WO2022009685A1

WO2022009685A1 - Method for producing heteroconductive member

Info

Publication number: WO2022009685A1
Application number: PCT/JP2021/023917
Authority: WO
Inventors: 吉則堀田
Original assignee: 富士フイルム株式会社
Priority date: 2020-07-10
Filing date: 2021-06-24
Publication date: 2022-01-13
Also published as: JPWO2022009685A1; TW202209355A; JP7369871B2

Abstract

The purpose of the present invention is to provide a method for producing a heteroconductive member in which it is possible to suppress variations in the heights of protruding portions of a conductive path. A method for producing a heteroconductive member comprising an insulating base material, a plurality of pass-through paths that pass through the insulating base material in the thickness direction thereof, and a plurality of conductive paths composed of a conductive material that fills the inside of the plurality of pass-through paths, one end of the plurality of conductive paths being provided so as to protrude from at least one surface of the insulating base material, the method comprising: a preparation step in which a metal-filled microstructure having an unfilled region therein is prepared; a water repellency step in which the inner walls of the pass-through paths in the unfilled region are made to be water repellant; and a protrusion step in which, after the water repellency step, a treatment liquid is applied to the surface of the metal-filled microstructure, the surface of the insulating base material is selectively and partially removed in the thickness direction, and one end of the plurality of conductive paths is made to protrude from the surface of the insulating base material.

Description

Manufacturing method of anisotropic conductive member

The present invention relates to a method for manufacturing an anisotropic conductive member.

A structure in which a plurality of through holes provided in an insulating base material are filled with a conductive substance such as metal is one of the fields that have been attracting attention in nanotechnology in recent years, for example, as an anisotropic conductive member. Is expected to be used.
An anisotropic conductive member is inserted between an electronic component such as a semiconductor element and a circuit board, and an electrical connection can be obtained between the electronic component and the circuit board simply by applying pressure. Therefore, the electronic component such as a semiconductor element can be used. It is widely used as an electrical connection member, an inspection connector for performing a functional inspection, and the like.
In particular, electronic components such as semiconductor devices are significantly downsized. As a method of directly connecting a wiring board such as conventional wire bonding, flip-chip bonding, thermocompression bonding, etc., the stability of electrical connection of electronic components cannot be sufficiently guaranteed, so that it can be used as an electronic connection member. An anisotropic conductive member is attracting attention.

Regarding the method for manufacturing such an anisotropic conductive member, for example, Patent Document 1 describes (1) an anodic oxidation treatment step of anodicating an aluminum substrate to form an alumina film having micropores, and (2) the above-mentioned anode. After the oxidation treatment step, the penetration treatment step of penetrating the pores formed by the micropores generated by the anodic oxidation to obtain the insulating base material, and (3) the insulating group obtained after the penetration treatment step. The conductive member filling step of filling the inside of the through hole in the material to obtain the anisotropic conductive member, (4) after the conductive member filling step, the surface of the insulating base material and the surface of the insulating base material A surface smoothing treatment step for smoothing the back surface and (5) a conduction path projecting step for forming a structure in which the conductive member protrudes from the front surface and the back surface of the insulating base material are provided after the surface smoothing step. A method for manufacturing an anisotropic conductive member is described ([claim 1] to [claim 3]). Further, in Patent Document 1, regarding the conduction path projecting step, "(5-a) Conductivity is obtained from the front surface and the back surface of the insulating base material by removing a part of the front surface and the back surface of the insulating base material. "Treatment for forming a structure in which the member protrudes" is described ([claim 5]), and specifically, by contacting the anisotropic conductive member after the surface smoothing treatment step with an acid aqueous solution or an alkaline aqueous solution. , A process of partially dissolving and removing only the insulating base material on the surface of the anisotropic conductive member to project the conduction path is described ([0134]).

Japanese Unexamined Patent Publication No. 2008-270157

When the present inventor examined the method for manufacturing the anisotropic conductive member described in Patent Document 1, only a part of the insulating base material on the surface of the anisotropic conductive member was melted and removed to project the conduction path. If there is an unfilled region in which the conductive substance (conductive member) is not filled in at least a part of the inside of the through passage (through hole of the micropore) in the thickness direction in some of the conduction paths. It was clarified that the length of the protruding portion of the conduction path may vary depending on the conditions for melting the insulating base material. For example, in the vicinity of the conduction path or the through path where an unfilled region exists, the conduction path It was clarified that the protruding portion of the above may buckle due to pressurization at the time of joining or the like and come into contact with an adjacent conduction path, so that the insulating property may be impaired.

Therefore, it is an object of the present invention to provide a method for manufacturing an anisotropic conductive member capable of suppressing a variation in the height of a protruding portion of a conduction path.

As a result of diligent research to achieve the above problems, the present inventor applies treatments to a predetermined metal-filled microstructure by each of the water-repellent step and the projecting step to obtain the protruding portion of the conduction path. The present invention has been completed by finding that it is possible to suppress the variation in height.
That is, it was found that the above problem can be achieved by the following configuration.

[1] It has an insulating base material, a plurality of through-passages penetrating in the thickness direction of the insulating base material, and a plurality of conduction paths composed of a conductive substance filled inside the plurality of through-passages. A method for manufacturing an anisotropic conductive member, wherein one end of a plurality of conduction paths is provided so as to project from at least one surface of an insulating base material.
It has an insulating base material, a plurality of through-passages penetrating in the thickness direction of the insulating base material, and a plurality of conduction paths made of a conductive substance filled inside the plurality of through-passages. Preparation for preparing a metal-filled microstructure in which an unfilled region in which at least a part of the inside of the gangway in the thickness direction is not filled with a conductive substance exists in some of the conductive paths. Process and
A water-repellent step that makes the inner wall of the gangway in the unfilled area water-repellent,
After the water-repellent step, a treatment liquid is applied to the surface of the metal-filled microstructure, the surface of the insulating base material is selectively partially removed in the thickness direction, and one end of a plurality of conduction paths is made of the insulating base material. A method for manufacturing an anisotropic conductive member, which comprises a projecting step of projecting from a surface.

[2] In the water repellent step, a water repellent agent is applied to the surface of the through-passage in the unfilled region on the opening side of the metal-filled microstructure, and the inner wall and surface of the through-passage in the unfilled region are both coated. The method for producing an anisotropic conductive member according to [1], which comprises a first step of making water repellent and a second step of removing a water repellent agent on the surface after the first step.
[3] The method for producing an anisotropic conductive member according to [1] or [2], wherein the water repellent step is a treatment step using at least one of a silicon-containing compound and a fluorine-containing compound.
[4] The method for manufacturing an anisotropic conductive member according to any one of [1] to [3], wherein the insulating base material is a valve metal anodic oxide film.
[5] The method for manufacturing an anisotropic conductive member according to [4], wherein the valve metal is aluminum.
[6] The method for producing an anisotropic conductive member according to any one of [1] to [5], wherein the conductive substance is copper.
[7] The anisotropic conductive member according to any one of [1] to [6], wherein the height of the protruding portions of the plurality of conduction paths protruding from the surface of the insulating base material by the protruding step is 50 nm or more. Manufacturing method.

According to the present invention, it is possible to provide a method for manufacturing an anisotropic conductive member capable of suppressing a variation in the height of a protruding portion of a conduction path.

FIG. 1A shows a state of a metal-filled microstructure before a water-repellent step in a schematic cross-sectional view for explaining an example (first aspect) of the method for manufacturing an anisotropic conductive member of the present invention. It is a schematic sectional view. FIG. 1B is a schematic cross-sectional view showing a state after the water repellent step in a schematic cross-sectional view for explaining an example (first aspect) of the method for manufacturing an anisotropic conductive member of the present invention. be. FIG. 1C is a schematic cross-sectional view showing a state after the projecting step in a schematic cross-sectional view for explaining an example (first aspect) of the method for manufacturing an anisotropic conductive member of the present invention.

FIG. 2A is a schematic cross-sectional view for explaining another example (second aspect) of the method for manufacturing an anisotropic conductive member of the present invention, which is a metal-filled microstructure with a substrate before the water repellent step. It is a schematic cross-sectional view which shows the state of. FIG. 2B is a schematic cross-sectional view for explaining another example (second aspect) of the method for manufacturing an anisotropic conductive member of the present invention, which is a schematic cross-sectional view showing a state after the water-repellent step. It is a figure. FIG. 2C is a schematic cross-sectional view showing a state after the projecting step in a schematic cross-sectional view for explaining another example (second aspect) of the method for manufacturing an anisotropic conductive member of the present invention. be. FIG. 2D is a schematic cross-sectional view showing a state after the substrate removing step in a schematic cross-sectional view for explaining another example (second aspect) of the method for manufacturing an anisotropic conductive member of the present invention. Is. FIG. 3 is a reference drawing in which one end (outermost surface) of the projected conduction path is overlapped so that the height of the contour lines becomes zero. FIG. 4 is a reference drawing of the frequency distribution of the height of the protruding portion of the conduction path.

Hereinafter, the present invention will be described in detail.
The description of the constituent elements described below may be based on the representative embodiments of the present invention, but the present invention is not limited to such embodiments.
In the present specification, the numerical range represented by using "-" means a range including the numerical values before and after "-" as the lower limit value and the upper limit value.

[Manufacturing method of anisotropic conductive member]
The method for manufacturing an anisotropic conductive member of the present invention (hereinafter, also abbreviated as "the manufacturing method of the present invention") includes an insulating base material, a plurality of through passages penetrating in the thickness direction of the insulating base material, and a plurality of through paths. It has a plurality of conduction paths made of a conductive material filled in the inside of the through path, and one end of the plurality of conduction paths is provided in a state of protruding from at least one surface of the insulating base material. A method for manufacturing a conductive member (hereinafter, also abbreviated as "specific anisotropic conductive member").
It has an insulating base material, a plurality of through-passages penetrating in the thickness direction of the insulating base material, and a plurality of conduction paths made of a conductive substance filled inside the plurality of through-passages, and has a plurality of conduction paths. A metal-filled microstructure in which an unfilled region in which at least a part of the inside of the through-passage in the thickness direction is not filled with a conductive substance exists in some of the conductive paths (hereinafter, "" Also abbreviated as "specific metal-filled microstructure") and the preparatory step;
A water-repellent step that makes the inner wall of the gangway in the unfilled area water-repellent;
After the water-repellent step, a treatment liquid is applied to the surface of the metal-filled microstructure, the surface of the insulating base material is selectively partially removed in the thickness direction, and one end of a plurality of conduction paths is made of the insulating base material. With the protrusion process of protruding from the surface;
It is a method of manufacturing an anisotropic conductive member having.

In the present invention, as described above, the specific metal-filled microstructure is treated by each of the water-repellent step and the projecting step to suppress the variation in the height of the projecting portion of the conduction path. Can be done.
This is not clear in detail, but it is presumed to be as follows.
First, the present inventor finds that if an unfilled region exists in the conduction path (gangway) of the metal-filled microstructure, the treatment liquid is in the unfilled region when the insulating base material is removed in the projecting step. Since it penetrates into the gangway and the insulating base material dissolves from the inside, the protruding part of the gangway is seated by pressurization at the time of joining or the like in the vicinity of the gangway or the gangway where the unfilled region exists. It was revealed that he would give in.
Therefore, in the present invention, by making the inner wall of the through-passage in the unfilled region of the specific metal-filled microstructure water-repellent, the insulating base material is used when the insulating base material is removed in the subsequent projecting step. Since it is possible to prevent unintentional dissolution, it is considered that the variation in the height of the protruding portion of the conduction path can be suppressed.

Next, the outline of each step in the manufacturing method of the present invention will be described with reference to FIGS. 1A to 1C and FIGS. 2A to 2D, and then each processing step will be described in detail.

<First aspect>
As shown in FIGS. 1A to 1C (hereinafter, these are collectively abbreviated as “FIG. 1”), the specific anisotropic conductive member 20 is a Dt in the thickness direction of the insulating base material 3 and the insulating base material 3. It has a plurality of through-passages 4 provided so as to penetrate the through-passage and a plurality of conduction paths 5 composed of a conductive material filled inside the plurality of through-passages 4, and among the plurality of conduction paths 5. A preparatory step for preparing a specific metal-filled microstructure 10 in which an unfilled region 6 in which a conductive substance is not filled is present in at least a part of the inside of the through-passage 4 in the thickness direction in some conduction paths. (See FIG. 1A); A water repellent agent is applied to the surface 10a on the opening side of the through-passage 4 of the unfilled region 6 in the specified metal-filled microstructure 10, and the inner wall of the through-passage 4 in the unfilled region 6 and A water-repellent step of removing the water-repellent agent on the surface 10a by scraping the surface layer of the surface 10a after making the surface 10a water-repellent (see FIG. 1B); A treatment liquid is applied to the surface 10a of the structure 10, the surface of the insulating base material 3 is selectively partially removed in the thickness direction Dt, and one end of the plurality of conducting paths 5 protrudes from the surface of the insulating base material 3. It can be produced by a manufacturing method having a protrusion step (see FIG. 1C);

<Second aspect>
From the viewpoint of workability, the production method of the present invention preferably uses a specific metal-filled microstructure with a substrate attached as the specific metal-filled microstructure used in the water-repellent step and the projecting step.
For example, as shown in FIGS. 2A to 2D (hereinafter, these are collectively abbreviated as “FIG. 2”), the specific anisotropic conductive member 20 prepares a specific metal-filled microstructure 10 having a substrate 1. Preparation step to be performed (see FIG. 2A); A water-repellent step of removing the water-repellent agent on the surface 10a by scraping the surface layer of the surface 10a (the surface opposite to the substrate 1) after making the inner wall and the surface 10a of 4 water-repellent (FIG. 2B). (See); After the water repellent step, a treatment liquid is applied to the surface 10a of the specific metal-filled microstructure 10 to which the substrate 1 is attached, and the surface of the insulating base material 3 is selectively partially removed in the thickness direction Dt. , A manufacturing method including a protrusion step of projecting one end of a plurality of conduction paths 5 from the surface of the insulating base material 3 (see FIG. 2C); a substrate removal step of removing the substrate 1 (see FIG. 2D); be able to.

<Other aspects>
In FIGS. 1 and 2, one surface 10a of the specific metal-filled microstructure 10 is treated by each of the water-repellent step and the projecting step, but the manufacturing method of the present invention is used. The other surface of the specific metal-filled microstructure 10 may also be treated by each of the water-repellent step and the projecting step.
For example, the state shown in FIGS. 1D and 2D, that is, the insulating base material 3 and the plurality of conduction paths 5 provided so as to penetrate in the thickness direction of the insulating base material 3 are provided, and the plurality of conduction paths 5 are provided. The back surface of the specific anisotropic conductive member 20 provided with one end protruding from one surface of the insulating base material 4 is treated by each step of the water repellent step and the protruding step. May be good.

[Preparation process]
The preparation step of the manufacturing method of the present invention is a step of preparing a specific metal-filled microstructure.
Here, as a preparatory step, a conventionally known method can be used, for example, the method described in claim 1 of Patent Document 1 (Japanese Unexamined Patent Publication No. 2008-270157), International Publication No. 2018/155273. Examples thereof include the method described in claim 1, the method described in paragraphs [0027] to [0031] of JP-A-2019-153415, and the like.
In the specific metal-filled microstructure, in some of the conductive paths, the unfilled region in which at least a part of the inside of the through-passage in the thickness direction is not filled with the conductive substance is described above. By performing the preparatory process by the method, it will inevitably exist at a certain rate.

<Insulating base material>
The insulating base material of the specified metal-filled microstructure has an electrical resistivity ( ^{about 10 14} Ω · cm) similar to that of the insulating base material constituting a conventionally known anisotropic conductive film or the like. If there is, it is not particularly limited.

Examples of the insulating base material include a metal oxide base material, a metal nitride base material, a glass base material, a ceramic base material such as silicon carbide and silicon nitride, a carbon base material such as diamond-like carbon, and a polyimide base material. Examples thereof include these composite materials. As the insulating base material, for example, a ceramic material or an inorganic material containing 50% by mass or more of a carbon material may be formed on an organic material having through holes.

As the insulating base material, a metal oxide base material is preferable because micropores having a desired average opening diameter are formed as through paths and it is easy to form a conduction path described later, and an anode of a valve metal is preferable. It is more preferably an oxide film.
Here, examples of the valve metal include, for example, aluminum, tantalum, niobium, titanium, hafnium, zirconium, zinc, tungsten, bismuth, antimony and the like. Of these, aluminum is preferable because it has good dimensional stability and is relatively inexpensive.
Therefore, it is preferable to use an aluminum substrate to form an anodic oxide film which is an insulating base material to manufacture an anisotropic conductive member.

The aluminum substrate is not particularly limited, and specific examples thereof include a pure aluminum plate; an alloy plate containing aluminum as a main component and containing a trace amount of a foreign element; high-purity aluminum is vapor-deposited on low-purity aluminum (for example, a recycled material). A substrate; a substrate obtained by coating the surface of a silicon wafer, quartz, glass or the like with high-purity aluminum by a method such as vapor deposition or sputtering; a resin substrate laminated with aluminum; and the like.

The surface of the aluminum substrate to be anodized is preferably 99.5% by mass or more, more preferably 99.9% by mass or more, and 99.99% by mass or more. Is more preferable. When the aluminum purity is in the above range, the regularity of the through-hole arrangement is sufficient.

Further, it is preferable that the surface of the aluminum substrate to be anodized is previously subjected to heat treatment, degreasing treatment and mirror finish treatment.
Here, regarding the heat treatment, the degreasing treatment, and the mirror finish treatment, the same treatments as those described in paragraphs [0044] to [0054] of JP-A-2008-270158 can be applied.

<Gangway>
The through-passage of the specific metal-filled microstructure is preferably composed of micropores provided so as to penetrate in the thickness direction of the anodic oxide film of the valve metal.

<Conduction path>
The conduction path of the specific metal-filled microstructure is made of a conductive substance, and is made of a metal filled in a micropore (through path) provided so as to penetrate in the thickness direction of the anodic oxide film of the valve metal. It is preferably configured.
The metal is preferably an electrical resistivity of less materials 10 ³ Ω · cm, and specific examples thereof include gold (Au), silver (Ag), copper (Cu), aluminum (Al), magnesium ( Mg), nickel (Ni), zinc (Zn) and the like are preferably exemplified.
Of these, Cu, Au, Al, and Ni are preferable, Cu and Au are more preferable, and Cu is even more preferable, from the viewpoint of electrical conductivity.

[Water repellent process]
The water-repellent step of the manufacturing method of the present invention is a step of making the inner wall of the gangway repellency in an unfilled region where at least a part of the inside of the gangway in the thickness direction is not filled with a conductive substance. ..
As a method for making water repellent, it is preferable to make it water repellent by a water repellent agent, and when applied to a flat aluminum oxide plate, the water contact angle can be increased by 5 ° or more. Watering is more preferred.

In the present invention, the water-repellent step is at least one of a silicon-containing compound and a fluorine-containing compound as a water-repellent agent because the water-repellent effect can be maintained even for the etchant used for dissolving the anodic oxide film. The treatment step using one of them is preferable, and the treatment step using a fluorine-containing compound is more preferable.

Examples of the fluorine-containing compound include at least one fluorine-containing compound selected from the group consisting of the following formulas (I), (II), (III), (IV) and (V). In addition, these fluorine-containing compounds may have any form such as a monomer, a macromer, an oligomer and the like.

CH ₂ = CR ¹ COOR ² R ^f ... (I)
Wherein, ^{R 1} represents a hydrogen atom or a methyl group, ^{R 2} is _{_{_{_{-C p H 2p -, - C}}}} (C p H 2p + 1) H -, - CH 2 C (C p H 2p + 1) H- or -CH ₂ CH ₂ O-, R ^f are -C _n F _{2n + 1} ,-(CF ₂ ) _n H, -C _n F _{2n + 1} -CF ₃ ,-(CF ₂ ) _p OC _n H _2n C _i F _{2i + 1} ,-(CF ₂₎ ) _P OC _m H _2m C _i F _2i H, -N (C _p H _{2p + 1} ) COC _n F _{2n + 1} , -N (C _p H _{2p + 1} ) SO ₂ C _n F _{2n + 1} . However, p is an integer of 1 to 10, n is an integer of 1 to 16, m is an integer of 0 to 10, and i is an integer of 0 to 16. ]

CF ₂ = CFOR ^g ... (II)
(R ^{g in the} formula represents a fluoroalkyl group having 1 to 20 carbon atoms.)

CH ₂ = CHR ^g ... (III)
(R ^{g in the} formula represents a fluoroalkyl group having 1 to 20 carbon atoms.)

CH ₂ = CR ³ COOR ⁵ R ^j R ⁶ OCOCR ⁴ = CH ₂ ... (IV)
[In the formula, R ³ and R ⁴ are hydrogen atoms or methyl groups, R ⁵ and R ⁶ are -C _q H _2q- , -C (C _q H _{2q + 1} ) H-, -CH ₂ C (C _q H _{2q + 1} ). H- or -CH ₂ CH ₂ O-, R ^j is -C _t F ₂ t. However, q is an integer of 1 to 10 and t is an integer of 1 to 16. ]

CH ₂ = CR ⁷ COOCH ₂ (CH ₂ R ^k ) CHOCOCR ⁸ = CH ₂ ... (V)
(In the formula, R ⁷ and R ⁸ are hydrogen atoms or methyl groups, and R ^k is −C _y F _{2y + 1.} However, y is an integer of 1 to 16.)

Specific examples of the compound represented by the above formula (I) include CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ OCOCH = CH ₂ , CF ₃ CH ₂ OCOCH = CH ₂ , and CF ₃ (CF _2). ) ₄ CH ₂ CH ₂ OCOC (CH ₃ ) = CH ₂ , C ₇ F ₁₅ CON (C ₂ H ₅ ) CH ₂ OCOC (CH ₃ ) = CH ₂ , CF ₃ (CF ₂ ) ₇ SO ₂ N (CH ₃₎ ) CH ₂ CH ₂ OCOCH = CH ₂ , CF ₃ (CF ₂ ) ₇ SO ₂ N (C ₃ H ₇ ) CH ₂ CH ₂ OCOCH = CH ₂ , C ₂ F ₅ SO ₂ N (C ₃ H ₇ ) CH ₂ _{_{_{_{CH 2 OCOC (CH 3) =}}}} CH 2, (CF 3) 2 CF (CF 2) 6 (CH 2) 3 OCOCH = CH 2, (CF 3) 2 CF (CF 2) 10 (CH 2) 3 OCOC ( CH ₃ ) = CH ₂ , CF ₃ (CF ₂ ) ₄ CH (CH ₃ ) OCOC (CH ₃ ) = CH ₂ ,

, CF ₃ CH ₂ OCH ₂ CH ₂ OCOCH = CH ₂ , C ₂ F ₅ (CH ₂ CH ₂ O) ₂ CH ₂ OCOCH = CH ₂ , (CF ₃ ) ₂ CFO (CH ₂ ) ₅ OCOCH = CH ₂ , CF ₃ (CF ₂ ) ₄ OCH ₂ CH ₂ OCOC (CH ₃ ) = CH ₂ , C ₂ F ₅ CON (C ₂ H ₅ ) CH ₂ OCOCH = CH ₂ , CF ₃ (CF ₂ ) ₂ CON (CH ₃ ) CH (CH ₃ ) CH ₂ OCOCH = CH ₂ , H (CF ₂ ) ₆ C (C ₂ H ₅ ) OCOC (CH ₃ ) = CH ₂ , H (CF ₂ ) ₈ CH ₂ OCOCH = CH ₂ , H (CF ₂₎ ) ₄ CH ₂ OCOCH = CH ₂ , H (CF ₂ ) CH ₂ OCOC (CH ₃ ) = CH ₂ ,

, CF ₃ (CF ₂ ) ₇ SO ₂ N (CH ₃ ) CH ₂ CH ₂ OCOC (CH ₃ ) = CH ₂ , CF ₃ (CF ₂ ) ₇ SO ₂ N (CH ₃ ) (CH ₂ ) ₁₀ OCOCH = CH ₂ , C ₂ F ₅ SO ₂ N (C ₂ H ₅ ) CH ₂ CH ₂ OCOC (CH ₃ ) = CH ₂ , CF ₃ (CF ₂ ) ₇ SO ₂ N (CH ₃ ) (CH ₂ ) ₄ OCOCH = CH ₂ , C ₂ F ₅ SO ₂ N (C ₂ H ₅ ) C (C ₂ H ₅ ) HCH ₂ OCOCH = CH _{2 and the} like.

Specific examples of the compounds represented by the above formulas (II) and (III) include, for example, C ₃ F ₇ CH = CH ₂ , C ₄ F ₉ CH = CH ₂ , C ₁₀ F ₂₁ CH =. CH ₂ , C ₃ F ₇ OCF = CF ₂ , C ₇ F ₁₅ OCF = CF ₂ and C ₈ F ₁₇ OCF = CF _{2 and the} like.

Specific examples of the compounds represented by the above formulas (IV) and (V) include, for example, CH ₂ = CHCOOCH ₂ (CF ₂ ) ₃ CH ₂ OCOCH = CH ₂ , CH ₂ = CHCOOCH ₂ CH (CH _2). C ₈ F ₁₇ ) OCOCH = CH _{2 and the} like.

Further, in the present invention, from the viewpoint of workability, in the water-repellent step, not only the inner wall of the gangway, but also the surface on the opening side of the gangway in the unfilled region of the specific metal-filled microstructure. It may be made water repellent.

Further, in the present invention, from the viewpoint of workability, in the water-repellent step, it is preferable to perform the water-repellent treatment and then the drying treatment.
The conditions for the drying treatment are not particularly limited, and examples thereof include a treatment in which the product is left to stand for 1 minute to 1 hour in an environment of 20 to 90 ° C.

In the manufacturing method of the present invention, from the viewpoint of workability, the water-repellent step is also abbreviated as the surface on the opening side of the gangway of the unfilled region in the metal-filled microstructure (hereinafter, also referred to as "specific surface" in this paragraph. ), A water repellent agent is applied to both the inner wall of the gangway in the unfilled region and the specific surface to make it water repellent, and after the first step, the water repellent agent on the specific surface is applied. It is preferable to have a second step of removing.
Here, as a method for removing the water repellent agent in the second step, for example, a method of wiping off the water repellent agent on the specific surface, a method of scraping the surface layer of the specific surface, and the like can be mentioned. The method of shaving is preferable.
In the method of scraping the surface layer of the specific surface, the thickness of the surface layer of the specific surface to be scraped is preferably 0.5 to 2 μm.
The method for scraping the surface layer of a specific surface is not particularly limited, and examples thereof include mechanical polishing treatment, chemical mechanical polishing (CMP) treatment, electrolytic polishing treatment, and ion milling treatment, which are shown below.

<Mechanical polishing process>
As the mechanical polishing treatment, for example, a polishing cloth having a particle size of # 800 to # 1500 (for example, a SiC cloth) is used for wrapping, the thickness is adjusted, and then polishing is performed with a diamond slurry having an average particle size of 1 to 3 μm. Further, by polishing with a diamond slurry having an average particle diameter of 0.1 to 0.5 μm, a mirror surface state can be obtained.
Here, the polishing thickness of the electrode surface is preferably 0.5 μm to 20 μm, while the polishing thickness of the opening surface is preferably 10 μm to 50 μm.
The rotation speed is preferably 10 rpm to 100 rpm, more preferably 20 to 60 rpm.
The load is preferably 0.01 to 0.1 kgf / cm ² , more preferably 0.02 to 0.08 kgf / cm ² .

<Chemical mechanical polishing (CMP) treatment>
For the CMP treatment, a CMP slurry such as PNANERLITE-7000 manufactured by Fujimi Incorporated, GPX HSC800 manufactured by Hitachi Chemical Co., Ltd., and CL-1000 manufactured by Asahi Glass Co., Ltd. can be used.

<Electropolishing treatment>
Examples of electrolytic polishing include "Aluminum Handbook", 6th edition, edited by Japan Aluminum Association, 2001, p. Various methods described in 164-165; methods described in US Pat. No. 2,708,655; "Practical Surface Techniques", vol. 33, No. 3, 1986, p. The methods described in 32-38; etc. are preferably mentioned.

<Ion milling treatment>
The ion milling treatment is performed when more precise polishing than the above-mentioned CMP treatment or electrolytic polishing treatment is required, and a known technique can be used. It is preferable to use a general argon ion as the ion species.

[Protrusion process]
In the projecting step of the production method of the present invention, after the water repellent step, a treatment liquid is applied to the surface of the specific metal-filled microstructure, and the surface of the insulating base material is selectively partially removed in the thickness direction. This is a step of projecting one end of a plurality of conduction paths from the surface of the insulating base material.

As the treatment liquid, for example, an acid aqueous solution that does not dissolve the metal (for example, copper or the like) constituting the above-mentioned conduction path but dissolves an insulating base material (for example, aluminum oxide which is an anodic oxide film of aluminum). Alternatively, an alkaline aqueous solution may be mentioned.
In addition, examples of the method of applying the treatment liquid to the surface of the metal-filled microstructure include a dipping method and a spraying method. Above all, the dipping method is preferable.

When an aqueous acid solution is used, it is preferable to use an aqueous solution of an inorganic acid such as sulfuric acid, phosphoric acid, nitric acid, or hydrochloric acid, or a mixture thereof. Above all, an aqueous solution containing no chromic acid is preferable because it is excellent in safety. The concentration of the aqueous acid solution is preferably 1 to 10% by mass. The temperature of the aqueous acid solution is preferably 25 to 60 ° C.
When an alkaline aqueous solution is used, it is preferable to use at least one alkaline aqueous solution selected from the group consisting of sodium hydroxide, potassium hydroxide and lithium hydroxide. The concentration of the alkaline aqueous solution is preferably 0.1 to 5% by mass. The temperature of the alkaline aqueous solution is preferably 20 to 35 ° C.
Specifically, for example, a 50 g / L, 40 ° C. phosphoric acid aqueous solution, a 0.5 g / L, 30 ° C. sodium hydroxide aqueous solution, or a 0.5 g / L, 30 ° C. potassium hydroxide aqueous solution is preferably used. ..
The immersion time in the acid aqueous solution or the alkaline aqueous solution is preferably 8 to 120 minutes, more preferably 10 to 90 minutes, still more preferably 15 to 60 minutes. Here, the soaking time means the total of each soaking time when the soaking treatment for a short time is repeated. A cleaning treatment may be performed between the immersion treatments.

In the present invention, the height of the projecting portion where one end of the plurality of conduction paths protrudes from the surface of the insulating base material by the projecting step is 50 nm for the reason that the bondability with the surface of the member having low flatness is good. The above is preferable, 0.1 to 0.8 μm is more preferable, and 0.2 to 0.5 μm is further preferable.
Here, the height of the protruding portion is 10 fields at a magnification of 60,000 times using a field emission scanning electron microscope (FE-SEM) for a cross section in the thickness direction of the metal-filled microstructure. It is the average value of the values measured by observing and measuring the height of the protruding portion protruding from the surface of the insulating base material for each of a plurality of conduction paths.

[Washing process]
The production method of the present invention preferably has a cleaning step of cleaning the surface of the specific metal-filled microstructure after the projecting step.
Examples of the cleaning method include a method of immersing in a rinse solution and a method of spraying the rinse solution using a conventionally known rinse solution.

The rinse solution preferably contains water as a main component.
Further, the rinsing liquid may contain a water-miscible solvent such as alcohols, acetone, tetrahydrofuran and the like as a solvent other than water.
Further, the rinse liquid preferably contains a surfactant.

[Substrate removal process]
As shown in the second aspect (FIG. 2) described above, in the manufacturing method of the present invention, when a specific metal-filled microstructure with a substrate is used, the substrate is removed after the second removal step. It may have a process.
The method for removing the substrate is not particularly limited, and examples thereof include a method for removing the substrate by dissolution. The method of removing the aluminum substrate by melting will be described in detail below.

<Dissolution of aluminum substrate>
For the dissolution of the aluminum substrate, it is preferable to use a treatment liquid that is difficult to dissolve the anodic oxide film and easily dissolves aluminum.
The dissolution rate of such a treatment liquid in aluminum is preferably 1 μm / min or more, more preferably 3 μm / min or more, and further preferably 5 μm / min or more. Similarly, the dissolution rate for the anodic oxide film is preferably 0.1 nm / min or less, more preferably 0.05 nm / min or less, and even more preferably 0.01 nm / min or less.
Specifically, it is preferable that the treatment liquid contains at least one metal compound having a lower ionization tendency than aluminum and has a pH of 4 or less or 8 or more, and the pH is 3 or less or 9 or more. Is more preferable, and 2 or less or 10 or more is further preferable.

Such treatment liquids are based on an acid or alkaline aqueous solution and include, for example, manganese, zinc, chromium, iron, cadmium, cobalt, nickel, tin, lead, antimony, bismuth, copper, mercury, silver, palladium, platinum, etc. It is preferably a compound containing a gold compound (for example, platinum chloride acid), these fluorides, these chlorides and the like.
Of these, an acid aqueous solution base is preferable, and a chloride blend is preferable.
In particular, a treatment liquid obtained by blending a hydrochloric acid aqueous solution with mercury chloride (hydrochloric acid / mercury chloride) and a treatment liquid obtained by blending a hydrochloric acid aqueous solution with copper chloride (hydrochloric acid / copper chloride) are preferable from the viewpoint of treatment latitude.
The composition of such a treatment liquid is not particularly limited, and for example, a bromine / methanol mixture, a bromine / ethanol mixture, aqua regia, or the like can be used.

The acid or alkali concentration of such a treatment liquid is preferably 0.01 to 10 mol / L, more preferably 0.05 to 5 mol / L.
Further, the treatment temperature using such a treatment liquid is preferably −10 ° C. to 80 ° C., preferably 0 ° C. to 60 ° C.

Further, the above-mentioned aluminum substrate is melted by contacting with the above-mentioned treatment liquid. The contact method is not particularly limited, and examples thereof include a dipping method and a spraying method. Above all, the dipping method is preferable. The contact time at this time is preferably 10 seconds to 5 hours, more preferably 1 minute to 3 hours.

The present invention will be described in more detail below based on examples. The materials, amounts used, ratios, treatment contents, treatment procedures, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the present invention. Therefore, the scope of the present invention should not be construed as limiting by the examples shown below.

[Example 1]
A specific anisotropic conductive member was produced by the following procedure.

(1) Preparation of Aluminum Substrate A plate (thickness 0.1 mm) obtained by rolling an ingot having an aluminum purity of 99.99% was used as the aluminum substrate.

(2) Electropolishing Treatment The aluminum substrate was subjected to electrolytic polishing treatment under the conditions of a voltage of 25 V, a liquid temperature of 65 ° C., and a liquid flow velocity of 3.0 m / min using an electrolytic polishing liquid having the following composition.
The cathode was a carbon electrode, and the power supply was GP0110-30R (manufactured by Takasago Seisakusho Co., Ltd.). The flow velocity of the electrolytic solution was measured using a vortex flow monitor FLM22-10PCW (manufactured by AS ONE Corporation).
The surface roughness Ra after electrolytic polishing was less than 0.03 um.
(Electrolytic polishing liquid composition)
・ 85% by mass phosphoric acid (reagent manufactured by Wako Pure Chemical Industries, Ltd.) 660 mL
・ Pure water 160mL
・ Sulfuric acid 150mL
・ Ethylene glycol 30mL

(3) Anodizing Treatment Step Next, the aluminum substrate after the electrolytic polishing treatment was subjected to anodizing treatment by a self-regulation method according to the procedure described in JP-A-2007-204802.
The aluminum substrate after the electrolytic polishing treatment was subjected to pre-anodizing treatment for 5 hours with an electrolytic solution of 0.50 mol / L oxalic acid under the conditions of a voltage of 40 V, a liquid temperature of 16 ° C., and a liquid flow rate of 3.0 m / min. ..
Then, the aluminum substrate after the pre-anodizing treatment was subjected to a demembrane treatment by immersing it in a 0.5 mol / L phosphoric acid aqueous solution (liquid temperature: 40 ° C.) for 20 minutes.
Then, a reanodizing treatment was performed for 5 hours with an electrolytic solution of 0.50 mol / L oxalic acid under the conditions of a voltage of 40 V, a liquid temperature of 16 ° C., and a liquid flow rate of 3.0 m / min, and an anodized film having a film thickness of 40 μm. Got
In both the pre-anodizing treatment and the re-anodizing treatment, a stainless steel electrode was used as the cathode, and GP0110-30R (manufactured by Takasago Seisakusho Co., Ltd.) was used as the power source. A NeoCool BD36 (manufactured by Yamato Kagaku Co., Ltd.) was used as the cooling device, and a pair stirrer PS-100 (manufactured by EYELA Tokyo Rika Kikai Co., Ltd.) was used as the stirring and heating device. Further, the flow velocity of the electrolytic solution was measured using a vortex type flow monitor FLM22-10PCW (manufactured by AS ONE Corporation).

(4) Barrier layer removal step Next, electrolytic treatment (electrolytic removal treatment) is performed while continuously lowering the voltage from 40 V to 0 V at a voltage drop rate of 0.2 V / sec under the same treatment liquid and treatment conditions as the above anodizing treatment. ) Was given.
Then, the surface of the anodic oxide film was washed with warm water at 50 ° C., NeutraClean 68 (manufactured by Rohm and Haas) at 45 ° C., and warm water at 50 ° C., and a sodium hydroxide aqueous solution (25) containing 5 g / L of zinc was continuously used. It was immersed in (° C.) and subjected to etching treatment (etching removal treatment) to remove the barrier layer at the bottom of the micropores of the anodic oxide film, and zinc was deposited on the exposed aluminum surface through the micropores.
Next, electroless nickel treatment was performed in order to suppress hydrogen generation during the plating treatment, and a plating seed layer in which zinc and nickel were laminated was formed on the bottom of the pore.

Here, the average opening diameter of the micropores present in the anodic oxide film after the barrier layer removing step was 60 nm. The average aperture diameter was calculated as an average value measured at 50 points by taking a surface photograph (magnification 50,000 times) by FE-SEM.
The average thickness of the anodic oxide film after the barrier layer removing step was 40 μm. For the average thickness, the anodic oxide film is cut in the thickness direction with a focused ion beam (FIB), and a surface photograph (magnification of 50,000 times) is taken of the cross section by FE-SEM. It was calculated as an average value measured by points.
The density of micropores present in the anodic oxide film was about 100 million / mm ² . The density of micropores was measured and calculated by the method described in paragraphs [0168] and [0169] of JP-A-2008-270158.
The degree of regularization of the micropores present in the anodic oxide film was 92%. The degree of regularization was calculated by taking a surface photograph (magnification 20000 times) with an FE-SEM and measuring by the method described in paragraphs [0024] to [0027] of JP-A-2008-270158.

(5) Metal filling process (electroplating process)
Next, an aluminum substrate was used as a cathode and copper was used as a cathode for electrolytic plating.
Specifically, a copper plating solution having the composition shown below was used and constant current electrolysis was performed to prepare a metal-filled microstructure having a conduction path in which copper was filled inside the micropores.
Here, for constant current electrolysis, a plating apparatus manufactured by Yamamoto Plating Tester Co., Ltd. is used, and a power source (HZ-3000) manufactured by Hokuto Denko Co., Ltd. is used to perform cyclic voltammetry in the plating solution for precipitation. After confirming the potential, the treatment was performed under the conditions shown below.
(Copper plating solution composition and conditions)
・ Copper sulfate 250g / L
・ Sulfuric acid 1g / L
・ Hydrochloric acid 0.05g / L
・ SPS (bis (3-sulfopropyl) disulfide) 5 mg / L
・ Polyethylene glycol 10 mg / L
・ Temperature 30 ℃
・ Current density 10A / dm ²

Observe the surface of the anodic oxide film after filling the micropores with metal by FE-SEM, and observe the presence or absence of metal sealing in 1000 micropores, and the sealing ratio (number of sealing micropores / 1000). When the number) was calculated, it was 96%.
In addition, the anodized oxide film after filling the micropores with metal is cut by FIB in the thickness direction, and a surface photograph (magnification of 50,000 times) of the cross section is taken by FE-SEM to show the inside of the micropores. Upon confirmation, it was found that the inside of the sealed micropore was completely filled with metal.

(6) Water-repellent step Next, protect sill CIT (manufactured by BASF) as a water-repellent agent is applied to the surface of the metal-filled microstructure on the opposite side of the aluminum substrate as the undiluted solution. The inner wall of the micropores in the filling region was made water repellent and dried at room temperature (23 ° C.) for 10 minutes.
Next, the water repellent agent applied to the surface of the metal-filled microstructure opposite to the aluminum substrate was wiped off with a skizer and dried.

(7) Projection Step Next, the metal-filled microstructure after the water-repellent step is immersed in a phosphoric acid solution to selectively dissolve the anodic oxide film, whereby a cylinder of the filled metal filled in a plurality of through holes is formed. Was projected to obtain a specific idiosyncratic conductive member. As the phosphoric acid solution, a 0.5 mol / L aqueous solution (liquid temperature: 40 ° C.) was used, and the treatment time was set to 10 minutes.

[Examples 2 to 9 and Comparative Examples 1 to 3]
A specific anisotropic conductive member was produced by the same method as in Example 1 except that the treatment conditions in the water repellent step and the projecting step were changed to the conditions shown in Table 1 below.
In the polishing in the water-repellent step performed in Examples 2 to 8, after the applied water-repellent agent was dried, silica abrasive grains were used to make the polishing thicker than the state before the water-repellent agent was applied. Polishing was performed until the surface layer of 0.5 μm was removed, and the water-repellent surface layer was removed.

[evaluation]
About the cross section of each specific anisotropic conductive member produced, 10 visual fields were observed at a magnification of 60,000 times using FE-SEM.
A contour line image with a pitch of 50 nm prepared in advance is superimposed on the obtained image so that one end (outermost surface) of the projected conduction path has the height of the contour line = 0 (see FIG. 3), and the conduction path is visually observed. The range of the contour lines where the height of the insulating substrate between them was located was determined and recorded.
This was put together for 10 fields of view to obtain a frequency distribution (see FIG. 4) of the height of the protruding portion of the conduction path.
This frequency distribution is statistically processed to calculate the average height and standard deviation of the protruding portion of the conduction path, and the latter three times (3σ) is the variation in the height of the protruding portion of the conduction path (variation width). ).

From the results shown in Table 1, it was found that the height of the protruding portion of the conduction path varies when the water repellent step is not performed (Comparative Examples 1 to 3).
On the other hand, it was found that when the water repellent step was performed, the height variation of the protruding portion of the conduction path could be suppressed (Examples 1 to 9).

1 Substrate 3 Insulating base material 4 Through-passage 5 Conduction path 5a Protruding part 6 Unfilled area 10 Specified metal-filled microstructure 10a Surface 20 Specified anisotropic conductive member Dt Thickness direction h Height of protruding part

Claims

It has an insulating base material, a plurality of through-passages penetrating in the thickness direction of the insulating base material, and a plurality of conduction paths made of a conductive substance filled inside the plurality of through-passages. A method for manufacturing an anisotropic conductive member provided with one end of the plurality of conduction paths protruding from at least one surface of the insulating base material.
It has an insulating base material, a plurality of through-passages penetrating in the thickness direction of the insulating base material, and a plurality of conduction paths made of a conductive substance filled inside the plurality of through-passages. Further, in a part of the conductive paths among the plurality of conductive paths, a metal-filled microstructure in which an unfilled region in which the conductive substance is not filled exists in at least a part of the inside of the through-passage in the thickness direction. The preparatory process to prepare the body and
A water-repellent step of making the inner wall of the gangway in the unfilled region water-repellent,
After the water-repellent step, a treatment liquid is applied to the surface of the metal-filled microstructure, a part of the surface of the insulating base material is selectively removed in the thickness direction, and one end of the plurality of conduction paths is described. A method for manufacturing an anisotropic conductive member, which comprises a projecting step of projecting from the surface of an insulating base material.
In the water-repellent step, a water-repellent agent is applied to the surface of the metal-filled microstructure on the opening side of the through-passage of the unfilled region, and the inner wall and the surface of the through-passage in the unfilled region are applied. The isotropic conductive member according to claim 1, further comprising a first step of making water repellent and a second step of removing the water repellent agent on the surface after the first step. Production method.
The method for producing an anisotropic conductive member according to claim 1 or 2, wherein the water repellent step is a treatment step using at least one of a silicon-containing compound and a fluorine-containing compound.
The method for manufacturing an anisotropic conductive member according to any one of claims 1 to 3, wherein the insulating base material is a valve metal anodic oxide film.
The method for manufacturing an anisotropic conductive member according to claim 4, wherein the valve metal is aluminum.
The method for manufacturing an anisotropic conductive member according to any one of claims 1 to 5, wherein the conductive substance is copper.
The anisotropic conductive member according to any one of claims 1 to 6, wherein the height of the protruding portion of the plurality of conduction paths protruding from the surface of the insulating base material by the protruding step is 50 nm or more. Manufacturing method.