JP2011123450A - Positive radiation-sensitive composition, interlayer insulating film, and forming method of the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polysiloxane based positive radiation sensitive composition which can form an interlayer insulation film having superior storage stability, radiation sensitivity, and melt flow-proofness, and high various performance such as surface hardness, refractive index, heat resistance, transparency, or low dielectric property. <P>SOLUTION: The positive radiation sensitive composition includes [A] polysiloxane, [B] photoacid generator or photobase generator, and [C] metal chelate compound. Preferably, [A] polysiloxane is polysiloxane obtained by hydrolysis condensation of hydrolyzable silane compound under presence of [C] metal chelate compound, and [B] photoacid generator contains quinonediazide. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a radiation-sensitive composition suitable as a material for forming an interlayer insulating film such as a liquid crystal display element or an organic EL element, an interlayer insulating film formed from the composition, and a method for forming the interlayer insulating film About.

  A liquid crystal display element, an organic EL element, and the like are generally provided with an interlayer insulating film in order to insulate between wirings arranged in layers. As a material for forming the interlayer insulating film, a radiation-sensitive composition is widely used because a material having a small number of steps for obtaining a required pattern shape and having sufficient flatness is preferable.

  For example, in an interlayer insulating film of a liquid crystal display element, it is necessary to form a contact hole pattern for fine wiring. With negative compositions, it is difficult to form contact holes with hole diameters that can be used practically. Therefore, in order to form an interlayer insulating film of a liquid crystal display element, positive radiation sensitive characteristics are obtained. The radiation-sensitive composition which has is widely used (refer Unexamined-Japanese-Patent No. 2001-354822).

  As a component of the radiation sensitive composition for forming an interlayer insulating film, an acrylic resin is mainly used. On the other hand, an attempt has been made to use a polysiloxane material, which is superior in heat resistance and transparency as compared with an acrylic resin, as a component of the radiation-sensitive composition (JP 2000-1648 A, JP 2006-178436 A). Issue gazette).

  However, the polysiloxane or silane compound of the polysiloxane-based material itself is susceptible to hydrolysis, and thus may cause the same or different condensation reactions. If such a secondary reaction occurs in the prepared radiation-sensitive composition, the storage stability of the radiation-sensitive composition is impaired, and the shelf life as a product is shortened.

  As one of the measures for suppressing the side reaction as described above, it is conceivable to suppress the condensation reaction by controlling the structure such as the molecular weight or the branched structure of polysiloxane. Regarding the structure control of polysiloxane, it has been reported that polysiloxanes having different molecular weights can be obtained depending on the acid catalyst, metal chelate compound, and alkali catalyst (see Japanese Patent Application Laid-Open No. 2003-163209). However, although this publication discloses a film-forming composition using polysiloxanes having various molecular weights, no consideration is given to radiation sensitivity characteristics, and various characteristics necessary as an interlayer insulating film are disclosed. However, no consideration has been given to the above, except for the dielectric constant.

  Under such circumstances, the radiation sensitive composition has excellent radiation sensitivity, storage stability, and melt flow resistance, and when cured, generally requires surface hardness, refractive index, and heat resistance as an interlayer insulating film. Therefore, development of a polysiloxane-based positive radiation sensitive composition having a sufficiently high level of transparency and low dielectric constant is strongly desired.

JP 2001-354822 A JP 2000-1648 A JP 2006-178436 A JP 2003-163209 A

  As a result of intensive studies aimed at a radiation-sensitive composition having the above properties, the present inventors have obtained the following knowledge.

  That is, generally, an acid or an alkali catalyst is used in synthesizing polysiloxane. When polysiloxane is synthesized using an acid or alkali catalyst, it is often difficult to control the molecular weight. In addition, when the molecular weight of the polysiloxane is small, the heat resistance and surface hardness of the cured film obtained using the polysiloxane are insufficient. On the other hand, when the molecular weight of the polysiloxane is large, the developability during patterning is low. May fall. Furthermore, a trace amount of acid or alkali catalyst used as a catalyst for polysiloxane synthesis remains in the radiation-sensitive composition solution containing polysiloxane, thereby promoting a crosslinking reaction between polysiloxanes and causing an increase in molecular weight. As a result, the storage stability of the radiation sensitive composition is lowered.

  From these findings, it is effective to construct a system that can prevent the acid catalyst or the base catalyst from remaining during the synthesis of polysiloxane in the positive radiation sensitive composition and appropriately control the molecular weight of polysiloxane. The conclusion was reached.

  The present invention has been made based on the above circumstances, and its purpose is excellent in radiation sensitivity, storage stability, and melt flow resistance, as well as surface hardness, refractive index, heat resistance, transparency, low dielectric constant. It is to provide an interlayer insulating film polysiloxane-based positive radiation sensitive composition excellent in various properties such as properties, an interlayer insulating film formed from the composition, and a method for forming the same.

The invention made to solve the above problems is
[A] polysiloxane,
[B] A positive radiation sensitive composition containing a photoacid generator or a photobase generator, and [C] a metal chelate compound.

  The metal chelate compound contained in the positive radiation-sensitive composition is inactivated and does not exhibit a catalytic action for the hydrolysis reaction of polysiloxane, so that the storage stability of the radiation-sensitive composition containing polysiloxane is stable. The shelf life of the positive radiation-sensitive composition can be suppressed without affecting the properties. Moreover, when a metal chelate compound is used for the synthesis of polysiloxane, it is possible to synthesize polysiloxane with a molecular weight suitable for the radiation-sensitive composition. Thereby, the positive radiation sensitive composition can form an interlayer insulating film having excellent melt flow resistance and excellent surface hardness, refractive index, heat resistance, transparency, low dielectric constant, and the like. In addition, after synthesizing a polysiloxane using an acid or base, removal of the acid catalyst or base catalyst for the purpose of improving storage stability requires considerable complexity and cost. For activation, it is only necessary to add a quencher, which is advantageous in terms of production efficiency and cost. In addition, since the positive radiation-sensitive composition contains [A] component polysiloxane and [B] component photoacid generator or photobase generator, the polysiloxane and photoacid generator are included. Alternatively, positive radiation sensitive characteristics and excellent radiation sensitivity can be achieved with a photobase generator.

  In the positive radiation sensitive composition, [A] polysiloxane is a polysiloxane obtained by hydrolysis condensation of a hydrolyzable silane compound in the presence of [C] metal chelate compound, and [B] photoacid It is preferable to contain quinonediazide as a generator. In terms of increasing the heat resistance and surface hardness of the resulting cured film by controlling the molecular weight of the polysiloxane to an appropriate value, the positive radiation sensitive composition specifically uses [C] metal chelate compound. [A] Polysiloxane may be synthesized. Moreover, the patternability of the said composition can be improved by using quinonediazide.

（式（１）中、Ｒ^１はキレート剤であり、Ｍは金属原子であり、Ｒ^２は炭素数２〜５のアルキル基又は炭素数６〜２０のアリール基である。ｊは金属Ｍの原子価であり、ｐは１〜ｊの整数である。Ｒ^１及びＲ^２が複数の場合、それぞれ同一でも異なっていてもよい。） In the positive radiation sensitive composition, the metal chelate compound is preferably a compound represented by the following formula (1).

(In the formula (1), R ¹ is a chelating agent, M is a metal atom, R ² is an alkyl group having 2 to 5 carbon atoms or an aryl group having 6 to 20 carbon atoms. And p is an integer of ^{1 to} j. When R ¹ and R ² are plural, they may be the same or different.

  In the positive radiation sensitive composition, a polysiloxane having an appropriately controlled molecular weight can be prepared by using the compound represented by the above (1) as the metal chelate compound. As a result, the storage stability, radiation sensitivity, and melt flow resistance of the composition can be improved, and the mechanical properties, optical properties, and electrical properties of the obtained interlayer insulating film can be enhanced.

  In the positive radiation sensitive composition, the metal M in the above formula (1) is preferably at least one selected from the group consisting of aluminum, titanium and zirconium. By using the above metal as the central metal of the metal chelate compound, the catalytic activity is enhanced, the reaction yield of the condensation reaction of the hydrolyzable silane compound is improved, and the molecular weight control of the polysiloxane is facilitated.

（式（２）中、Ｘ^１は、エポキシ基、ビニル基、アリル基、（メタ）アクリロイルオキシ基、スチリル基、又はビニルベンジロキシ基である。Ｙ^１は単結合、メチレン基又は炭素数２〜６のアルキレン基である。Ｒ^３は、炭素数１〜６のアルコキシ基又は炭素数２〜６のアシルオキシ基である。Ｒ^４は、炭素数１〜６のアルキル基又は炭素数６〜１２の置換若しくは非置換のアリール基である。ａ及びｂは、それぞれ１〜３の整数であり、ｃは０〜２の整数であり、そしてａ＋ｂ＋ｃ＝４の関係を満たす。）

（式（３）中、Ｒ^５は、炭素数１〜６の置換若しくは非置換のアルコキシ基、炭素数６〜１８の置換若しくは非置換のアリールオキシ基、又は炭素数２〜６のアシルオキシ基である。Ｒ^６は、炭素数１〜６の置換若しくは非置換のアルキル基、又は炭素数６〜１８の置換若しくは非置換のアリール基である。ｇは１〜４の整数であり、ｈは０〜３の整数であり、そしてｇ＋ｈ＝４の関係を満たす。） In the positive radiation sensitive composition, the hydrolyzable silane compound comprises (a1) a silane compound represented by the following formula (2) and (a2) a silane compound represented by the following formula (3). It is preferable that it is at least one selected from more.

(In Formula (2), X ¹ is an epoxy group, a vinyl group, an allyl group, a (meth) acryloyloxy group, a styryl group, or a vinylbenzyloxy group. Y ¹ is a single bond, a methylene group, or a carbon number of 2 R ³ is an alkoxy group having 1 to 6 carbon atoms or an acyloxy group having 2 to 6 carbon atoms, and R ⁴ is an alkyl group having 1 to 6 carbon atoms or 6 to 12 carbon atoms. A and b are each an integer of 1 to 3, c is an integer of 0 to 2, and a relationship of a + b + c = 4 is satisfied.)

(In Formula (3), R ⁵ is a substituted or unsubstituted alkoxy group having 1 to 6 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 18 carbon atoms, or an acyloxy group having 2 to 6 carbon atoms. R ⁶ is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms or a substituted or unsubstituted aryl group having 6 to 18 carbon atoms, g is an integer of 1 to 4, and h is 0 An integer of ˜3 and satisfies the relationship g + h = 4.)

  The use of the specific hydrolyzable silane compound as described above in the polysiloxane of the positive radiation sensitive composition enables the molecular weight control to be achieved at a higher level. The storage stability, radiation sensitivity, and melt flow resistance of the radiation composition can be further improved. In addition, an interlayer insulating film formed from the positive radiation-sensitive composition containing such a specific polysiloxane achieves excellent surface hardness, refractive index, heat resistance, transparency, low dielectric constant, etc. Can do.

  The interlayer insulating film of the present invention is formed from the positive radiation sensitive resin composition. As a result, the interlayer insulating film has an advantage of being excellent in various performances such as surface hardness, refractive index, heat resistance, transparency, and low dielectric properties.

The method for forming an interlayer insulating film of the present invention includes:
(1) The process of forming the coating film of the said positive type radiation sensitive composition on a board | substrate,
(2) A step of irradiating at least a part of the coating film formed in step (1),
(3) a step of developing the coating film irradiated with radiation in step (2), and (4) a step of heating the coating film developed in step (3). Since the positive radiation sensitive resin composition is used in the forming method, the interlayer insulating film excellent in various performances can be efficiently formed.

  As described above, since the positive radiation sensitive composition of the present invention contains the above-mentioned components [A] and [B], the surface hardness, refractive index, heat resistance, transparency, and low dielectric properties are common. It is possible to efficiently form an interlayer insulating film that satisfies various required characteristics in a well-balanced manner. The radiation-sensitive composition can exhibit excellent storage stability, radiation sensitivity, and melt flow resistance.

  The positive radiation sensitive composition of the present invention contains [A] polysiloxane, [B] a photoacid generator or photobase generator, and [C] a metal chelate compound, and other optional components ([D ], [E] other silane compounds and [F] dehydrating agents, etc.).

[A] component: polysiloxane The polysiloxane of the [A] component is not particularly limited as long as it is a polymer of a compound having a siloxane bond. Such a polysiloxane is obtained by hydrolytic condensation of a hydrolyzable silane compound. Specifically, the molecular weight is controlled at a high level by synthesizing a polysiloxane by hydrolytic condensation of a hydrolyzable silane compound in the presence of a [C] metal chelate compound, which will be described later. The storage stability, radiation sensitivity, and melt flow resistance of the radiation sensitive composition can be improved. Further, when the positive radiation sensitive resin composition contains a silane compound of the [E] component described later, the [A] component is condensed together with the silane compound of the [E] component to form a cured product. At this time, the condensation of some [A] components may occur.

Hydrolyzable silane compound The hydrolyzable silane compound is not particularly limited as long as it is a silane compound having a hydrolyzable group. The “hydrolyzable group” of the hydrolyzable silane compound in the present application is usually heated in the temperature range of room temperature (about 25 ° C.) to about 100 ° C. in the presence of a catalyst and excess water, It refers to a group capable of forming a silanol group upon hydrolysis or a group capable of forming a siloxane condensate. On the other hand, the “non-hydrolyzable group” refers to a group that does not undergo hydrolysis or condensation and exists stably under such hydrolysis conditions.

  In the hydrolysis reaction of the hydrolyzable silane compound, some hydrolyzable groups may remain in an unhydrolyzed state. Further, the “hydrolyzable condensate of hydrolyzable silane compound” referred to herein means a hydrolyzed condensate obtained by reacting and condensing some silanol groups of the hydrolyzed silane compound.

  As said hydrolysable silane compound, 1 type (s) or 2 or more types can be used in combination. Considering the surface hardness, refractive index, heat resistance, etc. of the resulting cured film, the polysiloxane of [A] component is preferably a cocondensate of two or more hydrolyzable silane compounds.

  The [A] polysiloxane of the positive radiation sensitive composition includes (a1) a silane compound represented by the above formula (2) (hereinafter simply referred to as “(a1) hydrolyzable silane” as the hydrolyzable silane compound. And (a2) at least one selected from the group consisting of silane compounds represented by the above formula (3) (hereinafter also simply referred to as “(a2) hydrolyzable silane compound”). A co-condensate obtained is preferred.

(A1) Hydrolyzable silane compound (a1) The hydrolyzable silane compound has a reactive group other than the hydrolyzable group. This reactive group can impart an appropriate degree of branching to the resulting polysiloxane. As a result, the melt flow resistance of the positive radiation-sensitive composition, the surface hardness of the resulting interlayer insulating film, the heat resistance Etc. can be improved.

Y ¹ in the above formula (2) is preferably a methylene group or an alkylene group having 2 to 3 carbon atoms. Among these, examples of the alkylene group having 2 to 3 carbon atoms include an ethylene group and a trimethylene group. . In addition, R ³ in the above formula (2) is preferably an alkoxy group having 1 to 3 carbon atoms or an acyloxy group having 2 to 4 carbon atoms. Examples of such groups include a methoxy group, an ethoxy group, and an n-propoxy group. , I-propoxy group, acetoxy, propanoyloxy group and the like. In addition, R ⁴ in the above formula (2) is preferably an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 8 carbon atoms. Examples of such groups include a methyl group, an ethyl group, and a phenyl group. Can be mentioned. Examples of the substituent for the substituted aryl group represented by R ⁴ include a halogen atom, a cyano group, a nitro group, or an alkyl group having 1 to 6 carbon atoms.

As a specific example of the hydrolyzable silane compound represented by the above formula (2),
(Oxetane-3-yl) methyltrimethoxysilane, (oxetane-3-yl) methyltriethoxysilane, (oxetane-3-yl) methyltri-n-propoxysilane, (oxetane-3-yl) methyltri-i-propoxy Silane, (oxetane-3-yl) methyltriacetoxysilane, (oxetane-3-yl) methylmethyldimethoxysilane, (oxetane-3-yl) methylmethyldiethoxysilane, (oxetane-3-yl) methylmethyldi-n- Propoxysilane, (oxetane-3-yl) methylmethyldi-i-propoxysilane, (oxetane-3-yl) methylmethyldiacetoxysilane, (oxetane-3-yl) methylethyldimethoxysilane, (oxetane-3-yl) methyl Ethyldiethoxysilane, ( Xetane-3-yl) methylethyldi-n-propoxysilane, (oxetane-3-yl) methylethyldi-i-propoxysilane, (oxetane-3-yl) methylethyldiacetoxysilane, (oxetane-3-yl) methylphenyldimethoxy Silane, (oxetane-3-yl) methylphenyldiethoxysilane, (oxetane-3-yl) methylphenyldi-n-propoxysilane, (oxetane-3-yl) methylphenyldi-i-propoxysilane, (oxetane- 3-yl) methylphenyldiacetoxysilane, 2- (oxetane-3′-yl) ethyltrimethoxysilane, 2- (oxetane-3′-yl) ethyltriethoxysilane, (oxetane-3-yl) ethyltri-n -Propoxysilane, 2- (oxetane-3'- L) Ethyltri-i-propoxysilane, 2- (oxetane-3'-yl) ethyltriacetoxysilane, 2- (oxetane-3'-yl) ethylmethyldimethoxysilane, 2- (oxetane-3'-yl) ethyl Methyldiethoxysilane, 2- (oxetane-3′-yl) ethylmethyldi-n-propoxysilane, 2- (oxetane-3′-yl) ethylmethyldi-i-propoxysilane, 2- (oxetane-3′-yl) ethyl Methyldiacetoxysilane, 2- (oxetane-3′-yl) ethylethyldimethoxysilane, 2- (oxetane-3′-yl) ethylethyldiethoxysilane, 2- (oxetane-3′-yl) ethylethyldi-n- Propoxysilane, 2- (oxetane-3′-yl) ethylethyldi-i-propoxysilane, 2- (o Cetane 3'-yl) ethyl ethyl diacetoxy silane,

  2- (oxetane-3′-yl) ethylphenyldimethoxysilane, 2- (oxetane-3′-yl) ethylphenyldiethoxysilane, 2- (oxetane-3′-yl) ethylphenyldi-n-propoxysilane, 2- (oxetane-3′-yl) ethylphenyldi-i-propoxysilane, 2- (oxetane-3′-yl) ethylphenyldiacetoxysilane, 3- (oxetane-3′-yl) propyltrimethoxysilane, 3- (Oxetane-3′-yl) propyltriethoxysilane, 3- (oxetane-3′-yl) propyltri-n-propoxysilane, 3- (oxetane-3′-yl) propyltri-i-propoxysilane , 3- (Oxetane-3′-yl) propyltriacetoxysilane, 3- (oxetane-3′-yl) Propylmethyldimethoxysilane, 3- (oxetane-3′-yl) propylmethyldiethoxysilane, 3- (oxetane-3′-yl) propylmethyldi-n-propoxysilane, 3- (oxetane-3′-yl) ) Propylmethyldi-i-propoxysilane, 3- (oxetane-3′-yl) propylmethyldiacetoxysilane, 3- (oxetane-3′-yl) propylethyldimethoxysilane, 3- (oxetane-3′-yl) ) Propylethyldiethoxysilane, 3- (oxetane-3′-yl) propylethyldi-n-propoxysilane, 3- (oxetane-3′-yl) propylethyldi-i-propoxysilane, 3- (oxetane- 3'-yl) propylethyldiacetoxysilane, 3- (oxetane-3'-yl) propyl Nyldimethoxysilane, 3- (oxetane-3′-yl) propylphenyldiethoxysilane, 3- (oxetane-3′-yl) propylphenyldi-n-propoxysilane, 3- (oxetane-3′-yl) propyl Phenyldi-i-propoxysilane, 3- (oxetane-3′-yl) propylphenyldiacetoxysilane, (3-methyloxetan-3-yl) methyltrimethoxysilane, (3-methyloxetan-3-yl) methyl Triethoxysilane, (3-methyloxetane-3-yl) methyltri-n-propoxysilane, (3-methyloxetane-3-yl) methyltri-i-propoxysilane, (3-methyloxetane-3-yl) methyltri Acetoxysilane,

  (3-methyloxetane-3-yl) methylmethyldimethoxysilane, (3-methyloxetane-3-yl) methylmethyldiethoxysilane, (3-methyloxetane-3-yl) methylmethyldi-n-propoxysilane, (3 -Methyloxetane-3-yl) methylmethyldi-i-propoxysilane, (3-methyloxetane-3-yl) methylmethyldiacetoxysilane, (3-methyloxetane-3-yl) methylethyldimethoxysilane, (3-methyl Oxetane-3-yl) methylethyldiethoxysilane, (3-methyloxetane-3-yl) methylethyldi-n-propoxysilane, (3-methyloxetane-3-yl) methylethyldi-i-propoxysilane, (3-methyl Oxetane-3-yl) methylethyldiacetoxy Silane, (3-methyloxetane-3-yl) methylphenyldimethoxysilane, (3-methyloxetane-3-yl) methylphenyldiethoxysilane, (3-methyloxetane-3-yl) methylphenyldi-n-propoxy Silane, (3-methyloxetane-3-yl) methylphenyldi-i-propoxysilane, (3-methyloxetane-3-yl) methylphenyldiacetoxysilane, 2- (3′-methyloxetane-3′-yl) ) Ethyltrimethoxysilane, 2- (3′-methyloxetane-3′-yl) ethyltriethoxysilane, 2- (3′-methyloxetane-3′-yl) ethyltri-n-propoxysilane, 2- (3 '-Methyloxetane-3'-yl) ethyltri-i-propoxysilane, 2- (3'-methylo Cetane-3′-yl) ethyltriacetoxysilane, 2- (3′-methyloxetane-3′-yl) ethylmethyldimethoxysilane, 2- (3′-methyloxetane-3′-yl) ethylmethyldiethoxysilane 2- (3′-methyloxetane-3′-yl) ethylmethyldi-n-propoxysilane, 2- (3′-methyloxetane-3′-yl) ethylmethyldi-i-propoxysilane, 2- (3′-methyl) Oxetane-3′-yl) ethylmethyldiacetoxysilane, 2- (3′-methyloxetane-3′-yl) ethylethyldimethoxysilane, 2- (3′-methyloxetane-3′-yl) ethylethyldiethoxy Silane, 2- (3′-methyloxetane-3′-yl) ethylethyldi-n-propoxysilane, 2- (3′-methyl) Luoxetane-3′-yl) ethylethyldi-i-propoxysilane, 2- (3′-methyloxetane-3′-yl) ethylethyldiacetoxysilane, 2- (3′-methyloxetane-3′-yl) ethylphenyl Dimethoxysilane, 2- (3′-methyloxetane-3′-yl) ethylphenyldiethoxysilane, 2- (3′-methyloxetane-3′-yl) ethylphenyldi-n-propoxysilane, 2- (3 '-Methyloxetane-3'-yl) ethylphenyldi-i-propoxysilane, 2- (3'-methyloxetane-3'-yl) ethylphenyldiacetoxysilane,

  3- (3′-methyloxetane-3′-yl) propyltrimethoxysilane, 3- (3′-methyloxetane-3′-yl) propyltriethoxysilane, 3- (3′-methyloxetane-3′- Yl) propyltri-n-propoxysilane, 3- (3′-methyloxetane-3′-yl) propyltri-i-propoxysilane, 3- (3′-methyloxetane-3′-yl) propyltriacetoxysilane 3- (3′-methyloxetane-3′-yl) propylmethyldimethoxysilane, 3- (3′-methyloxetane-3′-yl) propylmethyldiethoxysilane, 3- (3′-methyloxetane-3) '-Yl) propylmethyldi-n-propoxysilane, 3- (3'-methyloxetane-3'-yl) propylmethyldi-i-pro Xysilane, 3- (3'-methyloxetane-3'-yl) propylmethyldiacetoxysilane, 3- (3'-methyloxetane-3'-yl) propylethyldimethoxysilane, 3- (3'-methyloxetane- 3′-yl) propylethyldiethoxysilane, 3- (3′-methyloxetane-3′-yl) propylethyldi-n-propoxysilane, 3- (3′-methyloxetane-3′-yl) propylethyl Di-i-propoxysilane, 3- (3′-methyloxetane-3′-yl) propylethyldiacetoxysilane, 3- (3′-methyloxetane-3′-yl) propylphenyldimethoxysilane, 3- (3 '-Methyloxetane-3'-yl) propylphenyldiethoxysilane, 3- (3'-methyloxetane-3'- L) Propylphenyldi-n-propoxysilane, 3- (3'-methyloxetane-3'-yl) propylphenyldi-i-propoxysilane, 3- (3'-methyloxetane-3'-yl) propylphenyl Diacetoxysilane, (3′-ethyloxetane-3′-yl) methyltrimethoxysilane, (3-ethyloxetane-3-yl) methyltriethoxysilane, (3-ethyloxetane-3-yl) methyltri-n- Propoxysilane, (3-ethyloxetane-3-yl) methyltri-i-propoxysilane, (3-ethyloxetane-3-yl) methyltriacetoxysilane,

  (3-ethyloxetane-3-yl) methylmethyldimethoxysilane, (3-ethyloxetane-3-yl) methylmethyldiethoxysilane, (3-ethyloxetane-3-yl) methylmethyldi-n-propoxysilane, (3 -Ethyloxetane-3-yl) methylmethyldi-i-propoxysilane, (3-ethyloxetane-3-yl) methylmethyldiacetoxysilane, (3-ethyloxetane-3-yl) methylethyldimethoxysilane, (3-ethyl Oxetane-3-yl) methylethyldiethoxysilane, (3-ethyloxetane-3-yl) methylethyldi-n-propoxysilane, (3-ethyloxetane-3-yl) methylethyldi-i-propoxysilane, (3-ethyl Oxetane-3-yl) methylethyldiacetoxy Silane, (3-ethyloxetane-3-yl) methylphenyldimethoxysilane, (3-ethyloxetane-3-yl) methylphenyldiethoxysilane, (3-ethyloxetane-3-yl) methylphenyldi-n-propoxy Silane, (3-ethyloxetane-3-yl) methylphenyldi-i-propoxysilane, (3-ethyloxetane-3-yl) methylphenyldiacetoxysilane, 2- (3′-ethyloxetane-3′-yl) ) Ethyltrimethoxysilane, 2- (3′-ethyloxetane-3′-yl) ethyltriethoxysilane, 2- (3′-ethyloxetane-3′-yl) ethyltri-n-propoxysilane, 2- (3 '-Ethyloxetane-3'-yl) ethyltri-i-propoxysilane, 2- (3'-ethyloxy) Cetane-3′-yl) ethyltriacetoxysilane, 2- (3′-ethyloxetane-3′-yl) ethylmethyldimethoxysilane, 2- (3′-ethyloxetane-3′-yl) ethylmethyldiethoxysilane 2- (3′-ethyloxetane-3′-yl) ethylmethyldi-n-propoxysilane, 2- (3′-ethyloxetane-3′-yl) ethylmethyldi-i-propoxysilane,

  2- (3′-ethyloxetane-3′-yl) ethylmethyldiacetoxysilane, 2- (3′-ethyloxetane-3′-yl) ethylethyldimethoxysilane, 2- (3′-ethyloxetane-3 ′) -Yl) ethylethyldiethoxysilane, 2- (3'-ethyloxetane-3'-yl) ethylethyldi-n-propoxysilane, 2- (3'-ethyloxetane-3'-yl) ethylethyldi-i-propoxysilane 2- (3′-ethyloxetane-3′-yl) ethylethyldiacetoxysilane, 2- (3′-ethyloxetane-3′-yl) ethylphenyldimethoxysilane, 2- (3′-ethyloxetane-3) '-Yl) ethylphenyldiethoxysilane, 2- (3'-ethyloxetane-3'-yl) ethylphenyldi-n-propyl Poxysilane, 2- (3′-ethyloxetane-3′-yl) ethylphenyldi-i-propoxysilane, 2- (3′-ethyloxetane-3′-yl) ethylphenyldiacetoxysilane, 3- (3 ′ -Ethyloxetane-3'-yl) propyltrimethoxysilane, 3- (3'-ethyloxetane-3'-yl) propyltriethoxysilane, 3- (3'-ethyloxetane-3'-yl) propyltri- n-propoxysilane, 3- (3′-ethyloxetane-3′-yl) propyltri-i-propoxysilane, 3- (3′-ethyloxetane-3′-yl) propyltriacetoxysilane, 3- (3 '-Ethyloxetane-3'-yl) propylmethyldimethoxysilane, 3- (3'-ethyloxetane-3'-yl) propyl Tildiethoxysilane, 3- (3′-ethyloxetane-3′-yl) propylmethyldi-n-propoxysilane, 3- (3′-ethyloxetane-3′-yl) propylmethyldi-i-propoxysilane 3- (3′-ethyloxetane-3′-yl) propylmethyldiacetoxysilane, 3- (3′-ethyloxetane-3′-yl) propylethyldimethoxysilane, 3- (3′-ethyloxetane-3) '-Yl) propylethyldiethoxysilane, 3- (3'-ethyloxetane-3'-yl) propylethyldi-n-propoxysilane, 3- (3'-ethyloxetane-3'-yl) propylethyldi -I-propoxysilane, 3- (3'-ethyloxetane-3'-yl) propylethyldiacetoxysilane, 3- (3'-ethyl) Luoxetane-3′-yl) propylphenyldimethoxysilane, 3- (3′-ethyloxetane-3′-yl) propylphenyldiethoxysilane, 3- (3′-ethyloxetane-3′-yl) propylphenyldi- n-propoxysilane, 3- (3′-ethyloxetane-3′-yl) propylphenyldi-i-propoxysilane, 3- (3′-ethyloxetane-3′-yl) propylphenyldiacetoxysilane and the like;

  Glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, glycidoxymethyltri-n-propoxysilane, glycidoxymethyltri-i-propoxysilane, glycidoxymethyltriacetoxysilane, glycidoxymethyl Methyldimethoxysilane, glycidoxymethylmethyldiethoxysilane, glycidoxymethylmethyldi-n-propoxysilane, glycidoxymethylmethyldi-i-propoxysilane, glycidoxymethylmethyldiacetoxysilane, glycidoxymethyl Ethyldimethoxysilane, glycidoxymethylethyldiethoxysilane, glycidoxymethylethyldi-n-propoxysilane, glycidoxymethylethyldi-i-propoxysilane, glycidoxymethylethyldiacetoxysilane, group Sidoxymethylphenyldimethoxysilane, glycidoxymethylphenyldiethoxysilane, glycidoxymethylphenyldi-n-propoxysilane, glycidoxymethylphenyldi-i-propoxysilane, glycidoxymethylphenyldiacetoxysilane, 2 -Glycidoxyethyltrimethoxysilane, 2-glycidoxyethyltriethoxysilane, 2-glycidoxyethyltri-n-propoxysilane, 2-glycidoxyethyltri-i-propoxysilane, 2-glycidoxy Ethyltriacetoxysilane, 2-glycidoxyethylmethyldimethoxysilane, 2-glycidoxyethylmethyldiethoxysilane, 2-glycidoxyethylmethyldi-n-propoxysilane, 2-glycidoxyethylmethyldi-i -Propoxysilane, 2 Glycidoxyethylmethyldiacetoxysilane, 2-glycidoxyethylethyldimethoxysilane, 2-glycidoxyethylethyldiethoxysilane, 2-glycidoxyethylethyldi-n-propoxysilane, 2-glycidoxyethyl Ethyldi-i-propoxysilane, 2-glycidoxyethylethylacetoxysilane, 2-glycidoxyethylphenyldimethoxysilane, 2-glycidoxyethylphenyldiethoxysilane, 2-glycidoxyethylphenyldi-n -Propoxysilane, 2-glycidoxyethylphenyldi-i-propoxysilane, 2-glycidoxyethylphenyldiacetoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3 -Glycidoxypropyltri -N-propoxysilane, 3-glycidoxypropyltri-i-propoxysilane, 3-glycidoxypropyltriacetoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropylmethyldi-n-propoxysilane, 3-glycidoxypropylmethyldi-i-propoxysilane, 3-glycidoxypropylmethyldiacetoxysilane, 3-glycidoxypropylethyldimethoxysilane, 3 -Glycidoxypropylethyldiethoxysilane, 3-glycidoxypropylethyldi-n-propoxysilane, 3-glycidoxypropylethyldi-i-propoxysilane, 3-glycidoxypropylethyldiacetoxysilane, 3 -Glycidoxypropyl fe Rudimethoxysilane, 3-glycidoxypropylphenyldiethoxysilane, 3-glycidoxypropylphenyldi-n-propoxysilane, 3-glycidoxypropylphenyldi-i-propoxysilane, 3-glycidoxypropylphenyl Diacetoxysilane,

  (3,4-epoxycyclohexyl) methyltrimethoxysilane, (3,4-epoxycyclohexyl) methyltriethoxysilane, (3,4-epoxycyclohexyl) methyltri-n-propoxysilane, (3,4-epoxycyclohexyl) methyl Triacetoxysilane, (3,4-epoxycyclohexyl) methylmethyldimethoxysilane, (3,4-epoxycyclohexyl) methylmethyldiethoxysilane, (3,4-epoxycyclohexyl) methylmethyldi-n-propoxysilane, (3,4 -Epoxycyclohexyl) methylmethyldiacetoxysilane, (3,4-epoxycyclohexyl) methylethyldimethoxysilane, (3,4-epoxycyclohexyl) methylethyldiethoxysilane, (3,4-epoxysilane) (Hexyl) methylethyldi-n-propoxysilane, (3,4-epoxycyclohexyl) methylethyldiacetoxysilane, (3,4-epoxycyclohexyl) methylphenyldimethoxysilane, (3,4-epoxycyclohexyl) methylphenyldiethoxysilane, (3,4-epoxycyclohexyl) methylphenyldi-n-propoxysilane, (3,4-epoxycyclohexyl) methylphenyldiacetoxysilane, 2- (3 ′, 4′-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3 ′, 4′-epoxycyclohexyl) ethyltriethoxysilane, 2- (3 ′, 4′-epoxycyclohexyl) ethyltri-n-propoxysilane, 2- (3 ′, 4′-epoxycyclohexyl) ethyltriacetoxy 2- (3 ′, 4′-epoxycyclohexyl) ethylmethyldimethoxysilane, 2- (3 ′, 4′-epoxycyclohexyl) ethylmethyldiethoxysilane, 2- (3 ′, 4′-epoxycyclohexyl) ethylmethyldi -N-propoxysilane, 2- (3 ', 4'-epoxycyclohexyl) ethylmethyldiacetoxysilane, 2- (3', 4'-epoxycyclohexyl) ethylethyldimethoxysilane, 2- (3 ', 4'- Epoxycyclohexyl) ethylethyldiethoxysilane, 2- (3 ′, 4′-epoxycyclohexyl) ethylethyldi-n-propoxysilane, 2- (3 ′, 4′-epoxycyclohexyl) ethylethyldiacetoxysilane, 2- (3 ', 4'-epoxycyclohexyl) ethylphenyldimethoxy Silane, 2- (3 ′, 4′-epoxycyclohexyl) ethylphenyldiethoxysilane, 2- (3 ′, 4′-epoxycyclohexyl) ethylphenyldi-n-propoxysilane, 2- (3 ′, 4′- Epoxycyclohexyl) ethylphenyldiacetoxysilane, 3- (3 ′, 4′-epoxycyclohexyl) propyltrimethoxysilane, 3- (3 ′, 4′-epoxycyclohexyl) propyltriethoxysilane, 3- (3 ′, 4 '-Epoxycyclohexyl) propyltri-n-propoxysilane, 3- (3', 4'-epoxycyclohexyl) propyltriacetoxysilane, 3- (3,4-epoxycyclohexyl) propylmethyldimethoxysilane, 3- (3 ' , 4'-epoxycyclohexyl) propylmethyldiethoxy Lan, 3- (3 ′, 4′-epoxycyclohexyl) propylmethyldi-n-propoxysilane, 3- (3 ′, 4′-epoxycyclohexyl) propylmethyldiacetoxysilane, 3- (3 ′, 4′- Epoxycyclohexyl) propylethyldimethoxysilane, 3- (3 ′, 4′-epoxycyclohexyl) propylethyldiethoxysilane, 3- (3 ′, 4′-epoxycyclohexyl) propylethyldi-n-propoxysilane, 3- ( 3 ′, 4′-epoxycyclohexyl) propylethyldiacetoxysilane, 3- (3 ′, 4′-epoxycyclohexyl) propylphenyldimethoxysilane, 3- (3 ′, 4′-epoxycyclohexyl) propylphenyldiethoxysilane, 3- (3 ′, 4′-epoxycyclohexyl) Ropirufeniruji -n- propoxysilane, 3- (3 ', 4'-epoxycyclohexyl) propyl phenyl diacetoxy silane;

  Vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri-n-propoxysilane, vinyltri-i-propoxysilane, vinyltriacetoxysilane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, vinylmethyldi-n-propoxysilane, vinylmethyldi-i -Propoxysilane, vinylmethyldiacetoxysilane, vinylethyldimethoxysilane, vinylethyldiethoxysilane, vinylethyldi-n-propoxysilane, vinylethyldi-i-propoxysilane, vinylethyldiacetoxysilane, vinylphenyldimethoxysilane, vinylphenyldiethoxy Silane, vinylphenyldi-n-propoxysilane, vinylphenyldi-i-propoxysilane, vinylphenyldiacetoxysilane and the like;

  Allyltrimethoxysilane, allyltriethoxysilane, allyltri-n-propoxysilane, allyltri-i-propoxysilane, allyltriacetoxysilane, allylmethyldimethoxysilane, allylmethyldiethoxysilane, allylmethyldi-n-propoxysilane, allylmethyldi-i -Propoxysilane, allylmethyldiacetoxysilane, allylethyldimethoxysilane, allylethyldiethoxysilane, allylethyldi-n-propoxysilane, allylethyldi-i-propoxysilane, allylethyldiacetoxysilane, allylphenyldimethoxysilane, allylphenyldiethoxy Silane, allylphenyldi-n-propoxysilane, allylphenyldi-i-propoxysilane, allylphenyldiacetoxysilane, etc .;

  (Meth) acryloxymethyltrimethoxysilane, (meth) acryloxymethyltriethoxysilane, (meth) acryloxymethyltri-n-propoxysilane, (meth) acryloxymethyltriacetoxysilane, (meth) acryloxymethylmethyl Dimethoxysilane, (meth) acryloxymethylmethyldiethoxysilane, (meth) acryloxymethylmethyldi-n-propoxysilane, (meth) acryloxymethylmethyldiacetoxysilane, (meth) acryloxymethylethyldimethoxysilane, ( (Meth) acryloxymethylethyldiethoxysilane, (meth) acryloxymethylethyldiacetoxysilane, (meth) acryloxymethylethyldi-n-propoxysilane, (meth) acryloxymethylphenyldimethoxysilane, (Meth) acryloxymethylphenyldiethoxysilane, (meth) acryloxymethylphenyldi-n-propoxysilane, (meth) acryloxymethylphenyldiacetoxysilane, 2- (meth) acryloxyethyltri-n-propoxysilane, 2- (meth) acryloxyethyltrimethoxysilane, 2- (meth) acryloxyethyltriethoxysilane, 2- (meth) acryloxyethylmethyldimethoxysilane, 2- (meth) acryloxyethyltriacetoxysilane, 2- (Meth) acryloxyethylmethyldiethoxysilane, 2- (meth) acryloxyethylmethyldi-n-propoxysilane, 2- (meth) acryloxyethylmethyldiacetoxysilane, 2- (meth) acryloxyethylethyldimethoxy Silane, 2- (meta Acryloxyethylethyldiethoxysilane, 2- (meth) acryloxyethylethyldi-n-propoxysilane, 2- (meth) acryloxyethylethyldiacetoxysilane, 2- (meth) acryloxyethylphenyldimethoxysilane, 2 -(Meth) acryloxyethylphenyldiethoxysilane, 2- (meth) acryloxyethylphenyldi-n-propoxysilane, 2- (meth) acryloxyethylphenyldiacetoxysilane, 3- (meth) acryloxypropyltri Methoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 3- (meth) acryloxypropyltri-n-propoxysilane, 3- (meth) acryloxypropyltriacetoxysilane, 3- (meth) acryloxypropyl Methyldimethoxysilane 3- (meth) acryloxypropylmethyldiethoxysilane, 3- (meth) acryloxypropylmethyldi-n-propoxysilane, 3- (meth) acryloxypropylmethyldiacetoxysilane, 3- (meth) acryloxy Propylethyldimethoxysilane, 3- (meth) acryloxypropylethyldiethoxysilane, 3- (meth) acryloxypropylethyldi-n-propoxysilane, 3- (meth) acryloxypropylethyldiacetoxysilane, 3- ( (Meth) acryloxypropylphenyldimethoxysilane, 3- (meth) acryloxypropylphenyldiethoxysilane, 3- (meth) acryloxypropylphenyldi-n-propoxysilane, 3- (meth) acryloxypropylphenyldiacetoxysilane etc;

  p-styryltrimethoxysilane, p-styryltriethoxysilane, p-styryltri-n-propoxysilane, p-styryltriacetoxysilane, p-styrylmethyldimethoxysilane, p-styrylmethyldiethoxysilane, p-styrylmethyldi N-propoxysilane, p-styrylmethyldiacetoxysilane, p-styrylethyldimethoxysilane, p-styrylethyldiethoxysilane, p-styrylethyldi-n-propoxysilane, p-styrylethyldiacetoxysilane, p- Styrylphenyldimethoxysilane, p-styrylphenyldiethoxysilane, p-styrylphenyldi-n-propoxysilane, p-styrylphenyldiacetoxysilane, m-styryltrimethoxysilane, m-styryltriethoxysilane M-styryltri-n-propoxysilane, m-styryltriacetoxysilane, m-styrylmethyldimethoxysilane, m-styrylmethyldiethoxysilane, m-styrylmethyldi-n-propoxysilane, m-styrylmethyldiacetoxy Silane, m-styrylethyldimethoxysilane, m-styrylethyldiethoxysilane, m-styrylethyldi-n-propoxysilane, m-styrylethyldiacetoxysilane, m-styrylphenyldimethoxysilane, m-styrylphenyldiethoxysilane M-styrylphenyl di-n-propoxysilane, m-styrylphenyldiacetoxysilane, etc .;

p-vinylbenzyloxytrimethoxysilane, p-vinylbenzyloxytriethoxysilane, p-vinylbenzyloxytri-n-propoxysilane, p-vinylbenzyloxytriacetoxysilane, p-vinylbenzyloxymethyldimethoxysilane, p- Vinyl benzyloxymethyldiethoxysilane, p-vinylbenzyloxymethyldi-n-propoxysilane, p-vinylbenzyloxymethyldiacetoxysilane, p-vinylbenzyloxyethyldimethoxysilane, p-vinylbenzyloxyethyldiethoxysilane, p-vinylbenzyloxyethyldi-n-propoxysilane, p-vinylbenzyloxyethyldiacetoxysilane, p-vinylbenzyloxyphenyldimethoxysilane, p-vinylbenzyloxyphenyldiethoxysilane, p- Nylbenzyloxyphenyldi-n-propoxysilane, p-vinylbenzyloxyphenyldiacetoxysilane, m-vinylbenzyloxytrimethoxysilane, m-vinylbenzyloxytriethoxysilane, m-vinylbenzyloxytri-n-propoxysilane , M-vinylbenzyloxytriacetoxysilane, m-vinylbenzyloxymethyldimethoxysilane, m-vinylbenzyloxymethyldiethoxysilane, m-vinylbenzyloxymethyldi-n-propoxysilane, m-vinylbenzyloxymethyldiacetoxy Silane, m-vinylbenzyloxyethyldimethoxysilane, m-vinylbenzyloxyethyldiethoxysilane, m-vinylbenzyloxyethyldi-n-propoxysilane, m-vinylbenzyloxyethyldiacetoxysilane m- vinyl benzyloxycarbonyl phenyl dimethoxysilane, m- vinyl benzyloxycarbonyl phenyl diethoxy silane, m- vinyl benzyloxycarbonyl phenyl di -n- propoxysilane, mention may be made of m- vinyl benzyloxycarbonyl phenyl diacetoxy silane, respectively.

  Of these, 3-glycidoxypropyltrimethoxysilane, 3-methacrylic acid, and the like are intended to improve the storage stability, radiation sensitivity, surface hardness of the resulting interlayer insulating film, heat resistance, and the like of the positive radiation-sensitive composition. Roxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, p-styryltrimethoxysilane, p-styryltriethoxysilane are preferred. Used. Such (a1) hydrolyzable silane compounds may be used singly or in combination of two or more.

(A2) Hydrolyzable silane compound In the above formula (3), the substituted or unsubstituted alkoxy group having 1 to 6 carbon atoms of R ⁵ includes a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, Examples thereof include an n-butoxy group and an n-pentaoxy group. In this, a C1-C4 alkoxy group is preferable and a methoxy group, an ethoxy group, n-propoxy group, and i-propoxy group are especially preferable. Examples of the substituted or unsubstituted aryloxy group having 6 to 18 carbon atoms of R ⁵ include a phenoxy group, a naphthyloxy group, and an anthranyloxy group. Among these, an aryloxy group having 6 to 12 carbon atoms is preferable, and a phenoxy group and a naphthyloxy group are particularly preferable. Examples of the acyloxy group having 2 to 6 carbon atoms include the same groups as those in the above formula (2). Among them, an acyloxy group having 2 to 4 carbon atoms is preferable, and an acetoxy group is particularly preferable. Examples of the substituent of the alkoxy group having 1 to 6 carbon atoms of R ⁵ include a methoxy group and an ethoxy group. Examples of the substituent of the aryloxy group having 6 to 18 carbon atoms of R ⁵ include halogen An atom, a cyano group, a nitro group or an alkyl group having 1 to 6 carbon atoms can be mentioned, and a 4-chlorophenoxy group, a 4-cyanophenoxy group, a 4-nitrophenoxy group, a 4-toluyloxy group, etc. can be mentioned. Can do.

（式（Ｋ）中、Ｙ^２は、メチレン基、炭素数２〜６のアルキレン基又は炭素数６〜１２のアリーレン基である。） In the formula (3), the substituted or unsubstituted alkyl group having 1 to 6 carbon atoms ^{R 6,} a methyl group, an ethyl group, n- propyl, i- propyl, n- butyl, n- pentyl group , N-hexyl group and the like. In this, a C1-C5 alkyl group is preferable and a methyl group, an ethyl group, n-propyl group, i-propyl group, and a pentyl group are especially preferable. Among the substituted or unsubstituted aryl groups having 6 to 18 carbon atoms of R ⁶ , aryl groups having 6 to 8 carbon atoms are preferable, and phenyl groups are particularly preferable. Examples of the substituent of the substituted alkyl group having 1 to 6 carbon atoms include a hydroxyl group, a hydroxyphenylcarbonyloxy group, a mercapto group, and a group represented by the following formula (K).

(In Formula (K), Y ² represents a methylene group, an alkylene group having 2 to 6 carbon atoms, or an arylene group having 6 to 12 carbon atoms.)

Examples of the substituent of the substituted aryl group having 6 to 18 carbon atoms of R ⁶ include a halogen atom, a hydroxyl group, a cyano group, a nitro group, a mercapto group, or an alkyl group having 1 to 6 carbon atoms.

As a specific example of the (a2) hydrolyzable silane compound represented by the above formula (3),
Tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane;
Monoalkyltrisilanes such as methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, cyclohexyltriethoxysilane Alkoxysilanes;
Phenyltrimethoxysilane, phenyltriethoxysilane, phenyltripropoxysilane, naphthyltriethoxysilane, 4-chlorophenyltriethoxysilane, 4-cyanophenyltriethoxysilane, 4-nitrophenyltriethoxysilane, 4-methylphenyltriethoxysilane Monoaryltrialkoxysilanes such as
Monoaryloxy such as phenoxytriethoxysilane, naphthyloxytriethoxysilane, 4-chlorophenyloxytriethoxysilane, 4-cyanophenyltrioxyethoxysilane, 4-nitrophenyloxytriethoxysilane, 4-methylphenyloxytriethoxysilane Trialkoxysilane;

Dialkyl dialkoxysilanes such as dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldi-n-propoxysilane, methyl (ethyl) diethoxysilane, methyl (cyclohexyl) diethoxysilane;
Monoalkylmonoaryl dialkoxysilanes such as methyl (phenyl) diethoxysilane;
Diaryl dialkoxysilanes such as diphenyldiethoxysilane;
Diaryloxy dialkoxysilanes such as diphenoxydiethoxysilane;
Monoalkyl monoaryloxy dialkoxysilanes such as methyl (phenoxy) diethoxysilane;
Monoaryl monoaryloxy dialkoxysilanes such as phenyl (phenoxy) diethoxysilane;
Trialkyl monoalkoxysilanes such as trimethylmethoxysilane, trimethylethoxysilane, trimethyl-n-propoxysilane, dimethyl (ethyl) ethoxysilane, dimethyl (cyclohexyl) ethoxysilane;
Dialkyl monoaryl monoalkoxysilanes such as dimethyl (phenyl) ethoxysilane;
Monoalkyldiarylmonoalkoxysilanes such as methyl (diphenyl) ethoxysilane;
Triaryloxymonoalkoxysilanes such as triphenoxyethoxysilane;
Monoalkyldiaryloxymonoalkoxysilanes such as methyl (diphenoxy) ethoxysilane;
Monoaryldiaryloxymonoalkoxysilanes such as phenyl (diphenoxy) ethoxysilane;
Dialkylmonoaryloxymonoalkoxysilanes such as dimethyl (phenoxy) ethoxysilane;
Diarylmonoaryloxymonoalkoxysilanes such as diphenyl (phenoxy) ethoxysilane;
Monoalkylmonoarylmonoaryloxymonoalkoxysilanes such as methyl (phenyl) (phenoxy) ethoxysilane;

  Hydroxymethyltrimethoxysilane, hydroxymethyltriethoxysilane, hydroxymethyltri-n-propoxysilane, hydroxymethyltri-i-propoxysilane, hydroxymethyltriacetoxysilane, hydroxymethyltri (methoxyethoxy) silane, hydroxymethylmethyldimethoxysilane , Hydroxymethylmethyldiethoxysilane, hydroxymethylmethyldi-n-propoxysilane, hydroxymethylmethyldi-i-propoxysilane, hydroxymethylmethyldiacetoxysilane, hydroxymethylethyldimethoxysilane, hydroxymethylethyldiethoxysilane, hydroxymethyl Ethyldi-n-propoxysilane, hydroxymethylethyldi-i-propoxysilane, hydroxymethylethyldia Toxisilane, hydroxymethylethyldi (methoxyethoxy) silane, hydroxymethylphenyldimethoxysilane, hydroxymethylphenyldiethoxysilane, hydroxymethylphenyldi-n-propoxysilane, hydroxymethylphenyldi-i-propoxysilane, hydroxymethylphenyldiacetoxy Silane, hydroxymethylphenyldi (methoxyethoxy) silane, 2-hydroxyethyltrimethoxysilane, 2-hydroxyethyltriethoxysilane, 2-hydroxyethyltri-n-propoxysilane, 2-hydroxyethyltri-i-propoxysilane, 2-hydroxyethyltriacetoxysilane, 2-hydroxyethyltri (methoxyethoxy) silane,

  2-hydroxyethylmethyldimethoxysilane, 2-hydroxyethylmethyldiethoxysilane, 2-hydroxyethylmethyldi-n-propoxysilane, 2-hydroxyethylmethyldi-i-propoxysilane, 2-hydroxyethylmethyldiacetoxysilane, 2-hydroxyethylethyldimethoxysilane, 2-hydroxyethylethyldiethoxysilane, 2-hydroxyethylethyldi-n-propoxysilane, 2-hydroxyethylethyldi-i-propoxysilane, 2-hydroxyethylethyldiacetoxysilane, 2-hydroxyethylethyldi (methoxyethoxy) silane, 2-hydroxyethylphenyldimethoxysilane, 2-hydroxyethylphenyldiethoxysilane, 2-hydroxyethylphenyldi-n-propo Sisilane, 2-hydroxyethylphenyldi-i-propoxysilane, 2-hydroxyethylphenyldiacetoxysilane, 2-hydroxyethylphenyldi (methoxyethoxy) silane, 3-hydroxypropyltrimethoxysilane, 3-hydroxypropyltriethoxysilane 3-hydroxypropyltri-n-propoxysilane, 3-hydroxypropyltri-i-propoxysilane, 3-hydroxypropyltriacetoxysilane, 3-hydroxypropyltri (methoxyethoxy) silane, 3-hydroxypropylmethyldimethoxysilane, 3-hydroxypropylmethyldiethoxysilane, 3-hydroxypropylmethyldi-n-propoxysilane, 3-hydroxypropylmethyldi-i-propoxysilane, 3-hydroxy Propylmethyldiacetoxysilane, 3-hydroxypropylethyldimethoxysilane, 3-hydroxypropylethyldiethoxysilane, 3-hydroxypropylethyldi-n-propoxysilane, 3-hydroxypropylethyldi-i-propoxysilane, 3-hydroxy Propylethyldiacetoxysilane, 3-hydroxypropylethyldi (methoxyethoxy) silane, 3-hydroxypropylphenyldimethoxysilane, 3-hydroxypropylphenyldiethoxysilane, 3-hydroxypropylphenyldi-n-propoxysilane, 3-hydroxy Propylphenyldi-i-propoxysilane, 3-hydroxypropylphenyldiacetoxysilane, 3-hydroxypropylphenyldi (methoxyethoxy) silane,

  4-hydroxyphenyltrimethoxysilane, 4-hydroxyphenyltriethoxysilane, 4-hydroxyphenyltri-n-propoxysilane, 4-hydroxyphenyltri-i-propoxysilane, 4-hydroxyphenyltriacetoxysilane, 4-hydroxyphenyl Tri (methoxyethoxy) silane, 4-hydroxyphenylmethyldimethoxysilane, 4-hydroxyphenylmethyldiethoxysilane, 4-hydroxyphenylmethyldi-n-propoxysilane, 4-hydroxyphenylmethyldi-i-propoxysilane, 4- Hydroxyphenylmethyldiacetoxysilane, 4-hydroxyphenylethyldimethoxysilane, 4-hydroxyphenylethyldiethoxysilane, 4-hydroxyphenylethyldi-n-propoxy Silane, 4-hydroxyphenylethyldi-i-propoxysilane, 4-hydroxyphenylethyldiacetoxysilane, 4-hydroxyphenylethyldi (methoxyethoxy) silane, 4-hydroxyphenylphenyldimethoxysilane, 4-hydroxyphenylphenyldiethoxy Silane, 4-hydroxyphenylphenyldi-n-propoxysilane, 4-hydroxyphenylphenyldi-i-propoxysilane, 4-hydroxyphenylphenyldiacetoxysilane, 4-hydroxyphenylphenyldi (methoxyethoxy) silane,

（式（Ｌ）中、Ｙ^２は、上記式（Ｋ）におけるのと同じ意味であり、Ｙ^３は、メチレン基又は炭素数２〜６のアルキレン基である。Ｒ^Ｔは、それぞれ独立に、炭素数１〜６のアルキル基又は炭素数２〜６のアシル基である。）
で表される化合物等； 4-hydroxy-5- (p-hydroxyphenylcarbonyloxy) pentyltrimethoxysilane, 4-hydroxy-5- (p-hydroxyphenylcarbonyloxy) pentyltriethoxysilane, 4-hydroxy-5- (p-hydroxyphenylcarbonyl) Oxy) pentyltri-n-propoxysilane, 4-hydroxy-5- (p-hydroxyphenylcarbonyloxy) pentyltri-i-propoxysilane, 4-hydroxy-5- (p-hydroxyphenylcarbonyloxy) pentyltriacetoxysilane, 4 -Hydroxy-5- (p-hydroxyphenylcarbonyloxy) pentyltri (methoxyethoxy) silane, 4-hydroxy-5- (p-hydroxyphenylcarbonyloxy) pentylmethyldimethoxysilane, 4 Hydroxy-5- (p-hydroxyphenylcarbonyloxy) pentylmethyldiethoxysilane, 4-hydroxy-5- (p-hydroxyphenylcarbonyloxy) pentylmethyldi-n-propoxysilane, 4-hydroxy-5- (p- Hydroxyphenylcarbonyloxy) pentylmethyldi-i-propoxysilane, 4-hydroxy-5- (p-hydroxyphenylcarbonyloxy) pentylmethyldiacetoxysilane, 4-hydroxy-5- (p-hydroxyphenylcarbonyloxy) pentylethyl Dimethoxysilane, 4-hydroxy-5- (p-hydroxyphenylcarbonyloxy) pentylethyldiethoxysilane, 4-hydroxy-5- (p-hydroxyphenylcarbonyloxy) pentylethyldi-n-propyl Poxysilane, 4-hydroxy-5- (p-hydroxyphenylcarbonyloxy) pentylethyldi-i-propoxysilane, 4-hydroxy-5- (p-hydroxyphenylcarbonyloxy) pentylethyldiacetoxysilane, 4-hydroxy-5 -(P-hydroxyphenylcarbonyloxy) pentylethyldi (methoxyethoxy) silane, 4-hydroxy-5- (p-hydroxyphenylcarbonyloxy) pentylphenyldimethoxysilane, 4-hydroxy-5- (p-hydroxyphenylcarbonyloxy) ) Pentylphenyldiethoxysilane, 4-hydroxy-5- (p-hydroxyphenylcarbonyloxy) pentylphenyldi-n-propoxysilane, 4-hydroxy-5- (p-hydroxyphenylcarbonyl) Ruoxy) pentylphenyldi-i-propoxysilane, 4-hydroxy-5- (p-hydroxyphenylcarbonyloxy) pentylphenyldiacetoxysilane, 4-hydroxy-5- (p-hydroxyphenylcarbonyloxy) pentylphenyldi (methoxy) Ethoxy) silane, formula (L)

(In the formula (L), ^{Y 2} is the same meaning as in the formula (K), ^{Y 3} is a methylene group or an alkylene group having 2 to 6 carbon atoms .R ^T are each independently, (It is an alkyl group having 1 to 6 carbon atoms or an acyl group having 2 to 6 carbon atoms.)
A compound represented by:

As a silane compound containing a mercapto group,
Mercaptomethyltrimethoxysilane, mercaptomethyltriethoxysilane, mercaptomethyltri-n-propoxysilane, mercaptomethyltri-i-propoxysilane, mercaptomethyltriacetoxysilane, mercaptomethyltri (methoxyethoxy) silane, mercaptomethylmethyldimethoxysilane , Mercaptomethylmethyldiethoxysilane, mercaptomethylmethyldi-n-propoxysilane, mercaptomethylmethyldi-i-propoxysilane, mercaptomethylmethyldiacetoxysilane, mercaptomethylethyldimethoxysilane, mercaptomethylethyldiethoxysilane, mercaptomethyl Ethyldi-n-propoxysilane, mercaptomethylethyldi-i-propoxysilane, mercaptomethylethyldia Toxisilane, mercaptomethylethyldi (methoxyethoxy) silane, mercaptomethylphenyldimethoxysilane, mercaptomethylphenyldiethoxysilane, mercaptomethylphenyldi-n-propoxysilane, mercaptomethylphenyldi-i-propoxysilane, mercaptomethylphenyldiacetoxy Silane, mercaptomethylphenyldi (methoxyethoxy) silane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, 2-mercaptoethyltri-n-propoxysilane, 2-mercaptoethyltri-i-propoxysilane, 2-mercaptoethyltriacetoxysilane, 2-mercaptoethyltri (methoxyethoxy) silane, 2-mercaptoethylmethyldimethoxysilane, 2 Mercaptoethylmethyldiethoxysilane, 2-mercaptoethylmethyldi-n-propoxysilane, 2-mercaptoethylmethyldi-i-propoxysilane, 2-mercaptoethylmethyldiacetoxysilane, 2-mercaptoethylethyldimethoxysilane, 2- Mercaptoethylethyldiethoxysilane, 2-mercaptoethylethyldi-n-propoxysilane, 2-mercaptoethylethyldi-i-propoxysilane, 2-mercaptoethylethyldiacetoxysilane, 2-mercaptoethylethyldidi (methoxyethoxy) Silane, 2-mercaptoethylphenyldimethoxysilane, 2-mercaptoethylphenyldiethoxysilane, 2-mercaptoethylphenyldi-n-propoxysilane, 2-mercaptoethylphenyldi-i- Propoxysilane, 2-mercaptoethylphenyldiacetoxysilane, 2-mercaptoethylphenyldi (methoxyethoxy) silane,

  3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyltri-n-propoxysilane, 3-mercaptopropyltri-i-propoxysilane, 3-mercaptopropyltriacetoxysilane, 3-mercaptopropyl Tri (methoxyethoxy) silane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropylmethyldiethoxysilane, 3-mercaptopropylmethyldi-n-propoxysilane, 3-mercaptopropylmethyldi-i-propoxysilane, 3- Mercaptopropylmethyldiacetoxysilane, 3-mercaptopropylethyldimethoxysilane, 3-mercaptopropylethyldiethoxysilane, 3-mercaptopropylethyldi-n-propoxy Silane, 3-mercaptopropylethyldi-i-propoxysilane, 3-mercaptopropylethyldiacetoxysilane, 3-mercaptopropylethyldi (methoxyethoxy) silane, 3-mercaptopropylphenyldimethoxysilane, 3-mercaptopropylphenyldiethoxy Examples include silane, 3-mercaptopropylphenyldi-n-propoxysilane, 3-mercaptopropylphenyldi-i-propoxysilane, 3-mercaptopropylphenyldiacetoxysilane, 3-mercaptopropylphenyldi (methoxyethoxy) silane, and the like. .

  Among these (a2) hydrolyzable silane compounds, the storage stability of the radiation-sensitive composition, the radiation sensitivity, the surface hardness of the resulting interlayer insulating film, the heat resistance and the like are improved, (a1) the hydrolyzable silane compound From the point of co-condensation reactivity in the presence of tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, Diphenyldimethoxysilane, diphenyldiethoxysilane, and 3-mercaptopropyltrimethoxysilane can be preferably used. Such (a2) hydrolyzable silane compounds may be used singly or in combination of two or more. Further, (a1) one hydrolyzable silane compound and (a2) one hydrolyzable silane compound may be combined and co-condensed. (A1) two or more hydrolyzable silane compounds and (a2) hydrolyzed Two or more decomposable silane compounds may be combined and co-condensed.

  The conditions for hydrolyzing and condensing the hydrolyzable silane compound are as follows: in the presence of a catalyst that promotes hydrolytic condensation, at least a part of the hydrolyzable silane compound is hydrolyzed to convert the hydrolyzable group into a silanol group. Although it does not specifically limit as long as it converts and raise | generates a condensation reaction, it can implement as follows as an example.

  The water used for hydrolysis / condensation of the hydrolyzable silane compound is preferably water purified by a method such as reverse osmosis membrane treatment, ion exchange treatment or distillation. By using such purified water, side reactions can be suppressed and the reactivity of hydrolysis can be improved. The amount of water used is preferably 0.1 with respect to 1 mol of the total amount of hydrolyzable groups of the hydrolyzable silane compound (various groups having an —OR structure in the above formulas (2) and (3)). -3 mol, more preferably 0.3-2 mol, particularly preferably 0.5-1.5 mol. By using such an amount of water, the reaction rate of hydrolysis / condensation can be optimized.

  The solvent that can be used for the hydrolysis / condensation of the hydrolyzable silane compound is not particularly limited. Can be used. Preferable examples of such a solvent include ethylene glycol monoalkyl ether acetate, diethylene glycol dialkyl ether, propylene glycol monoalkyl ether, propylene glycol monoalkyl ether acetate, and propionic acid esters. Among these solvents, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, and diacetone alcohol are particularly preferable.

  As the catalyst for promoting the hydrolysis condensation, a [C] metal chelate compound described later is preferable from the viewpoint of controlling the molecular weight of polysiloxane and improving the storage stability of the positive radiation-sensitive composition. In addition, as a catalyst for promoting the hydrolysis condensation, for example, an acid catalyst (for example, an inorganic acid such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid; formic acid, acetic acid, oxalic acid, trifluoroacetic acid) is used unless the effects of the present invention are impaired , Organic acids such as trifluoromethanesulfonic acid; acidic ion exchange resins; various Lewis acids), basic catalysts (eg, nitrogen-containing compounds such as ammonia, primary amines, secondary amines, tertiary amines, pyridine, etc .; bases Ion exchange resin; hydroxide such as sodium hydroxide; carbonate such as potassium carbonate; carboxylate such as sodium acetate; various Lewis bases] or alkoxide (for example, zirconium alkoxide, titanium alkoxide, aluminum alkoxide) You may go out.

  The amount of the catalyst for promoting hydrolysis condensation is preferably 0.2 mol or less, more preferably 1 mol of the monomer of the hydrolyzable silane compound, from the viewpoint of promoting the hydrolysis / condensation reaction. 0.00001 to 0.1 mol.

  The reaction temperature and reaction time in the hydrolysis / condensation of the hydrolyzable silane compound are appropriately set. For example, the following conditions can be adopted. The reaction temperature is preferably 40 to 200 ° C, more preferably 50 to 150 ° C. The reaction time is preferably 30 minutes to 24 hours, more preferably 1 to 12 hours. By setting such reaction temperature and reaction time, hydrolysis / condensation reaction can be most efficiently performed. In this hydrolysis / condensation, the hydrolyzable silane compound, water and catalyst may be added to the reaction system at a time to carry out the reaction in one step, or the hydrolyzable silane compound, water and catalyst may be added, The hydrolysis and condensation reaction may be performed in multiple stages by adding them into the reaction system in several times.

  In particular, when a metal chelate compound is used, after performing hydrolysis / condensation reaction to a desired degree as described above, acetylacetone or the like is used to inactivate the metal chelate compound and quench the hydrolysis condensation reaction. the addition of a quencher. The addition amount of the quencher varies depending on the amount and type of the metal chelate compound present in the reaction system, but it may be added in an amount of 2 to 10 times the mass of the metal chelate compound. In the positive-type radiation-sensitive composition, when polysiloxane is synthesized using a metal chelate compound, undesired hydrolytic condensation after the reaction can be suppressed only by adding a quencher. preferable.

  After the hydrolysis / condensation reaction, water and the produced alcohol can be removed from the reaction system by adding a dehydrating agent and then subjecting it to evaporation. In this concentrate, a metal chelate complex derived from a metal chelate compound deactivated by a quencher may be present. Note that the dehydrating agent used in this stage is generally used in the radiation-sensitive composition because excess water is adsorbed or included and the dehydrating ability is completely consumed or removed by evaporation. It is not included in the category of the dehydrating agent of the later-described [F] component added to.

  The molecular weight of the hydrolysis-condensation product of the hydrolyzable silane compound can be measured as a number average molecular weight in terms of polystyrene using GPC (gel permeation chromatography) using tetrahydrofuran as a mobile phase. The number average molecular weight of the hydrolysis-condensation product is usually preferably a value within the range of 500 to 10,000, and more preferably within the range of 1000 to 5000. By setting the value of the number average molecular weight of the hydrolysis condensate to 500 or more, the film formability of the coating film of the radiation sensitive composition can be improved. On the other hand, the fall of the radiation sensitivity of a radiation sensitive composition can be prevented by making the value of the number average molecular weight of a hydrolysis-condensation product into 10,000 or less.

[B] Component: Photoacid generator or photobase generator [B] The photoacid generator or photobase generator is a compound that generates an acid or a base by irradiation with radiation. When the positive radiation sensitive composition contains [B] a photoacid generator or a photobase generator, positive radiation sensitive characteristics can be exhibited.

[B1]: Photoacid generator [B1] The photoacid generator is not particularly limited as long as it is a compound that generates an acid (for example, carboxylic acid, sulfonic acid, etc.) by irradiation with radiation. [B1] As the photoacid generator, [B1-1] quinonediazide can be suitably used. [B1-2] Other photoacid generators can be used instead of [B1-1] quinonediazide, or [B1- 1] Can be used together with quinonediazide.

[B1-1]: Quinonediazide [B1-1] quinonediazide is a compound that generates carboxylic acid when irradiated with radiation. Such a radiation-sensitive composition containing quinonediazide has a positive radiation-sensitive property in which an exposed portion in the radiation irradiation process is removed in the development process. As [B1-1] quinonediazide, a compound obtained by esterifying a compound having a phenolic hydroxyl group and naphthoquinonediazidesulfonic acid halide can be preferably used. Examples of the compound having a phenolic hydroxyl group include compounds in which the ortho position and the para position of the phenolic hydroxyl group are each independently hydrogen or a substituent represented by the following formula (4).

（式中、Ｒ^７、Ｒ^８及びＲ^９は、各々独立して炭素数１〜１０のアルキル基、カルボキシル基、フェニル基、置換フェニル基のいずれかを表す。また、Ｒ^７、Ｒ^８及びＲ^９のうちの２つ又は３つによって環が形成されていてもよい。）

(In the formula, R ⁷ , R ⁸ and R ⁹ each independently represents any of an alkyl group having 1 to 10 carbon atoms, a carboxyl group, a phenyl group and a substituted phenyl group. Also, R ⁷ , R ⁸ and A ring may be formed by two or three of R ^9. )

In the substituent represented by the above formula (4), when R ⁷ , R ⁸ , R ⁹ is an alkyl group having 1 to 10 carbon atoms, the alkyl group may be substituted or substituted. It does not have to be. Examples of such alkyl groups include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-hexyl, cyclohexyl, n -Heptyl group, n-octyl group, trifluoromethyl group, 2-carboxyethyl group may be mentioned. Moreover, a hydroxyl group is mentioned as a substituent of a substituted phenyl group. Examples of the cyclic group formed by two or three of R ⁷ , R ⁸ and R ⁹ include a cyclopentane ring, a cyclohexane ring, an adamantane ring and a fluorene ring.

  Examples of the compound having a phenolic hydroxyl group include compounds represented by the following formulas (5) and (6).

  Other examples of compounds having a phenolic hydroxyl group include 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol, 1,1,1 -Tri (p-hydroxyphenyl) ethane and the like can be mentioned.

  As the naphthoquinone diazide sulfonic acid halide, 4-naphthoquinone diazide sulfonic acid halide or 5-naphthoquinone diazide sulfonic acid halide can be used. An ester compound (quinonediazide) obtained from 4-naphthoquinonediazidesulfonic acid halide is suitable for i-line exposure because it has absorption in the i-line (wavelength 365 nm) region. In addition, an ester compound (quinonediazide) obtained from 5-naphthoquinonediazidesulfonic acid halide is suitable for exposure in a wide range of wavelengths since absorption exists in a wide range of wavelengths. It is preferable to select an ester compound obtained from 4-naphthoquinone diazide sulfonic acid halide or an ester compound obtained from 5-naphthoquinone diazide sulfonic acid halide depending on the wavelength to be exposed. Examples of particularly preferred quinonediazides include 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol (1.0 mol) and 1,2- Condensation product with naphthoquinonediazide-5-sulfonic acid chloride (3.0 mol), 1,1,1-tri (p-hydroxyphenyl) ethane (1.0 mol) and 1,2-naphthoquinonediazide-5-sulfone Mention may be made of condensates with acid chlorides (3.0 mol).

  The molecular weight of naphthoquinone diazide is preferably 300 to 1500, and more preferably 350 to 1200. By setting the molecular weight of naphthoquinone diazide to 300 or more, the transparency of the obtained interlayer insulating film can be maintained high. On the other hand, by setting the molecular weight of naphthoquinone diazide to 1500 or less, it is possible to suppress a decrease in pattern forming ability of the positive radiation-sensitive composition.

  These [B1-1] quinonediazides can be used alone or in combination of two or more. The amount of [B1-1] quinonediazide used in the radiation-sensitive composition is preferably 1 to 100 parts by mass and more preferably 5 to 50 parts by mass with respect to 100 parts by mass of the [A] component. By setting the amount of [B1-1] quinonediazide to be used in the range of 1 to 100 parts by mass, the difference in solubility between the irradiated part and the unirradiated part in the alkaline aqueous solution used as the developer is large, and the patterning performance is improved. The resulting interlayer insulating film also has good solvent resistance.

[B-2]: Other photoacid generators [B-2] Other photoacid generators include diphenyliodonium salts, triphenylsulfonium salts, sulfonium salts, benzothiazonium salts, ammonium salts, phosphonium salts, Examples include onium salts such as tetrahydrothiophenium salts and sulfonimide compounds.

  Examples of diphenyliodonium salts include diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluorophosphonate, diphenyliodonium hexafluoroarsenate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium trifluoroacetate, diphenyliodonium-p-toluenesulfonate, diphenyl Iodonium butyltris (2,6-difluorophenyl) borate, 4-methoxyphenylphenyliodonium tetrafluoroborate, bis (4-t-butylphenyl) iodonium tetrafluoroborate, bis (4-t-butylphenyl) iodonium hexafluoroarce Bis (4-tert-butylphenyl) iodonium trifluorometa Examples include sulfonate, bis (4-tert-butylphenyl) iodonium trifluoroacetate, bis (4-tert-butylphenyl) iodonium-p-toluenesulfonate, bis (4-tert-butylphenyl) iodonium camphorsulfonic acid, and the like. .

  Examples of triphenylsulfonium salts include triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium camphorsulfonic acid, triphenylsulfonium tetrafluoroborate, triphenylsulfonium trifluoroacetate, triphenylsulfonium-p-toluenesulfonate, triphenyl And sulfonium butyl tris (2,6-difluorophenyl) borate.

  Examples of the sulfonium salt include alkylsulfonium salts, benzylsulfonium salts, dibenzylsulfonium salts, substituted benzylsulfonium salts and the like.

As these sulfonium salts,
Examples of the alkylsulfonium salt include 4-acetoxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium hexafluoroarsenate, dimethyl-4- (benzyloxycarbonyloxy) phenylsulfonium hexafluoroantimonate, dimethyl-4- ( Benzoyloxy) phenylsulfonium hexafluoroantimonate, dimethyl-4- (benzoyloxy) phenylsulfonium hexafluoroarsenate, dimethyl-3-chloro-4-acetoxyphenylsulfonium hexafluoroantimonate, etc .;
Examples of benzylsulfonium salts include benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, 4-acetoxyphenylbenzylmethylsulfonium hexafluoroantimonate, and benzyl-4-methoxyphenylmethyl. Sulfonium hexafluoroantimonate, benzyl-2-methyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl-3-chloro-4-hydroxyphenylmethylsulfonium hexafluoroarsenate, 4-methoxybenzyl-4-hydroxyphenylmethyl Sulfonium hexafluorophosphate, etc .;
Examples of the dibenzylsulfonium salt include dibenzyl-4-hydroxyphenylsulfonium hexafluoroantimonate, dibenzyl-4-hydroxyphenylsulfonium hexafluorophosphate, 4-acetoxyphenyl dibenzylsulfonium hexafluoroantimonate, dibenzyl-4-methoxyphenylsulfonium hexa Fluoroantimonate, dibenzyl-3-chloro-4-hydroxyphenylsulfonium hexafluoroarsenate, dibenzyl-3-methyl-4-hydroxy-5-t-butylphenylsulfonium hexafluoroantimonate, benzyl-4-methoxybenzyl-4 -Hydroxyphenylsulfonium hexafluorophosphate and the like;
Examples of substituted benzylsulfonium salts include p-chlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, p-nitrobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, and p-chlorobenzyl-4-hydroxyphenylmethylsulfonium. Hexafluorophosphate, p-nitrobenzyl-3-methyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 3,5-dichlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, o-chlorobenzyl-3-chloro Examples include -4-hydroxyphenylmethylsulfonium hexafluoroantimonate.

  Examples of benzothiazonium salts include 3-benzylbenzothiazonium hexafluoroantimonate, 3-benzylbenzothiazonium hexafluorophosphate, 3-benzylbenzothiazonium tetrafluoroborate, 3- (p-methoxy Benzyl) benzothiazonium hexafluoroantimonate, 3-benzyl-2-methylthiobenzothiazonium hexafluoroantimonate, 3-benzyl-5-chlorobenzothiazonium hexafluoroantimonate, and the like.

  Examples of tetrahydrothiophenium salts include 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium Nonafluoro-n-butanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium-1,1,2,2-tetrafluoro-2- (norbornan-2-yl) ethanesulfonate, 1- (4-n-Butoxynaphthalen-1-yl) tetrahydrothiophenium-2- (5-t-butoxycarbonyloxybicyclo [2.2.1] heptan-2-yl) -1,1,2, 2-tetrafluoroethanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydro Ofenium-2- (6-t-butoxycarbonyloxybicyclo [2.2.1] heptan-2-yl) -1,1,2,2-tetrafluoroethanesulfonate, 1- (4,7-dibutoxy-1 -Naphthalenyl) tetrahydrothiophenium trifluoromethanesulfonate and the like.

  Examples of the sulfonimide compound include N- (trifluoromethylsulfonyloxy) succinimide (trade name “SI-105” (manufactured by Midori Chemical Co., Ltd.)), N- (camphorsulfonyloxy) succinimide (trade name “SI-”). 106 "(manufactured by Midori Chemical Co., Ltd.)), N- (4-methylphenylsulfonyloxy) succinimide (trade name" SI-101 "(manufactured by Midori Chemical Co., Ltd.)), N- (2-trifluoromethylphenyl) Sulfonyloxy) succinimide, N- (4-fluorophenylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (camphorsulfonyloxy) phthalimide, N- (2-trifluoromethylphenylsulfonyloxy) phthalimide N- (2-fluoropheny Sulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide (trade name “PI-105” (manufactured by Midori Chemical Co., Ltd.)), N- (camphorsulfonyloxy) diphenylmaleimide, 4-methylphenylsulfonyloxy ) Diphenylmaleimide, N- (2-trifluoromethylphenylsulfonyloxy) diphenylmaleimide, N- (4-fluorophenylsulfonyloxy) diphenylmaleimide, N- (4-fluorophenylsulfonyloxy) diphenylmaleimide, N- (phenylsulfonyl) Oxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide (trade name “NDI-100” (manufactured by Midori Chemical Co., Ltd.)), N- (4-methylphenylsulfonyloxy) ) Bishik [2.2.1] Hept-5-ene-2,3-dicarboxylimide (trade name “NDI-101” (manufactured by Midori Chemical Co., Ltd.)), N- (trifluoromethanesulfonyloxy) bicyclo [2. 2.1] Hept-5-ene-2,3-dicarboxylimide (trade name “NDI-105” (manufactured by Midori Chemical Co., Ltd.)), N- (nonafluorobutanesulfonyloxy) bicyclo [2.2. 1] Hept-5-ene-2,3-dicarboxylimide (trade name “NDI-109” (manufactured by Midori Chemical Co., Ltd.)), N- (camphorsulfonyloxy) bicyclo [2.2.1] hept- 5-ene-2,3-dicarboxylimide (trade name “NDI-106” (manufactured by Midori Chemical Co., Ltd.)), N- (camphorsulfonyloxy) -7-oxabicyclo [2.2.1] hept- 5- Ene-2,3-dicarboxylimide, N- (trifluoromethylsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (4- Methylphenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (4-methylphenylsulfonyloxy) -7-oxabicyclo [2.2.1] hept -5-ene-2,3-dicarboxylimide, N- (2-trifluoromethylphenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- ( 2-trifluoromethylphenylsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (4- (Luorophenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (4-fluorophenylsulfonyloxy) -7-oxabicyclo [2.2.1] Hept-5-ene-2,3-dicarboxylimide, N- (trifluoromethylsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboxylimide, N- ( Camphorsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboxylimide, N- (4-methylphenylsulfonyloxy) bicyclo [2.2.1] heptane-5 6-oxy-2,3-dicarboxylimide, N- (2-trifluoromethylphenylsulfonyloxy) bicyclo [2.2.1] heptane- , 6-oxy-2,3-dicarboxylimide, N- (4-fluorophenylsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboxylimide, N- ( Trifluoromethylsulfonyloxy) naphthyl dicarboximide (trade name “NAI-105” (manufactured by Midori Chemical Co., Ltd.)), N- (camphorsulfonyloxy) naphthyl dicarboxyimide (trade name “NAI-106” (Midori Chemical) N- (4-methylphenylsulfonyloxy) naphthyl dicarboxylimide (trade name “NAI-101” (manufactured by Midori Chemical Co., Ltd.)), N- (phenylsulfonyloxy) naphthyl dicarboxylimide (Trade name “NAI-100” (manufactured by Midori Chemical Co., Ltd.)), N- (2-trifluoromethylphenol) Nylsulfonyloxy) naphthyl dicarboxylimide, N- (4-fluorophenylsulfonyloxy) naphthyl dicarboxylimide, N- (pentafluoroethylsulfonyloxy) naphthyl dicarboxylimide, N- (heptafluoropropylsulfonyloxy) naphthyl dicarboxyl Imido, N- (nonafluorobutylsulfonyloxy) naphthyl dicarboxylimide (trade name “NAI-109” (manufactured by Midori Chemical Co., Ltd.)), N- (ethylsulfonyloxy) naphthyl dicarboxylimide, N- (propylsulfonyl) Oxy) naphthyl dicarboxylimide, N- (butylsulfonyloxy) naphthyl dicarboxylimide (trade name “NAI-1004” (manufactured by Midori Chemical Co., Ltd.)), N- (pentylsulfonyloxy) na Tildicarboxylimide, N- (hexylsulfonyloxy) naphthyldicarboxylimide, N- (heptylsulfonyloxy) naphthyldicarboxylimide, N- (octylsulfonyloxy) naphthyldicarboxylimide, N- (nonylsulfonyloxy) naphthyldi Carboxylimide etc. are mentioned

  Among these photoacid generators, from the viewpoint of improving the radiation sensitivity of the positive-type radiation-sensitive composition and the adhesion of the resulting cured product, triphenylsulfonium salt, sulfonium salt, benzothiazonium salt, tetrahydrothio Phenium salts and sulfonimide compounds are preferably used. Among these, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium camphorsulfonic acid, 4-acetoxyphenyldimethylsulfonium hexafluoroarsenate, benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 4-acetoxyphenylbenzylmethylsulfonium Hexafluoroantimonate, dibenzyl-4-hydroxyphenylsulfonium hexafluoroantimonate, 4-acetoxyphenylbenzylmethylsulfonium hexafluoroantimonate, 3-benzylbenzothiazonium hexafluoroantimonate, benzyl-4-hydroxyphenylmethylsulfonium hexa Fluorophosphate, 1- (4-n-butoxynaphtha N-1-yl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (4,7-dibutoxy-1-naphthalenyl) tetrahydrothiophenium trifluoromethanesulfonate, N- (trifluoromethylsulfonyloxy) naphthyl dicarboxylimide preferably used.

  [B1-2] Other photoacid generators may be used alone or in combination of two or more. Moreover, you may use together with [B1-1] quinonediazide. [B1-2] The amount of the photoacid generator used is preferably 0.1 parts by mass or more and 20 parts by mass or less, more preferably 1 part by mass or more and 10 parts by mass with respect to 100 parts by mass of the component [A]. Or less. [B2] By using the component in an amount of 0.1 parts by mass or more and 20 parts by mass or less, a radiation-sensitive composition excellent in balance between melt flow resistance and heat resistance of the formed interlayer insulating film is obtained. In addition, it is possible to prevent the formation of precipitates in the coating film forming step and facilitate the formation of the coating film. In addition, what is necessary is just to set so that the total amount of both may become the said range, when using together [B1-1] quinonediazide and [B1-2] other photoacid generators.

[B2]: Photobase generator [B2] The photobase generator is not particularly limited as long as it is a compound that generates a base (such as an amine) by irradiation with radiation. Examples of the photobase generator include transition metal complexes such as cobalt, orthonitrobenzyl carbamates, α, α-dimethyl-3,5-dimethoxybenzyl carbamates, acyloxyiminos and the like.

  Examples of transition metal complexes include bromopentammonium cobalt perchlorate, bromopentamethylamine cobalt perchlorate, bromopentapropylamine cobalt perchlorate, hexaammonia cobalt perchlorate, hexamethylamine cobalt perchlorate. Examples include chlorate and hexapropylamine cobalt perchlorate.

  Examples of orthonitrobenzyl carbamates include [[(2-nitrobenzyl) oxy] carbonyl] methylamine, [[(2-nitrobenzyl) oxy] carbonyl] propylamine, [[(2-nitrobenzyl) oxy, ] Carbonyl] hexylamine, [[(2-nitrobenzyl) oxy] carbonyl] cyclohexylamine, [[(2-nitrobenzyl) oxy] carbonyl] aniline, [[(2-nitrobenzyl) oxy] carbonyl] piperidine, bis [[(2-Nitrobenzyl) oxy] carbonyl] hexamethylenediamine, bis [[(2-nitrobenzyl) oxy] carbonyl] phenylenediamine, bis [[(2-nitrobenzyl) oxy] carbonyl] toluenediamine, bis [ [(2-Nitrobenzyl) oki ] Carbonyl] diaminodiphenylmethane, bis [[(2-nitrobenzyl) oxy] carbonyl] piperazine, [[(2,6-dinitrobenzyl) oxy] carbonyl] methylamine, [[(2,6-dinitrobenzyl) oxy] Carbonyl] propylamine, [[(2,6-dinitrobenzyl) oxy] carbonyl] hexylamine, [[(2,6-dinitrobenzyl) oxy] carbonyl] cyclohexylamine, [[(2,6-dinitrobenzyl) oxy ] Carbonyl] aniline, [[(2,6-dinitrobenzyl) oxy] carbonyl] piperidine, bis [[(2,6-dinitrobenzyl) oxy] carbonyl] hexamethylenediamine, bis [[(2,6-dinitrobenzyl ) Oxy] carbonyl] phenylenediamine, bis [(2,6-dinitrobenzyl) oxy] carbonyl] toluenediamine, bis [[(2,6-dinitrobenzyl) oxy] carbonyl] diaminodiphenylmethane, bis [[(2,6-dinitrobenzyl) oxy] carbonyl] piperazine Etc.

  Examples of α, α-dimethyl-3,5-dimethoxybenzyl carbamates include [[(α, α-dimethyl-3,5-dimethoxybenzyl) oxy] carbonyl] methylamine, [[(α, α-dimethyl. −3,5-dimethoxybenzyl) oxy] carbonyl] propylamine, [[(α, α-dimethyl-3,5-dimethoxybenzyl) oxy] carbonyl] hexylamine, [[(α, α-dimethyl-3,5 -Dimethoxybenzyl) oxy] carbonyl] cyclohexylamine, [[(α, α-dimethyl-3,5-dimethoxybenzyl) oxy] carbonyl] aniline, [[(α, α-dimethyl-3,5-dimethoxybenzyl) oxy ] Carbonyl] piperidine, bis [[(α, α-dimethyl-3,5-dimethoxybenzyl) oxy] carbonyl] hexa Tylenediamine, bis [[(α, α-dimethyl-3,5-dimethoxybenzyl) oxy] carbonyl] phenylenediamine, bis [[(α, α-dimethyl-3,5-dimethoxybenzyl) oxy] carbonyl] toluenediamine Bis [[(α, α-dimethyl-3,5-dimethoxybenzyl) oxy] carbonyl] diaminodiphenylmethane, bis [[(α, α-dimethyl-3,5-dimethoxybenzyl) oxy] carbonyl] piperazine, and the like. It is done.

Examples of acyloxyiminos include propionyl acetophenone oxime, propionyl benzophenone oxime, propionyl acetone oxime, butyryl acetophenone oxime, butyryl benzophenone oxime, butyryl acetone oxime, adipoyl acetophenone oxime, adipoyl benzophenone oxime, adipoyl Acetone oxime, acryloyl acetophenone oxime, acryloyl benzophenone oxime, acryloyl acetone oxime and the like can be mentioned.
As other examples of the radiation sensitive base generator, 2-nitrobenzylcyclohexyl carbamate, O-carbamoylhydroxyamide and O-carbamoylhydroxyamide are particularly preferable.

  [B2] One photobase generator may be used alone, or two or more photobase generators may be mixed and used. Moreover, as long as the effect of this invention is not impaired, you may use together [B2], a photobase generator, and a [B1] photoacid generator. [B2] The amount of the photobase generator used is preferably 0.1 parts by mass or more and 20 parts by mass or less, more preferably 1 part by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the component [A]. It is. [B2] By using the component in an amount of 0.1 parts by mass or more and 20 parts by mass or less, a radiation-sensitive composition excellent in balance between melt flow resistance and heat resistance of the formed interlayer insulating film is obtained. In addition, it is possible to prevent the formation of precipitates in the coating film forming step and facilitate the formation of the coating film.

[C] Component: Metal Chelate Compound The metal chelate compound is a compound in which a chelating agent and other ligands are coordinated to a metal (hereinafter also referred to as a central metal). Although it does not specifically limit as a metal chelate compound as long as it is a compound which accelerates | stimulates the hydrolytic condensation of a hydrolysable silane compound, The compound represented by the said Formula (1) is preferable.

  Examples of the central metal which is M in the above formula (1) include aluminum, titanium, zirconium, beryllium, calcium, cobalt, copper, iron, hafnium, iridium, palladium, manganese, molybdenum, niobium, nickel, platinum, tin, Examples include metals such as ruthenium, tantalum, vanadium, tungsten, and zinc. Among these metals, at least one selected from the group consisting of aluminum, titanium, and zirconium is preferable from the viewpoints of reactivity, structure controllability, availability, and the like.

In the above formula (1), the chelating agent for R ¹ is not particularly limited as long as it exhibits a chelate structure by coordination with the central metal. For example, acetylacetonate, ethylacetoacetate, 2,2,6,6-tetra Methyl-3,5-heptanedionate, benzoylacetonate, 1,3-diphenyl-1,3-propanedionate, methylacetoacetate, methacryloxyethyl acetate, allyl acetoacetate, tetramethylheptanedionate, hexanedionate , Heptanedionate, benzoyl acetate and the like. Among these chelating agents, acetylacetonate and ethylacetoacetate are preferable from the viewpoints of structure controllability, high coordination power, and the like.

Among R ² in the formula (1), examples of the alkyl group having 2 to 5 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, and an n-butyl group. Moreover, a phenyl group etc. are mentioned as a C6-C20 aryl group. In these alkyl groups or aryl groups, part of the hydrogen atoms may be substituted with other substituents.

Specific examples of the metal chelate compound include, for example, tris (acetylacetonato) aluminum, tris (ethylacetoacetate) aluminum, di (i-propoxy) · monoacetylacetonate aluminum, di (i-propoxy) · monomethylacetoacetate. Aluminum chelate compounds such as tate aluminum, di (i-propoxy) monoethyl acetoacetate aluminum, bisethyl acetoacetate monoacetyl acetonate aluminum;

  Triethoxy mono (acetylacetonato) titanium, tri-n-propoxy mono (acetylacetonato) titanium, tri-i-propoxy mono (acetylacetonato) titanium, di-i-propoxybisacetylacetonate titanium, Di-i-propoxy bisethyl acetoacetate titanium, tri-n-butoxy mono (acetylacetonato) titanium, tri-sec-butoxy mono (acetylacetonato) titanium, tri-t-butoxy mono (acetylacetate) Natto) titanium, diethoxy bis (acetylacetonato) titanium, di-n-propoxy bis (acetylacetonato) titanium, di-i-propoxy bis (acetylacetonato) titanium, di-n-butoxy bis ( Acetylacetonate) Titanium, Di-se -Butoxy bis (acetylacetonato) titanium, di-t-butoxy bis (acetylacetonato) titanium, monoethoxy tris (acetylacetonato) titanium, mono-n-propoxy tris (acetylacetonato) titanium, Mono-i-propoxy-tris (acetylacetonato) titanium, mono-n-butoxy-tris (acetylacetonato) titanium, mono-sec-butoxy-tris (acetylacetonato) titanium, mono-t-butoxy-tris ( Acetylacetonato) titanium, tetrakis (acetylacetonato) titanium, triethoxy mono (ethyl acetoacetate) titanium, tri-n-propoxy mono (ethyl acetoacetate) titanium, tri-i-propoxy mono (ethyl acetoacetate) titanium Tri-n-butoxy mono (ethyl acetoacetate) titanium, tri-sec-butoxy mono (ethyl acetoacetate) titanium, tri-t-butoxy mono (ethyl acetoacetate) titanium, diethoxy bis (ethyl acetoacetate) Titanium, di-n-propoxy bis (ethyl acetoacetate) titanium, di-i-propoxy bis (ethyl acetoacetate) titanium, di-n-butoxy bis (ethyl acetoacetate) titanium, di-sec-butoxy Bis (ethyl acetoacetate) titanium, di-t-butoxy bis (ethyl acetoacetate) titanium, monoethoxy tris (ethyl acetoacetate) titanium, mono-n-propoxy tris (ethyl acetoacetate) titanium, mono-i -Propoxy Tris (Eth Ruacetoacetate) titanium, mono-n-butoxy tris (ethyl acetoacetate) titanium, mono-sec-butoxy tris (ethyl acetoacetate) titanium, mono-t-butoxy tris (ethyl acetoacetate) titanium, tetrakis ( Titanium such as ethyl acetoacetate) titanium, mono (acetylacetonato) tris (ethylacetoacetate) titanium, bis (acetylacetonato) bis (ethylacetoacetate) titanium, tris (acetylacetonato) mono (ethylacetoacetate) titanium Chelating compounds;

  Triethoxy mono (acetylacetonato) zirconium, tri-n-propoxy mono (acetylacetonato) zirconium, tri-i-propoxy mono (acetylacetonato) zirconium, tri-n-butoxymono (acetylacetonate) Zirconium, tri-sec-butoxy mono (acetylacetonato) zirconium, tri-t-butoxymono (acetylacetonato) zirconium, diethoxybis (acetylacetonato) zirconium, di-n-propoxybis (acetylacetate) Nato) zirconium, di-i-propoxy bis (acetylacetonato) zirconium, di-n-butoxy bis (acetylacetonato) zirconium, di-sec-butoxy bis (acetylacetonato) zirc Ni, di-t-butoxy bis (acetylacetonato) zirconium, monoethoxy tris (acetylacetonato) zirconium, mono-n-propoxytris (acetylacetonato) zirconium, mono-i-propoxytris (acetyl) Acetonato) zirconium, mono-n-butoxy-tris (acetylacetonato) zirconium, mono-sec-butoxy-tris (acetylacetonato) zirconium, mono-t-butoxy-tris (acetylacetonato) zirconium, tetrakis (acetyl) Acetonato) zirconium, triethoxy mono (ethyl acetoacetate) zirconium, tri-n-propoxy mono (ethyl acetoacetate) zirconium, tri-i-propoxy mono (ethyl acetate) Acetate) zirconium, tri-n-butoxy mono (ethyl acetoacetate) zirconium, tri-sec-butoxy mono (ethyl acetoacetate) zirconium, tri-t-butoxy mono (ethyl acetoacetate) zirconium, diethoxy bis ( Ethyl acetoacetate) zirconium, di-n-propoxy bis (ethyl acetoacetate) zirconium, di-i-propoxy bis (ethyl acetoacetate) zirconium, di-n-butoxy bis (ethyl acetoacetate) zirconium, di- sec-butoxy bis (ethyl acetoacetate) zirconium, di-t-butoxy bis (ethyl acetoacetate) zirconium, monoethoxy tris (ethyl acetoacetate) zirconium, mono-n- Propoxy tris (ethyl acetoacetate) zirconium, mono-i-propoxy tris (ethyl acetoacetate) zirconium, mono-n-butoxy tris (ethyl acetoacetate) zirconium, mono-sec-butoxy tris (ethyl acetoacetate) Zirconium, mono-t-butoxy-tris (ethylacetoacetate) zirconium, tetrakis (ethylacetoacetate) zirconium, mono (acetylacetonato) tris (ethylacetoacetate) zirconium, bis (acetylacetonato) bis (ethylacetoacetate) Zirconium chelate compounds such as zirconium and tris (acetylacetonate) mono (ethyl acetoacetate) zirconium are exemplified.

  Among these metal chelate compounds, from the viewpoint of promoting and structure control of the hydrolysis condensation reaction, di (i-propoxy) monoethyl acetoacetate aluminum, di -i- propoxy bis ethylacetoacetate titanium, di - n-Butoxy bis (ethyl acetoacetate) zirconium is preferred.

  The content of the [C] metal chelate compound in the positive radiation-sensitive composition may be approximately the same as the amount used in the synthesis of [A] polysiloxane.

[D] Component: Surfactant The surfactant of the [D] component is added to improve the coating property of the positive radiation-sensitive composition, to reduce coating unevenness, and to improve the developability of the radiation irradiated part. be able to. Examples of preferred surfactants include nonionic surfactants, fluorine surfactants, and silicone surfactants.

  Nonionic surfactants include, for example, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether; polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, and the like. Polyoxyethylene aryl ethers; polyethylene glycol dialkyl esters such as polyethylene glycol dilaurate and polyethylene glycol distearate; (meth) acrylic acid copolymers and the like. As an example of (meth) acrylic acid-based copolymers, Polyflow No. 57, no. 95 (manufactured by Kyoeisha Chemical Co., Ltd.).

  Examples of the fluorosurfactant include 1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl) ether, 1,1,2,2-tetrafluorooctyl hexyl ether, octa Ethylene glycol di (1,1,2,2-tetrafluorobutyl) ether, hexaethylene glycol (1,1,2,2,3,3-hexafluoropentyl) ether, octapropylene glycol di (1,1,2, , 2-tetrafluorobutyl) ether, hexapropylene glycol di (1,1,2,2,3,3-hexafluoropentyl) ether, and other fluoroethers; sodium perfluorododecyl sulfonate; 1,1,2, 2,8,8,9,9,10,10-decafluorododecane, 1,1,2,2,3,3-hexa Fluoroalkanes such as lurodecane; sodium fluoroalkylbenzenesulfonates; fluoroalkyloxyethylene ethers; fluoroalkylammonium iodides; fluoroalkylpolyoxyethylene ethers; perfluoroalkylpolyoxyethanols; perfluoroalkylalkoxylates And fluorine-based alkyl esters.

  Commercially available products of these fluorosurfactants include F-top EF301, 303, and 352 (manufactured by Shin-Akita Kasei Co., Ltd.), MegaFuck F171, 172, and 173 (manufactured by Dainippon Ink and Co., Ltd.), Florard FC430, 431 (manufactured by Sumitomo 3M Co., Ltd.), Asahi Guard AG710, Surflon S-382, SC-101, 102, 103, 104, 105, 106 (manufactured by Asahi Glass Co., Ltd.), FTX-218 (manufactured by Neos Co., Ltd.) Etc. can be mentioned.

  Examples of silicone-based surfactants are commercially available under the trade names SH200-100cs, SH28PA, SH30PA, ST89PA, SH190, SH8400 FLUID (manufactured by Toray Dow Corning Silicone), organosiloxane polymer KP341 (Shin-Etsu) Chemical Industry Co., Ltd.).

  [D] The amount of the surfactant used is preferably 0.01 parts by mass or more and 10 parts by mass or less, more preferably 0.05 parts by mass or more and 5 parts by mass with respect to 100 parts by mass of the component [A]. It is as follows. [D] By making the usage-amount of surfactant into 0.01 mass part or more and 10 mass parts or less, the applicability | paintability of a positive radiation sensitive composition can be optimized.

[E] Component: Other Silane Compound In addition to [A], [B] and [C] as essential components and [D] as an optional component, the positive radiation-sensitive composition of the present invention includes [E] and others. The silane compound may be included. The component [E] is a silane compound represented by the following formula (7) or (9). This [E] component is condensed together with the polysiloxane of the above-mentioned [A] component (preferably (a1) hydrolyzable silane compound and / or (a2) hydrolysis condensate of hydrolyzable silane compound), and cured product. Form.

（式（７）中、Ｒ^１０及びＲ^１２は、それぞれ独立に炭素数１〜４のアルキル基である。Ｒ^１１は、メチレン基、炭素数２〜６のアルキレン基、フェニレン基又は下記式（８）で示される基である。）

(In Formula (7), R ¹⁰ and R ¹² are each independently an alkyl group having 1 to 4 carbon atoms. R ¹¹ is a methylene group, an alkylene group having 2 to 6 carbon atoms, a phenylene group, or the following formula ( It is a group represented by 8).)

（式（８）中、ｑは１〜４の整数である。）

(In formula (8), q is an integer of 1 to 4.)

（式（９）中、Ｒ^１３、Ｒ^１４及びＲ^１５は、それぞれ独立に炭素数１〜４のアルキル基である。ｒは１〜６の整数である。）

(In Formula (9), R <^13> , R <^14> and R < ¹⁵ > are respectively independently a C1-C4 alkyl group. R is an integer of 1-6.)

Preferable specific examples of R ¹⁰ and R ^{12 in} the formula (7) include a methyl group, an ethyl group, a propyl group, and a butyl group. Among these alkyl groups, a methyl group and an ethyl group are more preferable. Preferable specific examples of R ^{11 in} the formula (7) include a methylene group, an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, and a phenylene group. Among these groups, a methylene group, an ethylene group, and a phenylene group are more preferable. When R ¹¹ is a group represented by the formula (8), q in the formula (8) is preferably 1 or 2. By using the silane compound of the above formula (7) having such a preferred structure as the component [E], the reactivity with the component [A] is improved.

Preferable specific examples of R ¹³ , R ¹⁴ and R ^{15 in} the formula (9) include methyl group, ethyl group, propyl group and butyl group from the viewpoint of reactivity with the component [A]. Among these alkyl groups, a methyl group is more preferable. Moreover, r in Formula (9) is preferably an integer of 1 to 3 from the viewpoint of reactivity with the [A] component and compatibility.

  When the said radiation sensitive composition contains an [E] component, the [E] component may be used individually by 1 type, or may be used in combination of 2 or more type. Of the silane compounds of the formulas (7) and (9), a silane compound having an isocyanuric ring represented by the formula (9) is more preferable. Thus, by using a silane compound having an isocyanuric ring having three trialkoxysilyl groups bonded in one molecule, a radiation-sensitive composition showing high radiation sensitivity can be obtained and formed from the composition. The degree of crosslinking of the interlayer insulating film can be improved. Furthermore, the radiation-sensitive composition containing such an isocyanuric ring-containing silane compound exhibits high resistance to melt flow in the heating step after development.

  Specific examples of the silane compounds represented by the formulas (7) and (9) include bistriethoxysilylethane, bis (trimethoxysilyl) methane, bis (triethoxysilyl) methane, and bis-1,2- (trimethoxysilyl). ) Ethane, bis-1,2- (triethoxysilyl) ethane, bis-1,6- (trimethoxysilyl) hexane, bis-1,6- (triethoxysilyl) hexane, bis-1,4- (tri Methoxysilyl) benzene, bis-1,4- (triethoxysilyl) benzene, 1,4-bis (trimethoxysilylmethyl) benzene, 1,4-bis (trimethoxysilylethyl) benzene, 1,4-bis ( Triethoxysilylmethyl) benzene, 1,4-bis (triethoxysilylethyl) benzene, tris- (3-trimethoxysilylmethyl) Isocyanurate, tris- (3-triethoxysilylmethyl) isocyanurate, tris- (3-trimethoxysilylethyl) isocyanurate, tris- (3-triethoxysilylethyl) isocyanurate, tris- (3-trimethoxysilyl) Propyl) isocyanurate, tris- (3-triethoxysilylpropyl) isocyanurate and the like. Of these, 1,4-bis (trimethoxysilylmethyl) benzene, bis (triethoxysilyl) ethane, tris- (3-tri-), from the viewpoint of improving radiation sensitivity and melt flow resistance in the heating step after development. Methoxysilylethyl) isocyanurate, tris- (3-trimethoxysilylpropyl) isocyanurate, tris- (3-triethoxysilylpropyl) isocyanurate are particularly preferred.

  When the said radiation sensitive composition contains an [E] component, Preferably the usage-amount of an [E] component is 5 mass parts or more and 70 mass parts or less with respect to 100 mass parts of [A] components, More preferably, 10 It is not less than 50 parts by mass. [E] By making the usage-amount of a component into 5 mass parts or more and 70 mass parts or less, the radiation sensitive composition excellent in the balance of radiation sensitivity and the melt flow resistance in the heating process after image development can be obtained. .

Other optional components The positive radiation-sensitive composition of the present invention comprises the above-mentioned [A] component, [B] component and [C] component as essential components, and [D] component and [E] component as optional components. In addition, other optional components such as a dehydrating agent for the [F] component can be contained as necessary within the range not impairing the intended effect.

  The dehydrating agent of the component [F] is defined as a substance that can convert water into a substance other than water by a chemical reaction or trap water by physical adsorption or inclusion. By arbitrarily including [F] dehydrating agent in the radiation-sensitive composition, moisture entering from the environment, condensation of [A] in the heating step after development of the radiation-sensitive composition, or [A] Moisture generated as a result of condensation of the component and the [E] component can be reduced. Therefore, by using the [F] dehydrating agent, it is possible to reduce the water content in the composition, and as a result, it is possible to improve the storage stability of the composition. Furthermore, it is considered that the condensation reactivity of the components [A] and [E] can be increased and the melt flow resistance of the radiation-sensitive composition can be improved. As such [F] dehydrating agent, at least one compound selected from the group consisting of carboxylic acid esters, acetals (including ketals), and carboxylic acid anhydrides can be preferably used.

  Preferable examples of the carboxylic acid ester include, for example, orthocarboxylic acid ester and carboxylic acid silyl ester. Specific examples of orthocarboxylic acid esters include methyl orthoformate, ethyl orthoformate, propyl orthoformate, butyl orthoformate, methyl orthoacetate, ethyl orthoacetate, propyl orthoacetate, butyl orthoacetate, methyl orthopropionate, orthopropionic acid And ethyl. Of these orthocarboxylic acid esters, orthoformate such as methyl orthoformate is particularly preferred. Specific examples of the carboxylic acid silyl ester include trimethylsilyl acetate, tributylsilyl acetate, trimethylsilyl formate, and trimethylsilyl oxalate.

  Preferable examples of acetals include a reaction product of a ketone and an alcohol, a reaction product of a ketone and a dialcohol, and a ketene silyl acetal. Specific examples of the reaction product of ketones and alcohol include dimethyl acetal, diethyl acetal, dipropyl acetal and the like.

  Preferable examples of the carboxylic anhydride include formic anhydride, acetic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, benzoic anhydride, benzoic anhydride, and the like. Among these carboxylic acid anhydrides, acetic anhydride and succinic anhydride are preferable from the viewpoint of dehydration effect.

  [F] The amount of dehydrating agent used is preferably 0.001 to 50 parts by mass, more preferably 0.01 to 30 parts by mass, with respect to 100 parts by mass of component [A]. It is not more than part by mass, particularly preferably not less than 0.05 part by mass and not more than 10 parts by mass. [G] The storage stability of the radiation-sensitive composition can be optimized by using the dehydrating agent in an amount of 0.001 to 50 parts by mass.

Radiation-sensitive composition The positive radiation-sensitive composition of the present invention comprises the above-mentioned [A] component polysiloxane, [B] component photoacid generator or photobase generator, and [C] component metal chelate. It is prepared by mixing a compound and optional components (surfactant of [D] component, other silane compound of [E] component, etc.). Moreover, unless the effect of this invention is impaired, you may coexist the polysiloxane prepared without using a metal chelate compound, and the polysiloxane prepared using a metal chelate compound. Usually, the radiation-sensitive composition is preferably prepared and used in a state dissolved or dispersed in an appropriate solvent. For example, the radiation-sensitive composition can be prepared by mixing the [A] component, the [B] component and the [C] component, and an optional component in a solvent in a predetermined ratio.

  As the solvent that can be used for the preparation of the positive radiation-sensitive composition, a solvent that uniformly dissolves or disperses each component and does not react with each component is preferably used. Examples of such solvents include alcohols, ethers, glycol ethers, ethylene glycol alkyl ether acetates, diethylene glycol alkyl ethers, propylene glycol monoalkyl ethers, propylene glycol alkyl ether acetates, propylene glycol alkyl ether acetates. , Aromatic hydrocarbons, ketones, esters and the like.

As these solvents,
Examples of alcohols include benzyl alcohol and diacetone alcohol;
Examples of ethers include dialkyl ethers such as tetrahydrofuran, diisopropyl ether, di n-butyl ether, di n-pentyl ether, diisopentyl ether, and di n-hexyl ether;
Examples of diethylene glycol alkyl ethers include ethylene glycol monomethyl ether and ethylene glycol monoethyl ether;
Examples of ethylene glycol alkyl ether acetates include methyl cellosolve acetate and ethyl cellosolve acetate;
As diethylene glycol alkyl ethers, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether and the like;
Examples of propylene glycol monoalkyl ethers include propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, propylene glycol butyl ether;
Examples of propylene glycol alkyl ether acetates include propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol butyl ether acetate, and the like;
Examples of propylene glycol alkyl ether acetates include propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate, and propylene glycol butyl ether propionate;

As aromatic hydrocarbons, toluene, xylene, etc .;
Examples of ketones include methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone, 4-hydroxy-4-methyl-2-pentanone, etc.
Examples of esters include methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, methyl hydroxyacetate, ethyl hydroxyacetate, butyl hydroxyacetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, Ethyl 2-hydroxy-2-methylpropionate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, protyl 3-hydroxypropionate, butyl 3-hydroxypropionate Methyl 2-hydroxy-3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, propyl ethoxyacetate, ethoxy Butyl acetate, methyl propoxyacetate, ethyl propoxyacetate, propylpropoxyacetate, butyl propoxyacetate, methyl butoxyacetate, ethyl butoxyacetate, propylbutoxyacetate, butylbutoxyacetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2 -Propyl methoxypropionate, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, 2- Ethyl butoxypropionate, propyl 2-butoxypropionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-methoxypropionate prop Butyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate Propyl 3-propoxypropionate, butyl 3-propoxypropionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate, butyl 3-butoxypropionate, etc. .

  Among these solvents, ethers such as dialkyl ethers, ethylene glycol alkyls, etc. from the viewpoint of excellent solubility or dispersibility, non-reactivity with each component, and ease of film formation. Ethers, ethylene glycol alkyl ether acetates, propylene glycol monoalkyl ethers, propylene glycol alkyl ether acetates, ketones and esters are preferred, and in particular, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, methyl cellosolve acetate, ethyl cellosolve acetate , Propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate , Cyclohexanone, propyl acetate, isopropyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl lactate, ethyl lactate, lactic acid Propyl, butyl lactate, methyl 2-methoxypropionate and ethyl 2-methoxypropionate are preferred. These solvents can be used alone or in admixture of two or more.

  In addition to the solvents described above, benzyl ethyl ether, dihexyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl acetate, ethyl benzoate, diethyl oxalate, A high boiling point solvent such as diethyl maleate, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate or carbitol acetate can also be used in combination.

  When preparing the radiation-sensitive composition as a solution or dispersion, the proportion of components other than the solvent in the solution (that is, the total amount of [A], [B] and [C] components and other optional components) is Depending on the purpose of use and desired film thickness, etc., it can be arbitrarily set, but preferably 5% by mass or more and 50% by mass or less, more preferably 10% by mass or more and 40% by mass or less, and further preferably 15% by mass. It is 35 mass% or less.

Formation of Interlayer Insulating Film Next, a method for forming a cured film of the interlayer insulating film on the substrate using the radiation sensitive composition will be described. The method includes the following steps.
(1) The process of forming the coating film of the said positive type radiation sensitive composition on a board | substrate,
(2) A step of irradiating at least a part of the coating film formed in step (1),
(3) A step of developing the coating film irradiated with radiation in the step (2), and (4) A step of heating the coating film developed in the step (3).

(1) Step of forming a coating film of a radiation sensitive composition on a substrate In the above step (1), after applying the solution or dispersion of the positive radiation sensitive composition of the present invention on a substrate, preferably The applied surface is heated (prebaked) to remove the solvent and form a coating film. Examples of the substrate that can be used include glass, quartz, silicon, and resin. Specific examples of the resin include polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, polyimide, a ring-opening polymer of cyclic olefin, and hydrogenated products thereof.

  The coating method of the composition solution or dispersion is not particularly limited, and an appropriate method such as a spray method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, a bar coating method, or the like is employed. be able to. Among these coating methods, a spin coating method or a slit die coating method is particularly preferable. Prebaking conditions vary depending on the type of each component, the blending ratio, and the like, but can be preferably about 70 to 120 ° C. for about 1 to 10 minutes.

(2) Step of irradiating at least a part of the coating film In the step (2), at least a part of the formed coating film is exposed. In this case, when exposing to a part of coating film, it exposes normally through the photomask which has a predetermined pattern. As radiation used for exposure, visible light, ultraviolet rays, far ultraviolet rays, electron beams, X-rays, and the like can be used, for example. Among these radiations, radiation having a wavelength in the range of 190 to 450 nm is preferable, and radiation containing ultraviolet light of 365 nm is particularly preferable.

The exposure amount in this step is preferably 100 to 10,000 J / m ² , more preferably 500 to 6 as a value obtained by measuring the intensity of radiation at a wavelength of 365 nm with an illuminometer (OAI model 356, manufactured by OAI Optical Associates Inc.). 1,000 J / m ² .

(3) Development process In the said process (3), an unnecessary part (radiation irradiation part) is removed by developing the coating film after exposure, and a predetermined pattern is formed. The developer used in the development step is preferably an aqueous solution of an alkali (basic compound). Examples of alkalis include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and ammonia; quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide. be able to.

  In addition, an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant can be added to such an alkaline aqueous solution. The concentration of the alkali in the alkaline aqueous solution is preferably from 0.1% by mass to 5% by mass from the viewpoint of obtaining appropriate developability. As a developing method, for example, an appropriate method such as a liquid filling method, a dipping method, a rocking dipping method, a shower method, or the like can be used. The development time varies depending on the composition of the radiation-sensitive composition, but is preferably about 10 to 180 seconds. Following such development processing, for example, after washing with running water for 30 to 90 seconds, a desired pattern can be formed by, for example, air drying with compressed air or compressed nitrogen.

(4) Heating step In the above step (4), the patterned thin film is heated at a relatively high temperature using a heating device such as a hot plate or an oven, whereby the above [A] component alone or the [A] component and The condensation reaction of the component [E] can be promoted and a cured product can be obtained with certainty. The heating temperature in the said process is 120-250 degreeC, for example. Although heating time changes with kinds of heating apparatus, for example, when performing a heating process on a hotplate, it can be set to 30 to 90 minutes when performing a heating process in an oven. The step baking method etc. which perform a heating process 2 times or more can also be used. In this way, a patterned thin film corresponding to the target interlayer insulating film can be formed on the surface of the substrate.

Interlayer Insulating Film The film thickness of the interlayer insulating film thus formed is preferably 0.1 to 8 μm, more preferably 0.1 to 6 μm, and further preferably 0.1 to 4 μm.

  The interlayer insulating film formed from the positive-type radiation-sensitive composition of the present invention generally has surface hardness, refractive index, heat resistance, transparency and low dielectric property, as will be apparent from the following examples. Satisfying required characteristics in a well-balanced manner. Therefore, the interlayer insulating film is suitably used for liquid crystal display elements and organic EL elements.

  The present invention will be described more specifically with reference to synthesis examples and examples. However, the present invention is not limited to the following examples.

The number average molecular weight (Mn) and the weight average molecular weight (Mw) of the hydrolysis condensate of the hydrolyzable silane compound obtained from each of the following synthesis examples were measured by gel permeation chromatography (GPC) according to the following specifications.
Apparatus: GPC-101 (made by Showa Denko KK)
Column: GPC-KF-801, GPC-KF-802, GPC-KF-803 and GPC-KF-804 (manufactured by Showa Denko KK) Mobile phase: Tetrahydrofuran

[A] Synthesis Example of Polysiloxane [Synthesis Example 1]
After charging 25 parts by mass of propylene glycol monomethyl ether into a vessel equipped with a stirrer, 30 parts by mass of methyltrimethoxysilane, 23 parts by mass of phenyltrimethoxysilane, and di (i-propoxy) monoethylacetoacetate aluminum 2 .5 parts by mass was charged and heated until the solution temperature reached 60 ° C. After the solution temperature reached 60 ° C., 18 parts by mass of ion-exchanged water was charged, heated to 75 ° C. and held for 3 hours. Next, 14 parts by mass of distilled acetylacetone was added. Furthermore, the solution temperature was set to 40 ° C., and evaporation was performed while maintaining the temperature to remove ion-exchanged water and methanol generated by hydrolysis condensation, and the solution was concentrated so that the solid content concentration was about 40% by mass. The hydrolysis condensate (A-1) was obtained by the above procedure. The solid content concentration of the hydrolysis condensate (A-1) is 40.5% by mass, the number average molecular weight (Mn) of the obtained hydrolysis condensate is 2,000, and the molecular weight distribution (Mw / Mn) is 1. .8.

[Synthesis Example 2]
After charging 25 parts by mass of propylene glycol monomethyl ether into a vessel equipped with a stirrer, 18 parts by mass of methyltrimethoxysilane, 15 parts by mass of tetraethoxysilane, 20 parts by mass of phenyltrimethoxysilane, and di (i-propoxy) -2.5 parts by mass of monoethyl acetoacetate aluminum was charged and heated until the solution temperature reached 60 ° C. After the solution temperature reached 60 ° C., 18 parts by mass of ion-exchanged water was charged, heated to 75 ° C. and held for 3 hours. Next, 14 parts by mass of distilled acetylacetone was added. Furthermore, the solution temperature was set to 40 ° C., and evaporation was performed while maintaining the temperature to remove ion-exchanged water and methanol generated by hydrolysis condensation, and the solution was concentrated so that the solid content concentration was about 40% by mass. The hydrolysis condensate (A-2) was obtained by the above procedure. The solid content concentration of the hydrolysis condensate (A-2) is 40.4% by mass, the number average molecular weight (Mn) of the obtained hydrolysis condensate is 1,600, and the molecular weight distribution (Mw / Mn) is 2. 0.0.

[Synthesis Example 3]
In a container equipped with a stirrer, 25 parts by mass of propylene glycol monomethyl ether was charged, followed by 22 parts by mass of methyltrimethoxysilane, 12 parts by mass of 3-glycidoxypropyltrimethoxysilane, 20 parts by mass of phenyltrimethoxysilane, And 2.5 mass parts of di (i-propoxy) monoethyl acetoacetate aluminum was prepared, and it heated until the solution temperature became 60 degreeC. After the solution temperature reached 60 ° C., 18 parts by mass of ion-exchanged water was charged, heated to 75 ° C. and held for 3 hours. Next, 14 parts by mass of distilled acetylacetone was added. Furthermore, the solution temperature was set to 40 ° C., and evaporation was performed while maintaining the temperature to remove ion-exchanged water and methanol generated by hydrolysis condensation, and the solution was concentrated so that the solid content concentration was about 40% by mass. The hydrolysis condensate (A-3) was obtained by the above procedure. The solid content concentration of the hydrolysis condensate (A-3) is 39.8% by mass, the number average molecular weight (Mn) of the obtained hydrolysis condensate is 1,800, and the molecular weight distribution (Mw / Mn) is 2. 0.0.

[Synthesis Example 4]
After charging 25 parts by mass of propylene glycol monomethyl ether in a container equipped with a stirrer, 22 parts by mass of methyltrimethoxysilane, 12 parts by mass of 3-methacryloxypropyltrimethoxysilane, 20 parts by mass of phenyltrimethoxysilane, and di 2.5 parts by mass of (i-propoxy) .monoethyl acetoacetate aluminum was charged and heated until the solution temperature reached 60 ° C. After the solution temperature reached 60 ° C., 18 parts by mass of ion-exchanged water was charged, heated to 75 ° C. and held for 3 hours. Next, 14 parts by mass of distilled acetylacetone was added. Furthermore, the solution temperature was set to 40 ° C., and evaporation was performed while maintaining the temperature to remove ion-exchanged water and methanol generated by hydrolysis condensation, and the solution was concentrated so that the solid content concentration was about 40% by mass. The hydrolysis condensate (A-4) was obtained by the above procedure. The solid content concentration of the hydrolysis condensate (A-4) is 40.3% by mass, the number average molecular weight (Mn) of the obtained hydrolysis condensate is 2,200, and the molecular weight distribution (Mw / Mn) is 2. 0.0.

[Synthesis Example 5]
After charging 25 parts by mass of propylene glycol monomethyl ether into a vessel equipped with a stirrer, 30 parts by mass of methyltrimethoxysilane, 23 parts by mass of phenyltrimethoxysilane, and di-i-propoxy bisethylacetoacetate titanium2. 5 parts by mass were charged and heated until the solution temperature reached 60 ° C. After the solution temperature reached 60 ° C., 18 parts by mass of ion-exchanged water was charged, heated to 75 ° C. and held for 3 hours. Next, 14 parts by mass of distilled acetylacetone was added. Furthermore, the solution temperature was set to 40 ° C., and evaporation was performed while maintaining the temperature to remove ion-exchanged water and methanol generated by hydrolysis condensation, and the solution was concentrated so that the solid content concentration was about 40% by mass. The hydrolysis condensate (A-5) was obtained by the above procedure. The solid content concentration of the hydrolysis condensate (A-5) is 40.5% by mass, the number average molecular weight (Mn) of the obtained hydrolysis condensate is 2,500, and the molecular weight distribution (Mw / Mn) is 2.3.

[Synthesis Example 6]
After charging 25 parts by mass of propylene glycol monomethyl ether into a vessel equipped with a stirrer, 30 parts by mass of methyltrimethoxysilane, 23 parts by mass of phenyltrimethoxysilane, and di-n-butoxy bis (ethylacetoacetate) zirconium 2.5 parts by mass were heated until the solution temperature reached 60 ° C. After the solution temperature reached 60 ° C., 18 parts by mass of ion-exchanged water was charged, heated to 75 ° C. and held for 3 hours. Next, 14 parts by mass of distilled acetylacetone was added. Furthermore, the solution temperature was set to 40 ° C., and evaporation was performed while maintaining the temperature to remove ion-exchanged water and methanol generated by hydrolysis condensation, and the solution was concentrated so that the solid content concentration was about 40% by mass. The hydrolysis condensate (A-6) was obtained by the above procedure. The solid content concentration of the hydrolysis condensate (A-6) is 40.5% by mass, the number average molecular weight (Mn) of the obtained hydrolysis condensate is 2,500, and the molecular weight distribution (Mw / Mn) is 2. .4.

[Comparative Synthesis Example 1]
In a vessel equipped with a stirrer, 25 parts by mass of propylene glycol monomethyl ether was charged, followed by 17 parts by mass of methyltrimethoxysilane, 15 parts by mass of tetraethoxysilane, 12 parts by mass of 3-glycidoxypropyltrimethoxysilane, and phenyl. By adding 15 parts by mass of trimethoxysilane and 1 part by mass of oxalic acid, a hydrolysis condensate (a-1) was obtained in the same manner as in Synthesis Example 1. The solid content concentration of the hydrolysis condensate (a-1) is 40.9% by mass, the number average molecular weight (Mn) of the obtained hydrolysis condensate is 1,700, and the molecular weight distribution (Mw / Mn) is 2. .1.

[Comparative Synthesis Example 2]
In a vessel equipped with a stirrer, 25 parts by mass of propylene glycol monomethyl ether was charged, followed by 17 parts by mass of methyltrimethoxysilane, 15 parts by mass of tetraethoxysilane, 12 parts by mass of 3-glycidoxypropyltrimethoxysilane, and phenyl. By adding 15 parts by mass of trimethoxysilane and 2 parts by mass of triethylamine, a hydrolysis condensate (a-1) was obtained in the same manner as in Synthesis Example 1. The solid content concentration of the hydrolysis condensate (a-1) is 40.9% by mass, the number average molecular weight (Mn) of the obtained hydrolysis condensate is 4,000, and the molecular weight distribution (Mw / Mn) is 2. .3.

Preparation of radiation sensitive composition [Example 1]
In the solution containing the hydrolysis condensate (A-1) obtained in Synthesis Example 1 (the amount corresponding to 100 parts by mass (solid content) of the hydrolysis condensate (A-1)), (B) -1) 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol (1.0 mol) and 1,2-naphthoquinonediazide-5 Add 10 parts by weight of a condensate of sulfonic acid chloride (2.0 mol), 0.1 parts by weight of silicone surfactant (“SH 8400 FLUID” manufactured by Toray Dow Corning Co., Ltd.) as [D] component, Propylene glycol monomethyl ether was added so that the partial concentration was 25% by mass to prepare a radiation sensitive composition.

[Examples 2 to 10 and Comparative Examples 1 to 3]
A radiation-sensitive composition was prepared in the same manner as in Example 1 except that the type and amount of each component were as shown in Table 1.

Evaluation of Physical Properties Using the radiation-sensitive composition prepared as described above, various characteristics as the composition, interlayer insulating film and liquid crystal cell were evaluated as follows.

[Evaluation of radiation sensitivity of radiation-sensitive composition]
For Examples 1 to 9 and Comparative Examples 1 to 3 on a silicon substrate, each composition was applied using a spinner, and then prebaked on a hot plate at 100 ° C. for 2 minutes to obtain a film thickness of 4.0 μm. The coating film was formed. For Example 10, after applying the composition using a slit die coater, the pressure was reduced to 0.5 Torr at room temperature over 15 seconds, the solvent was removed, and then prebaked on a hot plate at 100 ° C. for 2 minutes. As a result, a coating film having a film thickness of 4.0 μm was formed. The obtained coating film is exposed through a mask having a 6.0 μm line-and-space (one-to-one) pattern using a PLA-501F exposure machine (extra-high pressure mercury lamp) manufactured by Canon Inc. After performing exposure while changing the time, the film was developed with a 2.38 mass% tetramethylammonium hydroxide aqueous solution at 25 ° C. for 80 seconds by a puddle method. Next, the substrate was washed with running ultrapure water for 1 minute and then dried to form a pattern on the silicon substrate. At this time, the minimum exposure amount necessary for the space line width (bottom) to be 6.0 μm was measured. This minimum exposure amount is shown in Table 1 as radiation sensitivity. When the minimum exposure amount is 600 (J / m ² ) or less, it can be said that the sensitivity is good.

[Evaluation of Melt Flow Resistance of Pattern Shape in Heating Process of Radiation Sensitive Composition]
As in the above “Evaluation of Radiation Sensitivity”, a pattern with a space line width (bottom) of 6.0 μm was formed, and the resulting pattern was subjected to a PLA-501F exposure machine (extra-high pressure mercury lamp) manufactured by Canon Inc. Then, after exposing so that the integrated irradiation amount becomes 3,000 J / m ² , it was post-baked by heating at 220 ° C. for 1 hour in a clean oven. Furthermore, it heated at 230 degreeC for 10 minute (s), the pattern was made to melt flow, and the dimension of the pattern bottom part was measured with SEM (scanning electron microscope). At this time, when the dimension of the pattern bottom is less than 6.35 μm, it can be said that the melt flow resistance is good. On the other hand, when the dimension of the pattern bottom is 6.35 μm or more, it can be said that the melt flow resistance is poor. Table 1 shows the results of dimensional measurement at the bottom of the pattern as an evaluation of melt flow resistance.

[Evaluation of surface hardness of interlayer insulation film]
A coating film was formed on the silicon substrate in the same manner except that the exposure was not performed in the above "Evaluation of radiation sensitivity". Thereafter, the obtained coating film was exposed to a cumulative irradiation amount of 3,000 J / m ² by using a PLA-501F exposure machine (extra-high pressure mercury lamp) manufactured by Canon Inc. A cured film was obtained by heating at 220 ° C. for 1 hour in a clean oven. The cured film was scratched by scraping the pencil core with a paper file in order of increasing hardness from pencil hardness, and the hardest pencil hardness that the film could not be removed was defined as the surface hardness (pencil hardness) of the film.

[Evaluation of heat resistance of interlayer insulation film]
A cured film was formed on the silicon substrate in the same manner as in the above “Evaluation of surface hardness”, and the thickness (T2) of the obtained cured film was measured. Next, the silicon substrate on which the cured film is formed is additionally baked in a clean oven at 240 ° C. for 1 hour, and then the thickness (t2) of the cured film is measured, and the rate of change in film thickness due to the additional baking {| t2−T2 | / T2} × 100 [%] was calculated. The results of the film thickness change rate are shown in Table 1 as heat resistance evaluation. When this value is less than 3%, it can be said that the heat resistance is good.

[Evaluation of light transmittance (transparency) of interlayer insulation film]
In the above “Evaluation of surface hardness”, a cured film was formed on a glass substrate in the same manner except that a glass substrate “Corning 7059” (manufactured by Corning) was used instead of the silicon substrate. The light transmittance of the glass substrate on which this cured film was formed was measured at a wavelength in the range of 400 to 800 nm using a spectrophotometer “150-20 type double beam” (manufactured by Hitachi, Ltd.). Table 1 shows the values of the minimum light transmittance at that time. When the minimum light transmittance is 95% or more, it can be said that the light transmittance is good.

[Evaluation of relative dielectric constant (low dielectric constant) of interlayer insulating film]
For Examples 1 to 9 and Comparative Examples 1 to 3 on a polished SUS304 substrate, each composition was applied using a spinner and then pre-baked on a hot plate at 100 ° C. for 2 minutes. A 3.0 μm coating film was formed. For Example 10, after applying the composition using a slit die coater, the solvent was removed by reducing the pressure to 0.5 Torr over 15 seconds at room temperature, and then pre-baking on a hot plate at 100 ° C. for 2 minutes. As a result, a coating film having a thickness of 3.0 μm was formed. The resulting coating film was exposed to a cumulative irradiation amount of 3,000 J / m ² using a Canon-made PLA-501F exposure machine (extra-high pressure mercury lamp), and then in a clean oven. A cured film was formed on the substrate by heating at 220 ° C. for 1 hour. On this cured film, a Pt / Pd electrode pattern was formed by vapor deposition to prepare a sample for measuring relative permittivity. About the obtained sample, the relative dielectric constant in the frequency of 10 kHz was measured by CV method using the HP16451B electrode and HP4284A precision LCR meter by Yokogawa and Hewlett-Packard Co., Ltd. The results are shown in Table 1. In the evaluation of the relative dielectric constant, since the patterning of the film to be formed is unnecessary, the development process was omitted, and only the coating film forming process, the radiation irradiation process, and the heating process were performed for evaluation.

[Evaluation of storage stability of radiation-sensitive composition]
Using a viscometer (“ELD viscometer” manufactured by Tokyo Keiki Co., Ltd.), the viscosity of the radiation-sensitive composition at 25 ° C. was measured. Then, the viscosity at 25 ° C. was measured every 24 hours while the composition was allowed to stand at 25 ° C. The number of days required to increase the viscosity by 5% based on the viscosity of the radiation-sensitive composition immediately after preparation was determined, and this number of days is shown in Table 1 as an evaluation of storage stability.

In Table 1, the abbreviations of [B1-1] quinonediazide, [B1-2] other photoacid generator, [B2] photobase generator, and [D] surfactant respectively represent the following.
B1-1-1: 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol (1.0 mol) and 1,2-naphthoquinonediazide Condensate B1-1-2 of -5-sulfonic acid chloride (2.0 mol): 1,1,1-tri (p-hydroxyphenyl) ethane (1.0 mol) and 1,2-naphthoquinonediazide-5 -Condensate B1-2-1 of sulfonic acid chloride (2.0 mol) N- (trifluoromethylsulfonyloxy) naphthyl dicarboxylimide B1-2-2: benzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate B2 : 2-nitrobenzylcyclohexyl carbamate D-1: Silicone surfactant (“SH 8400 manufactured by Toray Dow Corning Co., Ltd.) LUID "

  As is clear from the results of Table 1, the radiation-sensitive compositions of Examples 1 to 10 containing the components [A], [B] and [C] are those of Comparative Examples 1 to 3 which do not use the [A] component. Compared to radiation-sensitive compositions, it has excellent storage stability and radiation sensitivity, as well as extremely high resistance to melt flow in the heating process after development, surface hardness, refractive index, heat resistance, transparency and low It was found that an interlayer insulating film satisfying all of the general required characteristics of dielectric properties can be formed.

  As described above, the positive radiation-sensitive composition of the present invention has excellent melt flow resistance in the heating step in addition to storage stability and radiation sensitivity, and has general heat resistance and transparency. An interlayer insulating film that satisfies all the required characteristics can be formed. Therefore, the radiation sensitive composition is suitably used for forming an interlayer insulating film for liquid crystal display elements and organic EL elements.

Claims (8)

[A] polysiloxane,
[B] A positive radiation sensitive composition containing a photoacid generator or a photobase generator, and [C] a metal chelate compound. [A] The polysiloxane is a polysiloxane obtained by hydrolytic condensation of a hydrolyzable silane compound in the presence of a [C] metal chelate compound,
[B] The positive radiation-sensitive composition according to claim 1, comprising quinonediazide as a photoacid generator. The positive radiation sensitive composition according to claim 1 or 2, wherein the metal chelate compound is a compound represented by the following formula (1).

(In the formula (1), R ¹ is a chelating agent, M is a metal atom, R ² is an alkyl group having 2 to 5 carbon atoms or an aryl group having 6 to 20 carbon atoms. And p is an integer of ^{1 to} j. When R ¹ and R ² are plural, they may be the same or different.   The positive radiation sensitive composition according to claim 3, wherein the metal M in the formula (1) is at least one selected from the group consisting of aluminum, titanium, and zirconium. The hydrolyzable silane compound is at least one selected from the group consisting of (a1) a silane compound represented by the following formula (2) and (a2) a silane compound represented by the following formula (3). Item 5. The positive radiation-sensitive composition according to any one of items 1 to 4.

(In Formula (2), X ¹ is an epoxy group, a vinyl group, an allyl group, a (meth) acryloyloxy group, a styryl group, or a vinylbenzyloxy group. Y ¹ is a single bond, a methylene group, or a carbon number of 2 R ³ is an alkoxy group having 1 to 6 carbon atoms or an acyloxy group having 2 to 6 carbon atoms, and R ⁴ is an alkyl group having 1 to 6 carbon atoms or 6 to 12 carbon atoms. A and b are each an integer of 1 to 3, c is an integer of 0 to 2, and a relationship of a + b + c = 4 is satisfied.)

(In Formula (3), R ⁵ is a substituted or unsubstituted alkoxy group having 1 to 6 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 18 carbon atoms, or an acyloxy group having 2 to 6 carbon atoms. R ⁶ is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms or a substituted or unsubstituted aryl group having 6 to 18 carbon atoms, g is an integer of 1 to 4, and h is 0 An integer of ˜3 and satisfies the relationship g + h = 4.)   The positive radiation-sensitive composition according to any one of claims 1 to 5, which is used for forming an interlayer insulating film. (1) The process of forming the coating film of the positive radiation sensitive composition of Claim 6 on a board | substrate,
(2) A step of irradiating at least a part of the coating film formed in step (1),
(3) A method for forming an interlayer insulating film, comprising: a step of developing the coating film irradiated with radiation in step (2); and (4) a step of heating the coating film developed in step (3).   An interlayer insulating film formed from the positive radiation-sensitive composition according to claim 6.