JP2006091818A - Cured film forming method, pattern forming method, pattern usage, electronic component, and optical waveguide - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a cured film forming method for obtaining a hardener superior in pattern precision even when an exposure amount is comparatively small, and to provide a pattern forming method. <P>SOLUTION: The cured film forming method includes a process for obtaining an application film by drying to apply a radiation curable composition containing a siloxane resin on a substrate, and a process for exposing the application film. The application film is not heated after an exposing process. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to 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. 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, it is clear that both require a large amount of exposure and are not excellent in mass productivity. It was. Further, when a photosensitive polysilazane composition containing polysilazane and a photoacid generator disclosed in Patent Document 3 and Patent Document 4 is used, the exposure amount is small, but it is immersed in pure water after exposure or requires a humidification treatment. It has become clear that the process becomes complicated and it becomes 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 provides a cured film forming method and a pattern forming method capable of obtaining a cured product having excellent pattern accuracy even when the exposure amount is relatively small, and also used the same. A pattern use method, an electronic component, and an optical waveguide 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 make a pattern accuracy improvement and reduction of an exposure amount compatible.

  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 temperature of the post-exposure bake (PEB) process 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) step after exposure is lowered or PEB is not performed, curing of the exposed portion does not proceed. As a result, it becomes difficult to form a pattern with high accuracy.

  As a result of extensive research, 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 includes a step of applying a radiation curable composition containing a siloxane resin on a substrate and drying to obtain a coating film, a step of exposing the coating film, and a coating film after the exposing step. A method for forming a cured film without heating 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.

  In the present invention, a radiation curable composition containing a siloxane resin is applied onto a substrate and dried to obtain a coating film, the coating film is exposed to light, and the coating film is exposed to 70 to 110 after the exposure process. And a method of forming a cured film having a step of heating to ° C. Thereby, the spreading | diffusion of the acid at the time of a heating can be suppressed more.

The present invention includes a step of applying a radiation curable composition containing a siloxane resin on a substrate and drying to obtain a coating film, and a step of exposing the coating film by irradiation with light of a light amount of 5 to 100 mJ / cm ^2. A method for forming a cured film is provided. By setting the amount of light within the above range, exposure control is facilitated and production efficiency tends to be improved. In this case, you may provide the process of heating a coating film after the process of exposing.

The present invention includes a step of applying a radiation curable composition containing a siloxane resin on a substrate and drying to obtain a coating film, and a step of exposing the coating film by irradiation with light of a light amount of 5 to 100 mJ / cm ^2. And a method of forming a cured film having a step of heating the coating film to 70 to 110 ° C. after the step of exposing.

This invention is the said cured film formation method using the radiation curable composition containing a siloxane resin, Comprising: The siloxane resin is 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 cured film formation method containing resin obtained by hydrolytic condensation of the compound represented by these is provided.

The present invention includes a step of applying a radiation curable composition containing a siloxane resin on a substrate and drying to obtain a coating film, and the coating film is 5 to 100 mJ / cm. ² A cured film forming method in which the coating film is not heated after the exposure step.

The present invention provides the following general formula (8):
SiX ₄   ... (8)
(In the formula, X represents a hydrolyzable group.)
A resin obtained by hydrolysis condensation using as an essential component a compound represented by general formula (8), a multimer of the compound represented by general formula (8), and / or a partial condensate of the compound represented by general formula (8). A step of applying a radiation-curable composition containing a siloxane resin to a substrate and drying to obtain a coating film; and 5 to 100 mJ / cm of the coating film ² And a step of exposing by irradiation with light of a certain amount of light.

This invention is the said cured film formation method using the radiation-curable composition containing a siloxane resin, Comprising: The resin obtained by hydrolytic condensation is a compound represented by the said General formula (8), General formula ( A multimer of the compound represented by 8) and / or a partial condensate of the compound represented by the general formula (8), and 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 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 group having 1 to 20 carbon atoms. , X represents a hydrolyzable group, n represents an integer of 1 to 2, and when n is 2, each R ¹ may be the same or different. When n is 1 to 2, each X is the same But it may be different.)
A resin obtained by hydrolytic condensation using, as an essential component, a compound represented by general formula (1), a multimer of the compound represented by general formula (1), and / or a partial condensate of the compound represented by general formula (1) A method for forming a cured film is provided.

The present invention provides the following general formula (1);
R ¹ _n SiX _4-n   ... (1)
(Wherein 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, and X is hydrolyzable. 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. )
A resin obtained by hydrolysis condensation using as an essential component a compound represented by general formula (1), a multimer of the compound represented by general formula (1), and / or a partial condensate of the compound represented by general formula (1). A radiation curable composition containing a siloxane resin, wherein the H atom, F atom, B atom, and N atom bonded to the Si atom with respect to 1 mol of the Si atom in the resin obtained by hydrolysis and condensation A radiation curable composition in which the total content of at least one atom selected from the group consisting of Al atom, P atom, Si atom, Ge atom, Ti atom and C atom is 0.90 to 0.20 Applying and drying on top to obtain a coating film, and the coating film is 5 to 100 mJ / cm ² And a step of exposing by irradiation with light of a certain amount of light.

This invention is the said cured film formation method using the radiation curable composition containing a siloxane resin, Comprising: R in the said General formula (1) ¹ Provides a method for forming a cured film containing at least one atom selected from the group consisting of H atom, F atom, N atom, Si atom, Ti atom and C atom.

This invention is the said cured film formation method using the radiation curable composition containing a siloxane resin, Comprising: R in the said General formula (1) ¹ Provides a cured film forming method comprising at least one atom selected from the group consisting of H atom, F atom, N atom, Si atom and C atom.

This invention is the said cured film formation method using the radiation curable composition containing a siloxane resin, Comprising: In the resin obtained by the said hydrolysis condensation, H couple | bonded with Si atom with respect to 1 mol of Si atoms. The total content of at least one atom selected from the group consisting of atoms, F atoms, B atoms, N atoms, Al atoms, P atoms, Si atoms, Ge atoms, Ti atoms, and C atoms is 0.80 to 0 A cured film forming method is provided.

The present invention includes a step of applying a radiation curable composition containing a siloxane resin dissolved in an ether acetate solvent or an aprotic solvent containing an ether solvent on a substrate and drying to obtain a coating film, 5-100 mJ / cm of membrane ² And a step of exposing by irradiation with light of a certain amount of light.

The present invention includes a step of applying a radiation curable composition containing a siloxane resin and an acid generator on a substrate and drying to obtain a coating film, and the coating film is 5 to 100 mJ / cm. ² A cured film forming method in which the coating film is not heated after the exposure step.

This invention is the said cured film formation method using the radiation-curable composition containing a siloxane resin, Comprising: The said siloxane resin is following General formula (1);
R ¹ _n SiX _4-n   ... (1)
(Wherein 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, and X is hydrolyzable. 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. )
A cured film comprising a resin obtained by hydrolytic condensation of a compound represented by general formula (1), a multimer of the compound represented by general formula (1), and / or a partial condensate of the compound represented by general formula (1) A forming method is provided.

  The present invention comprises a step of applying a radiation curable composition containing a siloxane resin 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. And 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 a radiation curable composition containing a siloxane resin on a substrate and drying to obtain a coating, a step of exposing the coating through a mask, and a coating after the step of exposing. The pattern formation method which has the process of heating to 70-110 degreeC, and the process of removing the unexposed part of a coating film by image development after the heating process is provided. Thereby, the spreading | diffusion of the acid at the time of a heating can be suppressed more.

The present invention includes a step of applying a radiation curable composition containing a siloxane resin onto a substrate and drying to obtain a coating film, and irradiating the coating film with a light of 5 to 100 mJ / cm ² through a mask. The pattern formation method which has the process of exposing by this and the process of removing the unexposed part of a coating film by image development is provided. By setting the amount of light within the above range, exposure control is facilitated and production efficiency tends to be improved. In this case, you may provide the process of heating a coating film after the process of exposing.

The present invention includes a step of applying a radiation curable composition containing a siloxane resin onto a substrate and drying to obtain a coating film, and irradiating the coating film with a light of 5 to 100 mJ / cm ² through a mask. A pattern forming method comprising: a step of exposing to a film; a step of heating the coated film to 70 to 110 ° C. after the step of exposing; and a step of removing an unexposed portion of the coated film by development after the step of heating. .

This invention is the said pattern formation method using the radiation curable composition containing a siloxane resin, Comprising: The siloxane resin is 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 pattern formation method containing resin obtained by hydrolytic condensation of the compound represented by these is provided.

The present invention includes a step of applying a radiation curable composition containing a siloxane resin on a substrate and drying to obtain a coating film, and the coating film is formed in a thickness of 5 to 100 mJ / cm through a mask. ² There is provided a pattern forming method which includes a step of exposing by irradiation with light of a certain amount of light and a step of removing an unexposed portion of the coating film by development, and does not heat the coating film after the exposing step.

The present invention provides the following general formula (8):
SiX ₄   ... (8)
(In the formula, X represents a hydrolyzable group.)
A resin obtained by hydrolysis condensation using as an essential component a compound represented by general formula (8), a multimer of the compound represented by general formula (8), and / or a partial condensate of the compound represented by general formula (8). A step of applying a radiation curable composition containing a siloxane resin to a substrate and drying it to obtain a coating film; and 5 to 100 mJ / cm of the coating film through a mask. ² There is provided a pattern forming method comprising a step of exposing by irradiation with light of a certain amount of light and a step of removing an unexposed portion of the coating film by development.

This invention is the said pattern formation method using the radiation curable composition containing a siloxane resin, Comprising: The resin obtained by hydrolytic condensation is a compound represented by the said General formula (8), General formula (8) ) And / or a partial condensate of the compound represented by the general formula (8), and the following general formula (1);
R ¹ _n SiX _4-n   ... (1)
(Wherein 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, and X is hydrolyzable. N represents an integer of 1 to 2, and when n is 2, each R ¹ May be the same or different. When n is 1 to 2, each X may be the same or different. )
A resin obtained by hydrolysis and condensation using, as an essential component, a compound represented by general formula (1), a multimer of the compound represented by general formula (1), and / or a partial condensate of the compound represented by general formula (1) A pattern forming method is provided.

The present invention provides the following general formula (1);
R ¹ _n SiX _4-n   ... (1)
(Wherein 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, and X is hydrolyzable. 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. )
A resin obtained by hydrolysis condensation using as an essential component a compound represented by general formula (1), a multimer of the compound represented by general formula (1), and / or a partial condensate of the compound represented by general formula (1). A radiation curable composition containing a siloxane resin, wherein the H atom, F atom, B atom, and N atom bonded to the Si atom with respect to 1 mol of the Si atom in the resin obtained by hydrolysis and condensation A radiation curable composition in which the total content of at least one atom selected from the group consisting of Al atom, P atom, Si atom, Ge atom, Ti atom and C atom is 0.90 to 0.20, The process of applying on a substrate and drying to obtain a coating film, and the coating film through a mask 5-100 mJ / cm ² There is provided a pattern forming method comprising a step of exposing by irradiation with light of a certain amount of light and a step of removing an unexposed portion of the coating film by development.

This invention is the said pattern formation method using the radiation curable composition containing a siloxane resin, Comprising: R in the said General formula (1) ¹ Provides a pattern formation method comprising at least one atom selected from the group consisting of H atom, F atom, N atom, Si atom, Ti atom and C atom.

This invention is the said pattern formation method using the radiation curable composition containing a siloxane resin, Comprising: R in the said General formula (1) ¹ Provides a pattern forming method comprising at least one atom selected from the group consisting of H atom, F atom, N atom, Si atom and C atom.

The present invention is the above pattern formation method using a radiation curable composition containing a siloxane resin, and in the resin obtained by hydrolysis condensation, H atoms bonded to Si atoms with respect to 1 mol of Si atoms. , F atom, B atom, N atom, Al atom, P atom, Si atom, Ge atom, Ti atom, and a total content ratio of at least one atom selected from the group consisting of C atom is 0.80-0. A pattern forming method is provided.

The present invention comprises a step of applying a radiation curable composition containing a siloxane resin dissolved in an ether acetate solvent or an aprotic solvent containing an ether solvent on a substrate and drying to obtain a coating film, and a mask. 5 to 100 mJ / cm through the coating film ² There is provided a pattern forming method comprising a step of exposing by irradiation with light of a certain amount of light and a step of removing an unexposed portion of the coating film by development.

The present invention includes a step of applying a radiation curable composition containing a siloxane resin and an acid generator on a substrate and drying to obtain a coating film, and the coating film is formed in a thickness of 5 to 100 mJ / cm through a mask. ² There is provided a pattern forming method which includes a step of exposing by irradiation with light of a certain amount of light and a step of removing an unexposed portion of the coating film by development, and does not heat the coating film after the exposing step.

This invention is the said pattern formation method using the radiation curable composition containing a siloxane resin, Comprising: The siloxane resin is the following general formula (1);
R ¹ _n SiX _4-n   ... (1)
(Wherein 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, and X is hydrolyzable. 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. )
Formation of a pattern comprising a resin obtained by hydrolytic condensation of a compound represented by formula (1), a multimer of the compound represented by formula (1), and / or a partial condensate of the compound represented by formula (1) Provide a method.

  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 a cured film formed by the above-described cured film forming method.

The present invention provides a pattern formed by the above pattern forming method.

  This invention provides an electronic component provided with the cured film formed by the said cured film formation method.

  This invention provides an optical waveguide provided with the cured film formed by the said cured film formation method.

  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 cured film forming method and the pattern forming method using the radiation curable composition having such a component structure, a cured product having excellent pattern accuracy can be formed even if the exposure amount is relatively small, and the exposure amount is small. It is possible to solve the conventional problem that it is impossible to achieve both good pattern accuracy and high accuracy.

  In the present invention, the details of the mechanism that provides such an effect that has not been achieved in the past are still unclear. However, the present inventors, for example, do not need to use an acid diffusion control agent that suppresses the diffusion of the generated acid, or when an aprotic solvent is used as a solvent that accelerates curing. Therefore, it is presumed that the exposure amount required for curing can be reduced in the present invention.

  Further, when the curing accelerating catalyst is further contained as an additive, the above-described effects can be more effectively exhibited. This is considered due to the fact that the radiation curable composition is sufficiently cured with a smaller exposure amount.

  The improvement in pattern accuracy is presumed to originate from the fact that when an aprotic solvent is used as a solvent for promoting curing, the curing reaction of the radiation curable composition occurs before the diffusion of the acid. Further, by further containing a curing accelerating catalyst as an additive, the pattern accuracy is further improved. This is presumed to be because the curing reaction occurs at an earlier timing than the acid diffuses. 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.

  By 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 if 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, embodiments of the present invention will be described in detail.

<(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: 10 μL of radiation curable composition
Standard polystyrene: Standard polystyrene manufactured by Tosoh Corporation (molecular weight: 190000, 17900, 9100, 2980, 578, 474, 370, 266)
Detector: RI-monitor manufactured by Hitachi, Ltd., trade name “L-3000”
Integrator: GPC integrator manufactured by Hitachi, Ltd., trade name “D-2200”
Pump: manufactured by Hitachi, Ltd., trade name “L-6000”
Degassing device: Showa Denko Co., Ltd., trade name "Shodex DEGAS"
Column: Hitachi Chemical Co., Ltd., trade names “GL-R440”, “GL-R430”, “GL-R420” connected in this order and used as 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, a halogen atom, an acetoxy group, an isocyanate group, and a hydroxyl group. Among these, an alkoxy group is preferable from the viewpoint of liquid stability of the composition itself, coating characteristics, and the like.

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

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

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

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

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

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

  Examples of the acid catalyst include organic acids and inorganic acids. Examples of organic acids include formic acid, maleic acid, fumaric acid, phthalic acid, malonic acid, succinic acid, tartaric acid, malic acid, lactic acid, citric acid, acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid , Octanoic acid, nonanoic acid, decanoic acid, oxalic acid, adipic acid, sebacic acid, butyric acid, oleic acid, stearic acid, linoleic acid, linolenic acid, salicylic acid, benzenesulfonic acid, benzoic acid, p-aminobenzoic acid, p- Examples thereof include toluenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, trifluoroethanesulfonic acid, and the like. Examples of the inorganic acid include hydrochloric acid, phosphoric acid, nitric acid, boric acid, sulfuric acid, and hydrofluoric acid. These are used singly or in combination of two or more.

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

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

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

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

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

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

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

In addition, the total number (M) of a specific bond atom can be calculated | required from the preparation amount of 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 specific bond atoms, and M2 is bonded to two silicon atoms among the specific bond atoms. M3 represents the total number of atoms bonded to three silicon atoms among the specific bonded atoms, and Msi represents the total number of Si atoms.

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

<(B) component>
The component (b) is 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 formula, R ² represents a monovalent organic group having 1 to 30 carbon atoms, may include an aromatic ring having a methoxy group or a nitro group in the side chain, and R ³ represents 1 to 1 carbon atoms. 20 represents a 1-4 valent organic group, and m is an integer of 1-4.

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

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

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

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

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

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

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

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

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

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

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

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

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

  In 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.

  In addition, when the radiation curable composition is stored as a single liquid, it is preferably stored at a temperature of 0 ° C. or lower, for example. The lower limit of this temperature is preferably equal to or higher than the freezing point of the solvent in the radiation curable composition, and is preferably −50 ° C.

<(C) component>
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, in this invention, it is thought that it becomes possible to make improvement of pattern accuracy and reduction of exposure amount compatible.

  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. From the viewpoints of sensitivity and pattern accuracy during pattern formation, and mechanical strength of the cured product, Tell 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.

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

  Examples of such protic solvents include methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, t-butanol, n-pentanol, i-pentanol, 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, methyl cycl Alcohol solvents such as hexanol, benzyl alcohol, ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol; ethylene glycol methyl ether, ethylene glycol ethyl ether , Ethylene glycol monophenyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol mono-n-hexyl ether, ethoxytriglycol, tetraethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether, di Propylene glycol monomethyl ether Dipropylene glycol monoethyl ether, ether solvents such as tripropylene glycol monomethyl ether; methyl lactate, ethyl lactate, n- butyl, ester solvents such as lactic acid n- amyl and the like. These are used singly or in combination of two or more.

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

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

  Furthermore, although the radiation-curable composition of the present invention may contain water as necessary, it is preferably within a range that does not impair the intended properties. The amount of water used is preferably 10% by weight or less, more preferably 5% by weight or less, and particularly preferably 2% by weight or less based on the total amount of the radiation curable composition. If the amount of water used exceeds 10% by weight, the coating property and the stability of the coating solution tend to deteriorate. Although details are not clear, the amount of exposure may be reduced by adding some water.

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

<(D) component>
The component (d) in the present invention is a curing accelerating catalyst. By adding it to the radiation curable composition, the photoacid generator amount or photobase generator amount can be reduced, the exposure amount can be reduced, or PEB This is preferable because a temperature lowering effect can be expected. This curing accelerating catalyst is different from a normal photoacid generator or photobase generator that generates an active substance by the light of component (b). Therefore, it is usually distinguished from onium salts such as those used as photoacid generators or photobase generators. However, any material that has both photoacid generation ability or photobase generation ability and curing acceleration catalytic ability can be used.

  The catalyst is considered to be a peculiar one that does not show a catalytic action in a solution and shows activity in a coated film. In the exposed area, the curing reaction by the curing accelerating catalyst proceeds with the generation of the acidic active substance or basic active substance, so that it is less likely that the pattern accuracy is further reduced due to acid or base diffusion, that is, the pattern accuracy is further improved. .

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

  1. A composition comprising the component (a) and the component (c) is prepared.

  2. The composition prepared in 1 above is applied to a silicon wafer so that the film thickness after baking is 1.0 ± 0.1 μm, and the film is baked at a predetermined temperature for 30 seconds to measure the film thickness.

  3. The silicon wafer on which the film is formed is immersed in a 2.38 wt% tetramethylammonium hydroxide (TMAH) aqueous solution at 23 ± 2 ° C. for 30 seconds, and the film loss after rinsing and drying is observed. At this time, the minimum temperature at the time of baking at which the change in film thickness before and after immersion in the TMAH aqueous solution is within 20% is defined as the insoluble temperature.

  4). In the composition prepared in 1 above, 0.01% by weight of the compound whose curing acceleration catalytic ability is to be confirmed is added to the total amount of the component (a) to obtain a composition. Determine the insoluble temperature. If the insolubility temperature is lowered by adding a compound for which curing acceleration catalytic ability is desired, the compound has curing acceleration catalytic ability.

  Examples of the curing accelerating catalyst as component (d) include alkali metals 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, an onium salt is preferable and a quaternary ammonium salt is more preferable from the viewpoint that the electric characteristics and mechanical strength of the obtained cured product can be improved and the stability of the composition can be improved.

  One example of the onium salt compound is 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. The atoms bonded to nitrogen of the above (d-1) nitrogen-containing compound are composed 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 selected from the group. 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 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.

  Further, the ammonium moiety of the ammonium salt compound is methylammonium, dimethylammonium, trimethylammonium, tetramethylammonium, ethylammonium, triethylammonium, tetraethylammonium, propylammonium, dipropylammonium, tripropylammonium, tetrapropylammonium, Examples also include ammonium salt compounds substituted with butylammonium, dibutylammonium, tributylammonium, tetrabutylammonium, ethanolammonium, diethanolammonium, triethanolammonium, and the like.

  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 weight% with respect to the total amount of (a) component in a radiation-curable composition, and is 0.0001-1 weight%. Is more preferable. If the amount used is less than 0.0001% by weight, a large amount of exposure tends to be required for curing. When the amount used exceeds 5% by weight, the stability of the composition and the film formability tend to be inferior, and the electrical properties and process suitability of the cured product tend to be lowered.

  Further, from the viewpoint of sensitivity and stability, the amount of the curing accelerating catalyst which is the component (d) is 0.0001 to 0.1% by weight based on the total amount of the component (a) in the radiation curable composition. It is preferable that it is 0.0001-0.05 weight%, and it is especially preferable that it is 0.0005-0.01 weight%.

  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 radiation-curable 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.

  When the radiation curable composition of the present invention is used for an electronic component, it is desirable not to contain an alkali metal or an alkaline earth metal, and even if included, the concentration of those metal ions in the composition is 1000 ppm or less. It is preferable that it is 1 ppm or less. 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 radiation curable composition of the present invention will be described with reference to a spin coating method that is generally excellent in film formability and film uniformity. 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 radiation curable composition is spin-coated on a substrate such as a silicon wafer or a glass substrate, preferably at 500 to 5,000 revolutions / minute, more preferably at 500 to 3,000 revolutions / minute, to form a film. If the rotational speed is less than 500 revolutions / minute, the film uniformity tends to deteriorate, and if it exceeds 5000 revolutions / minute, the film formability may deteriorate.

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

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

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

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

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

  Moreover, you may add a heating (post-exposure bake: PEB) process as needed 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, particularly preferably 70 to 110 ° C, and extremely preferably 70 to 100 ° C. In general, when the temperature is high, the generated acid is likely to diffuse, so this temperature should be low. In addition, the heating temperature of the PEB process of the conventional general siloxane type radiation curable composition is about 115-120 degreeC.

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

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

  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 in the air or under reduced pressure in an inert atmosphere such as N ₂ , Ar, or He, but there is no particular limitation as long as the characteristics required for the intended use are satisfied. If the heating temperature is less than 100 ° C, sufficient curing tends to be not achieved, and electrical insulation tends to be inferior. If the heating temperature exceeds 500 ° C, the material used for the lower layer may be deteriorated.

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

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

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

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

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 can be finally cured by heat treatment, if necessary. Note that the interlayer insulating films 8 and 10 may have the same composition or different compositions.

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

  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. Working in an environment that does not include the sensitizer's photosensitive wavelength.

( Reference Example 1 )
In a solution prepared by dissolving 317.9 g of tetraethoxysilane and 247.9 g of methyltriethoxysilane in 1116.7 g of diethylene glycol dimethyl ether, 167.5 g of nitric acid prepared to 0.644% by weight was added dropwise over 30 minutes with stirring. did. After the completion of the dropwise addition, the reaction was allowed to proceed for 3 hours, and then part of the generated ethanol and diethylene glycol dimethyl ether were distilled off in a warm bath under reduced pressure to obtain 1077.0 g of a polysiloxane solution. To 525.1 g of this polysiloxane solution, 74.9 g of diethylene glycol dimethyl ether was added and dissolved by stirring at room temperature (25 ° C.) for 30 minutes to obtain a polysiloxane solution for a radiation curable composition. It was 870 when the weight average molecular weight of polysiloxane was measured by GPC method. A photoacid generator (PAI-1001, manufactured by Midori Chemical Co., Ltd.) 0.150 g was blended with 10.0 g of this polysiloxane solution for a radiation curable composition to prepare a radiation curable composition. In addition, the usage-amount of (a) component was 15 weight% with respect to the radiation-curable composition total amount, and the usage-amount of (b) component was 1.5 weight% with respect to the radiation-curable composition total amount. .

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

(Example 1 )
In a solution prepared by dissolving 317.9 g of tetraethoxysilane and 247.9 g of methyltriethoxysilane in 1116.7 g of diethylene glycol dimethyl ether, 167.5 g of nitric acid prepared to 0.644% by weight was added dropwise over 30 minutes with stirring. did. After the completion of the dropwise addition, the reaction was allowed to proceed for 3 hours, and then part of the generated ethanol and diethylene glycol dimethyl ether were distilled off in a warm bath under reduced pressure to obtain 1077.0 g of a polysiloxane solution. To 525.1 g of this polysiloxane solution was added 53.0 g of diethylene glycol dimethyl ether and a tetramethylammonium nitrate aqueous solution (pH 3.6) prepared to 2.38 wt% and 3.0 g of water, and the mixture was stirred at room temperature (25 ° C.) for 30 minutes. It melt | dissolved and the polysiloxane solution for radiation-curable compositions was obtained. It was 830 when the weight average molecular weight of polysiloxane was measured by GPC method. A photoacid generator (PAI-1001, manufactured by Midori Chemical Co., Ltd.) 0.193 g was mixed with 10.0 g of this polysiloxane solution for radiation curable composition to prepare a radiation curable composition. In addition, the usage-amount of (a) component is 15 weight% with respect to the radiation-curable composition total amount, The usage-amount of (b) component is 1.9 weight% with respect to a radiation-curable composition total amount, The amount of component (d) used was 0.075% by weight based on the total amount of the radiation curable composition.

2 mL of the radiation curable composition is dropped on the center of a 5-inch silicon wafer, and a coating film is formed on the wafer by spin coating (rotating for 30 seconds at 700 rotations / minute). Dry for 30 seconds above. Thereafter, the dried coating film is irradiated with ultraviolet light of 200 mJ / cm ² with an exposure machine (PLA-600F, manufactured by Canon Inc.) through a negative mask having a line pattern with a minimum line width of 10 μm. did. The wafer provided with the coated film after exposure was immersed in a developer composed of an aqueous 2.38 wt% tetramethylammonium hydroxide (TMAH) solution for 30 seconds to dissolve the unexposed area. Thereafter, the wafer was washed with water and spin-dried. Then, using a furnace body, the spin-dried wafer was heated at 350 ° C. for 30 minutes in a nitrogen atmosphere to obtain a radiation cured product on the wafer. When the pattern shape of the radiation cured product was observed from above with an optical microscope and the cross-sectional shape was observed with SEM, it was found that the line was formed with high accuracy and the pattern accuracy was 10 μm.

(Example 2 )
In a solution obtained by dissolving 74.77 g of tetraethoxysilane and 128.68 g of methyltriethoxysilane in 437.86 g of cyclohexanone, 58.71 g of nitric acid prepared to 0.644% by weight was added dropwise over 10 minutes with stirring. . After the completion of the dropwise addition, the reaction was allowed to proceed for 3 hours, and then part of the generated ethanol and cyclohexanone was distilled off in a warm bath under reduced pressure to obtain 343.62 g of a polysiloxane solution for a radiation curable composition. It was 1020 when the weight average molecular weight of polysiloxane was measured by GPC method. A photo-acid generator (PAI-101, manufactured by Midori Kagaku Co., Ltd.) (0.042 g) was blended with 5.0 g of this radiation-curable composition polysiloxane solution to prepare a radiation-curable composition. In addition, the usage-amount of (a) component was 20 weight% with respect to the radiation-curable composition total amount, and the usage-amount of (b) component was 0.8 weight% with respect to the radiation-curable composition total amount. .

2 mL of the radiation curable composition is dropped onto the center of a 6-inch silicon wafer, and a coating film is formed on the wafer by spin coating (rotating for 30 seconds at 700 rpm). Dry for 30 seconds above. Thereafter, ultraviolet light is applied to the dried coating film with an exposure machine (FPA-3000 iW, manufactured by Canon Inc.) through a negative mask having a line pattern with a minimum line width of 2 μm at 100 mJ / cm ^2. Irradiated. The wafer with the coated film after exposure is heated on a hot plate at 100 ° C. for 30 seconds, allowed to cool naturally until the wafer reaches room temperature, and then developed with an aqueous 2.38 wt% tetramethylammonium hydroxide (TMAH) solution. The wafer was immersed in the solution for 30 seconds to perform paddle development, and the unexposed portion was dissolved. Thereafter, the wafer was washed with water and spin-dried. Then, using a furnace body, the spin-dried wafer was heated at 350 ° C. for 30 minutes in a nitrogen atmosphere to obtain a radiation cured product on the wafer. When the pattern shape of the radiation cured product was observed from above with an optical microscope and the cross-sectional shape was observed with an SEM, it was found that the line was formed with high accuracy and the pattern accuracy was 2 μm.

(Example 3 )
In a solution prepared by dissolving 96.13 g of tetraethoxysilane and 165.44 g of methyltriethoxysilane in 562.99 g of propylene glycol methyl ether acetate, 75.47 g and 2.38% by weight of nitric acid prepared to 0.644% by weight. 18.9 g of a tetramethylammonium nitrate aqueous solution (pH 3.6) prepared in 1 above was added dropwise over 5 minutes with stirring. After the completion of the dropwise addition, the reaction was allowed to proceed for 3 hours, and then part of the produced ethanol and propylene glycol methyl ether acetate was distilled off in a warm bath under reduced pressure to obtain 359.94 g of a polysiloxane solution. Propylene glycol methyl ether acetate was added thereto to obtain 450.02 g of a polysiloxane solution for a radiation curable composition. It was 1110 when the weight average molecular weight of polysiloxane was measured by GPC method. 0.080 g of a photoacid generator (PAI-101, manufactured by Midori Chemical Co., Ltd.) was blended with 20.0 g of this polysiloxane solution for a radiation curable composition to prepare a radiation curable composition. In addition, the usage-amount of (a) component is 20 weight% with respect to a radiation-curable composition total amount, The usage-amount of (b) component is 0.4 weight% with respect to a radiation-curable composition total amount, The amount of component (d) used was 0.1% by weight based on the total amount of the radiation curable composition.

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

(Example 4 )
A 0.040 g photobase generator (NBC-101, manufactured by Midori Chemical Co., Ltd.) was mixed with 10.0 g of the polysiloxane solution for radiation curable composition obtained in Example 3 to prepare a radiation curable composition. In addition, the usage-amount of (a) component is 20 weight% with respect to a radiation-curable composition total amount, The usage-amount of (b) component is 0.4 weight% with respect to a radiation-curable composition total amount, The amount of component (d) used was 0.1% by weight based on the total amount of the radiation curable composition.

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

(Example 5 )
10.0 g of the polysiloxane solution for radiation curable composition obtained in Example 3 is added to 0.040 g of a photoacid generator (PAI-101, manufactured by Midori Chemical Co., Ltd.), and polypropylene glycol (manufactured by Aldrich Co., Ltd.) as a thermally decomposable compound. , PPG725) 0.5 g was blended to prepare a radiation curable composition. In addition, the usage-amount of (a) component is 20 weight% with respect to a radiation-curable composition total amount, The usage-amount of (b) component is 0.4 weight% with respect to a radiation-curable composition total amount, The amount of component (d) used was 0.1% by weight based on the total amount of the radiation curable composition.

2 mL of the radiation curable composition is dropped onto the center of a 6-inch silicon wafer, and a coating film is formed on the wafer by spin coating (rotating for 30 seconds at 700 rpm). Dry for 30 seconds above. Thereafter, ultraviolet light is applied to the dried coating film with an exposure machine (FPA-3000 iW, manufactured by Canon Inc.) through a negative mask having a line pattern with a minimum line width of 2 μm at 100 mJ / cm ^2. Irradiated. The wafer with the exposed coating film was heated on a hot plate at 100 ° C. for 30 seconds, allowed to cool naturally until the wafer reached room temperature, and then 2.38 weight by a coater / developer (Mark 7, Tokyo Electron). The wafer was immersed for 30 seconds in a developer composed of an aqueous solution of% tetramethylammonium hydroxide (TMAH) and subjected to paddle development to dissolve unexposed portions. Thereafter, the wafer was washed with water and spin-dried. Then, using a furnace body, the spin-dried wafer was heated at 350 ° C. for 30 minutes in a nitrogen atmosphere to obtain a radiation cured product on the wafer. The film thickness of the radiation cured product was 3.0 μm, but no defects such as cracks were observed. When the pattern shape of the radiation cured product was observed from above with an optical microscope and the cross-sectional shape was observed with an SEM, it was found that the line was formed with high accuracy and the pattern accuracy was 2 μm.

(Comparative Example 1)
In a solution of 132.31 g of tetraethoxysilane and 103.19 g of methyltriethoxysilane dissolved in 464.79 g of propylene glycol monomethyl ether, 69.73 g of nitric acid prepared to 0.644% by weight was stirred for 10 minutes. And dripped. After the completion of the dropwise addition, the reaction was allowed to proceed for 3 hours, and then part of the produced ethanol and propylene glycol monomethyl ether was distilled off in a warm bath under reduced pressure to obtain 487.79 g of a polysiloxane solution. To this, 16.5 g of an aqueous tetramethylammonium nitrate solution (pH 3.6) prepared to 2.38% by weight was dropped over 5 minutes with stirring to obtain a polysiloxane solution for a radiation curable composition. The weight average molecular weight of the polysiloxane measured by GPC method was 1040. A photoacid generator (PAI-1001, manufactured by Midori Chemical Co., Ltd.) 0.150 g was blended with 10.0 g of this polysiloxane solution for a radiation curable composition to prepare a radiation curable composition. In addition, the usage-amount of (a) component is 15 weight% with respect to the radiation-curable composition total amount, The usage-amount of (b) component is 1.5 weight% with respect to a radiation-curable composition total amount, The amount of component (d) used was 0.08% by weight based on the total amount of the radiation curable composition.

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

(Comparative Example 2)
Development was performed in the same manner as in Comparative Example 1 except that the exposure of ultraviolet light 200 mJ / cm ² was changed to 1000 mJ / cm ² of ultraviolet light. After development, the wafer was washed with water and spin dried. Then, using a furnace body, the spin-dried wafer was heated at 350 ° C. for 30 minutes in a nitrogen atmosphere to obtain a radiation cured product on the wafer. When the pattern shape of the radiation-cured product was observed from above with an optical microscope and the cross-sectional shape was observed with SEM, a line with a width of 10 μm was formed, but the shape was not good. A cross-sectional SEM photograph is shown in FIG.

(Comparative Example 3)
In a solution obtained by dissolving 44.86 g of tetraethoxysilane, 77.22 g of methyltriethoxysilane, and 0.88 g of tetramethylammonium nitrate aqueous solution (pH 3.6) prepared to 2.38% by weight in 122.72 g of ethanol, 35.22 g of nitric acid prepared to 0.644% by weight was added dropwise over 10 minutes with stirring. After the completion of the dropwise addition, the reaction was allowed to proceed for 3 hours, and then a portion of the produced ethanol was distilled off in a warm bath under reduced pressure to obtain 205.74 g of a polysiloxane solution for a radiation curable composition. It was 870 when the weight average molecular weight of polysiloxane was measured by GPC method. Although 0.150 g of a photoacid generator (PAI-1001, manufactured by Midori Chemical Co., Ltd.) was blended with 10.0 g of this polysiloxane solution for radiation curable composition, it did not dissolve. In addition, the usage-amount of (a) component is 20 weight% with respect to a radiation-curable composition total amount, The usage-amount of (b) component is 1.5 weight% with respect to a radiation-curable composition total amount, The amount of component (d) used was 0.01% by weight relative to the total amount of the radiation curable composition.

(Comparative Example 4)
In a solution of 128.87 g of tetraethoxysilane and 100.51 g of methyltriethoxysilane dissolved in 229.97 g of propylene glycol monomethyl ether, 67.91 g of nitric acid prepared to 0.644% by weight was stirred for 10 minutes. And dripped. After completion of the dropwise addition, reaction was performed for 3 hours to obtain 527.26 g of a polysiloxane solution for a radiation curable composition. It was 980 when the weight average molecular weight of polysiloxane was measured by GPC method. A photoacid generator (PAI-1001, manufactured by Midori Chemical Co., Ltd.) 0.150 g was blended with 10.0 g of this polysiloxane solution for a radiation curable composition to prepare a radiation curable composition. In addition, the usage-amount of (a) component was 15 weight% with respect to the radiation-curable composition total amount, and the usage-amount of (b) component was 1.5 weight% with respect to the radiation-curable composition total amount. .

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

(Comparative Example 5)
Development was performed in the same manner as in Comparative Example 4 except that the exposure of ultraviolet light 200 mJ / cm ² was changed to ultraviolet light 1000 mJ / cm ² . After development, the wafer was washed with water and spin dried. Then, using a furnace body, the spin-dried wafer was heated at 350 ° C. for 30 minutes in a nitrogen atmosphere to obtain a radiation cured product on the wafer. When the pattern shape of the radiation-cured product was observed from above with an optical microscope and the cross-sectional shape was observed with SEM, a line with a width of 10 μm was formed, but the shape was not good. A cross-sectional SEM photograph is shown in FIG.

(Comparative Example 6)
To a solution of 44.90 g of tetraethoxysilane and 77.20 g of methyltriethoxysilane dissolved in 122.75 g of ethanol, 35.24 g of nitric acid prepared to 0.644% by weight was added dropwise over 10 minutes with stirring. . After the completion of the dropwise addition, the reaction was allowed to proceed for 3 hours, and then a portion of the generated ethanol was distilled off in a warm bath under reduced pressure to obtain 210.05 g of a polysiloxane solution for a radiation curable composition. The weight average molecular weight of the polysiloxane measured by GPC method was 910. Although 0.150 g of a photoacid generator (PAI-1001, manufactured by Midori Chemical Co., Ltd.) was blended with 10.0 g of this polysiloxane solution for radiation curable composition, it did not dissolve. In addition, the usage-amount of (a) component was 20 weight% with respect to the radiation-curable composition total amount, and the usage-amount of (b) component was 1.5 weight% with respect to the radiation-curable composition total amount. .

The results are shown in Table 1 for Examples 1 to 5, Reference Example 1 and Comparative Examples 1 to 6.

(Example 6 )
When the radiation curable composition obtained in Example 2 was stored in an atmosphere at −20 ° C. for 30 days, the storage stability was superior to that of the same radiation curable composition stored in an ambient temperature atmosphere for 30 days. It was. The radiation curable composition stored in an atmosphere at −20 ° C. could be patterned even after storage for 30 days, but the radiation curable composition stored for 30 days in an atmosphere at room temperature was patterned after storage for 7 days. I can't do it. This is considered to be due to the condensation of the siloxane resin proceeding in the radiation curable composition stored for 7 days in a normal temperature atmosphere, and water accompanying it.

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

1 is a schematic end view showing a preferred embodiment of an electronic component according to the present invention. It is a SEM photograph which shows the pattern shape which concerns on the Example of this invention. It is a SEM photograph which shows the pattern shape which concerns on the Example of this invention. It is a SEM photograph which shows the pattern shape which concerns on the comparative example of this invention. It is a SEM photograph which shows the pattern shape which concerns on the comparative example of this 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 (18)

  A step of applying a radiation curable composition containing a siloxane resin onto a substrate and drying to obtain a coating film; and a step of exposing the coating film; and the coating film is applied after the exposing step. A method for forming a cured film without heating.   A step of applying a radiation curable composition containing a siloxane resin on a substrate and drying to obtain a coating film, a step of exposing the coating film, and a step of exposing the coating film to 70 to 110 ° C. after the exposing step And a heating step. A step of applying a radiation-curable composition containing a siloxane resin on a substrate and drying to obtain a coating film; and a step of exposing the coating film by irradiation with light of a light amount of 5 to 100 mJ / cm ^2. A cured film forming method.   The cured film formation method of Claim 3 which has the process of heating the said coating film after the said process to expose. A step of applying a radiation curable composition containing a siloxane resin on a substrate and drying to obtain a coating; a step of exposing the coating by irradiation with light of 5 to 100 mJ / cm ² ; and the exposure. And a step of heating the coating film to 70 to 110 ° C. after the step of performing a cured film forming method. The siloxane resin has 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 cured film formation method as described in any one of Claims 1-5 containing resin obtained by hydrolytic condensation of the compound represented by these.   Applying a radiation-curable composition containing a siloxane resin on a substrate and drying to obtain a coating film, exposing the coating film through a mask, and removing unexposed portions of the coating film by development And a pattern forming method in which the coating film is not heated after the exposing step.   Applying the radiation curable composition containing a siloxane resin on a substrate and drying to obtain a coating film, exposing the coating film through a mask, and exposing the coating film after the exposing step. A pattern forming method comprising: a step of heating to ˜110 ° C., and a step of removing an unexposed portion of the coating film by development after the heating step. A step of applying a radiation curable composition containing a siloxane resin on a substrate and drying to obtain a coating film; and a step of exposing the coating film by irradiation with light of 5 to 100 mJ / cm ² through a mask. And a step of removing an unexposed portion of the coating film by development.   The pattern formation method of Claim 9 which has the process of heating the said coating film after the said process to expose. A step of applying a radiation curable composition containing a siloxane resin on a substrate and drying to obtain a coating film; and a step of exposing the coating film by irradiation with light of 5 to 100 mJ / cm ² through a mask. And a step of heating the coating film to 70 to 110 ° C. after the exposing step, and a step of removing an unexposed portion of the coating film by development after the heating step. The siloxane resin has 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 pattern formation method as described in any one of Claims 7-11 containing resin obtained by hydrolytic condensation of the compound represented by these.   The pattern forming method according to claim 7, wherein an aqueous tetramethylammonium hydroxide solution is used as a developer in the removing step.   The pattern usage method which uses the pattern formed by the pattern formation method as described in any one of Claims 7-12 as a resist mask.   An electronic component provided with the cured film formed by the cured film formation method as described in any one of Claims 1-6.   An optical waveguide provided with the cured film formed by the cured film formation method as described in any one of Claims 1-6.   An electronic component provided with the pattern formed by the pattern formation method as described in any one of Claims 7-12.   An optical waveguide provided with the pattern formed by the pattern formation method as described in any one of Claims 7-12.

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