JP2008277771A - Method for film formation, structure having insulating film and its manufacturing method and electronic component - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for forming an even film on at least the inner wall face of a hole, a structure having an insulating film using the method, and its manufacturing method and an electronic component. <P>SOLUTION: The method for film formation comprises a solvent coating step of coating a solvent on a substrate having the hole having an opening area of 25 to 10,000 μm<SP>2</SP>and a depth of 10 to 200 μm, a resin composition coating step of coating a resin composition to the substrate so as to come into contact with the solvent in the hole, the resin composition containing the resin component and the solvent, the ratio (V<SB>1</SB>/V<SB>2</SB>) of viscosity V<SB>1</SB>(mPa s) in the shearing speed 6 rpm to the viscosity V<SB>2</SB>(mPa s) in the shearing speed 60 rpm is 1.1 or higher, and a drying step of drying the coating film. Further, the film containing the resin component is formed on at least the inner wall face of the inner wall face and bottom face in the hole. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a film forming method, a structure having an insulating film, a manufacturing method thereof, and an electronic component. More specifically, the present invention relates to a method for forming a uniform film on at least an inner wall surface of a bottomed hole provided in a silicon substrate or the like, a structure having an insulating film using this method, a method for manufacturing the structure, and an electronic component.

Conventionally, an insulating substrate having through holes, via inner wall surfaces, and metal conductor layers formed on both sides of the substrate has a viscosity of 20 to 200 mPa · s, a surface tension of 30 mN / m or less, and a thixotropic value of 1. A method is disclosed in which an insulating film is formed at least on the inner wall surface of a through-hole by immersing it in a 0.0 to 3.0 photosensitive resist solution and pulling it up (see Patent Document 1). A through electrode can be formed by filling the through hole with metallic copper or the like.
Non-Patent Document 1 discloses a silicon chip penetrating vertically and a penetrating electrode having a through hole filled with metallic copper. The manufacturing method includes a step of forming a deep hole in a silicon wafer by dry etching, a step of forming a SiO ₂ film on the inner wall of the hole by a CVD method, a step of filling the inside of the hole with metal copper by electrolytic copper plating, and from the back side of the wafer. A polishing process and the like are provided.

JP-A-2005-158907 Manabu Tomisaka “Denso Technical Review” Vol. 6 No. 2 (2001) p. 78-84

According to the photosensitive resist solution disclosed in Patent Document 1, it is possible to form a film on the inner wall surface for through-holes, but not through-holes, but micro-holes (hereinafter, When a film is formed on the inner wall surface of “holes”), there is a problem that sedimentation of the composition occurs and the holes are filled with the composition.
An object of the present invention is to provide a method for forming a uniform film on at least an inner wall surface of a hole, a structure having an insulating film, a method for manufacturing the same, and an electronic component using this method.

As a result of earnest research to solve the above problems, the present inventors have used a method of forming a uniform film on at least the inner wall surface of the hole using a composition having excellent film forming properties, and this method has been used. The inventors have found a structure having an insulating film, a method for manufacturing the structure, and an electronic component.
The present invention is shown below.
1. A substrate having a hole with an opening area of 25 to 10,000 μm ² and a depth of 10 to 200 μm, a solvent application step for applying a solvent, a resin component and a solvent, and a shear rate of 6 rpm The resin composition having a ratio (V ₁ / V ₂ ) of the viscosity V ₁ (mPa · s) to the viscosity V ₂ (mPa · s) at a shear rate of 60 rpm of 1.1 or more is the above-mentioned resin composition. A resin composition coating step for coating the substrate so as to come into contact with the solvent in the hole, and a drying step for drying the coating film, and at least the inner wall surface of the inner wall surface and the bottom surface of the hole portion And forming a film containing the resin component on the surface.

2. 2. The film forming method according to 1 above, wherein the film is formed on both the inner wall surface and the bottom surface of the hole.
3. 3. The film forming method according to 1 or 2 above, wherein the solid content concentration of the resin composition is in the range of 5 to 80% by mass.
4). The viscosity _V 1 is film-forming method according to any one of the above 1 to 3 in the range of 10 to 10,000 mPa · s.
5. In the resin composition, the ratio (V ₃ / V ₄ ) of the viscosity V ₃ (mPa · s) at a shear rate of 1.5 rpm and the viscosity V ₄ (mPa · s) at a shear rate of 600 rpm is 2.0 or more. 5. The method for forming a film according to any one of 1 to 4 above.
6). 6. The method for forming a film according to any one of 1 to 5, wherein the resin composition further contains metal oxide particles.
7). 7. The film forming method according to any one of 1 to 6, wherein the resin composition further contains particles made of a crosslinked polymer.

8). A resin composition used for the film forming method according to any one of 1 to 5 above,
A resin composition comprising an alkali-soluble resin, silica that has been hydrophobized and has an average particle diameter of 1 to 100 nm, a solvent, and a crosslinking agent.
9. Furthermore, it contains a compound having a quinonediazide group, and the content of the silica is more than 20% by mass and not more than 60% by mass when the solid content of the composition is 100% by mass. 9. The resin composition as described in 8 above.

10. The coating film formed on the surface of the substrate and the coating film formed on the bottom surface of the hole portion of the substrate obtained by the method according to any one of 1 to 7 above are removed, and the inside of the hole portion is removed. An insulating film comprising: a surface bottom side film removing step for leaving a film formed on the wall surface; and a heat curing step for heating the film remaining on the inner wall surface of the hole. Manufacturing method of structure.
11. The insulating film containing the cured product of the resin component obtained by heating the film formed on the entire surface of the substrate including the inner wall surface and the bottom surface of the hole, obtained by the method according to any one of 1 to 7 above. A heat curing step for forming a film, an insulating film formed on the surface of the substrate, and an insulating film formed on the bottom surface of the hole portion of the substrate are removed to form an inner wall surface of the hole portion. A method for producing a structure having an insulating film, comprising: a step of removing an insulating film on the front and bottom side to leave the insulating film.
12 The structure having the insulating film according to 10 or 11, further comprising a polishing step in which the substrate is polished from a surface having no hole in the structure having the insulating film, and the hole is used as a through hole. Production method.
13. 13. A structure having an insulating film obtained by the method according to any one of 10 to 12 above.
14 A member comprising a structure having an insulating film obtained by the method according to any one of 10 to 12 above and an electrode portion in which a conductive material is filled in at least a through hole of the structure. And electronic parts.

According to the film forming method of the present invention, a uniform film can be formed on the inner wall surface of the hole of the substrate by using a resin composition having specific thixotropic properties. In addition, a uniform film can be formed on the bottom surface of the hole.
According to the method for manufacturing a structure having an insulating film of the present invention, a uniform insulating film can be efficiently formed on the inner wall of the through hole. Therefore, the obtained structure can easily form the through electrode by filling the through hole with the insulating film as the inner wall with metal copper or the like. It is also suitable for modifying porous membranes.
The electronic component of the present invention is suitable for mounting a semiconductor device such as a CPU, a memory, and an image sensor.

  Hereinafter, the present invention will be described in detail. In the present specification, “(meth) acryl” means acryl and methacryl, and “(meth) acrylate” means acrylate and methacrylate.

1. Film Forming Method The film forming method of the present invention comprises a solvent coating step of applying a solvent to a substrate having a hole having an opening area of 25 to 10,000 μm ² and a depth of 10 to 200 μm, and a resin. containing component and a solvent, and the viscosity _V 1 at a shear rate 6rpm (mPa · s), the ratio of the viscosity _V 2 (mPa · s) at a shear rate of 60rpm _(V 1 / V ₂₎ is 1.1 or more A resin composition coating step for applying the resin composition to the substrate so that the resin composition comes into contact with the solvent in the hole, and a drying step for drying the coating film. A film containing the resin component is formed on at least the inner wall surface of the inner wall surface and the bottom surface.

Examples of the constituent material of the substrate used in the film forming method of the present invention include silicon, various metals, various metal sputtered films, alumina, glass epoxy, paper phenol, and glass. The thickness of this substrate is usually 100 to 1,000 μm.
As shown in the cross-sectional view of FIG. 1, the substrate 11 is formed on at least one surface of the substrate 11 in the vertical direction from the surface to the inside, and has an opening area of 25 to 10,000 μm ² , preferably 100. It has a hole 111 having a thickness of 10 to 10,000 μm ² , more preferably 250 to 7,000 μm ² and a depth of 10 to 200 μm, preferably 30 to 120 μm, more preferably 50 to 100 μm.
The shape and number of the holes are not particularly limited. Further, the shape of the hole can be a columnar shape (see FIG. 1A), a forward tapered shape (see FIG. 1B), a reverse tapered shape (see FIG. 1C), etc. The cross-sectional shape can also be circular, elliptical, polygonal, or the like. In addition, when there are a plurality of holes, the size and depth of each hole may be different, and the interval (length) between adjacent holes is not particularly limited.

The hole shape is preferably a quadrangular (square or rectangular) columnar shape or a forward tapered shape.
When the hole has a columnar shape with a quadrangular cross section, the aspect ratio (ratio of the depth of the hole and the length of one side of the bottom of the hole) in the quadrangle of the vertical cross section is preferably 1 to 10, More preferably, it is 1-5, More preferably, it is 1-4.

  The film forming method of the present invention will be described with reference to FIG. 2. First, a solvent is applied to the substrate 11 by a solvent application process. At this time, the solvent 113 is usually filled in the hole 111 provided in the substrate 11 as shown in FIG. 2B, and the surface of the substrate 11 may be wetted uniformly. . Thereafter, the resin composition is applied to the substrate 11 by the resin composition application step to form the coating film 115 (FIG. 2C). At this time, in the hole part 111, the solvent by the said solvent application | coating process and the resin composition by a resin composition application | coating process are mixed. Next, a film formed on the entire surface of the substrate 11 including the inner surface of the hole 111 by removing the solvent in the hole 111 and the solvent in the resin composition contained in the hole 111 by a drying process. A coated substrate 1 having 119 is obtained.

Hereinafter, each step will be described.
The solvent application step is a step of applying a solvent to the substrate. Solvents used include ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate; propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, etc. Propylene glycol monoalkyl ethers; propylene glycol dialkyl ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether Propylene glycol monoalkyl ether acetates such as cetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate; cellosolves such as ethyl cellosolve and butyl cellosolve; carbitols such as butyl carbitol; methyl lactate, ethyl lactate, and lactate n Lactic acid esters such as propyl and isopropyl lactate; ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, isopropyl propionate, n-butyl propionate, propionic acid Aliphatic carboxylic acid esters such as isobutyl; methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxypropionate Other esters such as ethyl onate, methyl pyruvate and ethyl pyruvate; aromatic hydrocarbons such as toluene and xylene; ketones such as 2-heptanone, 3-heptanone, 4-heptanone and cyclohexanone; N-dimethyl Examples include amides such as formamide, N-methylacetamide, N, N-dimethylacetamide, and N-methylpyrrolidone; and lactones such as γ-butyrolacun. These can be used alone or in combination of two or more.

In the solvent application step, the method for applying the solvent to the substrate is not particularly limited, and examples thereof include a coating method such as a spray method and a spin coating method, and a dipping method.
In addition, the filling rate of the solvent when the solvent is filled in the hole by applying the solvent is not particularly limited.

The resin composition coating step is a step of coating a resin composition containing a resin component and a solvent and having a specific thixotropic property on the substrate such that the resin composition is in contact with the solvent in the hole. It is.
The resin composition has a ratio (V ₁ / V ₂ ) of a viscosity V ₁ (mPa · s) at a shear rate of 6 rpm and a viscosity V ₂ (mPa · s) at a shear rate of 60 rpm of 1.1 or more. , Preferably 1.1 to 10.0, more preferably 1.2 to 8.0, and still more preferably 1.3 to 5.0. When the ratio (V ₁ / V ₂ ) is in the above range, the film is excellent in film forming property on at least the inner wall surface of the inner wall surface and the bottom surface of the hole, and a uniform film can be obtained.
The solid content concentration of the resin composition is preferably 5 to 80% by mass, more preferably 20 to 60% by mass.

The viscosity V ₁ when the solid content concentration of the resin composition is in the range of 5 to 80% by mass is preferably 10 to 10,000 mPa · s, more preferably 20 to 7,000 mPa · s, and still more preferably. Is 50 to 5,000 mPa · s. When it is in the above range, it is excellent in film-forming properties for at least the inner wall surface of the inner wall surface and the bottom surface of the hole, and a more uniform film can be obtained.

The resin composition, as described above, the viscosity _V 1 (mPa · s) at a shear rate of 6 rpm, the ratio of the viscosity _V 2 (mPa · s) at a shear rate of 60rpm _(V 1 / V ₂₎ is 1 .1 or more. In order to obtain a more uniform coating, the resin composition has a ratio of the viscosity V ₃ (mPa · s) at a shear rate of 1.5 rpm to the viscosity V ₄ (mPa · s) at a shear rate of 600 rpm ( V ₃ / V ₄ ) is preferably 2.0 or more. A more preferable ratio (V ₃ / V ₄ ) is in the range of 2.0 to 80, more preferably 2.0 to 50, and particularly preferably 3.0 to 50.
The viscosity is a value measured at a temperature of 25 ° C. while increasing the shear rate from, for example, 1 rpm to 1,000 rpm.

It does not specifically limit as a solvent which comprises the said resin composition, What was illustrated as a solvent used in the said solvent application | coating process can be used. The solvent contained in the resin composition may be the same as or different from the solvent used in the solvent coating step.
Moreover, it does not specifically limit as a resin component which comprises the said resin composition, Although any of a thermosetting resin, a thermoplastic resin, and resin other than these may be sufficient, it is preferable that a thermosetting resin is included.

When the resin component constituting the resin composition contains a thermosetting resin, the resin composition may be either photosensitive or non-photosensitive.
When the resin composition is a photosensitive resin composition, either a positive photosensitive resin composition or a negative photosensitive resin composition may be used, but a positive photosensitive resin composition is preferable.

  Examples of the positive photosensitive resin composition include a resin having a phenolic hydroxyl group (hereinafter also referred to as “resin (A1)”); a monomer having a phenolic hydroxyl group and a (meth) acrylic ester. A copolymer obtained by using a monomer containing the monomer (hereinafter also referred to as “resin (A2)”); a resin having a carboxyl group (hereinafter also referred to as “resin (A3)”), and the like. Examples include a composition containing an alkali-soluble resin [A] and a compound [B] having a quinonediazide group.

As said resin (A1), the novolak resin obtained by condensing phenols and aldehydes in presence of a catalyst can be used, for example.
Phenols include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol, p-butylphenol, 2,3- Xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, Catechol, resorcinol, pyrogallol, α-naphthol, β-naphthol and the like can be mentioned.
Examples of aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, benzaldehyde and the like.
Examples of the novolak resin include phenol / formaldehyde condensed novolak resin, cresol / formaldehyde condensed novolak resin, phenol-naphthol / formaldehyde condensed novolak resin, and the like. These can be used alone or in combination of two or more.

  Examples of the resin (A1) other than the novolak resin include polyhydroxystyrene, copolymers of hydroxystyrene and other monomers (excluding (meth) acrylic acid and (meth) acrylic acid ester), polyisopropenylphenol , Copolymers of isopropenylphenol and other monomers (excluding (meth) acrylic acid and (meth) acrylic acid ester), phenol / xylylene glycol condensation resin, cresol / xylylene glycol condensation resin, phenol / Examples include dicyclopentadiene condensation resin. These can be used alone or in combination of two or more.

The resin (A2) includes a monomer containing a phenolic hydroxyl group and a (meth) acrylic acid ester and not containing a compound having a carboxyl group such as (meth) acrylic acid. It is the obtained copolymer.
Examples of the monomer having a phenolic hydroxyl group include p-hydroxystyrene, m-hydroxystyrene, o-hydroxystyrene, p-isopropenylphenol, m-isopropenylphenol, o-isopropenylphenol and the like.
Moreover, as (meth) acrylic acid ester, methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) ) Acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate and other (meth) acrylic acid alkyl esters. In addition, the hydrogen atom of the alkyl group in these (meth) acrylic acid alkyl esters may be substituted with a hydroxyl group.

In forming the resin (A2), in addition to the monomer having a phenolic hydroxyl group and the (meth) acrylic acid ester, a compound having a polymerizable unsaturated bond may be used as another monomer.
Other monomers include styrene, α-methyl styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene, ethyl styrene, vinyl xylene, o-methoxy styrene, m-methoxy styrene, p-methoxy styrene. Aromatic vinyl compounds such as: maleic anhydride, unsaturated acid anhydrides such as citraconic anhydride; esters of the unsaturated carboxylic acids; (meth) acrylonitrile, maleinonitrile, fumaronitrile, mesaconitrile, citraconic nitrile, itacon nitrile, etc. Unsaturated amides such as (meth) acrylamide, crotonamide, maleamide, fumaramide, mesaconamide, citraconic amide, itaconic amide; unsaturated imide such as maleimide, N-phenylmaleimide, N-cyclohexylmaleimide; Meth) unsaturated alcohols such as allyl alcohol; N- vinyl aniline, vinyl pyridine, N- vinyl -ε- caprolactam, N- vinyl pyrrolidone, N- vinylimidazole, N- vinylcarbazole, and the like. These can be used alone or in combination of two or more.

The resin (A3) may be a homopolymer or a copolymer, and is usually obtained using a monomer containing a compound having a carboxyl group (hereinafter referred to as “monomer (m)”). It is a polymer.
As the monomer (m), (meth) acrylic acid, maleic acid, fumaric acid, crotonic acid, mesaconic acid, citraconic acid, itaconic acid, 4-vinylbenzoic acid and other unsaturated carboxylic acids or unsaturated dicarboxylic acids A monoester of an unsaturated dicarboxylic acid; These can be used alone or in combination of two or more.

The resin (A3) is exemplified below.
[1] a copolymer obtained by using a monomer (m) and a monomer having a phenolic hydroxyl group [2] a monomer (m), a monomer having a phenolic hydroxyl group, Copolymer [3] monomer (m) obtained using (meth) acrylic acid ester, monomer having phenolic hydroxyl group, aromatic vinyl compound, (meth) acrylic acid ester, Copolymer [4] Monomer [m] Monomer (m), Aromatic Vinyl Compound, and Copolymer [5] Monomer (m) ), An aromatic vinyl compound, and a conjugated diolefin [6] monomer (m), a (meth) acrylic acid ester, and a conjugated diolefin. Copolymer [7] monomer (m), (meth) acrylic acid ester, fatty acid vinyl compound Copolymers obtained by using

In addition, in the said aspect, what was illustrated above can be used for the monomer which has a phenolic hydroxyl group, (meth) acrylic acid ester, and an aromatic vinyl compound.
Examples of the conjugated diolefin include 1,3-butadiene, isoprene, 1,4-dimethylbutadiene and the like.
Examples of the fatty acid vinyl compound include vinyl acetate and vinyl crotonic acid.

  The alkali-soluble resin [A] may be a single polymer or a combination of two or more polymers. In the present invention, a resin having a phenolic hydroxyl group is preferably contained, and in particular, a novolac resin and a copolymer obtained using hydroxystyrene are preferred.

  The weight average molecular weight of the alkali-soluble resin [A] can be measured by GPC (gel permeation chromatography), and is preferably 2000 or more, more preferably about 2000 to 50000. Within this range, the cured film obtained is excellent in mechanical properties, heat resistance and electrical insulation.

  The content of the alkali-soluble resin [A] constituting the positive photosensitive resin composition is preferably 20 to 90 mass when the solid content in the positive photosensitive resin composition is 100 mass%. %, More preferably, it is 20-80 mass%, More preferably, it is 30-70 mass%. When it exists in this range, while being excellent in alkali solubility, it is excellent in the mechanical physical property of the obtained cured film, heat resistance, and electrical insulation.

  Next, the quinonediazide compound [B] is 1,2-naphthoquinone-2-diazide-5-sulfonic acid ester or 1,2-naphthoquinone-2-diazide-4-sulfonic acid ester of a phenol compound.

Although the said phenol compound will not be specifically limited if it is a compound which has at least 1 phenolic hydroxyl group, The compound represented by following General formula (1)-(5) is preferable.
[Wherein, X ^{1 to} X ¹⁰ may be the same or different from each other, and are a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a hydroxyl group. Note that at least one of X ^{1 to} X ⁵ is a hydroxyl group. A is a single bond, O, S, CH ₂ , C (CH ₃ ) ₂ , C (CF ₃ ) ₂ , C═O, or SO ₂ . ]

[Wherein, X ^{11 to} X ²⁴ may be the same or different from each other, and are a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a hydroxyl group. Note that at least one of X ^{11 to} X ¹⁵ is a hydroxyl group. R ^{1 to} R ⁴ may be the same or different from each other, and are a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ]

[Wherein, X ^{25 to} X ³⁹ may be the same or different from each other, and are a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a hydroxyl group. Note that at least one of X ^{25 to} X ²⁹ and at least one of X ^{30 to} X ³⁴ are hydroxyl groups. R ⁵ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ]

[Wherein, X ^{40 to} X ⁵⁸ may be the same or different from each other, and are a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a hydroxyl group. At least one of X ^{40 to} X ⁴⁴ , at least one of X ^{45 to} X ⁴⁹ and at least one of X ^{50 to} X ⁵⁴ is a hydroxyl group. R ^{6 to} R ⁸ may be the same or different from each other, and are a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ]

^Wherein, X 59 ^{to X 72} may be the same or different from each other, respectively, a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group or a hydroxyl group having 1 to 4 carbon atoms. ^{Incidentally,} at least one of the at least one and ^X 63 ^{to X 67} of the X 59 ^{to X 62} is a hydroxyl group. ]

Examples of the phenol compound include 4,4′-dihydroxydiphenylmethane, 4,4′-dihydroxydiphenyl ether, 2,3,4-trihydroxybenzophenone, 2,3,4,4′-tetrahydroxybenzophenone, 2,3,4 , 2 ′, 4′-pentahydroxybenzophenone, tris (4-hydroxyphenyl) methane, tris (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 1,3- Bis [1- (4-hydroxyphenyl) -1-methylethyl] benzene, 1,4-bis [1- (4-hydroxyphenyl) -1-methylethyl] benzene, 4,6-bis [1- (4 -Hydroxyphenyl) -1-methylethyl] -1,3-dihydroxybenzene, 1,1-bis (4-hydroxy) Eniru) -1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl] ethane, and the like. These can be used alone or in combination of two or more.
Therefore, as the quinonediazide compound [B], at least one selected from these phenol compounds is reacted with 1,2-naphthoquinonediazide-4-sulfonic acid or 1,2-naphthoquinonediazide-5-sulfonic acid. The esterified product and the like obtained by allowing them to be used can be used singly or in combination of two or more.

  The content ratio of the quinonediazide compound [B] constituting the positive photosensitive resin composition is preferably 10 to 100 parts by mass, more preferably 10 when the alkali-soluble resin [A] is 100 parts by mass. -50 mass parts, More preferably, it is 15-50 mass parts. Within this range, the difference in solubility between the exposed and unexposed areas is large and the alkali solubility is excellent.

  The positive photosensitive resin composition further contains a crosslinking agent; metal oxide particles; particles made of a crosslinked polymer (hereinafter referred to as “crosslinked polymer particles”); a low molecular phenolic compound, and the like. can do.

  Examples of the cross-linking agent include a compound having at least two alkyl etherified amino groups in the molecule; an epoxy group-containing compound; a phenol compound having an aldehyde group; a phenol compound having a methylol group; a thiirane ring-containing compound; Group-containing compounds; isocyanate group-containing compounds (including blocked compounds) and the like.

Examples of the compound having at least two or more alkyl etherified amino groups in the molecule include nitrogen compounds such as (poly) methylol melamine, (poly) methylol glycoluril, (poly) methylol benzoguanamine, and (poly) methylol urea. A compound in which all or a part (at least two) of the active methylol groups (CH ₂ OH groups) therein are alkyl etherified can be used. Here, examples of the alkyl group constituting the alkyl ether include a methyl group, an ethyl group, and a butyl group, and the plurality of alkyl groups may be the same as or different from each other. In addition, the methylol group that is not alkyletherified may be self-condensed within one molecule, or may be condensed between two molecules, and as a result, an oligomer component may be formed. Specific examples include hexamethoxymethyl melamine, hexabutoxymethyl melamine, tetramethoxymethyl glycoluril, tetrabutoxymethyl glycoluril and the like. In addition, these can be used individually by 1 type or in combination of 2 or more types.

  Examples of the epoxy group-containing compound include phenol novolac type epoxy resins, cresol novolac type epoxy resins, bisphenol type epoxy resins, trisphenol type epoxy resins, tetraphenol type epoxy resins, phenol-xylylene type epoxy resins, and naphthol-xylylene type epoxy resins. Phenol-naphthol type epoxy resin, phenol-dicyclopentadiene type epoxy resin, alicyclic epoxy resin, aromatic epoxy resin, aliphatic epoxy resin, epoxycyclohexene resin and the like. These can be used alone or in combination of two or more.

  Among the above epoxy group-containing compounds, phenol novolac type epoxy resin, bisphenol A type epoxy resin, resorcinol diglycidyl ether, pentaerythritol glycidyl ether, trimethylolpropane polyglycidyl ether, glycerol polyglycidyl ether, phenyl glycidyl ether, neopentyl glycol Diglycidyl ether, ethylene / polyethylene glycol diglycidyl ether, propylene / polypropylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, sorbitol polyglycidyl ether, propylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether, etc. are preferred .

Examples of the phenol compound having an aldehyde group include o-hydroxybenzaldehyde.
Examples of the phenol compound having a methylol group include 2,6-bis (hydroxymethyl) -p-cresol.

  When the positive photosensitive resin composition contains the crosslinking agent, the content ratio is preferably 1 to 100 parts by mass, more preferably 100 parts by mass when the alkali-soluble resin [A] is 100 parts by mass. It is 10-75 mass parts, More preferably, it is 10-50 mass parts. When it exists in this range, while being excellent in alkali solubility, it is excellent in the mechanical physical property of the obtained cured film, heat resistance, and electrical insulation.

  Examples of the metal oxide particles include silica (colloidal silica, aerosil, glass, etc.), alumina, titania, zirconia, ceria, zinc oxide, copper oxide, lead oxide, yttrium oxide, tin oxide, indium oxide, magnesium oxide, and the like. It is done.

The surface of the metal oxide particles may be modified with a functional group or the like in order to increase the affinity or compatibility with the alkali-soluble resin [A].
Further, the shape of the metal oxide particles is not particularly limited, and may be spherical, elliptical, flat, rod-like, fiber-like, or the like.

The average particle diameter of the metal oxide particles is 1 to 500 nm, preferably 5 to 200 nm, more preferably 10 to 100 nm. When the average particle diameter of the metal oxide particles is in the above range, the transparency to radiation, alkali solubility, and the like are excellent.
The said metal oxide particle can be used individually by 1 type or in combination of 2 or more types.
As said metal oxide particle, a silica is preferable from the ease of control of thixotropy. In particular, silica partially hydrophobized (hereinafter also referred to as “hydrophobized silica”) is preferable.

The hydrophobicity of the hydrophobized silica is preferably 20 to 80%, more preferably 30 to 70%, still more preferably 40 to 70%. When the hydrophobization rate is 20 to 80%, the dispersibility of the hydrophobized silica in the solvent and the compatibility with the resin are improved, and the thixotropic property of the resin composition can be further exhibited. Therefore, it is preferable.
The hydrophobization rate of silica in the resin composition was determined by the following equation after measuring the number of silanol groups on the silica surface before and after hydrophobization by a neutralization titration method using a 0.1N sodium hydroxide aqueous solution. Value.
Hydrophobization rate (%) = (number of silanol groups after hydrophobization / number of silanol groups before hydrophobization) × 100

Moreover, when the said silica is hydrophobic silica, it is preferable that an average particle diameter is 1-100 nm, More preferably, it is 5-80 nm, More preferably, it is 10-50 nm. When this average particle diameter is 1 to 100 nm, sufficient transparency to exposure light, sufficient alkali solubility, and the like can be obtained.
The average particle size is a value measured by diluting a dispersion of silica particles according to a conventional method using a light scattering flow distribution measuring device (manufactured by Otsuka Electronics Co., Ltd., model number “LPA-3000”). The average particle diameter can be controlled by the dispersion conditions of the silica particles.

Moreover, it is preferable that the sodium content in the said hydrophobic silica is 1 ppm or less, More preferably, it is 0.5 ppm or less, More preferably, it is 0.1 ppm or less. When the sodium content is 1 ppm or less, the sodium content in the obtained resin composition can be 1 ppm or less.
The sodium content in the hydrophobized silica can be measured by an atomic absorption spectrometer (manufactured by Perkinelmer, model number “Z5100”) or the like.

When the positive photosensitive resin composition contains the metal oxide particles, the content is preferably 10 to 200 parts by mass when the alkali-soluble resin [A] is 100 parts by mass. Preferably it is 50-200 mass parts, More preferably, it is 70-150 mass parts. When the content ratio of the metal oxide particles is in the above range, it has suitable thixotropic properties, and a uniform film can be formed on the inner wall surface of the bottomed hole portion.
Moreover, when the said hydrophobized silica is contained as said metal oxide particle, the content rate of hydrophobized silica exceeds 20 mass% when the whole solid content in a resin composition is 100 mass%, 60 It is preferable that it is mass% or less, More preferably, it is 30 mass% or more and 60 mass% or less, More preferably, it is 30 mass% or more and 50 mass% or less. When this content ratio exceeds 20 mass% and is 60 mass% or less, sufficient thixotropy can be obtained, and a uniform film can be formed on the inner wall surface of the bottomed hole portion.

  The positive photosensitive resin composition includes carbonates such as calcium carbonate and magnesium carbonate; sulfates such as barium sulfate and calcium sulfate; phosphates such as calcium phosphate and magnesium phosphate; carbides; nitrides and the like. You may contain another inorganic particle.

As the cross-linked polymer particles, a homopolymer or copolymer of a monomer containing a cross-linkable compound having two or more polymerizable unsaturated bonds (hereinafter referred to as “cross-linkable monomer”) is used. Can do.
Examples of the crosslinkable monomer include divinylbenzene, diallyl phthalate, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, polyethylene glycol Examples include di (meth) acrylate and polypropylene glycol di (meth) acrylate. These can be used alone or in combination of two or more. Of the above, divinylbenzene is preferred.

  When the crosslinked polymer particles are a copolymer, the other monomer to be polymerized with the crosslinking monomer is not particularly limited, but includes a hydroxyl group, a carboxyl group, a nitrile group, an amide group, an amino group, An unsaturated compound having one or more functional groups such as an epoxy group; urethane (meth) acrylate; aromatic vinyl compound; (meth) acrylic acid ester; diene compound and the like can be used. These can be used alone or in combination of two or more.

  Examples of the crosslinked polymer particles include a copolymer (d1) comprising the crosslinking monomer, an unsaturated compound having a hydroxyl group and / or an unsaturated compound having a carboxyl group, and the crosslinking monomer. Preferred is a copolymer (d2) comprising an unsaturated compound having a hydroxyl group and / or an unsaturated compound having a carboxyl group and another monomer, and particularly preferred is a copolymer (d2).

Examples of the unsaturated compound having a hydroxyl group include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate and the like.
Examples of unsaturated compounds having a carboxyl group include (meth) acrylic acid, itaconic acid, succinic acid-β- (meth) acryloxyethyl, maleic acid-β- (meth) acryloxyethyl, phthalic acid-β- (meta ) Acryloxyethyl, hexahydrophthalic acid-β- (meth) acryloxyethyl, and the like.

Among the other monomers used for forming the copolymer (d2), the unsaturated compound having a nitrile group includes (meth) acrylonitrile, α-chloroacrylonitrile, α-chloromethylacrylonitrile, α-methoxyacrylonitrile. , Α-ethoxyacrylonitrile, crotonic acid nitrile, cinnamic acid nitrile, itaconic acid dinitrile, maleic acid dinitrile, fumaric acid dinitrile and the like.
Examples of unsaturated compounds having an amide group include (meth) acrylamide, dimethyl (meth) acrylamide, N, N′-methylenebis (meth) acrylamide, N, N′-ethylenebis (meth) acrylamide, and N, N′-hexa. Methylenebis (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N- (2-hydroxyethyl) (meth) acrylamide, N, N-bis (2-hydroxyethyl) (meth) acrylamide, crotonic acid amide, silicic acid Examples thereof include cinnamate amides.
Examples of the unsaturated compound having an amino group include dimethylamino (meth) acrylate and diethylamino (meth) acrylate.
Examples of unsaturated compounds having an epoxy group include glycidyl (meth) acrylate, (meth) allyl glycidyl ether, diglycidyl ether of bisphenol A, diglycidyl ether of glycol, (meth) acrylic acid, hydroxyalkyl (meth) acrylate, etc. And epoxy (meth) acrylate obtained by the reaction.

Examples of the urethane (meth) acrylate include compounds obtained by reaction of hydroxyalkyl (meth) acrylate and polyisocyanate.
Examples of the aromatic vinyl compound include styrene, α-methylstyrene, o-methoxystyrene, p-hydroxystyrene, p-isopropenylphenol and the like.
(Meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, and lauryl (meth) acrylate. , Polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate and the like.
Examples of the diene compound include butadiene, isoprene, dimethylbutadiene, chloroprene, and 1,3-pentadiene.

  When the crosslinked polymer particles are made of a copolymer (d2), the unit amount (d21) made of a crosslinkable monomer, the unit made of an unsaturated compound having a hydroxyl group, and / or the unsaturated compound having a carboxyl group The total amount of units consisting of (d22) and the unit amount of other monomers (d23) are the sum of the unit amounts constituting the copolymer (d2), that is, (d21), (d22) and When the sum of (d23) is 100 mol%, preferably 0.1 to 10 mol%, 5 to 50 mol%, and 40 to 94.9 mol%, more preferably 0.5 to 7 mol%, and 6 to 45 mol%, respectively. And 48-93.5 mol%, more preferably 1-5 mol%, 7-40 mol% and 55-92 mol%. When the ratio of each unit amount is in the above range, crosslinked polymer particles having excellent shape stability and compatibility with the alkali-soluble resin can be obtained.

  The crosslinked polymer particles may be rubber or resin, and the glass transition temperature (Tg) is not particularly limited. Preferable Tg is 20 ° C. or lower, more preferably 10 ° C. or lower, and further preferably 0 ° C. or lower. The lower limit is usually −70 ° C. or higher.

  The crosslinked polymer particles are in the form of particles, and the average particle size is preferably 30 to 100 nm, more preferably 40 to 90 nm, and still more preferably 50 to 80 nm. When the average particle diameter of the crosslinked polymer particles is in the above range, the compatibility with the alkali-soluble resin, the alkali solubility, and the like are excellent. In addition, the said average particle diameter is the value measured by diluting the dispersion liquid of a crosslinked polymer particle in accordance with a conventional method using the light-scattering flow distribution measuring apparatus "LPA-3000" (made by Otsuka Electronics Co., Ltd.).

  When the positive photosensitive resin composition contains the crosslinked polymer particles, the content is preferably 1 to 100 parts by mass when the alkali-soluble resin [A] is 100 parts by mass. Preferably it is 5-80 mass parts, More preferably, it is 5-50 mass parts. When the content ratio of the crosslinked polymer particles is in the above range, the cured film obtained has excellent thermal shock resistance and the like.

  Examples of the low-molecular phenolic compound include 4,4′-dihydroxydiphenylmethane, 4,4′-dihydroxydiphenyl ether, tris (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) -1- Phenylethane, tris (4-hydroxyphenyl) ethane, 1,3-bis [1- (4-hydroxyphenyl) -1-methylethyl] benzene, 1,4-bis [1- (4-hydroxyphenyl) -1 -Methylethyl] benzene, 4,6-bis [1- (4-hydroxyphenyl) -1-methylethyl] -1,3-dihydroxybenzene, 1,1-bis (4-hydroxyphenyl) -1- [4 -[1- (4-hydroxyphenyl) -1-methylethyl] phenyl] ethane, 1,1,2,2-tetra (4-hydroxy) Phenyl) ethane and the like. These can be used alone or in combination of two or more.

  When the positive photosensitive resin composition contains the low molecular phenolic compound, the content ratio is preferably 1 to 20 parts by mass when the alkali-soluble resin [A] is 100 parts by mass, More preferably, it is 2-15 mass parts, More preferably, it is 3-10 mass parts. When the content ratio of the low molecular weight phenolic compound is within the above range, the alkalinity can be improved without impairing the heat resistance of the resulting cured product.

  When the resin composition used in the resin composition coating step is the positive photosensitive resin composition, the solid content concentration is preferably 5 to 80% by mass, more preferably 10 to 60% by mass, and further Preferably it is 25-60 mass%.

When the said resin composition is a non-photosensitive resin composition, it is preferable that it is a curable resin composition containing alkali-soluble resin and a crosslinking agent.
As the alkali-soluble resin, it is preferable to use a resin having a phenolic hydroxyl group, a resin having a carboxyl group, a resin having a phenolic hydroxyl group and an alcoholic hydroxyl group, and a resin having a carboxyl group and an alcoholic hydroxyl group. These may be used alone or in combination. In addition, the resin illustrated as a structural component of the said positive type photosensitive resin composition can also be used as it is.

Further, as the crosslinking agent, it is preferable to use a compound having at least two alkyl etherified amino groups in the molecule and an epoxy group-containing compound. These may be used alone or in combination. In addition, the crosslinking agent illustrated as a structural component of the said positive photosensitive resin composition can also be used as it is.
When a compound having at least two or more alkyl etherified amino groups in the molecule is used as the crosslinking agent, the content ratio in the non-photosensitive resin composition is 100 parts by mass of the alkali-soluble resin. Preferably, it is 1-100 mass parts, More preferably, it is 5-50 mass parts. When the content ratio of the compound is in the above range, the obtained cured film is excellent in mechanical properties, heat resistance and electrical insulation.
When the epoxy group-containing compound is used as the crosslinking agent, the content in the non-photosensitive resin composition is preferably 1 to 70 parts by mass, more preferably 100 parts by mass when the alkali-soluble resin is 100 parts by mass. Is 3-30 parts by mass. When the content ratio of the epoxy group-containing compound is in the above range, the cured film obtained is excellent in mechanical properties, heat resistance and electrical insulation.

  The non-photosensitive resin composition may further contain metal oxide particles, crosslinked polymer particles, a low-molecular phenolic compound, and the like, and these constitute the positive-type photosensitive resin composition. What was illustrated as a component can be used as it is.

  The resin composition used in the film forming method of the present invention includes the alkali-soluble resin, the silica that has been hydrophobized and has an average particle diameter of 1 to 100 nm, the solvent, and the crosslinking agent. , May be contained. Furthermore, the compound having a quinonediazide group can be contained.

  When the resin composition used in the resin composition coating step is the non-photosensitive resin composition, the solid content concentration is preferably 5 to 80% by mass, more preferably 10 to 60% by mass.

In the resin composition application step, a method of applying a resin composition having specific physical properties to the substrate is a method in which the resin composition is applied so as to come into contact with the solvent in the hole, The method is not particularly limited, and examples thereof include spin coating, spraying, and bar coating. Of these, spin coating is preferred.
In the resin composition application step, the solid content concentration, viscosity, etc. of the resin composition are taken into consideration, and the thickness of the coating film formed on the surface of the substrate is 0.1 to 0.1 by the subsequent drying step. It is preferable to form the coating film so as to fall within the range of 10 μm.

  In the resin composition application step, when the resin composition is applied, a uniform coating film 115 is formed on the surface of the substrate 11, and in the holes, the solvent filled in the solvent application step and the resin A mixture 116 composed of the composition will be accommodated (see FIG. 2C).

Next, the drying step is a step of drying the coating film formed by the resin composition coating step, that is, a step of removing only the solvent contained in the coating film.
The drying temperature is selected in consideration of the boiling point of the solvent filled in the solvent coating step or the boiling point of the mixed solvent contained in the mixture 116 composed of the solvent filled in the solvent coating step and the resin composition. The
The drying conditions are not particularly limited, but may be performed at a constant temperature, may be performed while raising or lowering the temperature, or may be combined. Also, the pressure may be performed under atmospheric pressure or under vacuum. Furthermore, the atmosphere gas or the like is not particularly limited.

  According to the drying step, the solvent is removed, and a uniform film made of the solid content of the resin composition is formed on the substrate surface including at least the inner wall surface of the hole (see FIG. 2D). A substrate 1 with a film 1 shown in FIG. 2D is formed on a substrate 11 having a hole, a film 119 formed on the entire surface of the substrate 11 other than the hole, and an inner wall surface of the hole. A coating 117 and a coating 118 formed on the bottom surface of the hole are provided. These coatings usually form a continuous phase, but only coatings 117 and 118 may form a continuous phase. Further, regarding the thickness of each coating, although the thickness of the coating 119, the thickness of the coating 117 on the inner wall surface of the hole, and the thickness of the coating 118 on the bottom of the hole are usually different, Depending on the solid content concentration, viscosity, etc., the thickness of the coating 117 on the inner wall surface of the hole and the thickness of the coating 118 on the bottom of the hole may be the same or substantially the same.

2. Structure having Insulating Film and Method for Producing the Same A method for producing a structure having an insulating film of the present invention (hereinafter referred to as “structure producing method (I)”) is shown in FIGS. ), The coating film 119 formed on the surface of the substrate 11 and the bottom surface of the hole portion of the substrate 11 are used. Removing the coating 118 and leaving the coating 117 formed on the inner wall surface of the hole, and a heat curing process for heating the coating 117 remaining on the inner wall of the hole; It is characterized by providing.

In the structure manufacturing method (I) of the present invention, the coatings 117 to 119 are preferably made of a positive photosensitive resin composition, and this case will be described with reference to FIG.
The surface bottom side film removal step removes the film 119 formed on the surface of the substrate and the film 118 formed on the bottom surface of the hole of the substrate, and is formed on the inner wall surface of the hole. This is a step of leaving the coating 117 remaining.

First, the coated substrate 1 shown in FIG. 3A is irradiated with ultraviolet rays, visible rays, far ultraviolet rays, X-rays, electron beams, etc. from above to form a coating formed on the surface of the substrate 11. 119 and the coating 118 formed on the bottom surface of the hole of the substrate 11 are exposed. At this time, the coating 117 formed on the inner wall surface of the hole is not exposed.
The exposure amount is appropriately selected depending on the light source to be used, the thickness of the coating, and the like. For example, when a coating with a thickness of about 5 to 50 μm is irradiated with ultraviolet rays from a high-pressure mercury lamp, a preferable exposure amount is 1,000 to 20,000 J / m ² .
Since the film exposed portions 128 and 129 shown in FIG. 3B are alkali-soluble, the film 117 formed on the inner wall surface of the hole can be left by treatment with an alkaline solution. it can.
As the alkaline solution, an aqueous solution of sodium hydroxide, potassium hydroxide, ammonia, tetramethylammonium hydroxide, choline, or the like, or an appropriate amount of a water-soluble organic solvent such as methanol or ethanol, or a surfactant is added to this aqueous solution. An added solution or the like can be used.
After the treatment with the alkaline solution, the substrate having the coating 117 only on the inner wall surface of the hole can be obtained by washing with water and drying (see FIG. 3C).

The heat curing step is a step of heating the film 117 remaining on the inner wall surface of the hole, and through this process, the structure 2 having an insulating film can be obtained using the film 117 as the cured film 217 ( (Refer FIG.3 (d)).
Although a heating method is not specifically limited, Usually, it is preferable that it is about 30 minutes-10 hours at the temperature of the range of 100-250 degreeC. You may heat on fixed conditions and may heat in multiple steps. As the heating device, an oven, an infrared furnace, or the like can be used.
The structure 2 having an insulating film shown in FIG. 3D includes a substrate 11 having a hole and a cured film 217 formed on the inner wall surface of the hole of the substrate.

In addition, in the manufacturing method (I) of the structure of the present invention, after the heat curing step, a polishing step of polishing from the surface of the substrate 11 that does not have the hole portion to make the hole portion as the through hole 22 is further performed. It can be provided (see FIG. 3 (e)).
The polishing method is not particularly limited, but a chemical mechanical polishing method or the like can be applied.
A structure 2 ′ having an insulating film shown in FIG. 3 (e) includes a substrate 11 having a through hole 22 and a cured film 217 formed on the inner wall surface of the through hole 22.

  Another method of manufacturing a structure having an insulating film of the present invention (hereinafter referred to as “structure manufacturing method (II)”) is the above-described present invention shown in FIGS. 2 (d) and 4 (a). Using the coated substrate 1 obtained by the coating method, the coatings 117, 118, and 119 formed on the entire surface of the substrate including the inner wall surface and the bottom surface of the hole are heated to cure the resin component. A heat curing step for forming an insulating film containing an object, and the insulating film formed on the surface of the substrate and the insulating film formed on the bottom surface of the hole portion of the substrate are removed, and the inner wall surface of the hole portion is removed. And a front and bottom surface side insulating film removing step for leaving the formed insulating film.

In the structure production method (II) of the present invention, the coating is preferably made of a non-photosensitive resin composition, and this case will be described with reference to FIG.
The heat curing step is a step of heating the coating films 117, 118, and 119 formed on the entire surface of the substrate including the inner wall surface and the bottom surface of the hole to form an insulating film containing a cured product of the resin component. Yes (see FIG. 4B).
Although the heating method is not particularly limited, it can be the same as the heating and curing step in the structure production method (I) of the present invention.
The structure shown in FIG. 4B is obtained by the heat curing step, and this structure includes a substrate 11 having a hole, an insulating film 219 formed on the surface of the substrate, and the hole. And an insulating film 218 formed on the bottom surface of the hole.

Next, the surface bottom side insulating film removing step removes the insulating film 219 formed on the surface of the substrate and the insulating film 218 formed on the bottom surface of the hole of the substrate, This is a step of leaving the insulating film 217 formed on the inner wall surface.
Examples of a method for selectively removing the insulating films 218 and 219 include anisotropic etching (dry etching).
The structure 2 having the insulating film shown in FIG. 4C is obtained by the surface bottom side insulating film removing step, and this structure 2 includes the substrate 11 having a hole portion and the inside of the hole portion of the substrate. And a cured film 217 formed on the wall surface.

In the structure manufacturing method (II) of the present invention, the holes in the substrate 11 are formed after the surface bottom side insulating film removing step, as in the structure manufacturing method (I) of the present invention. Polishing can be further performed by polishing from the surface that does not have, and using the hole as the through hole 22 (see FIG. 4D).
A structure 2 ′ having an insulating film shown in FIG. 4D includes a substrate 11 having a through hole 22 and a cured film 217 formed on the inner wall surface of the through hole 22.

3. Electronic component The electronic component of the present invention includes a structure having an insulating film (a structure having a through-hole with an insulating film formed on the inner wall) obtained by the structure manufacturing method of the present invention, and the structure. And a member including an electrode portion (conductive material filling portion) in which at least a through hole is filled with a conductive material.
As an electronic component of the present invention, for example, the structure 2 ′ shown in FIGS. 3E and 4D and the electrode portion (conductive material filling portion) 311 in at least the through hole of the structure 2 ′. The member 3 (refer FIG.5 (g)) containing these can be provided.

The member 3 will be described.
As a forming material (conductive material) of the electrode part 311 constituting the member 3, a material selected from copper, silver, tungsten, tantalum, titanium, ruthenium, gold, tin, aluminum, and an alloy containing these, etc. Is used.
As shown in FIG. 5G, the electrode portion 311 may have a convex shape protruding from the smooth surface of the substrate 11 or may be flush with the substrate 11. Further, the surface of the electrode portion 311 may be a smooth surface or a rough surface.

An example of the manufacturing method of the member 3 shown by FIG.5 (g) is demonstrated using FIG.
First, a structure 2 having an insulating film shown in FIGS. 3D and 4C is prepared (see FIG. 5A). Cu sputtering or the like is performed on the surface of the structure 2 on the side having the hole, and a copper film (seed layer) 23a having a thickness of 10 to 200 nm is formed on all the structures 2 including the inner surface of the hole. And 23b are formed (see FIG. 5B). Thereafter, an insulating resist film 24 is formed by printing or the like on the surface of the copper film 23a other than the inner surface of the hole (see FIG. 5C). Next, Cu filling plating into the holes is performed using an aqueous copper sulfate solution or the like (see FIG. 5D). Thereafter, the insulating resist film 24 is peeled off using a predetermined stripping solution or the like (see FIG. 5E). Next, the copper film 23a formed on the surface of the substrate 11 is removed by etching using diluted sulfuric acid, diluted hydrochloric acid, or the like (see FIG. 5F). And it grind | polishes until the metal copper with which the hole was filled is exposed from the back surface of the board | substrate 11, and the member 3 provided with the penetration electrode which consists of the metal copper filling part 311 shown by FIG.5 (g) is obtained.

The member provided with the through electrode may be a member 3 ′ shown in FIG. This member 3 ′ includes a substrate 11 having a conductive material filling portion 311 filled with a conductive material in a through hole penetrating front and back and having an insulating film 217 formed on an inner wall surface, and the conductive material filling portion. 311 includes an electrode pad 313 that covers at least the lower exposed surface of 311 (the lower exposed surface of the drawing).
6 'is an electrode pad forming step for forming an electrode pad on the lower exposed surface (lower side of FIG. 5 (g)) of the conductive material filling portion 311 of the member 3 shown in FIG. 5 (g). It can manufacture by the method provided with. Specific methods for this electrode pad forming step include plating, application of a conductive paste, and the like. Other manufacturing methods will be described later.

Further, the member 3 ″ shown in FIG. 7 is an example using the member 3 shown in FIG. 5G or the member 3 ′ shown in FIG.
The member 3 ″ includes an upper member 31 in which electrode pads 313a and 313b are disposed on lower exposed surfaces (lower exposed surfaces in the drawing) of metal copper filling portions (penetrating electrodes) 311a and 311b, and metal The electrode pad of the upper member 31 is formed by using the lower member 32 in which the electrode pads 323a and 323b are disposed on the lower exposed surfaces (lower exposed surfaces in the drawing) of the copper filling portions (penetrating electrodes) 321a and 321b, respectively. The surface of 313a and the surface of the metal copper filling part (penetration electrode) 321a of the lower member 32 are joined, and the surface of the electrode pad 313b of the upper member 31 and the metal copper filling part (penetration) of the lower member 32 Electrode) is a composite member formed by joining the surface of 321b, and an insulating layer 34 is disposed on the interface between the upper member 31 and the lower member 32 (see FIG. 7). The bonding method of the filling portion (penetrating electrode) 321a and the like is not particularly limited, and examples thereof include a method such as thermocompression bonding (applying pressure while applying heat).

  The electronic component of the present invention may be provided with a member 3 shown in FIG. 5G, a member 3 ′ shown in FIG. 6, a member 3 ″ shown in FIG. 8, the electrode pads 323a and 323b of the member 3 ″ shown in FIG. 7 and the interposer 41 are electrically connected via two bumps 42 arranged on the surface of the interposer 41. Furthermore, bumps 43 are provided on the lower side of the interposer 41 for conducting connection with other members.

  The electronic component of the present invention is a composite including the above members 3, 3 ′, 3 ″ and the like, for example, a composite (circuit board, semiconductor) including other members such as another substrate, an interlayer insulating film, and other electrodes. Device, sensor, etc.).

The member 3 ′ shown in FIG. 6 has a conductive material layer 313 formed in advance, and a composite substrate in which the bottom surface of the hole is the conductive material layer 313 is used, and FIGS. Or the member 2 ′ (FIG. 3 (d) or FIG. 4 (d)) obtained by the steps of FIG. 4 (a) to FIG. 4 (c), below the opening of the through hole (under FIG. 3 (e)). The hole having the conductive material layer 313 on the side or the lower side of FIG. 4D can be manufactured by a method including a step of filling the conductive material by the steps of FIGS.
Furthermore, the laminated substrate 6 having the concave portion shown in FIG. 9A can be used to apply the coating film forming method of the present invention and the manufacturing method of the structure having an insulating film.
The laminated substrate 6 shown in FIG. 9A is made of silicon, various metals, various metal sputtered films, alumina, glass epoxy, paper phenol, glass, etc., and is columnar from one side to the other (see FIG. 1A). ), Forwardly tapered (see FIG. 1 (b)), reverse tapered (see FIG. 1 (c)) or the like substrate 61 and disposed on one surface of the substrate 61 so as to close the through hole. The conductive material layer 63 is provided. The laminated substrate 6 has a concave portion in which one of the through holes is closed by the conductive material layer 63. The laminated substrate 6 is obtained by cutting a laminated body composed of a flat substrate having no through holes and a conductive material layer so as not to penetrate the conductive material layer from the surface of the flat substrate. It can also be made.
Accordingly, the thickness of the substrate 61 is preferably 10 to 200 μm, more preferably 30 to 120 μm, still more preferably 50 to 100 μm, and the area of the opening of the recess, the cross-sectional shape, etc. By applying the coating film forming method of the present invention and the manufacturing method of the structure having an insulating film as described above in the formation method, the member 3 ′ shown in FIG. The member 3 ′ shown can be manufactured.

A method of manufacturing the member 3 ′ shown in FIG. 9 (e) will be briefly described. First, a solvent is applied to the surface of the substrate 61 constituting the multilayer substrate 6 (solvent application step), and then a resin composition having specific thixotropic properties as described above is applied (resin composition application step). To form a coating film. Next, the coating film made of the resin composition on the surface of the substrate 61 and the mixture in the recess are dried to remove the solvent, and the surface of the substrate 61, the inner wall surface of the recess, and the recess side of the conductive material layer 63 Films (621, 622, and 623, respectively) are formed on the surface to obtain a film-coated substrate 7 (see FIG. 9B).
Then, according to the kind of resin composition, the manufacturing method of the structure which has the said insulating film of this invention is applied, and the laminated structure 8 which has the insulating film 625 on the inner wall face of a recessed part is obtained (FIG.9 (c)). reference).

Next, an electrode pad 635 is formed by removing a part of the conductive material layer 63 by etching or the like so as not to penetrate the recess (see FIG. 9D), and copper, silver, tungsten, tantalum, titanium is formed in the recess. By filling a conductive material selected from ruthenium, gold, tin, aluminum, and an alloy containing these, an insulating film 625 penetrates the front and back surfaces shown in FIG. The formed through-hole covers at least a substrate 61 having a conductive material filling portion 66 filled with a conductive material and a lower exposed surface (lower side of FIG. 9E) of the conductive material filling portion 66. A member 3 ′ including the electrode pad 635 can be obtained.
Therefore, the electronic component of the present invention can be configured by using the member 3 ′ obtained by using the multilayer substrate 6 shown in FIG. 9A.

  Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.

[1] Example 1
(1) Preparation of resin composition and viscosity measurement Phenolic resin (trade name “Sumilite Resin S-2”, manufactured by Sumitomo Bakelite Co., Ltd.) 100 parts by mass, melamine crosslinking agent (trade name “Cymel 300”, manufactured by Mitsui Cytec Co., Ltd.) 30 parts by mass and 100 parts by mass of silica particles having an average particle diameter of 10 to 20 nm (trade name “MEK-ST”, manufactured by Shin-Nakamura Chemical Co., Ltd., sodium content: 800 ppm) have a solid content concentration of 47% by mass. Thus, it was dispersed in a mixed solvent of ethyl lactate and methyl ethyl ketone (mixing ratio 60/40) to obtain a resin composition.
About this resin composition, using a rheometer (model name “AR2000”, manufactured by T.A. Instruments Co., Ltd.), increasing the shear rate from 1 rpm to 1,000 rpm at a temperature of 25 ° C., 1.5, The viscosities at 5, 6, 50, 60 and 600 rpm were measured, and the ratio (V ₁ / V) of the viscosity V ₁ (= 900 mPa · s) at a shear rate of 6 rpm to the viscosity V ₂ (mPa · s) at a shear rate of 60 rpm. ₂ ) The ratio (V ₃ / V ₄ ) of the viscosity V ₃ (mPa · s) at a shear rate of 1.5 rpm to the viscosity V ₄ (mPa · s) at a shear rate of 600 rpm, and the viscosity V at a shear rate of 5 rpm The ratio (V ₅ / V ₆ ) between ₅ (mPa · s) and the viscosity V ₆ (mPa · s) at a shear rate of 50 rpm was calculated (see Table 1).

(2) Film formation On the surface, there is a forward tapered hole having a square shape (80 μm × 80 μm), a depth of 100 μm, and a bottom shape of a square (60 μm × 60 μm). A 500 μm thick silicon substrate (see FIG. 10) was spin-coated with propylene glycol monomethyl acetate as a solvent (1,000 rpm, 3 seconds), and the hole was filled with this solvent (see FIG. 1B).
Thereafter, the resin composition obtained above is subjected to two-stage spin coating (first stage; 300 rpm, 10 seconds, second stage; 600 rpm, 20 seconds), and applied to the surface of the silicon substrate including the solvent surface in the hole. A film was formed.
Next, the coated silicon substrate is allowed to stand on a hot plate having a temperature of 110 ° C. for 3 minutes, and the solvent is evaporated to form a coating on the surface of the silicon substrate and the inner wall surface and bottom surface of the hole. A silicon substrate was obtained (see FIG. 2D). FIG. 11 shows a cross-sectional photograph taken with an electron microscope. When the thickness of the coating was measured, it was 9.0 μm on the inner wall surface and 5.8 μm on the bottom surface (see Table 1). When the film forming property on the inner surface of the hole was visually observed, it was uniform.

[2] Comparative Example 1
A resin composition (solid content concentration: 47% by mass) was prepared in the same manner as in Example 1 except that the amount of silica particles was changed to 0 part by mass, and the viscosity was measured (V ₁ = 760 mPa · s). Thereafter, a film was formed (see FIG. 12). From FIG. 12, it can be seen that the solid material of the resin composition fills the pores (see Table 1).

[3] Examples 2 to 10 and Comparative Examples 2 to 6
(1) Preparation of resin composition (Example 2)
As shown in Table 2, (A) 100 mass parts of alkali-soluble resin (A-1), (B) 25 mass parts of quinonediazide compound (B-1), (C) 100 mass parts of silica (C-1), (E ) Adhesion aid (E-1) 2.5 parts by mass, (F) Surfactant (F-1) 0.1 parts by mass, (G) Crosslinker (G-1) 20 parts by mass and (G-2) ) 10 parts by mass and (H) 10 parts by mass of the crosslinked polymer (H-1) are dissolved in (D) 300 parts by mass of the solvent (D-1) so that the solid content concentration is 47% by mass. Thus, a resin composition was prepared.

(2) Preparation of resin composition (Examples 3 to 10 and Comparative Examples 2 to 6)
As in Example 2, as shown in Table 2 and Table 3, (A) alkali-soluble resin, (a) low molecular phenolic compound, (B) quinonediazide compound, (C) silica, (E) adhesion aid Each resin composition is prepared by dissolving (F) a surfactant, (G) a crosslinking agent, and (H) a crosslinked polymer in (D) a solvent so that the solid content concentration is 47% by mass. did.

The compositions described in Tables 2 and 3 are as follows.
<(A) Alkali-soluble resin>
A-1: Cresol novolak resin consisting of m-cresol / p-cresol = 60/40 (molar ratio), polystyrene-reduced weight average molecular weight (Mw) = 6500
A-2: Polyhydroxystyrene (manufactured by Maruzen Petrochemical, trade name “Marcalinker S-2P”), Mw = 5000
<(A) Low molecular phenolic compound>
a-1: 1,1-bis (4-hydroxyphenyl) -1- [4- {1- (4-hydroxyphenyl) -1-methylethyl} phenyl] ethane
<(B) Quinonediazide compound>
B-1: 1,1-bis (4-hydroxyphenyl) -1- [4- {1- (4-hydroxyphenyl) -1-methylethyl} phenyl] ethane and 1,2-naphthoquinonediazide-5 2.0 molar condensate with sulfonic acid

<(C) Silica>
C-1: Trade name “Quarton PL-2L” (manufactured by Fuso Chemical Industries, hydrophobized product (hydrophobization rate: 50%), average particle size: 20 nm, sodium content: 0.02 ppm)
C-2: Trade name “PMA-ST” (manufactured by Nissan Chemical Industries, hydrophobized product (hydrophobization rate: 60%), average particle size: 20 nm, sodium content: 600 ppm)
C-3: Trade name “Quarton PL-30” (manufactured by Fuso Chemical Industries, hydrophobized product (hydrophobization rate: 40%), average particle size: 300 nm, sodium content: 0.02 ppm)
<(D) Solvent>
D-1: Propylene glycol monomethyl ether acetate
<(E) Adhesion aid>
E-1: γ-glycidoxypropyltrimethoxysilane (manufactured by Nihon Unicar, trade name “A-187”)

<(F) Surfactant (leveling agent)>
F-1: Product name “FTX-218” (manufactured by Neos)
<(G) Crosslinking agent>
G-1: Hexamethoxymethylmelamine (trade name; Cymel 300, manufactured by Mitsui Cytec Co., Ltd.)
G-2: Phenol novolac type epoxy resin (trade name; EP-152, manufactured by Japan Epoxy Resin Co., Ltd.)
<Particles made of (H) crosslinked polymer>
H-1: Butadiene / hydroxybutyl methacrylate / methacrylic acid / divinylbenzene = 60/32/6/2 (mass%) (average particle diameter: 70 nm)

In addition, each hydrophobization rate in the said (C) silica is the value measured as follows.
<Hydrophobicization rate>
First, 30 g of sodium chloride was dissolved in 150 mL of a 10% aqueous dispersion of silica, and adjusted with 1N hydrochloric acid so as to have a pH of 4. Subsequently, 0.1N sodium hydroxide aqueous solution was dripped until it became pH9. Then, the number of silanol groups on the silica surface was determined by the following formula.
A = (a × 0.1 × N) / (W × S)
[However, A is the number of silanol groups (pieces / nm ² ), a is the drop amount (L) of 0.1N sodium hydroxide aqueous solution, N is the Avogadro number (pieces / mol), W is the silica weight (g), and S is It is a BET area (nm ² / g) of silica.
In this way, the number of silanol groups in the silica before and after hydrophobization was determined, and the hydrophobization rate of silica was calculated by the following equation.
Hydrophobization rate (%) = (number of silanol groups after hydrophobization / number of silanol groups before hydrophobization) × 100

[4] Evaluation of Resin Composition Each resin composition of Examples 2 to 10 and Comparative Examples 2 to 6 was evaluated according to the following method. The results are shown in Table 4.
(1) Film-forming property A forward tapered hole having a square shape (80 μm × 80 μm), a depth of 100 μm, and a bottom surface shape of square (60 μm × 60 μm) on the surface [FIG. The substrate was spin-coated with propylene glycol monomethyl acetate as a solvent (1000 rpm, 3 seconds) on a stepped Si substrate having a diameter of 150 mm and a thickness of 500 μm, and the hole was filled with this solvent [see FIG. ]. Thereafter, the photosensitive resin composition was spin-coated (first stage; 300 rpm, 10 seconds, second stage; 600 rpm, 20 seconds) to form a coating film on the surface of the stepped Si substrate including the solvent surface in the hole. Next, the coated Si substrate is allowed to stand on a hot plate at a temperature of 110 ° C. for 5 minutes, and the solvent is volatilized to form a coating on the surface of the Si substrate and the inner wall surface and bottom surface of the hole. A substrate was obtained [see FIG. 2 (d)].
And the cross-sectional shape of the hole part was observed with the electron microscope, and the film formation property was evaluated on the following references | standards.
○: When the shoulder of the surface opening is completely covered by the coating, and the thickness of the coating on the inner wall surface and the bottom surface of the hole is substantially constant (see FIG. 13)
Δ: The shoulder of the surface opening is completely covered by the coating, but the film thickness on the inner wall surface and the bottom surface of the hole is not substantially constant (see FIG. 14).
X: When the shoulder of the surface opening is not completely covered by the coating, or when the hole is completely filled (see FIG. 15)
For reference, a cross-sectional photograph taken with an electron microscope of the coated silicon substrate obtained in Example 3 is shown in FIG. Further, FIG. 17 shows a cross-sectional photograph of the coated silicon substrate obtained in Comparative Example 3 with an electron microscope.

(2) Physical properties of resin composition (viscosity measurement)
About each resin composition, using a rheometer (model name “AR2000”, manufactured by T.A. Instruments Co., Ltd.), increasing the shear rate from 1 rpm to 1,000 rpm at a temperature of 25 ° C., 1.5, The viscosity at 5, 6, 50, 60 and 600 rpm was measured, and the ratio (V ₁ / V ₂ ) between the viscosity V ₁ at a shear rate of 6 rpm and the viscosity V ₂ (mPa · s) at a shear rate of 60 rpm, the shear rate of 1 The ratio (V ₃ / V ₄ ) of the viscosity V ₃ (mPa · s) at ₅ rpm to the viscosity V ₄ (mPa · s) at a shear rate of 600 rpm, and the viscosity V ₅ (mPa · s) at a shear rate of 5 rpm And a ratio (V ₅ / V ₆ ) to the viscosity V ₆ (mPa · s) at a shear rate of 50 rpm.
In addition, Table 4 shows the value of the viscosity V ₁ (mPa · s) in each resin composition.

(3) Sodium content The resin composition was diluted with propylene glycol monomethyl ether acetate, and the sodium content was measured using an atomic absorption spectrometer (manufactured by PerkinElmer, model number “Z5100”).

(4) Resolution The resin composition was spin-coated on a 6-inch silicon wafer and heated at 110 ° C. for 5 minutes using a hot plate to produce a uniform resin film having a thickness of 10 μm. Then, using an aligner (manufactured by Suss Microtec, model number “MA-150”), UV light from a high-pressure mercury lamp was exposed through a pattern mask so that the exposure amount at a wavelength of 350 nm was 6000 J / m ² . Next, immersion development was performed at 23 ° C. for 3 minutes using an aqueous 2.38 mass% tetramethylammonium hydroxide solution. And the minimum dimension of the obtained pattern was made into the resolution.

(5) Electrical insulation (volume resistivity)
The resin composition was applied to the SUS substrate by a spin coater (model number “1H-360S”, manufactured by MIKASA). Then, it heated for 3 minutes at 110 degreeC using the hotplate, and formed the uniform thin film with a film thickness of 10 micrometers. Subsequently, it heated at 170 degreeC for 2 hours using the convection type oven, and the test piece (insulating layer) was obtained. The obtained test piece was treated for 168 hours under the conditions of temperature: 121 ° C., humidity: 100%, pressure: 2.1 atm using a pressure cooker test apparatus (manufactured by Tabai Espec). The volume resistivity (Ω · cm) between the layers before and after the treatment was measured and used as an index of electrical insulation.

It is a schematic sectional drawing which shows the hole provided in the board | substrate. It is a schematic sectional drawing explaining the film formation method of this invention. It is a schematic sectional drawing explaining an example of the manufacturing method of the structure which has an insulating film of this invention. It is a schematic sectional drawing explaining the other example of the manufacturing method of the structure which has an insulating film of this invention. It is a schematic sectional drawing explaining the manufacturing method of the component (member 3) of the electronic component of this invention. It is a schematic sectional drawing explaining member 3 'which comprises the electronic component of this invention. It is a schematic sectional drawing explaining the component (member 3 ") of the electronic component of this invention. It is a schematic sectional drawing explaining the example of the electronic component of this invention. It is a schematic sectional drawing explaining the other manufacturing method of the member 3 'of FIG. It is a perspective image which shows the hole fracture surface of the silicon substrate before film formation used in the Example. 2 is a perspective image showing a hole fracture surface of a coated silicon substrate obtained in Example 1. FIG. 4 is a perspective image showing a hole fracture surface of a coated silicon substrate obtained in Comparative Example 1. FIG. It is an image which shows the hole cross section in which the film was formed. It is an image which shows the hole cross section in which the film was formed. It is an image which shows the hole cross section in which the film was formed. It is a perspective image which shows the hole fracture surface of the silicon substrate with a film obtained in Example 3. It is a perspective image which shows the hole fracture surface of the silicon substrate with a film obtained in Comparative Example 3.

Explanation of symbols

1; coating substrate 11; substrate 111; hole 113; solvent 115; coating 116; resin mixture and solvent mixture 117; coating 118 on the inner wall surface of the hole; coating 119 on the bottom surface of the hole; Film exposure part 129 on the bottom surface of the hole part; Film exposure parts 2 and 2 ′ on the substrate surface; Structure 217 having an insulating film; Insulating film (cured film) on the inner wall surface of the hole part
218; Insulating film on bottom of hole (cured film)
219; insulating film (cured film) on substrate surface
22; Through-holes 23a and 23b; Copper film (seed layer)
24; insulating resist coating 26; metal copper filling portion 3, 3 'and 3 "; member 31; upper member 311; electrode portion (conductive material filling portion)
311a and 311b; penetration electrode (conductive material filling part)
313, 313a and 313b; electrode pad 32; lower members 321a and 321b; penetrating electrode (conductive material filling portion)
Electrode pad 34; Insulating layer 4; Electronic component 41; Interposer 42; Bump 43; Bump 6; Laminated substrate 61; Substrate 621, 622 and 623; Film 625; Insulating film 63; Conductive material layer 635; Pad 66; conductive material filling portion 7; coated substrate 8; laminated structure.

Claims (14)

A substrate having a hole with an opening area of 25 to 10,000 μm ² and a depth of 10 to 200 μm, a solvent application step for applying a solvent, a resin component and a solvent, and a shear rate of 6 rpm The resin composition having a ratio (V ₁ / V ₂ ) of the viscosity V ₁ (mPa · s) to the viscosity V ₂ (mPa · s) at a shear rate of 60 rpm of 1.1 or more is the above-mentioned resin composition. A resin composition coating step for coating the substrate so as to come into contact with the solvent in the hole, and a drying step for drying the coating film, and at least the inner wall surface of the inner wall surface and the bottom surface of the hole portion And forming a film containing the resin component on the surface.   The coating film forming method according to claim 1, wherein the coating film is formed on both the inner wall surface and the bottom surface of the hole.   The film forming method according to claim 1 or 2, wherein the solid content concentration of the resin composition is in the range of 5 to 80 mass%. The film forming method according to claim 1, wherein the viscosity V ₁ is in a range of 10 to 10,000 mPa · s. In the resin composition, the ratio (V ₃ / V ₄ ) of the viscosity V ₃ (mPa · s) at a shear rate of 1.5 rpm and the viscosity V ₄ (mPa · s) at a shear rate of 600 rpm is 2.0 or more. The film forming method according to claim 1, wherein:   The film forming method according to claim 1, wherein the resin composition further contains metal oxide particles.   The film forming method according to claim 1, wherein the resin composition further contains particles made of a crosslinked polymer. A resin composition used in the film forming method according to claim 1,
A resin composition comprising an alkali-soluble resin, silica that has been hydrophobized and has an average particle diameter of 1 to 100 nm, a solvent, and a crosslinking agent.   Furthermore, it contains a compound having a quinonediazide group, and the content of the silica is more than 20% by mass and not more than 60% by mass when the solid content of the composition is 100% by mass. The resin composition according to claim 8.   The coating film formed on the surface of the substrate and the coating film formed on the bottom surface of the hole portion of the substrate obtained by the method according to any one of claims 1 to 7 are removed, and the hole portion An insulating film comprising: a surface bottom side film removing step for leaving a film formed on the inner wall surface; and a heat curing step for heating the film remaining on the inner wall surface of the hole. A method for producing a structure having the same.   A film formed on the entire surface of the substrate including the inner wall surface and the bottom surface of the hole obtained by the method according to any one of claims 1 to 7 is heated to include a cured product of the resin component. A heat curing step for forming an insulating film, and the insulating film formed on the surface of the substrate and the insulating film formed on the bottom surface of the hole of the substrate are removed and formed on the inner wall surface of the hole; And a process for producing a structure having an insulating film, comprising:   The structure having an insulating film according to claim 10 or 11, further comprising a polishing step of polishing the substrate from a surface having no hole in the structure having the insulating film, and using the hole as a through hole. Manufacturing method.   A structure having an insulating film obtained by the method according to claim 10.   A member including a structure having an insulating film obtained by the method according to any one of claims 10 to 12 and an electrode portion in which a conductive material is filled in at least a through hole of the structure. Features electronic components.