium, methoxytris (acetylacetonato) titanium, ethoxytris (acetylacetonato) titanium, n-propoxytris (acetylacetonato) titanium, iso-propoxytris (acetylacetonato) Titanium, n-butoxytris (acetylacetonato) titanium, sec-butoxytris (acetylacetonato) titanium, tert-butoxytris (acetylacetonato) titanium, tetrakis (acetylacetonato) titanium, trimethoxy (ethylacetoacetate) titanium , Triethoxy (ethyl acetoacetate) titanium, tri-n-propoxy (ethyl acetoacetate) titanium, tri-iso-propoxy (ethyl acetoacetate) titanium, tri-n-butoxy Ethyl acetoacetate) titanium, tri-sec-butoxy (ethyl acetoacetate) titanium, tri-tert-butoxy (ethyl acetoacetate) titanium, dimethoxydi (ethyl acetoacetate) titanium, diethoxydi (ethyl acetoacetate) titanium, di-n-propoxy (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 , Methoxytris (ethyl acetoacetate) titanium, ethoxytris (ethyl acetoacetate) titanium, n-propoxytris (ethyl acetoacetate) titanium, iso-propyl Ropoxy tris (ethyl acetoacetate) titanium, n-butoxy tris (ethyl acetoacetate) titanium, sec-butoxy tris (ethyl acetoacetate) titanium, tert-butoxy tris (ethyl acetoacetate) titanium, tetrakis (ethyl acetoacetate) titanium, etc. Examples thereof include a metal chelate compound having titanium and a compound 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.

  When hydrolyzing and condensing the compound represented by the general formula (1), it is preferable to perform 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 are no particular restrictions on the method of removing the catalyst or the method of reacting with other compounds, but it may be removed using distillation or an ion chromatography column. Moreover, the hydrolysis product obtained from the compound represented by the general formula (1) may be extracted from 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. Similarly, when the catalyst is an acid catalyst, a method of adding an alkali catalyst and neutralizing it by an acid-base reaction or bringing the pH to the alkaline side can be mentioned.

  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 500 to 1,000,000, more preferably 500 to 500,000 from the viewpoints of solubility in a solvent, mechanical properties, moldability, and the like. More preferably, it is 100,000, particularly preferably 500-10000, and most preferably 500-5000. If this weight average molecular weight is less than 500, the film formability of the cured product tends to be inferior. If this weight average molecular weight exceeds 1,000,000, the compatibility with the solvent tends to decrease.

When the radiation curable composition requires adhesion to the substrate on which it is applied and mechanical strength, the H atom, the F atom, the B atom, the N atom, and the Al with respect to 1 mol of the Si atom in the general formula (1) The total content of at least one atom selected from the group consisting of atoms, P atoms, Si atoms, Ge atoms, Ti atoms, and C atoms (this is referred to as “specific bonding atom (R ¹ in the general formula (1) ) Is preferably 0.20 to 1.30 mol, more preferably 0.20 to 1.00 mol, and 0.20 to 0.90 mol. It is particularly preferable that it is 0.20 to 0.80 mol. If it does in this way, the adhesiveness to the other film | membrane (layer) of the 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 from the viewpoint of film formability of the cured product. It is preferable to contain atoms, and among them, from the viewpoint of dielectric properties and mechanical strength, at least one atom selected from the group consisting of H atoms, F atoms, N atoms, Si atoms and C atoms 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 a 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 the specific bonded atoms, and M2 is bonded to two Si atoms among the specific bonded atoms. M3 represents the total number of atoms bonded to three Si atoms among the specific bonded atoms, and Msi represents the total number of Si atoms.

  Such siloxane resins may be 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 a photoacid generator or a photobase generator. A photoacid generator or photobase generator is defined as a compound that can release an acidic active substance or a basic active substance by irradiating it with radiation. Here, the “acidic active substance or basic active substance” means an acidic substance or basic substance capable of curing (hydrolytic polycondensation) of the component (a).

  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. These 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 nifedipine compounds, 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. These 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はそれぞれ独立に炭素数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はそれぞれ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 each an integer of 0 to 2, and t + p + q = 3 is there.

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 blending ratio of the component (b) in the radiation curable composition is not particularly limited, but the sensitivity, efficiency, light source used, and desired cured product thickness of the photoacid generator or photobase generator used. Because of this, the range is wide. Specifically, the blending ratio of the component (b) is preferably 0.00010 to 50 parts by mass, and 0.0010 to 20 parts by mass with respect to 100 parts by mass of the component (a) in the radiation curable composition. Part is more preferable, and 0.010 to 10 parts by mass is particularly preferable. By setting the blending ratio of the component (b) in such a range, the photocurability of the radiation curable composition tends to be further improved. In other words, the exposure amount for curing the composition tends to be further reduced. Furthermore, by setting the blending ratio of the component (b) in such a range, the stability and film formability of the radiation curable composition tend to be further improved, and the electrical characteristics and process of the cured product are increased. There is a tendency for the compatibility to further improve.

  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 further improved. Examples of the photosensitizer include anthracene derivatives, perylene derivatives, anthraquinone derivatives, thioxanthone derivatives, and coumarins.

  In addition, when storing a radiation-curable composition by dividing into two liquids in order to improve storage stability, it is preferable to store the component (b) and the component (a) separately.

  Moreover, when storing a radiation curable composition by one liquid, it is preferable to store at the temperature of 0 degrees C or less, for example. The lower limit of this temperature is preferably equal to or higher than the freezing point of the solvent contained in the radiation curable composition, for example, 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 an aprotic solvent is preferably used. The present inventors presume that the use of 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 high electronegativity. Therefore, the protic solvent molecule forms a hydrogen bond with a nucleophile and solvates. That is, since the protic solvent solvates with the siloxane resin obtained by hydrolyzing the compound represented by the general formula (1), the solvent molecule can be removed in order for the siloxane resin to condense more efficiently. Presumed to be preferable. It is believed that the more protic solvent is present in the radiation curable composition, the more likely it is to inhibit the composition from curing at low temperatures.

  On the other hand, an aprotic solvent is a solvent that does not have a hydrogen atom bonded to an atom having a large electronegativity, and thus is less likely to cause the reaction inhibition as described above than a protic solvent. Therefore, when a coating film of a radiation curable composition using an aprotic solvent is exposed, the curing reaction proceeds with the generation of an acidic active substance or basic active substance in the exposed area, and pattern accuracy due to diffusion of acid or base, etc. It is considered that the pattern accuracy is further improved. This is different from the mechanism of the conventional acid diffusion controller that improves the pattern accuracy by deactivating (neutralizing) the generated acid. Thereby, it is considered that when the aprotic solvent is contained in the component (c), both 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. Can be mentioned.

  Among these, an ether solvent, an ester solvent, an ether acetate solvent, or a ketone solvent is preferable from the viewpoints of sensitivity and pattern accuracy during pattern formation and mechanical strength of the cured product. Moreover, it is preferable that it is a solvent which does not have a nitrogen atom. The inventors consider that among these, ether acetate solvents are preferred first, ether solvents are preferred second, and ketone solvents are preferred third. These solvents are used alone or in combination of two or more.

  Considering the stability of the radiation curable composition, the component (c) preferably has water solubility or water solubility, and has both water solubility and water solubility. Preferably it is. Therefore, when the aprotic solvent does not have water solubility or water solubility, it is preferable to add a protic solvent to the radiation curable composition. When the aprotic solvent does not have water solubility or water solubility, and the radiation curable composition does not contain a protic solvent, the compatibility of the component (a) with the solvent decreases, There is a tendency for stability to decrease. However, if sensitivity is required even at the expense of some stability, it is preferable to reduce the protic solvent.

  Examples of protic solvents include methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, t-butanol, n-pentanol, i-pentanol, and 2-methylbutanol. , Sec-pentanol, t-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, sec-heptanol, n-octanol, 2-ethylhexanol, sec- Octanol, n-nonyl alcohol, n-decanol, sec-undecyl alcohol, trimethylnonyl alcohol, sec-tetradecyl alcohol, sec-heptadecyl alcohol, phenol, cyclohexanol, methylcyclohexano , Benzyl alcohol, ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, and other alcohol solvents; ethylene glycol methyl ether, ethylene glycol ethyl ether , Ethylene glycol monophenyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol mono-n-hexyl ether, ethoxytriglycol, tetraethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether, di Propylene glycol monomethyl ether, dipropy Glycol monoethyl ether, ether solvents such as tripropylene glycol monomethyl ether; methyl lactate, ethyl lactate, n- butyl, ester solvents such as lactic acid n- amyl and the like. These are used singly or in combination of two or more.

  The proportion of the aprotic solvent is preferably 50% by mass or more, more preferably 70% by mass or more, and 90% by mass or more with respect to the total amount of the solvent in the radiation curable composition. Is particularly preferable, and it is extremely preferable that the content is 95% by mass or more. By adjusting the blending ratio to the above range, the photocurability of the radiation curable composition tends to be further improved. In other words, the exposure amount for curing the composition tends to be further reduced. Furthermore, by adjusting the blending ratio to the above range, the radiation curable composition tends to be sufficiently cured without performing heat treatment at a very high temperature. Since the diffusion of the base can be further suppressed, the pattern accuracy tends to be further improved.

  (C) Although the compounding method to the radiation curable composition of a component is not specifically limited, For example, (a) The method of using as a solvent at the time of preparing a component, (a) The method of adding after preparing a component, solvent exchange There is a method of performing, and (c) a method of adding a solvent after taking out component (a) by solvent distillation or the like.

  The blending ratio of this solvent (total of aprotic solvent and protic solvent) in the radiation curable composition is such that the blending ratio of the component (a) (siloxane resin) in the radiation curable composition is 3 to 60% by mass. The ratio is preferably such that By adjusting the mixing ratio of the solvent so that the mixing ratio of the component (a) is within this range, it tends to be easy to form a cured product having a desired film thickness. And the stability of the composition itself tends to be further improved.

<(D) component>
(D) component in this invention is a hardening acceleration | stimulation catalyst, By adding this to a radiation curable composition, the reduction effect of the compounding ratio of a photo-acid generator or a photobase generator, the reduction effect of an exposure amount, or It is considered that the effect of lowering the temperature of PEB can be expected. This curing accelerating catalyst has a curing accelerating catalytic ability and is different from a normal photoacid generator or photobase generator such as component (b) that generates an active substance by light. Therefore, it is usually distinguished from onium salts such as those used as photoacid generators or photobase generators. However, any material that has both photoacid generating ability or photobase generating ability and curing acceleration catalytic ability can also be used as a curing acceleration catalyst. Since a material having both photoacid generating ability or photobase generating ability and curing acceleration catalytic ability has both functions of the component (b) and the component (d), the radiation curable composition of the present invention has When such a material is contained, it is not necessary to further contain other component (b) or component (d).

  The catalyst is considered to be a peculiar one that exhibits no activity in the solution of the radiation curable composition and exhibits activity in the coated film after coating. Since the curing reaction by the curing accelerating catalyst proceeds with the generation of the acidic active substance and the basic active substance in the exposed portion of the coating film, it is presumed that the diffusion of acid and base is thereby suppressed. Therefore, it is presumed that the pattern accuracy is not easily lowered due to diffusion of acid or base, that is, the pattern accuracy is further improved.

Whether or not a certain compound has “curing promoting catalytic ability”, that is, whether or not it is a curing promoting catalyst is determined as follows.
1. First, a composition comprising the component (a) and the component (c) is prepared.
2. Then, the prepared composition is apply | coated on a silicon wafer so that the film thickness after baking (baking) may be set to 1.0 +/- 0.1 micrometer. Next, after the applied composition is baked at a predetermined temperature for 30 seconds, the film thickness of the resulting film is measured. At this time, the film thickness may be 1.0 ± 0.1 μm.
3. Subsequently, the silicon wafer on which the coating was laminated was immersed in a 2.38 mass% tetramethylammonium hydroxide (TMAH) aqueous solution at 23 ± 2 ° C. for 30 seconds, further washed with water and dried, and the thickness of the coating was measured again To do. At this time, the insoluble temperature is defined as the lowest temperature during baking at which the change in the film thickness before and after immersion in the TMAH aqueous solution is within 20% of the film thickness before immersion.
4). Next, a new composition obtained by adding 0.01% by mass of a compound to be checked for the presence or absence of curing accelerating catalytic ability to the composition comprising the components (a) and (c) with respect to the total amount of the component (a). The composition is subjected to the same treatment as 2 and 3 above, and the insoluble temperature of the new composition is determined.

  As a result, if the insoluble temperature of the composition is decreased by adding a compound for which the presence or absence of curing acceleration catalytic ability is to be confirmed, it is determined that the compound has curing acceleration catalytic ability.

  Examples of the curing accelerating catalyst that is component (d) include alkali metals having a curing accelerating catalytic ability such as sodium hydroxide, sodium chloride, potassium hydroxide, potassium chloride, and onium salts. These are used singly or in combination of two or more.

  Among these, from the viewpoint of improving the electrical properties and mechanical strength of the resulting cured product, and further improving the stability of the composition, the component (d) is an onium salt having a curing acceleration catalytic ability. Preferably, it is a quaternary ammonium salt having a curing accelerating catalytic ability.

  As one of the onium salts, for example, a salt formed from (d-1) a nitrogen-containing compound and (d-2) at least one selected from an anionic group-containing compound and a halogen atom can be mentioned. The atom which couple | bonds with nitrogen of said (d-1) nitrogen-containing compound is a group which consists of H atom, F atom, B atom, N atom, Al atom, P atom, Si atom, Ge atom, Ti atom, and C atom. It is preferably at least one kind of atom selected from the above. Examples of the anionic group include a hydroxyl group, a nitrate group, a sulfate group, a carbonyl group, a carboxyl group, a carbonate group, and a phenoxy group.

  Examples of onium salts include 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, ammonium maleate salt, fumarate. Ammonium salt, 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, Canoic acid ammonium salt, oxalic acid ammonium salt, adipic acid ammonium salt, sebacic acid ammonium salt, butyric acid ammonium salt, oleic acid ammonium salt, stearic acid ammonium salt, linoleic acid ammonium salt, linolenic acid ammonium salt, salicylic acid ammonium salt, benzenesulfone Ammonium salt, ammonium salt of benzoic acid, ammonium salt of p-aminobenzoic acid, ammonium salt of p-toluenesulfonic acid, ammonium salt of methanesulfonic acid, ammonium salt of trifluoromethanesulfonic acid, ammonium salt of trifluoroethanesulfonic acid, etc. Is mentioned.

  In addition, the ammonium ion of the above ammonium salt is methylammonium ion, dimethylammonium ion, trimethylammonium ion, tetramethylammonium ion, ethylammonium ion, diethylammonium ion, triethylammonium ion, tetraethylammonium ion, propylammonium ion, dipropylammonium ion. , Ammonium salt substituted with tripropylammonium ion, tetrapropylammonium ion, butylammonium ion, dibutylammonium ion, tributylammonium ion, tetrabutylammonium ion, ethanolammonium ion, diethanolammonium ion, triethanolammonium ion, etc. It is done.

  Among these onium salts, ammonium such as tetramethylammonium nitrate, tetramethylammonium acetate, tetramethylammonium propionate, tetramethylammonium maleate and tetramethylammonium sulfate is used from the viewpoint of accelerating the curing of the cured product. Salts are preferred.

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

  The blending ratio of the component (d) is preferably 0.00010 to 5.0 parts by weight, and 0.00010 to 1.0 parts by weight with respect to 100 parts by weight of the component (a) in the radiation curable composition. It is more preferable that By setting the blending ratio of the component (d) within this numerical range, the exposure amount for sufficiently curing the radiation curable composition tends to be further reduced, and the stability of the composition and film formation are further increased. There exists a tendency which can improve the electrical property and process compatibility of hardened | cured material while improving property etc.

  The onium salt can be adjusted to a desired concentration by dissolving or diluting in water or a solvent, if necessary, and then adding to the radiation curable composition. The timing of adding the onium salt to the radiation curable composition is not particularly limited. For example, when the hydrolysis of the component (a) is performed, during the hydrolysis, at the end of the reaction, before and after the solvent is distilled off, the acid generator is added. It may be the time of addition.

  Although water may be contained in the radiation curable composition of the present invention, the content is preferably 2% by mass or less with respect to the total amount of the radiation curable composition, and 1% by mass or less. More preferably, it is more preferably 0.5% by mass or less, and particularly preferably 0.1% by mass or less. Even if the radiation curable composition in which the content ratio of water is adjusted within the above range is patterned after being stored in an air atmosphere at 7 ° C. for 7 days, the same conditions (for example, the same A pattern can be formed with almost the same accuracy as when the patterning is performed with the exposure amount.

  Therefore, when water exceeding 2 mass% is contained in the radiation curable composition, it is preferable to remove the water and adjust it to 2 mass% or less. Although it does not specifically limit as a method of removing water, For example, the method of distilling a radiation-curable composition or using an evaporator or a dehydrating agent is mentioned.

  The water content in the radiation curable composition can be measured by a coulometric titration Karl Fischer moisture measuring device.

<Other ingredients>
Moreover, you may add a pigment | dye to the radiation-curable composition of this invention. By adding a dye, for example, an effect of adjusting photosensitivity, an effect of suppressing a standing wave effect, and the like can be obtained.

  In addition, a surfactant, a silane coupling agent, a thickener, an inorganic filler, a thermally decomposable compound such as polypropylene glycol, a volatile compound, and the like are included in the radiation curable composition as long as the object and effect of the present invention are not impaired. It may be added to the product. The thermally decomposable compound and the volatile compound are preferably decomposed or volatilized by heat (preferably 250 to 500 ° C.) and can form voids in the cured product. Further, the same void forming ability may be imparted to the siloxane resin as the component (a).

  In addition, when using the radiation curable composition of this invention for an electronic component, it is desirable not to contain an alkali metal or an alkaline-earth metal in the composition. In the case of containing those metals, the content ratio is preferably 1000 ppm by mass or less, more preferably 1 ppm by mass or less, based on the total amount of the composition. If the content ratio of these metals exceeds 1000 mass ppm, ions of those metals are likely to flow into electronic components such as semiconductor elements, so that it is difficult to obtain desired device characteristics. These alkali metals and alkaline earth metals are preferably removed by using an ion exchange filter or the like as necessary when preparing the radiation curable composition. However, when the radiation curable composition is used for an optical waveguide or other applications, this is not limited as long as the purpose is not impaired.

  Next, a method for forming a pattern on a substrate using the radiation curable composition of the present invention will be described. The method of applying the radiation curable composition on the substrate is not particularly limited, such as spin coating, spray coating, dip coating, flow coating, roll coating, slit coating, screen printing, etc. From the viewpoint of excellent film formability and film uniformity, a spin coating method is preferred. Hereinafter, the pattern forming method will be described by taking this spin coating method as an example. Note that the substrate on which the pattern is formed may have a flat surface, or may have an uneven surface on which electrodes are formed.

  First, a radiation curable composition is spin-coated on a substrate such as a Si wafer or a glass substrate, preferably at 500 to 5000 revolutions / minute, more preferably at 500 to 3000 revolutions / minute, to form a coating film. Form. At this time, if the rotational speed is less than 500 revolutions / minute, the film uniformity tends to be lowered. On the other hand, if it exceeds 5000 revolutions / minute, the film formability may be lowered.

  The film thickness of the coating film varies depending on the intended use. For example, the coating film when the obtained cured film (cured product) is used for an interlayer insulating film such as LSI has a cured film thickness of 0.010-2. The film thickness is preferably 0 μm, and the coating film when the cured film is used for the passivation layer preferably has a thickness such that the cured film thickness is 2.0 to 40 μm. When the cured film is used for liquid crystal, the coated film is preferably a film thickness such that the cured film has a thickness of 0.10 to 20 μm. The coated film when used for a photoresist is a cured film. The film thickness is preferably such that the film thickness is 0.10 to 2.0 [mu] m, and the coating film when used in an optical waveguide is preferably 1.0 to 50 [mu] m. Usually, the thickness of the cured film is generally preferably from 0.010 to 10 μm, more preferably from 0.010 to 5.0 μm, still more preferably from 0.010 to 3.0 μm, It is particularly preferable that the thickness is .010 to 2.0 μm, and it is very preferable that the thickness is 0.10 to 2.0 μm. In order to adjust the film thickness of the cured film, for example, the blending ratio 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. In the case where the film thickness is controlled by adjusting the blending ratio 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 (a) It can be controlled by lowering the concentration of the components. 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 and water in the coating film are volatilized with a hot plate or the like, preferably at 50 to 200 ° C., more preferably 70 to 150 ° C., and the coating film is dried. When the drying temperature is less than 50 ° C., the organic solvent tends to be not sufficiently volatilized. On the other hand, when the drying temperature exceeds 200 ° C., the coating film is difficult to dissolve in the developer during the subsequent development processing, and the pattern accuracy tends to be lowered.

Next, the coating film is exposed to radiation through a mask having a desired pattern. Thereby, the exposed part of the coating film irradiated with radiation is cured to form a cured film. Preferably this dose is 5.0~5000mJ / cm ^2, more preferably 5.0~1000mJ / cm ^2, particularly preferably from 5.0~500mJ / cm ^2, 5. It is very preferably 0 to 100 mJ / cm ² . The exposure amount may become difficult to control by the light source is less than ^{5.0mJ / 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 radiation curable composition is about 500-5000 mJ / cm < ² >.

  The radiation in the present invention refers to electromagnetic waves or particle beams, and examples thereof include visible light, ultraviolet rays, infrared rays, X-rays, α rays, β rays, and γ rays. Among these, 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.

  Moreover, you may pass through a heating (post exposure bake: PEB) process after exposure as needed. In the heat treatment in this step, at least an exposed portion (cured film) cured by exposure is heated by a heating means such as a hot plate. In that case, it is preferable to heat in the temperature range in which the solubility with respect to the developing solution of the coating film of an unexposed part does not fall. The heating temperature is preferably 50 to 200 ° C, more preferably 70 to 150 ° C, particularly preferably 70 to 110 ° C, and extremely preferably 70 to 100 ° C. In general, the higher the temperature, the more easily the generated acid diffuses, so the lower the heating temperature is better. In addition, the heating temperature in the PEB process of the conventional general siloxane type radiation curable composition is about 115-120 degreeC.

  Further, from the viewpoint of suppressing acid diffusion and increase in production cost, it is preferable not to provide the heating step as described above after exposure and before development.

  Subsequently, the unexposed portion of the radiation curable composition coating film is removed, that is, developed. The unexposed area where the irradiation of radiation is inhibited by the mask in the exposure process has sufficient solubility in the developer used in this development. On the other hand, in the exposed portion irradiated with radiation, an acidic active substance or a basic active substance is generated by exposure, a hydrolysis condensation reaction occurs, and the solubility in the developer is lowered. By this action, only the exposed portion (cured film) remains selectively on the substrate to form a pattern.

  For 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; fourth amines such as tetramethylammonium hydroxide (TMAH) and tetraethylammonium hydroxide An aqueous solution such as quaternary ammonium can be 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. When the radioactive curable composition is used in the production of an electronic component, the electronic component dislikes alkali metal contamination, and therefore, a tetramethylammonium hydroxide aqueous solution is preferable as the developer.

  The suitable development time depends on the film thickness and the solvent of the coating film and the cured film, but is preferably 5 seconds to 5 minutes, more preferably 30 seconds to 3 minutes, and 30 seconds to 1 minute. It is particularly preferred. 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. Although the processing temperature at the time of image development is not specifically limited, Generally it is 20-30 degreeC. As the developing method, for example, methods such as spraying, paddle, dipping, and ultrasonic waves are possible.

  The pattern formed by development may be rinsed with distilled water or the like as necessary.

  The cured film of the radiation curable composition thus patterned can be used as a resist mask as it is.

When the cured film patterned according to the present invention is left on the substrate or in the electronic component as an interlayer insulating film, a cladding layer, etc., for example, the cured film is baked at a heating temperature of 100 to 500 ° C. to perform final curing. It is preferable. This final curing is preferably performed under an inert atmosphere such as N ₂ , Ar, and He, in the air, under reduced pressure conditions, etc. However, if the characteristics required for the application are satisfied, the ambient atmosphere or pressure There are no particular restrictions on the conditions. By setting the heating temperature in the final curing to 100 ° C. to 500 ° C., the curability of the exposed portion can be further improved and the electrical insulation can be improved. Moreover, since the one where this heating temperature is low exists in the tendency which can suppress deterioration of the material used for lower layers of coating films, such as a board | substrate and a wafer, it is preferable.

  The heating time in the 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 film (cured product) include devices having an insulating film such as a semiconductor element and a multilayer wiring board. Specifically, in a semiconductor element, a cured film 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, a cured film 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.

  Furthermore, it can be used as a liquid crystal component, an organic transistor, an optical waveguide, a photoresist, or the like, but the application is not limited thereto.

FIG. 1 is a schematic end view showing an embodiment of a TFT (thin film transistor) according to the present invention, which is an electronic component provided in a TFT liquid crystal display. In this TFT, a conductive layer 3 made of polysilicon is provided on an undercoat film 2 formed on a glass substrate 1, and a source 4 and a drain 5 are arranged so as to sandwich the conductive layer 3 in the in-plane direction. Has been. A gate electrode 7 is provided on the conductive layer 3 through a gate oxide film 6 made of SiO ₂ as a constituent material. The gate oxide film 6 is provided so that the conductive layer 3 is not in direct contact with the gate electrode 7. The undercoat film 2, the conductive layer 3, the source 4, the drain 5, the gate oxide film 6, and the gate electrode 7 are covered with a first interlayer insulating film 8 to prevent a short circuit. A part is removed at the time of forming the TFT, and the metal wiring 9 is drawn out from the part while being connected to the source 4 and the drain 5 respectively. Among the metal wirings 9, the metal wiring 9 drawn out in a state of being connected to the drain 5 is electrically connected to the transparent electrode 11, and other portions are made of the second interlayer insulating film 10 so as not to be short-circuited. Covered.

  The cured film obtained from the radiation curable composition of the present invention is provided in this TFT mainly as the second interlayer insulating film 10, but may be used for the first interlayer insulating film 8. These interlayer insulating films 8 and 10 are formed as follows, for example. First, the radiation curable composition of the present invention is applied on the base by spin coating or the like and dried to obtain a coating film. Next, the coating film is exposed through a mask having a predetermined pattern, and a predetermined portion (in the case of the first interlayer insulating film 8, a portion other than the portion where the metal wiring 9 is to be formed, in the case of the second interlayer insulating film 10, a transparent electrode) 11 is cured, and further heat-treated as necessary. Then, the unexposed portions are removed by development processing, and interlayer insulating films 8 and 10 are obtained. Thereafter, it may be finally cured by heat treatment as necessary. Note that the interlayer insulating films 8 and 10 may have the same composition or different compositions.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples.

  In this example, the radiation curable composition is used until the development step of the radiation curable composition is completed so that the photo acid generator or photo base generator is not excited. And in an environment that does not include the photosensitive wavelength of the sensitizer.

Example 1
Tetraethoxysilane 320.4 g, methyltriethoxysilane 551.6 g, photoacid generator (PAI-101, manufactured by Midori Chemical Co., Ltd.) 6.05 g and 2.38 mass% tetramethylammonium nitrate aqueous solution (pH 3.6) An aqueous solution prepared by dissolving 1.62 g of 60% by mass nitric acid in 208.3 g of deionized water was added dropwise over 30 minutes with stirring to a solution obtained by dissolving 26 g in propylene glycol methyl ether acetate 1917.0 g. After the completion of the dropwise addition, the reaction was carried out 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 1063.6 g of a polysiloxane solution. 436.4 g of propylene glycol methyl ether acetate was added to 1063.6 g of this polysiloxane solution, and stirred and dissolved at room temperature (25 ° C.) for 30 minutes to obtain a radiation curable composition. It was 2690 when the weight average molecular weight of (a) component (polysiloxane) was measured by GPC method.

  In addition, as for the content rate of each component in the obtained radiation-curable composition, (a) component is 20 mass% with respect to the total amount of a composition, (b) component is 0.4 mass%. (D) component was 0.0020 mass%, and water was 0.1 mass%. Among these, the content rate of (a) component, (b) component, and (d) component is converted from preparation amount, and the content rate of water is content in the radiation-curable composition just before patterning mentioned later. Is converted from the value measured using the following coulometric titration type Karl Fischer moisture measuring device (the same applies hereinafter).

Trace moisture analyzer: Trade name “AQUACOUNTER AQ-2000”, manufactured by Hiranuma Sangyo Co., Ltd. Starr: Trade name “STIRRER K-2000”, manufactured by Hiranuma Sangyo Co., Ltd. : Product name “Hydranal Aqualite RS”, sold by Hiranuma Sangyo Co., Ltd. Moisture vaporizer: Product name “EVAPOTOR EV-2000L”, manufactured by Hiranuma Sangyo Co., Ltd. Solvent: Dehydrated toluene Toluene)
Heating furnace temperature: 120 ° C
Dry air flow rate: 50 mL / min Measurement temperature: 23 ° C.
Parameters: Interval Time = 10 sec, S-Timer = 0 min, T-Timer = 20 min

  First, 10 mL of dehydrated toluene was injected into the vaporization chamber of the moisture vaporizer and heated to 120 ° C. in a heating furnace. Into this, air passed through a drying tube filled with molecular sieve 3A was bubbled to further remove moisture in toluene. And after blank erasure | elimination was complete | finished with the trace moisture measuring apparatus, 100 microliters of radiation-curable compositions were introduce | transduced from the sample insertion port of the vaporization chamber, and content of the water in a radiation-curable composition was measured.

Next, patterning (pattern formation) was performed using this radiation curable composition. First, 2 mL of the radiation curable composition was dropped onto the center of a 6-inch silicon wafer, and a coating film was formed on the wafer by spin coating (rotating for 30 seconds at 700 rpm). Dry on a hot plate for 30 seconds. Then, i line | wire is 100 mJ / cm < ² > with an exposure machine (FPA-3000 iW, Canon Inc.) with respect to the dried coating film through the mask for negatives which has a linear pattern whose minimum line | wire width is 2 micrometers. Irradiated. The wafer provided with the coating film after exposure was heated on a hot plate at 100 ° C. for 30 seconds, and then cooled on a cooling plate (23 ° C.) for 30 seconds.

  Next, the wafer was subjected to paddle development for 30 seconds using a 2.38 mass% tetramethylammonium hydroxide (TMAH) aqueous solution as a developer using a coater / developer (Mark 7, manufactured by Tokyo Electron Ltd.). Dissolved. 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 on the wafer.

  When the pattern shape of the cured product was observed from above with an optical microscope and the cross-sectional shape was observed with SEM, a line was formed with high accuracy. From this, it was confirmed that when the radiation curable composition of Example 1 was used, the pattern accuracy was 2 μm or less.

  Moreover, after storing the radiation-curable composition of Example 1 for 7 days in an air atmosphere at 7 ° C., patterning was performed under the same conditions as described above, and the pattern shape was observed. The pattern accuracy was 2 μm or less. Was confirmed.

(Comparative Example 1)
The radiation-curable composition of Comparative Example 1 was obtained by adding 3 g of deionized water to 100 g of the radiation-curable composition obtained in Example 1. In addition, as for the content rate of each component in the obtained radiation-curable composition, (a) component is 19.4 mass% with respect to the total amount of a composition, (b) component is 0.39 mass%. The component (d) was 0.0019% by mass, and water was 2.9% by mass.

Next, patterning (pattern formation) was performed using this radiation curable composition. First, 2 mL of the radiation curable composition was dropped onto the center of a 6-inch silicon wafer, and a coating film was formed on the wafer by spin coating (rotating for 30 seconds at 700 rpm). Dry on a hot plate for 30 seconds. Then, i line | wire is 100 mJ / cm < ² > with an exposure machine (FPA-3000 iW, Canon Inc.) with respect to the dried coating film through the mask for negatives which has a linear pattern whose minimum line | wire width is 2 micrometers. Irradiated. The wafer provided with the coating film after exposure was heated on a hot plate at 100 ° C. for 30 seconds, and then cooled on a cooling plate (23 ° C.) for 30 seconds.

  Next, the wafer was subjected to paddle development for 30 seconds using a 2.38 mass% tetramethylammonium hydroxide (TMAH) aqueous solution as a developer using a coater / developer (Mark 7, manufactured by Tokyo Electron Ltd.). Dissolved. 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 on the wafer.

  When the pattern shape of the cured product was observed from above with an optical microscope and the cross-sectional shape was observed with SEM, a line was formed with high accuracy. From this, it was confirmed that when the radiation curable composition of Comparative Example 1 was used, the pattern accuracy was 2 μm or less.

  Moreover, after storing the radiation-curable composition of Comparative Example 1 in an air atmosphere at 7 ° C. for 7 days, patterning was performed under the same conditions as above, and the pattern shape was observed. It was confirmed that the shape was not good and the pattern accuracy exceeded 2 μm.

1 is a schematic end view showing a preferred embodiment of an electronic component according to the present invention.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 1 ... Glass substrate, 2 ... Undercoat film, 3 ... Conductive layer, 4 ... Source, 5 ... Drain, 6 ... Gate oxide film, 7 ... Gate electrode, 8 ... 1st interlayer insulation film, 9 ... Metal wiring, 10 ... Second interlayer insulating film, 11... Transparent electrode.

Claims (12)

(A) component: siloxane resin,
(B) component: a photoacid generator or a photobase generator,
(C) Component: a solvent capable of dissolving the component (a), and (d) component: a radiation curable composition comprising a curing accelerating catalyst , wherein the curing accelerating catalyst is a quaternary ammonium salt. And the radiation-curable composition whose content rate of the water in the radiation-curable composition is 2 mass% or less. The siloxane resin has the following general formula (1):
R ¹ _n SiX _4-n (1)
(In the formula, R ¹ is H atom or F atom, or B atom, N atom, Al atom, P atom, Si
An atom, a group containing a Ge atom or a 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, and when n is 2, each R ¹ may be the same or different. When n is 0 to 2, each X may be the same or different. )
The radiation curable composition of Claim 1 containing resin obtained by hydrolytic condensation of the compound represented by these. The process of apply | coating the radiation-curable composition of Claim 1 or 2 on a board | substrate and drying and obtaining a coating film, the process of exposing the said coating film, and heating the said coating film after this exposure process And a cured film forming method. The cured film formation method of Claim 3 which heats the said coating film at 70-110 degreeC in the said process to heat. The cured film formation method of Claim 3 or 4 which exposes the said coating film by irradiation of the light of the light quantity of 5.0-100 mJ / cm < ² > in the said process to expose. The step of applying the radiation curable composition according to claim 1 or 2 on a substrate and drying to obtain a coating film, the step of exposing the coating film through a mask, and the step of exposing after the step of exposing. The pattern formation method which has the process of removing the unexposed part of the said coating film by image development after the process of heating a film | membrane and the said process of heating. The pattern formation method of Claim 6 which heats the said coating film at 70-110 degreeC in the said process to heat. The pattern formation method according to claim 6 or 7 , wherein, in the exposing step, the coating film is exposed by irradiation with light having a light amount of 5.0 to 100 mJ / cm ² . The pattern forming method according to claim 6 , wherein in the removing step, an aqueous tetramethylammonium hydroxide solution is used as a developer. The pattern usage method which uses the pattern formed by the pattern formation method as described in any one of Claims 6-9 as a resist mask. An electronic component provided with the pattern formed by the pattern formation method as described in any one of Claims 6-9 . An optical waveguide provided with the pattern formed by the pattern formation method as described in any one of Claims 6-9 .

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