WO2009150918A1 - Structure having insulating coating film, method for producing the same, positive photosensitive resin composition and electronic device - Google Patents

Abstract

Disclosed is a structure comprising a uniform insulating coating film having excellent electrical insulation and thermal shock resistance.  A method for producing the structure, a positive photosensitive resin composition with excellent resolution which can form an insulating coating film, and an electronic device are also disclosed.  The method for producing a structure having an insulating coating film comprises a solvent application step wherein a solvent is applied over a substrate having a pore; a resin composition coating step wherein a positive photosensitive resin composition is coated over the substrate in such a manner that the resin composition is brought into contact with the solvent in the pore; a step wherein the coated composition is dried so that coating films (117, 118, 119) containing the resin component are formed on at least the inner wall surface among the inner wall surface and bottom surface of the pore; a top/bottom surface coating film removal step wherein a certain region of the coating film formed on the top surface of the substrate is exposed to light and subjected to a process using an alkaline solution, thereby having the coating film (117) formed on the inner wall surface of the pore remain thereon; and a heating/curing step wherein the coating film (117) remaining on the inner wall surface of the pore is heated.

Description

Structure having insulating film and method for producing the same, positive photosensitive resin composition, and electronic component

The present invention relates to a structure having an insulating coating, a method for producing the structure, a positive photosensitive resin composition, and an electronic component. More specifically, the present invention relates to a structure having a uniform insulating film excellent in electrical insulation and thermal shock, a method for producing the structure, and a positive photosensitive film which can form an insulating film and has excellent resolution. The present invention relates to a resin composition and an electronic component.

Conventionally, an insulating substrate having through holes, via inner wall surfaces, and metal conductor layers formed on both sides of a 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 0.0 to 3.0 and pulling 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 2005-158907 A

According to the photosensitive resin composition disclosed in Patent Document 1, it is possible to form a film on the inner wall surface for a through hole, but it is not a through-hole but a micro-hole (hereinafter referred to as an opening) having a small opening area. When the film is formed on the inner wall surface of the "hole part"), there is a problem in that sedimentation of the composition occurs and the hole part is filled with the composition.
Also, the insulating film formed on the inner wall surface of the through-hole must have excellent electrical insulation and excellent thermal shock resistance without cracking in the insulating film under high temperature and high humidity. It has been.
Furthermore, the resin composition for forming the insulating film is required to have excellent resolution.

The present invention relates to a structure having a uniform insulating film excellent in electrical insulation and thermal shock, a method for producing the structure, a positive photosensitive resin composition that can form an insulating film and is excellent in resolution, An object is to provide an electronic component.

As a result of intensive studies to solve the above problems, the present inventors have used a composition having excellent film forming properties, and have a structure having a uniform insulating film excellent in electrical insulation and thermal shock resistance, and its structure The present inventors have found a manufacturing method, a positive photosensitive resin composition capable of forming the insulating coating and having excellent resolution, and an electronic component.

The present invention is as follows.
[1] A 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 1 to 10;
Resin composition for coating a positive photosensitive resin composition containing the following (A) to (D) on the substrate so that the positive photosensitive resin composition is in contact with the solvent in the hole. An object application process;
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
Exposing a predetermined region of the film formed on the surface of the substrate, treating with an alkaline solution, and leaving a film formed on the inner wall surface of the hole to leave the film on the bottom surface side;
And a heat curing step for heating the coating film remaining on the inner wall surface of the hole. A method for producing a structure having an insulating coating film.
(A) an alkali-soluble resin,
(B) a quinonediazide compound,
(C) Inorganic particles (D) Solvent [2] The positive photosensitive resin composition further comprises (E) a compound (E1) having an alkyl etherified amino group, and an aliphatic polyglycidyl ether (E2). And the manufacturing method of the structure which has an insulating film as described in said [1] containing the crosslinking agent containing.
[3] The method for producing a structure having the insulating coating according to [1] or [2], wherein the positive photosensitive resin composition further contains (F) crosslinked polymer particles.
[4] The above [1] to [1], further comprising a polishing step of polishing the substrate from the surface having no hole in the structure including the through hole having the insulating coating, and using the hole as a through hole. 3] The manufacturing method of the structure which has an insulating film in any one of.
[5] A structure having an insulating film obtained by the method according to any one of [1] to [4].
[6] A member comprising a structure provided with a through-hole having an insulating film obtained by the method described in [4] above, and an electrode part in which at least the through-hole of the structure is filled with a conductive material An electronic component comprising:
[7] A 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 1 to 10,
A resin composition application step of applying a positive photosensitive resin composition to the substrate such that the positive photosensitive resin composition is in contact with 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
Exposing a predetermined region of the film formed on the surface of the substrate, treating with an alkaline solution, and leaving a film formed on the inner wall surface of the hole to leave the film on the bottom surface side;
A positive-type photosensitive resin composition used in a method for producing a structure having an insulating coating, comprising a heating and curing step of heating a coating remaining on the inner wall surface of the hole,
A positive photosensitive resin composition comprising (A) an alkali-soluble resin, (B) a quinonediazide compound, (C) inorganic particles, and (D) a solvent.
[8] The positive type as described in [7] above, further comprising (E) a crosslinking agent containing an alkyl etherified amino group-containing compound (E1) and an aliphatic polyglycidyl ether (E2). Photosensitive resin composition.
[9] The positive photosensitive resin composition according to [7] or [8], further including (F) crosslinked polymer particles.

According to the method for producing a structure having an insulating film of the present invention, a specific positive photosensitive resin composition is used, and the inner wall surface of the hole in the substrate is uniformly excellent in electrical insulation and crack resistance. Insulating film can be efficiently formed, and a structure having an insulating film can be easily obtained. 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 positive photosensitive resin composition of the present invention is excellent in resolution, and can be formed satisfactorily in the method for producing a structure having an insulating coating.

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. 2 is a perspective image showing a hole fracture surface of a coated silicon substrate obtained in 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 sectional drawing of the base material for thermal shock-proof evaluation. It is a schematic diagram of the base material for thermal shock evaluation.

DESCRIPTION OF SYMBOLS 1; Substrate with a film, 11; Substrate, 111; Hole, 113; Solvent, 115; Coating, 116; Mixture of resin composition and solvent, 117; Film on the inner wall surface of the hole, 118; 119; coating film on substrate surface, 128; coating exposure section on bottom surface of hole, 129; coating exposure section on substrate surface, 2 and 2 ′; structure having insulating coating, 217; insulating coating on inner wall surface of hole (curing) Membrane), 218; Insulating film (cured film) on bottom surface of hole, 219; Insulating film (cured film) on substrate surface, 22; Through hole, 23a and 23b; Copper film (seed layer), 24; Resist coating, 26; Metal copper filling part, 3, 3 ′ and 3 ″; Member, 31; Upper member, 311; Electrode part (conductive material filling part), 311a and 311b; Through electrode (conductive material filling part), 313 , 313a and 313b; electrode pads, 3 2; Lower member, 321a and 321b; Through electrode (conductive material filling portion), 323a and 323b; Electrode pad, 34; Insulating layer, 4; Electronic component, 41; Interposer, 42; Bump, 43; Laminated substrate 61; substrates 621, 622 and 623; coating 625; insulating coating 63; conductive material layer 635; electrode pad 66; conductive material filling portion 7; substrate with coating 8; Body, 9; substrate, 91; copper foil, 92; substrate.

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 coating The manufacturing method of a structure having an insulating coating 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 1 to 10, and a positive photosensitive resin composition so that the positive photosensitive resin composition is in contact with the solvent in the hole portion. A resin composition coating step to be applied to the substrate, a step of 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 the bottom surface of the hole, and the substrate Exposing a predetermined region of the film formed on the surface of the surface, treating the surface with an alkaline solution, and removing the surface bottom side film to leave the film formed on the inner wall surface of the hole, Add the film remaining on the inner wall. A heat curing step of, characterized in that it comprises a.

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 side 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 ~ 10,000 ^2, more preferably 250 ~ 7,000μm ² and a depth of 10 ~ 200 [mu] m, preferably having 30 ~ 120 [mu] m, the holes 111 and more preferably 50 ~ 100 [mu] m.
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 between 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 1 to 10, preferably Is 1 to 5, 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 Propylene glycol monoalkyl ether acetates such as tate, 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 acetate, 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 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 coating step, the solid content concentration, viscosity, etc. of the resin composition are taken into consideration, and the thickness of the 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.

In the step of forming the film, the solvent is removed, 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) Surface Bottom Side Film Removal Step The surface bottom side film removal step removes the film 119 formed on the surface of the substrate 11 and the film 118 formed on the bottom surface of the hole of the substrate 11. This is a step of leaving the coating film 117 formed on the inner wall surface of the hole.

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).

(V) Heat-curing step The heat-curing step is a step of heating the coating 117 remaining on the inner wall surface of the hole, and by this step, the coating 117 is used as the cured film 217 and a structure having an insulating coating. The body 2 can be obtained (refer FIG.3 (d)).
The heating method is not particularly limited, but it is usually preferable that the heating is performed at a temperature in the range of 100 to 250 ° C. for about 30 minutes to 10 hours. 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 the method for producing a structure having an insulating coating according to the present invention, after the heat curing step, polishing is performed from the surface of the substrate 11 that does not have a hole, and the hole is formed as a through hole 22. (See FIG. 3E). 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. 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.

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 the electronic component of the present invention, for example, a member 3 (including a structure 2 ′ shown in FIG. 3E) and an electrode part (conductive material filling part) 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. 3D 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 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 having the electrode pads 323a and 323b 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 at the interface between the upper member 31 and the lower member 32 (see FIG. 6). 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. 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.).

The member 3 ′ shown in FIG. 5 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. 4 (b) to (b) in the hole portion having the conductive material layer 313 on the lower side (lower side of FIG. 3 (e)) of the through hole of the member 2 ′ (FIG. 3 (d)) obtained by the process of FIG. 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, 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 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. 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. Positive photosensitive resin composition The positive photosensitive resin composition in the present invention contains (A) an alkali-soluble resin, (B) a quinonediazide compound, (C) inorganic particles, and (D) a solvent. Is.

(3-1) Alkali-soluble resin (A)
Examples of the alkali-soluble resin 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 acid ester. Examples thereof include a resin selected from a copolymer obtained by use (hereinafter also referred to as “resin (A2)”); a resin having a carboxyl group (hereinafter also referred to as “resin (A3)”), and the like. .
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 may be used individually by 1 type and may be used in combination of 2 or more type.

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

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.
Examples of (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, and 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, maleinamide, fumaramide, mesaconamide, citraconamide, itaconamide and the like; unsaturated imides such as maleimide, N-phenylmaleimide and 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 may be used individually by 1 type and may be used in combination of 2 or more type.

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

Examples of the resin (A3) include the following.
[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) obtained by using a monomer [m], an aromatic vinyl compound, and a copolymer [5] monomer (m) obtained by using a (meth) acrylic ester. ), 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) is preferably 20 to 90% by mass, more preferably 20 to 80% when the solid content in the positive photosensitive resin composition is 100% by mass. % By mass, more preferably 30 to 70% by mass. When this content ratio is in the above range, the alkali solubility is excellent, and the obtained cured film has excellent mechanical properties, heat resistance, and electrical insulation.

Moreover, in this invention, when the alkali solubility of alkali-soluble resin (A) is inadequate, phenolic low molecular weight compounds other than the said alkali-soluble resin (A) can be used together.
Examples of the phenolic low molecular weight 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 may be used individually by 1 type and may be used in combination of 2 or more type.

The content of the phenolic low molecular compound is preferably 1 to 20 parts by mass, more preferably 2 to 15 parts by mass, and still more preferably 100 parts by mass of the alkali-soluble resin (A). 3 to 10 parts by mass. When this content ratio is in the above range, the alkali solubility can be improved without impairing the heat resistance of the resulting cured product.

(3-2) Quinonediazide compound (B)
The quinonediazide compound (B) is a 1,2-naphthoquinone-2-diazide-5-sulfonic acid ester or a 1,2-naphthoquinone-2-diazide-4-sulfonic acid ester of a phenol compound.

The phenol compound is not particularly limited as long as it is a compound having at least one phenolic hydroxyl group, but compounds represented by the following general formulas (1) to (5) are 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 as or different from each other, and each represents 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 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, 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 ⁵⁹ to X ⁶² and at least one of X ⁶³ to X ⁶⁷ are hydroxyl groups. ]

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 may be used individually by 1 type and may be used in combination of 2 or more type.
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 obtained in this manner may be used alone or in combination of two or more.

The content of the quinonediazide compound (B) is preferably 10 to 100 parts by weight, more preferably 10 to 50 parts by weight, and still more preferably, based on 100 parts by weight of the alkali-soluble resin (A). 15 to 50 parts by mass. When this content ratio is in the above range, the difference in solubility between the exposed part and the unexposed part is large, and the alkali solubility is excellent.

(3-3) Inorganic particles (C)
Examples of the inorganic particles (C) 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. Can be mentioned.

The surface of the inorganic 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).
The shape of the inorganic particles is not particularly limited, and may be spherical, elliptical, flat, rod-like, fiber-like, or the like.

The average particle size of the inorganic particles is 1 to 500 nm, preferably 5 to 200 nm, more preferably 10 to 100 nm. When the average particle size of the inorganic particles is in the above range, the transparency to radiation, alkali solubility, and the like are excellent.
The said inorganic particle may be used individually by 1 type, and may be used in combination of 2 or more type.
Silica is preferable as the inorganic particles because of ease of control of thixotropic properties. In particular, silica partially hydrophobized (hereinafter also referred to as “hydrophobized silica”) is preferable.

Here, the example of a manufacturing method of the said hydrophobic silica is shown below.
Methanol is added to the aqueous silica sol, and the solvent is replaced with methanol using an ultrafilter. Thereafter, a hydrophobizing agent such as trimethylmethoxysilane and hexamethyldisilazane and propylene glycol monomethyl ether are added, and methanol is distilled off to obtain a desired hydrophobized silica.

The hydrophobicity of the hydrophobized silica is preferably 20 to 80%, more preferably 30 to 70%, and 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 thixotropy of the resin composition can be 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

When the silica is hydrophobic silica, the average particle diameter is preferably 1 to 100 nm, more preferably 5 to 80 nm, and still more preferably 10 to 50 nm. When the average particle diameter is 1 to 100 nm, sufficient transparency with respect to exposure light, sufficient alkali solubility, and the like can be obtained.
The average particle diameter 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.

The content of the inorganic particles (C) is preferably 10 to 200 parts by weight, more preferably 50 to 200 parts by weight, and still more preferably, when the alkali-soluble resin (A) is 100 parts by weight. 70 to 150 parts by mass. When this content ratio is in the above range, it has suitable thixotropic properties, and a uniform film can be formed on the inner wall surface of the hole.
Further, when the hydrophobic silica is contained as the inorganic particles (C), the content of the hydrophobic silica exceeds 20% by mass when the total solid content in the resin composition is 100% by mass, It is preferable that it is 60 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 hole.
This resin composition contains 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; other inorganic particles such as nitrides. You may contain.

(3-4) Solvent (D)
The solvent (D) 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 (D) may be the same as or different from the solvent used in the solvent application step.
The content of the solvent is such 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.

(3-5) Crosslinking agent (E)
In addition to the components (A) to (D), the positive photosensitive resin composition in the present invention may contain a crosslinking agent (E).
As said crosslinking agent (E), what contains the compound (E1) which has an alkyl etherified amino group, and aliphatic polyglycidyl ether (E2) is mentioned.
As the compound (E1) having an alkyl etherified amino group, an active methylol group in a nitrogen compound such as (poly) methylol melamine, (poly) methylol glycoluril, (poly) methylol benzoguanamine, (poly) methylol urea, etc. A compound in which all or a part (at least two) of (CH ₂ OH groups) is 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 aliphatic polyglycidyl ether (E2) include pentaerythritol glycidyl ether, trimethylolpropane polyglycidyl ether, glycerol polyglycidyl ether, neopentyl glycol diglycidyl ether, ethylene / polyethylene glycol diglycidyl ether, and propylene / polypropylene glycol. Examples thereof include diglycidyl ether, 1,6-hexanediol diglycidyl ether, sorbitol polyglycidyl ether, propylene glycol diglycidyl ether, and trimethylolpropane triglycidyl ether.
In addition, these may be used individually by 1 type and may be used in combination of 2 or more type.

In addition to the above (E1) and (E2), the crosslinking agent (E) is an epoxy group-containing compound, a phenol compound having an aldehyde group, a phenol compound having a methylol group, a thiirane ring-containing compound, an oxetanyl group-containing compound. , An isocyanate group-containing compound (including a blocked compound) and the like may be included.
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 types. Examples thereof include an epoxy resin, a phenol-naphthol type epoxy resin, a phenol-dicyclopentadiene type epoxy resin, an alicyclic epoxy resin, an aromatic epoxy resin, an aliphatic epoxy resin, and an epoxycyclohexene resin.
In addition, these epoxy group containing compounds may be used individually by 1 type, and may be used in combination of 2 or more type.

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 (E) is preferably 1 to 100 parts by mass, more preferably 10 to 75 parts by mass, and still more preferably, when the alkali-soluble resin (A) is 100 parts by mass. 10 to 50 parts by mass. When this content ratio is in the above range, the alkali solubility is excellent, and the obtained cured film has excellent mechanical properties, heat resistance, and electrical insulation.
When the crosslinking agent (E) is 100 parts by mass, the total content of the compound (E1) having an alkyl etherified amino group and the aliphatic polyglycidyl ether (E2) is 25 to 100 parts by mass. Parts, preferably 50 to 100 parts by mass, more preferably 75 to 100 parts by mass.

(3-6) Crosslinked polymer particles (F)
The positive photosensitive resin composition in the present invention may contain crosslinked polymer particles (F) in addition to the components (A) to (E).
The cross-linked polymer particles (F) include a monomer homopolymer or copolymer containing a cross-linkable compound having two or more polymerizable unsaturated bonds (hereinafter referred to as “cross-linkable monomer”). Can be used.
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. Of these, divinylbenzene is preferred.
In addition, these may be used individually by 1 type and may be used in combination of 2 or more type.

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. In addition, these may be used individually by 1 type and may be used in combination of 2 or more type.

Examples of the crosslinked polymer particles include a copolymer (f1) composed of the crosslinking monomer, an unsaturated compound having a hydroxyl group and / or an unsaturated compound having a carboxyl group, and the crosslinking monomer. And a copolymer (f2) comprising an unsaturated compound having a hydroxyl group and / or an unsaturated compound having a carboxyl group and another monomer is preferred, and the copolymer (f2) is particularly preferred.

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 (f2), unsaturated compounds having a nitrile group include (meth) acrylonitrile, α-chloroacrylonitrile, α-chloromethylacrylonitrile, α-methoxyacrylonitrile. , Α-ethoxyacrylonitrile, crotonate nitrile, cinnamic nitrile, itaconic dinitrile, maleic dinitrile, fumarate 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, 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, silica 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, 1,3-pentadiene, and the like.

When the crosslinked polymer particles are made of a copolymer (f2), the unit amount (f21) 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 (f22) of units consisting of, and the unit amount (f23) consisting of other monomers are the total of unit amounts constituting the copolymer (f2), that is, (f21), (f22) and When the sum of (f23) is 100 mol%, it is 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 to 93.5 mol%, more preferably 1 to 5 mol%, 7 to 40 mol%, and 55 to 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 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 alkali-soluble resin, the alkali solubility, and the like are excellent. The average particle diameter is a value measured by diluting a dispersion of crosslinked polymer particles according to a conventional method using a light scattering flow distribution measuring device “LPA-3000” (manufactured by Otsuka Electronics Co., Ltd.).

The content of the cross-linked polymer particles (F) is preferably 1 to 100 parts by mass, more preferably 5 to 80 parts by mass, with 100 parts by mass of the alkali-soluble resin (A). The amount is preferably 5 to 50 parts by mass. When this content ratio is in the above range, the resulting cured film is excellent in thermal shock resistance and the like.

(3-7) Other Additives In addition to the above components (A) to (F), the positive photosensitive resin composition in the present invention may contain other additives.
Examples of the other additives include adhesion assistants and surfactants.
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 alkali-soluble resin (A) is 100 parts by mass. . When this content ratio is in the above range, the adhesion of the cured product obtained by curing the resin composition to the substrate is improved.

Examples of the surfactant include, for example, “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.
Usually, the content of the surfactant is preferably 5 parts by mass or less when the alkali-soluble resin (A) is 100 parts by mass.

(3-8) Viscosity of Resin Composition Further, the positive photosensitive resin composition in the present invention usually has a viscosity V1 (mPa · s) at a shear rate of 6 rpm and a viscosity V2 (mPa · s) at a shear rate of 60 rpm. (V1 / V2) is preferably 1.1 or more, more preferably 1.1 to 10.0, still more preferably 1.2 to 8.0, and particularly preferably 1.3 to 5 .0 range. When this ratio (V1 / V2) is in the above range, a film having excellent film-forming properties for at least the inner wall surface and the inner wall surface of the hole 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 V1 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. 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.

As described above, the ratio (V1 / V2) of the viscosity V1 (mPa · s) at a shear rate of 6 rpm and the viscosity V2 (mPa · s) at a shear rate of 60 rpm is 1.1 or more. Preferably there is. In order to obtain a more uniform coating film, the resin composition has a ratio (V3 / s) of a viscosity V3 (mPa · s) at a shear rate of 1.5 rpm and a viscosity V4 (mPa · s) at a shear rate of 600 rpm. V4) is preferably 2.0 or more. A more preferred ratio (V3 / V4) 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.

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 Alkali-soluble resin (A) [phenol resin (trade name “Sumilite Resin S-2”, manufactured by Sumitomo Bakelite Co., Ltd.)] 100 parts by mass, crosslinking agent (E1) [melamine crosslinking agent (product Name “Cymel 300” manufactured by Mitsui Cytec)] 30 parts by mass, crosslinking agent (E2) [(trade name “Denacol EX-610U” manufactured by Nagase ChemteX)]] 10 parts by mass, inorganic particles (C) [silica Particles (trade name “PL-2L-PGME”, manufactured by Fuso Chemical Co., Ltd., average particle size: 10 to 20 nm, sodium content: 0.02 ppm)] 100 parts by mass, and 1,1- as quinonediazide compound (B) Bis (4-hydroxyphenyl) -1- [4- {1- (4-hydroxyphenyl) -1-methylethyl} phenyl] ethane and 1,2-naphthoquinonediazide-5-s 20 parts by mass of a 2.0 molar condensate with sulfonic acid in a solvent (D) [mixed solvent of ethyl lactate and methyl ethyl ketone (mixing ratio 60/40)] so that the solid content concentration is 47% by mass. A resin composition was obtained by dispersing.

(2) Formation of film 150 mm in diameter having a forward tapered hole having a square shape (80 μm × 80 μm), a depth of 100 μm, and a bottom shape of square (60 μm × 60 μm) on the surface. Propylene glycol monomethyl acetate was spin-coated (1,000 rpm, 3 seconds) as a solvent on a silicon substrate (see FIG. 9) having a thickness of 500 μm, and the hole was filled with this solvent (see FIG. 1 (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 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. 10 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] Examples 2 to 5 and Comparative Examples 1 to 4
(1) Preparation of resin composition (Example 2)
As shown in Table 1, (A) 100 parts by mass of alkali-soluble resin (A-1), (B) 20 parts by mass of quinonediazide compound (B-1), (C) 70 parts by mass of inorganic particles (C-1), ( E) 20 parts by mass of crosslinking agent (E-1) and 10 parts by mass of (E-2), (F) 15 parts by mass of crosslinked polymer particles (F-1), (G) adhesion aid (G-1) 2 .5 parts by mass and (H) 0.1 part by mass of surfactant (H-1) were dissolved in 210 parts by mass of (D) solvent (D-1) so that the solid content concentration was 47% by mass. Thus, a resin composition was prepared.

(2) Preparation of resin composition (Examples 3 to 5 and Comparative Examples 1 to 4)
As in Example 2, as shown in Table 1, (A) alkali-soluble resin, (B) quinonediazide compound, (C) inorganic particles, (E) cross-linking agent, (F) cross-linked polymer particles, (G) Each resin composition was prepared by dissolving the adhesion assistant and (H) surfactant in (D) solvent so that the solid content concentration was 47% by mass.

In addition, the composition described in Table 1 is as follows.
<(A) Alkali-soluble resin>
A-1: Cresol novolak resin comprising m-cresol / p-cresol = 60/40 (molar ratio), polystyrene-reduced weight average molecular weight (Mw) = 6500
<(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) inorganic particles (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)
<(D) Solvent>
D-1: Propylene glycol monomethyl ether acetate

<(E) Crosslinking agent>
E-1: Hexamethoxymethylmelamine (manufactured by Sanwa Chemical Co., Ltd., trade name “Nicalak MW-390”)
E-2: Product name “Denacol EX-610U” manufactured by Nagase ChemteX
<(F) Crosslinked polymer particles>
F-1: Butadiene / styrene / hydroxybutyl methacrylate / methacrylic acid / divinylbenzene = 48/24/20/6/2 (mass%) (average particle diameter: 70 nm, Tg = −35 ° C.)
<(G) Adhesion aid>
G-1: γ-glycidoxypropyltrimethoxysilane (manufactured by Nihon Unicar, trade name “A-187”)
<(H) Surfactant (Leveling Agent)>
H-1: Product name “FTX-218” (manufactured by Neos)

In addition, each hydrophobization rate in the said (C) inorganic particle (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

[3] Evaluation of Resin Composition Each resin composition of Examples 2 to 5 and Comparative Examples 1 to 4 was evaluated according to the following method. The results are shown in Table 2.
(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. 1B) On a stepped Si substrate having a diameter of 150 mm and a thickness of 500 μm, propylene glycol monomethyl acetate was spin-coated (1000 rpm, 3 seconds) as a solvent, and the hole was filled with this solvent [see FIG. ]. Thereafter, the 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 having a temperature of 110 ° C. for 3 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.
○: The shoulder of the surface opening is completely covered with the coating, and the thickness of the coating on the inner wall surface and bottom surface of the hole is substantially constant (see FIG. 11).
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. 12).
X: When the shoulder of the surface opening is not completely covered by the coating, or when the hole is completely filled (see FIG. 13)

(2) Thermal shock resistance (crack resistance)
As shown in FIGS. 14 and 15, a resin composition is applied to a base material 9 for thermal shock evaluation having a patterned copper foil 91 on a substrate 92, and is used at 110 ° C. using a hot plate. A substrate having a resin coating film having a thickness of 10 μm on the copper foil 91 was produced by heating for 5 minutes. Then, it heated at 190 degreeC for 1 hour using the convection oven, the resin coating film was hardened, and the cured film was obtained. This substrate was subjected to a resistance test using a thermal shock tester (manufactured by Tabai Espec, model number “TSA-40L”) at −65 ° C./30 minutes to 150 ° C./30 minutes as one cycle. After this treatment, it was observed at a magnification of 200 times using a microscope, and the number of cycles until a defect such as a crack occurred in the cured film was confirmed every 100 cycles.

(3) 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.

(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.

Claims (9)

1. A 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 1 to 10;
   Resin composition for coating a positive photosensitive resin composition containing the following (A) to (D) on the substrate so that the positive photosensitive resin composition is in contact with the solvent in the hole. An object application process;
   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
   Exposing a predetermined region of the film formed on the surface of the substrate, treating with an alkaline solution, and leaving a film formed on the inner wall surface of the hole to leave the film on the bottom surface side;
   And a heat curing step of heating the film remaining on the inner wall surface of the hole. A method for producing a structure having an insulating film.
   (A) Alkali-soluble resin (B) Quinonediazide compound (C) Inorganic particles (D) Solvent
2. The positive photosensitive resin composition further contains a crosslinking agent containing (E) a compound (E1) having an alkyl etherified amino group and an aliphatic polyglycidyl ether (E2). A method for producing a structure having an insulating coating according to 1.
3. The method for producing a structure having an insulating coating according to claim 1 or 2, wherein the positive photosensitive resin composition further comprises (F) crosslinked polymer particles.
4. The structure having a through hole having an insulating coating according to any one of claims 1 to 3, further comprising a polishing step of polishing the substrate from a surface having no hole in the structure having the insulating coating. Manufacturing method.
5. A structure having an insulating film obtained by the method according to any one of claims 1 to 4.
6. A member including a structure including a through-hole having an insulating film obtained by the method according to claim 4 and an electrode portion in which at least the through-hole of the structure is filled with a conductive material is provided. Features electronic components.
7. A 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 1 to 10;
   A resin composition application step of applying a positive photosensitive resin composition to the substrate such that the positive photosensitive resin composition is in contact with 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
   Exposing a predetermined region of the film formed on the surface of the substrate, treating with an alkaline solution, and leaving a film formed on the inner wall surface of the hole to leave the film on the bottom surface side;
   A positive-type photosensitive resin composition used in a method for producing a structure having an insulating coating, comprising a heating and curing step of heating a coating remaining on the inner wall surface of the hole,
   A positive photosensitive resin composition comprising (A) an alkali-soluble resin, (B) a quinonediazide compound, (C) inorganic particles, and (D) a solvent.
8. The positive photosensitive resin composition according to claim 7, further comprising a crosslinking agent containing (E) an alkyl etherified amino group-containing compound (E1) and an aliphatic polyglycidyl ether (E2). object.
9. The positive photosensitive resin composition according to claim 7 or 8, further comprising (F) crosslinked polymer particles.

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