JP2010010490A - Structure with insulating film and method of manufacturing the same, resin composition, and electronic component - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a structure which has a uniform insulating film with superior electric insulation and a method of manufacturing the same, a resin composition which can form the insulating film, and an electronic component. <P>SOLUTION: The method of manufacturing the structure which has the insulating film includes a step of coating a substrate having a hole portion with a solvent, a step of coating the substrate with the resin composition so that the resin composition may come into contact with the solvent in the hole portion, a step of forming films 117, 118, and 119 containing a resin component on at least an internal wall surface between the internal wall surface and a bottom surface of the hole portion by drying the coating, a heating and curing step of heating the film formed on the entire surface of the substrate including the internal wall surface and bottom surface of the hole portion into insulating films 217, 218, and 219 containing a cured body of the resin component, and a surface and bottom surface-side insulating film removing step of removing the insulating film 219 formed on the surface of the substrate and the insulating film 218 formed on the bottom surface of the hole portion of the substrate, and leaving the insulating film 217 formed on the internal wall surface of the hole portion. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a structure having an insulating coating, a method for producing the structure, a resin composition, and an electronic component. More specifically, the present invention relates to a structure having a uniform insulating film excellent in electrical insulation, a method for producing the structure, a resin composition capable of forming an insulating film, 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 dipping in a photosensitive resist solution of 0 to 3.0 and pulling up (see, for example, Patent Documents 1 and 2). 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 JP 2004-307701 A Manabu Tomisaka “Denso Technical Review” Vol. 6 No. 2 (2001) p. 78-84

According to the resin composition disclosed in Patent Document 1, it is possible to form a film on the inner wall surface for a through hole, but not a through hole, but a fine hole (hereinafter referred to as “ When a film is formed on the inner wall surface of the "hole part"), there is a problem that the composition is settled and the hole part is filled with the composition.
According to the resin composition disclosed in Patent Document 2, it is possible to form a film on the inner wall surface for through holes, but in order to impart thixotropy, metal oxide fine particles such as an inorganic filler are used. Since it is used, the obtained insulating coating film is inferior in adhesion to the inner wall surface for through holes, so that the structure having the insulating coating film is inferior in electrical insulation.

  An object of this invention is to provide the structure which has a uniform insulating film excellent in electrical insulation, its manufacturing method, the resin composition which can form an insulating film, and an electronic component.

  As a result of earnest research to solve the above problems, the present inventors have used a composition having excellent film forming properties, a structure having a uniform insulating film excellent in electrical insulation, and a method for producing the structure, It came to discover the resin composition and electronic component which can form an insulating film.

The present invention is as follows.
[1] Solvent application step of applying a solvent to a substrate having a hole having an opening area of 25 to 10,000 μm ² , a depth of 10 to 200 μm and an aspect ratio of 0.5 to 20 When,
A resin composition application step for applying the resin composition to the substrate such that the resin composition contacts the solvent in the hole;
Drying the coating film, and forming a coating film containing the resin component on at least the inner wall surface of the inner wall surface and bottom surface of the hole; and
A heating and curing step of heating the coating formed on the entire surface of the substrate including the inner wall surface and the bottom surface of the hole to form an insulating coating containing a cured product of the resin component;
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 the insulating film formed on the inner wall surface of the hole is left. A front bottom side insulating coating removal step, and
The resin composition contains (A) a repeating unit represented by the following general formula (1), a polyimide containing a repeating unit represented by the following general formula (2), and (B) a solvent. The manufacturing method of the structure which has an insulating film characterized by these.
[In General Formula (1), X represents a tetravalent aromatic or aliphatic hydrocarbon group, and A represents a divalent organic group. ]
[In General Formula (2), X represents a tetravalent aromatic or aliphatic hydrocarbon group, B represents a substituted or unsubstituted alkylene group having 2 to 20 carbon atoms, or the following General Formula (3) A divalent group. However, B and A are not the same. ]
[In General Formula (3), Z represents a substituted or unsubstituted alkylene group having 2 to 20 carbon atoms. ]
[2] A method for producing a structure having an insulating coating according to the above [1], wherein A in the general formula (1) is a divalent organic group having a hydroxyl group.
[3] The method for producing a structure having the insulating coating according to [1] or [2], wherein the resin composition further contains (C) a crosslinking agent.
[4] Any of the above [1] to [3], further comprising a polishing step of polishing the substrate from the surface having no hole in the structure having the insulating coating and using the hole as a through hole. A method for producing a structure having the insulating coating according to claim 1.
[5] A structure having an insulating film obtained by the method according to any one of [1] to [4].
[6] A member including a structure having an insulating film obtained by the method described in [4] above and an electrode portion in which a conductive material is filled in at least a through hole of the structure. Features electronic components.
[7] Solvent application step for applying a solvent to a substrate having a hole having an opening area of 25 to 10,000 μm ² , a depth of 10 to 200 μm and an aspect ratio of 0.5 to 20 When,
A resin composition application step for applying the resin composition to the substrate such that the resin composition contacts the solvent in the hole;
Drying the coating film, and forming a coating film containing the resin component on at least the inner wall surface of the inner wall surface and bottom surface of the hole; and
A heating and curing step of heating the coating formed on the entire surface of the substrate including the inner wall surface and the bottom surface of the hole to form an insulating coating containing a cured product of the resin component;
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 the insulating film formed on the inner wall surface of the hole is left. A resin composition used in a method for producing a structure having an insulating coating, comprising:
(A) A resin composition comprising: a repeating unit represented by the following general formula (1); a polyimide containing a repeating unit represented by the following general formula (2); and (B) a solvent. object.
[In General Formula (1), X represents a tetravalent aromatic or aliphatic hydrocarbon group, and A represents a divalent organic group. ]
[In General Formula (2), X represents a tetravalent aromatic or aliphatic hydrocarbon group, B represents a substituted or unsubstituted alkylene group having 2 to 20 carbon atoms, or the following General Formula (3) A divalent group. However, B and A are not the same. ]
[In General Formula (3), Z represents a substituted or unsubstituted alkylene group having 2 to 20 carbon atoms. ]
[8] The resin composition according to [7], further including (C) a crosslinking agent.

According to the method for producing a structure having an insulating coating of the present invention, a specific resin composition is used, and a uniform insulating coating excellent in electrical insulation is efficiently applied to the inner wall surface of the hole in the substrate. The structure which can be formed and has an insulating film can be obtained easily. Moreover, a through-electrode can be easily formed by filling metal copper or the like into a through-hole having an insulating film of the resulting structure as an inner wall. 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.
The resin composition of the present invention can satisfactorily form the insulating coating in the method for producing a structure having an insulating coating.

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. Manufacturing method of structure having insulating film The manufacturing method of the structure having an insulating film of the present invention has an opening area of 25 to 10,000 μm ² , a depth of 10 to 200 μm, and an aspect ratio. A solvent coating step of applying a solvent to a substrate having a hole portion of 0.5 to 20, and applying the resin composition to the substrate so that the resin composition is in contact with the solvent in the hole portion. A resin composition coating step, a step of drying the coating film to form a coating film containing the resin component on at least the inner wall surface and the bottom surface of the hole portion, and an inner wall surface and a bottom surface of the hole portion. A heating and curing step of heating the coating formed on the entire surface of the substrate including the above to form an insulating coating containing a cured product of the resin component, the insulating coating formed on the surface of the substrate, and the substrate Formed on the bottom of the hole That the insulating film is removed, characterized in that it and a front bottom side insulating film removing step of leaving the insulating film formed on the inner wall surface of the hole portion.

Examples of the constituent material of the substrate used in 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 quadrangular columnar cross-sectional shape, the aspect ratio (ratio of the depth of the hole and the length of one side of the bottom of the hole) in the square of the vertical section is usually 0.5 to 20. , Preferably 1 to 10, more preferably 1 to 4.

Hereinafter, each process is demonstrated using FIG.2 and FIG.3.
(I) Solvent application process The said solvent application process is a process of apply | coating a solvent to the said board | substrate.
More specifically, when the solvent is applied to the substrate 11, the solvent 113 is normally filled in the hole 111 provided in the substrate 11 as shown in FIG. The solvent may uniformly wet the surface of the substrate 11.

  Examples of the solvent 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 and the like. 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 acetate Propylene glycol monoalkyl ether acetates such as propylene glycol monopropyl ether acetate and propylene glycol monobutyl ether acetate; cellosolves such as ethyl cellosolve and butyl cellosolve; carbitols such as butyl carbitol; methyl lactate, ethyl lactate and lactic acid Lactic acid esters such as n-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, propion Aliphatic carboxylic acid esters such as isobutyl acid; methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxypropio Other esters such as ethyl acid, methyl pyruvate and ethyl pyruvate; aromatic hydrocarbons such as toluene and xylene; ketones such as 2-heptanone, 3-heptanone, 4-heptanone and cyclohexanone; N-dimethylformamide Amides such as N-methylacetamide, N, N-dimethylacetamide and N-methylpyrrolidone; lactones such as γ-butyrolacun. These may be used individually by 1 type and may be used in combination of 2 or more type.

In this solvent application step, the method for applying the solvent to the substrate is not particularly limited, and examples thereof include an application method such as a spray method and a spin coat method, and an immersion 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.

(II) Resin composition coating step The resin composition coating step is to form a coating film by coating a specific resin composition on the substrate such that the resin composition contacts the solvent in the hole. It is a process to do. In addition, about the said specific resin composition, the detail is demonstrated in a back | latter stage.

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).

(III) Step of forming a film In the step of forming the film, the coating film formed by the resin composition coating step is dried and applied to at least the inner wall surface of the inner wall surface 117 and the bottom surface 118 of the hole. This is a step of forming the coatings 117 to 119 containing the resin component, that is, a step of removing only the solvent contained in the coating.
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.

  The solvent is removed by the step of forming the film, and a uniform film made of a 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, the type of the resin composition, 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.

(IV) Heat-curing step The heat-curing step heats 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, and includes a cured product of the resin component. This is a process for forming an insulating film (see FIG. 3B).
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 shown in FIG. 3B is obtained by the heat curing step, and this structure has a substrate 11 having a hole, an insulating coating 219 formed on the surface of the substrate, and the hole. Insulating film 217 formed on the inner wall surface of the part, and insulating film 218 formed on the bottom surface of the hole.

(V) Front-and-bottom-side insulating coating removal step The front-and-bottom-side insulating coating removal step includes the insulating coating 219 formed on the surface of the substrate and the insulation formed on the bottom surface of the hole of the substrate. This is a step of removing the insulating coating 218 and leaving the insulating coating 217 formed on the inner wall surface of the hole.
Examples of a method for selectively removing the insulating coatings 218 and 219 include anisotropic etching (dry etching).
The structure 2 having the insulating coating shown in FIG. 3C is obtained by the front and bottom insulating coating removing step, and this structure 2 includes a substrate 11 having a hole and a hole in the substrate. And a cured film 217 formed on the inner wall surface.

In the method for producing a structure having an insulating coating according to the present invention, after the surface bottom insulating coating removing step, the substrate 11 is polished from the surface having no hole so that the hole is a through-hole. A polishing step of 22 can be further provided (see FIG. 3D). Through this step, a through-hole structure having an insulating coating can be obtained.
The polishing method at this time 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. 3D 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.

2. 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 method for producing a structure of the present invention. The structure includes a member including an electrode portion (conductive material filling portion) in which at least a through hole of the structure is filled with a conductive material.
As an electronic component of the present invention, for example, a member 3 (including a structure 2 ′ shown in FIG. 3D) and an electrode portion (conductive material filling portion) 311 in at least a through hole of the structure 2 ′ ( 4 (g)).

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. 4G, 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 a method for manufacturing the member 3 shown in FIG. 4G will be described with reference to FIG.
First, the structure 2 having an insulating film shown in FIG. 3C is prepared (see FIG. 4A). 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. 4B). 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. 4C). Next, Cu filling plating into the holes is performed using an aqueous copper sulfate solution or the like (see FIG. 4D). Thereafter, the insulating resist film 24 is peeled off using a predetermined peeling liquid or the like (see FIG. 4E). 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. 4F). 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.4 (g) is obtained.

The member provided with the through electrode may be a member 3 ′ shown in FIG. The member 3 ′ includes a substrate 11 having a conductive material filling portion 311 filled with a conductive material in a through hole penetrating the front and back and having an insulating film 217 formed on the inner wall surface, and the conductive material filling An electrode pad 313 covering at least the lower exposed surface (lower exposed surface in the drawing) of the portion 311.
The member 3 ′ in FIG. 5 forms an electrode pad on the lower exposed surface (the lower side in FIG. 4G) of the conductive material filling portion 311 of the member 3 shown in FIG. 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. 6 is an example using the member 3 shown in FIG. 4G 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) It is a composite member formed by joining the surface of 321b, and an insulating layer 34 is disposed at the interface between the upper member 31 and the lower member 32 (see FIG. 6). The bonding method of the filling portion (through 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. 4G, a member 3 ′ shown in FIG. 5, a member 3 ″ shown in FIG. 7, the electrode pads 323a and 323b of the member 3 ″ shown in FIG. 6 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.).

5A to 5C is formed using a composite substrate in which a conductive material layer 313 is formed in advance and the bottom surface of the hole portion is the conductive material layer 313. 4 (b) to (b) in the hole portion having the conductive material layer 313 on the lower side of the opening of the through hole (lower side of FIG. 3 (d)) of the member 2 ′ (FIG. 3 (d)) obtained by the above step. It can be manufactured by a method including a step of filling a conductive material by the step f).
Furthermore, it can also be manufactured by applying the method for manufacturing a structure having an insulating film of the present invention, using the laminated substrate 6 having the recesses shown in FIG.
The laminated substrate 6 shown in FIG. 8A is made of silicon, various metals, various metal sputtered films, alumina, glass epoxy, paper phenol, glass, etc., and is columnar from one surface 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, and still more preferably 50 to 100 μm. The area of the opening of the recess, the cross-sectional shape, etc. By applying this method in the same manner as the manufacturing method of the structure having a conductive film, the member 3 ′ shown in FIG. 8E, that is, the member 3 ′ shown in FIG. 5 can be manufactured.

A method for manufacturing the member 3 ′ shown in FIG. First, a coating film is formed by applying a solvent to the surface of the substrate 61 constituting the laminated substrate 6 (solvent application step) and then applying a specific resin composition (resin composition application step). 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. 8B).
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. 8 ( c)).

Next, part of the conductive material layer 63 is removed by etching or the like so as not to penetrate the recess, thereby forming an electrode pad 635 (see FIG. 8D), and copper, silver, tungsten, tantalum, titanium in the recess. By filling a conductive material selected from ruthenium, gold, tin, aluminum, and an alloy containing these, the insulating film 625 penetrates the front and back surfaces shown in FIG. 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. 8E) of the conductive material filling portion 66 are covered with the through hole formed with the conductive material. A member 3 ′ having an electrode pad 635 to be obtained can be obtained.
Therefore, the electronic component of the present invention can be configured using the member 3 ′ obtained by using the multilayer substrate 6 shown in FIG.

3. Resin composition The resin composition in this invention contains a specific polyimide (A) and a solvent (B).

(3-1) Polyimide (A)
The (A) polyimide (hereinafter also referred to as “polyamide (A)”) contained as the resin component in the resin composition of the present invention is a repeating unit represented by the following general formula (1) (hereinafter referred to as “repeating unit ( 1) ") and a repeating unit represented by the following general formula (2) (hereinafter also referred to as" repeating unit (2) "). Since the resin composition in the present invention contains a resin component having an imide structure in such a molecular structure, it is possible to obtain an insulating film having excellent film forming properties and excellent electrical insulating properties.

[In General Formula (1), X represents a tetravalent aromatic or aliphatic hydrocarbon group, and A represents a divalent organic group. ]

[In General Formula (2), X represents a tetravalent aromatic or aliphatic hydrocarbon group, B represents a substituted or unsubstituted alkylene group having 2 to 20 carbon atoms, or the following General Formula (3) A divalent group. However, B and A are not the same. ]

[In General Formula (3), Z represents a substituted or unsubstituted alkylene group having 2 to 20 carbon atoms. ]

X in the general formulas (1) and (2) is a tetravalent aromatic hydrocarbon group or a tetravalent aliphatic hydrocarbon group, preferably a tetravalent aliphatic hydrocarbon group.
X in the repeating unit (1) and X in the repeating unit (2) may be the same or different.

  Examples of the tetravalent aromatic hydrocarbon group include a tetravalent group in which four hydrogens in the mother skeleton of the aromatic hydrocarbon are substituted. Specifically, the following structures (X1-1) to (X1-6) can be exemplified.

Examples of the tetravalent aliphatic hydrocarbon group include a chain hydrocarbon group, an alicyclic hydrocarbon group, and an alkyl alicyclic hydrocarbon group. More specifically, a tetravalent group in which four hydrogens in the base skeleton of a chain hydrocarbon group, an alicyclic hydrocarbon, or an alkyl alicyclic hydrocarbon are substituted can be given. These tetravalent aliphatic hydrocarbon groups may contain an aromatic ring in at least a part of the structure.
Here, examples of the chain hydrocarbon include ethane, n-propane, n-butane, n-pentane, n-hexane, n-octane, n-decane, and n-dodecane.

Specific examples of the alicyclic hydrocarbon group include a monocyclic hydrocarbon group, a bicyclic hydrocarbon group, a tricyclic or higher hydrocarbon group, and the like.
Examples of monocyclic hydrocarbons include cyclopropane, cyclobutane, cyclopentane, cyclopentene, cyclohexane, cyclohexene, cyclooctane and the like.
Bicyclic hydrocarbons include bicyclo [2.2.1] heptane, bicyclo [3.1.1] heptane, bicyclo [3.1.1] hept-2-ene, bicyclo [2.2.2]. Examples include octane and bicyclo [2.2.2] oct-7-ene.
Tricyclic or higher hydrocarbons include tricyclo [5.2.1.0 ^2,6 ] decane, tricyclo [5.2.1.0 ^2,6 ] dec-4-ene, adamantane, and tetracyclo [6. 2.1.1 ^3,6 . 0 ^2,7 ] dodecane and the like.

Moreover, as said alkyl alicyclic hydrocarbon, what substituted said alicyclic hydrocarbon by alkyl groups, such as a methyl group, an ethyl group, a propyl group, a butyl group, can be mentioned. More specifically, methylcyclopentane, 3-ethyl-1-methyl-1-cyclohexene, 3-ethyl-1-cyclohexene and the like can be mentioned.
The tetravalent aliphatic hydrocarbon group containing an aromatic ring in at least a part of the structure preferably has 3 or less aromatic rings in one molecule. It is particularly preferable that More specifically, 1-ethyl-6-methyl-1,2,3,4-tetrahydronaphthalene, 1-ethyl-1,2,3,4-tetrahydronaphthalene and the like can be mentioned.

As a mother nucleus of a tetravalent group preferable as X, n-butane, cyclobutane, cyclopentane, cyclohexane, bicyclo [2.2.1] heptane, bicyclo [2.2.2] octane, bicyclo [2.2. 2] Oct-7-ene, tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodecane, methylcyclopentane and the like.

  Further, as X, the following structures (X2-1) to (X2-8) are more preferable, structures (X2-1) and (X2-6) are particularly preferable, and structure (X2-1) is most preferable. .

  A in the general formula (1) is a divalent organic group. Specific examples of the divalent organic group include a divalent group represented by the following general formula (4).

[In General Formula (4), R ¹ represents a single bond, an oxygen atom, a sulfur atom, or a divalent group, R ² independently of each other represents a hydrogen atom, an acyl group, or an alkyl group, and at least one of them Is a hydrogen atom. n ¹ and ^{n 2,} respectively, an integer of 0 to 2. ]

Examples of the divalent group in R ¹ of the general formula (4) include a sulfone group, a carbonyl group, a methylene group, an alkylene group (excluding a methylene group), a dimethylmethylene group, and a bis (trifluoromethyl) methylene group. Is mentioned.

Preferred examples acyl group in R ² of the general formula (4), for example, a formyl group, an acetyl group, a propionyl group, butyroyl group, isobutyroyl group, and the like.
Preferred examples of the alkyl group for R ² include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-octyl group, and an n-decyl group. , N-dodecyl group and the like.

Further, ^{n 1} and ^{n 2} in formula (4) are each an integer of 0 to 2, at least one of ^{n 1} and ^{n 2} is 1 or more is preferable from the viewpoint of film-forming.

  Specific examples of “A” in the general formula (1) include divalent groups having one hydroxyl group such as the following structures (A1) to (A3), and hydroxyl groups such as the following structures (A4) to (A13). A divalent group having two hydroxyl groups, a divalent group having three hydroxyl groups such as the following structures (A14) to (A16), and a divalent group having four hydroxyl groups such as the following structures (A17) to (A19): Etc. Among these, a divalent group having two hydroxyl groups is preferable, and (A4), (A8), and (A12) are particularly preferable.

B in the general formula (2) is a substituted or unsubstituted alkylene group having 2 to 20 carbon atoms or a divalent group represented by the general formula (3). However, it is not the same as A in the general formula (1).
Specifically, the substituted or unsubstituted alkylene group having 2 to 20 carbon atoms is preferably an alkylene group having 4 or more carbon atoms. Examples of the alkylene group having 4 or more carbon atoms include alkylene groups having 4 carbon atoms such as 1,4-butylene group; alkylene groups having 5 carbon atoms such as 1,5-pentylene group; 2-methyl-1,5 Examples thereof include alkylene groups having 6 carbon atoms such as a pentylene group and 1,6-hexylene group; alkylene groups having 7 to 20 carbon atoms such as a 1,10-decylene group and 1,12-dodecylene group. Of these, an alkylene group having 6 or more carbon atoms is preferable, and an alkylene group having 7 to 20 carbon atoms is more preferable from the viewpoint of improving the solubility of the polymer in a solvent.

Z in the said General formula (3) is a C2-C20 substituted or unsubstituted alkylene group.
Specifically, the substituted or unsubstituted alkylene group having 2 to 20 carbon atoms is preferably an alkylene group having 3 or more carbon atoms. Examples of the alkylene group having 3 or more carbon atoms include alkylene groups having 3 to 5 carbon atoms such as 1,3-propylene group, 2,2-dimethylpropylene group, 1,4-butylene group and 1,5-pentylene group. An alkylene group having 6 carbon atoms such as 2-methyl-1,5-pentylene group and 1,6-hexylene group; an alkylene group having 7 to 20 carbon atoms such as 1,10-decylene group and 1,12-dodecylene group; Etc.

  Moreover, as a bivalent group shown by the said General formula (3), the bivalent group of the following structure (B1)-(B4) is especially preferable.

  The polyamide (A) contains only one type of the repeating unit (1) represented by the general formula (1) and the repeating unit (2) represented by the general formula (2). It may be contained, or two or more kinds may be contained.

  Moreover, when the sum total of the repeating unit (1) and the repeating unit (2) which comprise the said polyimide (A) is 100 mol%, the content rate of a repeating unit (1) may be 40-100 mol%. More preferably, it is 60-100 mol%, More preferably, it is 70-100 mol%.

  The polyimide (A) includes, for example, a monomer represented by the following general formula (5) (hereinafter also referred to as “monomer (5)”), a monomer represented by the following general formula (6) (hereinafter referred to as “monomer (6)”). And a monomer represented by the following general formula (7) (hereinafter also referred to as “monomer (7)”) in a polymerization solvent to synthesize a polyamic acid, and further carry out an imidization reaction. Obtainable.

X ′ in the general formula (5) has the same meaning as X in the general formula (1), and the description of X can be applied as it is.
R ³ , R ⁴ , m ¹ and m ² in the general formula (6) have the same meanings as R ¹ , R ² , n ¹ and n ² in the general formula (4), respectively. It can be applied as it is.
B ′ in the general formula (7) has the same meaning as B in the general formula (2), and the description of B can be applied as it is.

  The following two types of methods are generally known for synthesizing the above polyamic acid, and may be synthesized by any method. That is, (i) a method in which the monomer (6) and the monomer (7) are dissolved in the polymerization solvent and then the monomer (5) is reacted; (ii) after the monomer (5) is dissolved in the polymerization solvent, the monomer ( 7) is reacted, and the monomer (6) is further reacted.

  Examples of the polymerization solvent are generally aprotic solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, γ-butyrolactone, and dimethyl sulfoxide; protic solvents such as metacresol Is used. If necessary, alcohol solvents such as methanol, ethanol, propanol, butanol, 2-methoxyethanol, 2-ethoxyethanol, 2- (2-methoxyethoxy) ethanol, 2- (2-ethoxyethoxy) ethanol; diglyme , Ether solvents such as triglyme; aromatic hydrocarbon solvents such as toluene and xylene may be added.

  As the imidization reaction, a heating imidization reaction and a chemical imidation reaction are usually known, but it is preferable to synthesize a polymer (A) by a heating imidization reaction. The heating imidization reaction is usually performed by heating a synthesis solution of polyamic acid at 120 to 210 ° C. for 1 to 16 hours. If necessary, the reaction may be performed while removing water in the system using an azeotropic solvent such as toluene or xylene.

Moreover, when synthesizing the polyamide (A), when the total of the monomers (5), (6) and (7) is 100 mol%, the ratio of the monomer (5) is usually 40 to 60 mol%. Yes, preferably 45 to 55 mol%. When the proportion of the monomer (5) is out of the above range, the molecular weight of the resulting polymer tends to decrease.
Moreover, when the sum total of the said monomer (6) and (7) is 100 mol%, the ratio of a monomer (6) is 10-99 mol% normally, Preferably it is 20-95 mol%, More preferably Is 30-90 mol%.

  The polystyrene-converted weight average molecular weight (hereinafter also referred to as “Mw”) measured by gel permeation chromatography (GPC) of the polyimide (A) is usually about 2,000 to 500,000, preferably 3,000. About 200,000. If Mw is less than 2,000, sufficient mechanical properties as an insulating film tend not to be obtained. On the other hand, when Mw exceeds 500,000, the solubility of the resin composition obtained using polyimide (A) in a solvent or a developer tends to be poor.

Moreover, the said polyimide (A) may be contained individually by 1 type in the resin composition in this invention, and may be contained 2 or more types.
The content ratio of the polyimide (A) is preferably 50 to 100% by mass, more preferably 60 to 100% by mass, and still more preferably, when the solid content in the resin composition is 100% by mass. It is 70-100 mass%. When this content ratio is in the above range, an insulating coating excellent in electrical insulation can be obtained.

(3-2) Solvent (B)
The solvent (B) which comprises the said resin composition is not specifically limited, What was illustrated in the solvent application | coating process in the manufacturing method of the structure which has the insulating film mentioned above can be used.
The solvent (B) may be the same as or different from the solvent used in the solvent application step.
The content of the solvent is used so that the solid content concentration of the resin composition is usually 5 to 80% by mass, preferably 10 to 60% by mass, and more preferably 25 to 60% by mass.

In addition to the components (A) and (B), the resin composition in the present invention may contain a crosslinking agent (C) for the purpose of improving the electrical insulation of the insulating coating.
(3-3) Crosslinking agent (C)
The crosslinking agent (C) includes 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; and a thiirane ring Compounds; oxetanyl group-containing compounds; isocyanate group-containing compounds (including blocked ones) 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 may be used individually by 1 type and may be used in combination of 2 or more type.

  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 may be used individually by 1 type and may be used in combination of 2 or more type.

  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.

  The content of the crosslinking agent (C) is preferably 1 to 100 parts by mass, more preferably 10 to 75 parts by mass, and still more preferably 10 to 100 parts by mass, when the polyimide (A) is 100 parts by mass. 50 parts by mass. When this content ratio is in the above range, an insulating coating excellent in electrical insulation can be obtained.

(3-4) Other Additives In addition to the components (A) to (C), the resin composition in the present invention may contain other additives.
Examples of the other additives include adhesion assistants, surfactants, and crosslinked polymer particles.
A functional silane coupling agent is preferably used as the adhesion aid. For example, the silane coupling agent which has reactive substituents, such as a carboxyl group, a methacryloyl group, an isocyanate group, an epoxy group, is mentioned. Specifically, trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, β -(3,4-epoxycyclohexyl) ethyltrimethoxysilane, 1,3,5-N-tris (trimethoxysilylpropyl) isocyanurate and the like. These may be used individually by 1 type and may be used in combination of 2 or more type.
The content ratio of the adhesion assistant is preferably 0.5 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, when the polyimide (A) is 100 parts by mass.

Examples of the surfactant include “BM-1000” and “BM-1100” manufactured by BM Chemie; “Megafac F142D”, “Same F172” and “Same F173” manufactured by Dainippon Ink and Chemicals, Inc. “Same F183”; “Florard FC-135”, “Same FC-170C”, “Same FC-430”, “Same FC-431” manufactured by Sumitomo 3M; “Surflon S-112” manufactured by Asahi Glass Co., Ltd. “S-113”, “S-131”, “S-141”, “S-145”; “SH-28PA”, “-190” manufactured by Toray Dow Corning Silicone Co., “ -193 "," SZ-6032 "," SF-8428 "; Fluorosurfactants such as" NBX-15 "manufactured by Neos;" Nonion S-6 "," Nonion O- "manufactured by Nippon Oil & Fats Co., Ltd. 4 "," Pronon 201 ""Plonon204"; manufactured by Kao Corp., "Emulgen A-60", "the A-90", it is possible to use nonionic surface active agents such as "the A-500". These may be used individually by 1 type and may be used in combination of 2 or more type.
In general, the content of the surfactant is preferably 5 parts by mass or less when the polyimide (A) is 100 parts by mass.

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 polyimide (A) 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 still more 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 polyimide (A) is 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 resin composition contains the crosslinked polymer particles, the content is preferably 1 to 100 parts by mass, more preferably 5 to 80 parts by mass when the polyimide (A) is 100 parts by mass. Parts, more preferably 5 to 50 parts by mass. 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.

(3-5) Solid content concentration of resin composition The solid content concentration of the resin composition is preferably 5 to 80 mass%, more preferably 20 to 60 mass%.
Further, the viscosity 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 further Preferably, it is 50 to 5,000 mPa · s. When this viscosity is in the above-mentioned range, it is excellent in film-forming properties for at least the inner wall surface of the hole and the bottom wall surface, and a more uniform film can be obtained.

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

[1] Synthesis of polymer (polyimide) (1) Monomers used In each of the following syntheses, compounds MA-1, MA-2, MB-1, MB-2, MC-1, MC- having the following structures: 2 was used as a monomer.

(2) Synthesis of polyimide (A-1) In a separable flask with a capacity of 500 mL, 2,2-bis (3-amino-4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane was added. [Monomer (MA-1)] 222.7 g (77 mol%), 1,10-decylylenediamine [monomer (MB-1)] 36.6 g (23 mol%), and N-methyl-2-pyrrolidone (NMP) 384 g was added. Subsequently, after stirring at room temperature to dissolve each monomer, 156.7 g (100 mol%) of 1,2,3,4-butanetetracarboxylic dianhydride [monomer (MC-2)] was charged. And after stirring at 120 degreeC for 5 hours under nitrogen, it heated up at 180 degreeC and performed dehydration reaction for 5 hours. After completion of the reaction, the reaction mixture was poured into water, and the product was reprecipitated, filtered, and vacuum dried to obtain 362 g of the polymer (A-1). The weight average molecular weight Mw of the obtained polymer was 19800. Further, as a result of IR analysis, it was confirmed that there was absorption at 1778 cm ⁻¹ indicating imide. Hereinafter, this polymer (A-1) is referred to as polyimide (A-1).

(3) Synthesis of polyimides (A-2) to (A-4) A polymer (A-) was prepared in the same manner as in Synthesis Example 1 except that each monomer and NMP were blended according to the blending formulation shown in Table 1. 2) to (A-4) were obtained. And the yield (g) and weight average molecular weight Mw of each polymer in this case were shown in Table 1. Moreover, it was confirmed by IR analysis that each polymer had an absorption of 1778 cm ⁻¹ indicating imide. Hereinafter, the polymers (A-2) to (A-4) are referred to as polyimides (A-2) to (A-4).

[2] Preparation of resin composition (1) Example 1
As shown in Table 2, 100 parts by mass of (A) resin [polyimide (A-1)] and 30 parts by mass of (C) cross-linking agent (C-1) so that the solid content concentration is 36% by mass, (B) A resin composition was prepared by dissolving in 230 parts by mass of the solvent (B-2).

(2) Examples 2-7 and Comparative Examples 1-3
In the same manner as in Example 1, as shown in Table 2, each resin composition was prepared by dissolving (A) the resin and (C) the crosslinking agent in (B) the solvent so that the solid content concentration was 36% by mass. A product was prepared.

In addition, the composition described in Table 2 is as follows.
<(A) Resin>
A-1 to A-4: Polyimide synthesized as described above A-5: Thermoplastic polyimide, manufactured by Shin Nippon Rika Co., Ltd., trade name “RIKACOAT SN-20”

AR-1: phenol novolac resin, manufactured by Sumitomo Bakelite Co., Ltd., trade name “Sumilite Resin S-2”
AR-2: p-hydroxystyrene-styrene copolymer, manufactured by Maruzen Petrochemical Co., Ltd., trade name “Marcalinker S-2P”
AR-3: Radical copolymer of acrylic acid / butyl acrylate / hydroxyethyl acrylate (weight average molecular weight: 10,000)
<(B) Solvent>
B-1: Ethyl lactate B-2: Propylene glycol monomethyl ether acetate B-3: N-methyl-2-pyrrolidone
<(C) Crosslinking agent>
C-1: Hexamethoxymethylmelamine (Mitsui Cytec Co., Ltd., trade name "Cymel 300")

[3] Evaluation of Resin Composition Each resin composition of Examples 1 to 7 and Comparative Examples 1 to 3 was evaluated according to the following method. The results are also shown in Table 2.
(1) Film-formability On the surface, 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) (FIG. 1B) 9) and a step Si substrate having a diameter of 150 mm and a thickness of 500 μm was spin-coated with propylene glycol monomethyl acetate as a solvent (1000 rpm, 3 seconds), and the hole was filled with this solvent (FIG. 2 ( b)). 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 volatilized to form a film on the surface of the silicon 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 with the coating, and the thickness of the coating on the inner wall surface and the bottom of the hole is substantially constant (see FIG. 10)
Δ: The shoulder of the surface opening is completely covered with the coating, but the film thickness on the inner wall surface and the bottom surface of the hole is not substantially constant (see FIG. 11).
X: When the shoulder of the surface opening is not completely covered by the coating, or when the hole is completely filled (see FIG. 12)

(2) 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 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. 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.

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 (cured film) on bottom of hole
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; Electrode pad 66; conductive material filling portion 7; coated substrate 8; laminated structure.

Claims (8)

A solvent application step of applying a solvent to a substrate having a hole portion having an opening area of 25 to 10,000 μm ² , a depth of 10 to 200 μm and an aspect ratio of 0.5 to 20;
A resin composition application step for applying the resin composition to the substrate such that the resin composition contacts the solvent in the hole;
Drying the coating film, and forming a coating film containing the resin component on at least the inner wall surface of the inner wall surface and bottom surface of the hole; and
A heating and curing step of heating the coating formed on the entire surface of the substrate including the inner wall surface and the bottom surface of the hole to form an insulating coating containing a cured product of the resin component;
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 the insulating film formed on the inner wall surface of the hole is left. A front bottom side insulating coating removal step, and
The resin composition contains (A) a repeating unit represented by the following general formula (1), a polyimide containing a repeating unit represented by the following general formula (2), and (B) a solvent. The manufacturing method of the structure which has an insulating film characterized by these.
[In General Formula (1), X represents a tetravalent aromatic or aliphatic hydrocarbon group, and A represents a divalent organic group. ]
[In General Formula (2), X represents a tetravalent aromatic or aliphatic hydrocarbon group, B represents a substituted or unsubstituted alkylene group having 2 to 20 carbon atoms, or the following General Formula (3) A divalent group. However, B and A are not the same. ]
[In General Formula (3), Z represents a substituted or unsubstituted alkylene group having 2 to 20 carbon atoms. ]   The method for producing a structure having an insulating coating according to claim 1, wherein A in the general formula (1) is a divalent organic group having a hydroxyl group.   The method for producing a structure having an insulating coating according to claim 1 or 2, wherein the resin composition further contains (C) a crosslinking agent.   The insulating property according to any one of claims 1 to 3, further comprising a polishing step of polishing the substrate from the surface having no hole portion in the structure having the insulating coating and using the hole portion as a through hole. A method for producing a structure having a coating.   A structure having an insulating film obtained by the method according to claim 1.   An electron comprising: a structure including an insulating film obtained by the method according to claim 4; and an electrode portion in which at least a through hole of the structure is filled with a conductive material. parts. A solvent application step of applying a solvent to a substrate having a hole portion having an opening area of 25 to 10,000 μm ² , a depth of 10 to 200 μm and an aspect ratio of 0.5 to 20;
A resin composition application step for applying the resin composition to the substrate such that the resin composition contacts the solvent in the hole;
Drying the coating film, and forming a coating film containing the resin component on at least the inner wall surface of the inner wall surface and bottom surface of the hole; and
A heating and curing step of heating the coating formed on the entire surface of the substrate including the inner wall surface and the bottom surface of the hole to form an insulating coating containing a cured product of the resin component;
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 the insulating film formed on the inner wall surface of the hole is left. A resin composition used in a method for producing a structure having an insulating coating, comprising:
(A) A resin composition comprising: a repeating unit represented by the following general formula (1); a polyimide containing a repeating unit represented by the following general formula (2); and (B) a solvent. object.
[In General Formula (1), X represents a tetravalent aromatic or aliphatic hydrocarbon group, and A represents a divalent organic group. ]
[In General Formula (2), X represents a tetravalent aromatic or aliphatic hydrocarbon group, B represents a substituted or unsubstituted alkylene group having 2 to 20 carbon atoms, or the following General Formula (3) A divalent group. However, B and A are not the same. ]
[In General Formula (3), Z represents a substituted or unsubstituted alkylene group having 2 to 20 carbon atoms. ]   Furthermore, (C) The resin composition of Claim 7 containing a crosslinking agent.