JP2009224146A - Laminated plate having anisotropic conductive member and method of manufacturing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a conductive material which is a laminated plate of an anisotropic conductive member using an anodic oxidation coating of aluminum and a conductive layer that is manufactured simply. <P>SOLUTION: The conductive material 100 uses a material in which a conductive layer 56 is laminated on an anodic oxidation coating 54 of aluminum having a conductive part in a micropore. In the conductive material, an anisotropic conductive member 100 having the anodic oxidation coating 54 of aluminum and a conductive material 52 which penetrates in thickness direction of the oxidation coating 54, and the conductive layer 56 are laminated, and the conductive material 52 is electrically connected to the conductive layer 56. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a conductive material, and more particularly, to a laminated plate of an anisotropic conductive member using an anodic oxide film of aluminum and a conductive layer.

Patent Document 1 discloses an anisotropic conductive substrate made of an anisotropic conductive material using a polyetherimide resin as an insulating material and an electric wire (copper) as a conductive material.
Non-Patent Document 1 discloses that an anodized aluminum plate is heated, melted and removed by YAG laser irradiation through the anodized film, that is, laser ablation occurs to remove the anodized film. A method for producing a patterned printed wiring board is disclosed.
JP 2000-31621 A Title: Fabrication of printed wiring board using anodization of aluminum (Surface Science Vol22, No6, pp370-375 2001 Takahashi)

  The anisotropic conductive materials described in these prior arts have a complicated manufacturing method, and the manufacturing method of an electrode for connecting to the anisotropic conductive material is also complicated. A simpler manufacturing method is desired to provide a product.

  The inventor can easily manufacture an anisotropic conductive material by using a material in which a conductive layer is laminated on an anodic oxide film of aluminum having a conductive portion in a micropore, and an arbitrary material used for connection to the material. The present invention was completed by finding out that it is easy to produce patterned electrodes.

That is, the present invention provides the following inventions.
(1) An anisotropic conductive member having an anodic oxide film of aluminum, a conductive material penetrating in the thickness direction of the oxide film, and a conductive layer are laminated, and the conductive material is electrically connected to the conductive layer. Conductive material to connect.
(2) The conductive material according to (1), further comprising a photosensitive resin layer on the conductive layer and / or the anisotropic conductive member.
(3) The conductive material according to (1) or (2), wherein the conductive layer has a wiring circuit pattern.
(4) A circuit board for a probe card for semiconductor inspection, comprising the conductive material according to any one of (1) to (3).
(5) A method for producing the circuit board, which is formed by removing the conductive layer of the conductive material according to any one of (1) to (3) except for electrodes and / or wiring portions.
(6) The removal step is removal by an etching method using a photolithographic method or heat removal by laser ablation.
(7) Preferably, a plurality of conductive paths made of a conductive material are insulated from each other in the anodic oxide film, and preferably 1 to 1000 × 10 ⁶ pieces / μm ^2, more preferably 3 to 300 × 10 ⁶ pieces. The conductive material according to any one of (1) to (3), which penetrates at a density of / μm ² .

  Since the conductive material of the present invention is configured by electrically connecting an anisotropic conductive member with a conductive layer made of a conductive material, the conductive layer is appropriately patterned using a commercially available laser marker or the like. It is possible. Furthermore, since the insulating material of the anisotropic conductive member is composed of an anodized film, the thermal conductivity is high and the heat dissipation efficiency is good. Furthermore, since it is anisotropically conductive, it is not necessary to form a through hole by patterning both sides. Furthermore, the conductive material of the present invention can be laminated to be multilayered.

The conductive material of another aspect of the present invention can be used as an electric circuit board because the conductive layer has a wiring circuit pattern. Furthermore, since the insulating material of the anisotropic conductive member is composed of an anodized film, the thermal conductivity is high and the heat dissipation efficiency is good. Furthermore, since it has anisotropic conductivity, it is not necessary to form a through hole by patterning both sides. Furthermore, they can be laminated to make a multilayer.
In the conductive material in which the photosensitive resin layer is further laminated on the conductive layer of another aspect of the present invention, the photosensitive resin layer is laminated. The conductive layer can be easily patterned into an arbitrary wiring layer.

(Conductive material)
As shown in FIG. 1A, the conductive material of the present invention is a conductive material 100 in which an anisotropic conductive member 21 and a conductive layer 56 are laminated, and the anisotropic conductive member 21 is an aluminum anode. An oxide film 54 and a conduction path 52 made of a conductive material penetrating in the thickness direction of the oxide film are provided, and the conductive material is electrically connected to the conductive layer.
In the anodic oxide film, a plurality of conductive paths made of a conductive material are insulated from each other, with a density of 1 to 1000 × 10 ⁶ pieces / μm ^2, more preferably 3 to 300 × 10 ⁶ pieces / μm ² . The penetration flatness is preferably a warpage rate of 5% or less and a twist rate of 5% or less. More preferably, the warp rate is 1% or less and the twist rate is 1% or less.
Furthermore, as shown to FIG. 7C, you may have the photosensitive resin layer 64 on the electroconductive layer 56, and may have the other layer selected suitably as needed. Each layer may be a single layer or two or more layers. Unless otherwise specified, the meanings of terms shall be those defined in JISC-5603-1987 [Printed wiring board terms].

(1) Conductive layer The conductive layer is a layer made of a conductive material, and the conductive material is a material having high electrical conductivity (conductivity). Also called a good conductor or simply a conductor. Electrical conductivity is a physical property value with a wide range of values depending on the substance, and varies from metal to ceramic. In general, a conductor whose conductivity is equal to or higher than that of graphite (electric conductivity 10 ⁶ S / m) is called a conductor. The electrical conductivity of 10 ⁶ S / m indicates the ease of passing electricity with a resistance of 1 Ω in a 1 m ² cross-sectional area of 1 mm ² .
Specifically, Au, Ag, Cu, and A1 are known as typical conductive materials. Ti, Mo, Ta, W or the like can be used as an alloy mainly composed of these metals or a metal having a high melting point.
The conductive layer can be formed by a method of diffusion bonding by thermocompression bonding, a method of attaching with a conductive adhesive layer, an electron beam evaporation method, a sputtering method, or a DVD method.
In addition, a graphite sheet, a conductive resin sheet, and the like are also included.
The conductive material of the present invention can be used as a multilayer wiring board by forming a low-k film (SiO ₂ , SiN) on a conductive layer such as Cu and forming a multilayer.

(2) Method for forming conductive layer In a method in which the conductive layer is formed by directly connecting to the anisotropic conductive member, the conductive layer is formed after polishing the surface of the anisotropic conductive member, for example. Metal foil materials such as gold, copper, and aluminum can be joined by thermocompression using diffusion bonding. A temperature of 200 ° C. to 350 ° C. and a pressure of 0.4 to 0.8 MPa can be used. There is also a method of attaching a conductive foil to the anisotropic conductive member. The conductive foil is most preferably a copper foil in view of conductivity and cost, and can be used as a copper clad laminate when copper is used. Also, aluminum, copper or aluminum alloy foil can be used as appropriate. An Invar alloy with a low thermal expansion coefficient or a Ti film excellent in corrosiveness can be formed by vacuum deposition, sputtering, or CVD. The metal vapor deposition film is preferably formed by a sputtering method because of good adhesion. When copper foil or the like is used as the conductive layer, a corrosion-resistant metal such as gold or titanium can be further deposited to prevent oxidation of the copper foil or the like. Furthermore, a commercially available graphite sheet or the like can be used as the conductive layer. Among metals, refractory metals such as tungsten (W), hard metals such as Ni and Cr, graphite sheets, and the like, which are difficult to be diffusion bonded, are difficult to connect by thermocompression bonding. Can be bonded with an anisotropic conductive adhesive. A method in which an adhesive is coated and laminated with a laminator is preferable because the thickness of the adhesive layer can be made uniform.

  Further, in the conductive material of the present invention, the anisotropic conductive member may have a conductive layer on one side or on both sides. Moreover, the kind of the electroconductive layer of front and back can be changed suitably. Metal foil can also be provided on both sides. If the absorption to the laser is slight, it is possible to perform ablation patterning directly by high-power laser exposure.

(3) Conductive adhesive layer The conductive adhesive layer is a mixture of a resin responsible for fixing and a metal responsible for conductivity (conductive filler), and has both the property of conducting electricity and the property of fixing substances together. . In general, epoxy resin and silver (Ag) are often combined. An anisotropic conductive adhesive is applied to the surface of the conductive layer and / or the anisotropic conductive member by screen printing or the like, and the adhesive surface is bonded and heat is applied to cure the adhesive. Usually, it can be bonded by applying heat at around + 150 ° C for about 30 minutes. An anisotropic conductive adhesive in which the deformed portion exhibits conductivity when pressure is applied is also commercially available and can be used according to the purpose.
The following are examples of commercially available anisotropic conductive adhesives that can be used.
Product name: Dodent Model number NH-070A (L)
Product name: 3300 series manufactured by ThreeBond Co., Ltd.
3380B Two-component epoxy conductive adhesive
3303N Silicone anisotropic conductive adhesive for SMD crystal unit
3305C Adhesive for hard disk drive magnetic head

In the case of using an adhesive, a flat plate pressure type thermocompression bonding apparatus can be used as the bonding apparatus when the solvent content is low or in the case of a high viscosity adhesive. When a long conductive material exceeding 3 m is required or when the number of stacked layers is one, a commercially available laminator can be used. In this case, as the adhesive, it is preferable to use a low-viscosity adhesive having a high solvent content in terms of flatness.
Adhesion between the conductive layer and the anisotropic conductive member can be realized by appropriately setting the viscosity of the adhesive, the flatness of the laminator roll, and the pressure.

(4) Anisotropic conductive member The anisotropic conductive member of the present invention and a method for manufacturing the same will be described in detail below.
In the anisotropic conductive member of the present invention, a plurality of conductive paths made of a conductive material penetrate through the insulating base material in the thickness direction while being insulated from each other. An anisotropic conductive member is provided in a state where one end of the passage is exposed on one surface of the insulating base and the other end of each conduction path is exposed on the other surface of the insulating base.
Next, the anisotropic conductive member of the present invention will be described with reference to FIG.

FIG. 1 is a simplified diagram showing a preferred example of an anisotropic conductive member, FIG. 2A is a front view, and FIG. 2B is a cross-sectional view taken along section line IB-IB in FIG. 2A.
The anisotropic conductive member 1 includes an insulating base 2 and a plurality of conduction paths 3 made of a conductive material.
The conductive path 3 has an axial length equal to or greater than the length (thickness) in the thickness direction Z of the insulating base material 2 and preferably 1 to 1000 × 10 ⁶ pieces / μm ^2, more preferably 3 to 300 × 10 6. ^The insulating base material 2 is provided so as to penetrate in a state of being insulated from each other so as to have a density of ⁶ pieces / μm ² .
In addition, the conductive path 3 is in a state in which one end of each conductive path 3 is exposed on one surface of the insulating base material 2 and the other end of each conductive path 3 is exposed on the other surface of the insulating base material 2. 2B, one end of each conduction path 3 protrudes from one surface 2a of the insulating base 2 and the other end of each conduction path 3 extends from the other surface 2b of the insulating base 2 as shown in FIG. 2B. It is preferable to be provided in a protruding state. That is, it is preferable that the both ends of each conduction path 3 have the protruding portions 4a and 4b protruding from 2a and 2b which are the main surfaces of the insulating base material.
Further, in this conduction path 3, at least a portion in the insulating base material 2 (hereinafter also referred to as “in-base conduction portion 5”) is substantially parallel to the thickness direction Z of the insulating base material 2 (FIG. 2). Are preferably provided so as to be parallel).
Next, materials, dimensions, formation methods, and the like will be described for each of the insulating base material and the conduction path.

[Insulating substrate]
The said insulating base material which comprises the anisotropically conductive member of this invention is a structure which consists of an anodic oxide film of the aluminum substrate which has a micropore. Alumina has an electrical resistivity of about 10 ¹⁴ Ω · cm, as in the case of an insulating base material (for example, a thermoplastic elastomer) constituting a conventionally known anisotropic conductive film or the like.

  The porous alumina film is also called an alumite film, and indicates an oxide film obtained by anodizing aluminum in an acidic aqueous solution, and is called an anodized film. The shape of the aluminum oxide film produced varies depending on the type of the electrolytic solution, and various electrolytic solutions are used depending on the purpose and application. The most prevalent anodic oxidation method is a method in which dilute sulfuric acid is used as an electrolyte, and the resulting anodized film is a porous film consisting of a barrier layer and countless fine pores, and is a collection of hexagonal column cells such as a honeycomb. Each body has a fine hole in the center, leading to the barrier layer formed at the substrate interface. In the present invention, the base aluminum and the barrier layer are removed to form a membrane (film), and then the conductive material is filled into the fine holes.

  In the present invention, the thickness of the insulating substrate (the portion represented by reference numeral 6 in FIG. 2B) is preferably 10 to 200 μm, more preferably 20 to 150 μm, and 30 to 100 μm. It is particularly preferred. When the thickness of the insulating substrate is within this range, the handleability of the insulating substrate is improved.

  Moreover, in this invention, it is preferable that the width | variety (the part represented with the code | symbol 7 in FIG. 2B) between the said conduction paths in the said insulating base material is 10 nm or more, and it is 20-500 nm more. Preferably, it is 30-450 nm. When the width between the conductive paths in the insulating substrate is within this range, the insulating substrate sufficiently functions as an insulating partition.

  In the present invention, the insulating base material preferably has a degree of ordering defined by the following formula (i) for micropores of 10% or more, more preferably 30% or more, and 50%. It is still more preferable that it is above.

  Ordering degree (%) = B / A × 100 (i)

  In the above formula (i), A represents the total number of micropores in the measurement range. B is centered on the center of gravity of one micropore, and when a circle with the shortest radius inscribed in the edge of another micropore is drawn, the center of gravity of the micropore other than the one micropore is placed inside the circle. This represents the number in the measurement range of the one micropore to be included. Details of the degree of ordering are described in Japanese Patent Application Laid-Open No. 2007-332437.

  In the present invention, the insulating base material can be manufactured by anodizing an aluminum substrate and penetrating micropores generated by the anodization. Here, the anodizing and penetrating treatment steps will be described in detail in the method for manufacturing an anisotropic conductive member of the present invention described later.

[Conduction path]
The conduction path constituting the anisotropic conductive member of the present invention is made of a conductive material.
The conductive material is not particularly limited as long as the electrical resistivity is 10 ³ Ω · cm or less, and specific examples thereof include gold (Au), silver (Ag), copper (Cu), and aluminum (Al). Suitable examples include so-called organic materials such as metals such as magnesium (Mg) and nickel (Ni), low melting point metals (alloys such as solder, Ga), conductive polymers, and carbon nanotubes.

Japanese Patent Application Laid-Open No. 2-68812 discloses an embodiment in which a conductive low-melting-point substance or a low-melting-point metal (alloy such as solder) is dissolved and charged while pressure is applied, or a conductive polymer monomer is charged and polymerized. And a method of filling a polymer monomer, polymerizing it, and baking it in an oxygen-free state to form a carbon material.
Further, JP-A-4-126307 discloses a method of electrolytically depositing Au and Ni and a method of filling a conductive material by a dry plating method such as metal paste, electroless plating, vapor deposition, sputtering, and CVD.

Among these, metals are preferable from the viewpoint of electrical conductivity, among which copper, gold, aluminum, and nickel are more preferable, and copper and gold are particularly preferable.
Further, from the viewpoint of cost, it is more preferable that only the surfaces of the conductive path exposed from both surfaces of the insulating substrate or the surfaces of the protruding surfaces (hereinafter also referred to as “end faces”) are formed of gold.

In the present invention, the conductive path is columnar, and the diameter (portion represented by reference numeral 8 in FIG. 2B) is preferably 15 nm or more, more preferably 20 to 350 nm, and more preferably 50 to 300 nm. More preferably.
When the diameter of the conductive path is within this range, a sufficient response can be obtained when an electric signal is passed, so the anisotropic conductive member of the present invention is more suitably used as an inspection connector for electronic components. Can do.

  Moreover, in this invention, when the both ends of the said conduction path protrude from both surfaces of the said insulating base material, in the protruded part (FIG. 2B), the part represented by code | symbol 4a and 4b. Hereinafter, it is also referred to as “bump”. ) Is preferably 5 to 500 nm, more preferably 10 to 200 nm. When the height of the bump is within this range, the bondability with the electrode (pad) portion of the electronic component is improved.

In the present invention, the conductive paths exist in a state of being insulated from each other by the insulating base material, but preferably 1 to 1000 × 10 ⁶ pieces / μm ^2, more preferably 3 to 300 × 10 ⁶ pieces / μm. A density of ² is more preferred.
When the density of the conduction paths is within this range, the anisotropic conductive member of the present invention can be used as a connector for inspection of electronic parts such as semiconductor elements even at the present time when the integration is further advanced.

  In the present invention, the distance between the centers of adjacent conductive paths (the portion represented by reference numeral 9 in FIG. 2, hereinafter also referred to as “pitch”) is preferably 50 to 600 nm, and preferably 90 to 550 nm. More preferably, it is 190 to 520 nm. When the pitch is within this range, it is easy to balance the conduction path diameter and the width between the conduction paths (insulating partition wall thickness).

In the present invention, the conductive path can be manufactured by, for example, filling a conductive material into the inside of a hole formed by a micropore formed in the insulating base material.
Here, the process of filling the conductive material will be described in detail in the method for manufacturing the anisotropic conductive member of the present invention described later.

  As described above, the anisotropic conductive member of the present invention maintains a high insulating property when the thickness of the insulating base material is 30 to 100 μm and the diameter of the conductive path is 50 to 350 nm. However, it is preferable for the reason that conduction can be confirmed at a high density.

The method for manufacturing an anisotropic conductive member is a method for manufacturing the anisotropic conductive member for manufacturing the anisotropic conductive member of the present invention described above, and at least,
(1) Anodizing step of anodizing an aluminum substrate to form an alumina film having micropores;
(2) After the anodizing treatment step, a penetration treatment step for penetrating holes by the micropores generated by the anodization to obtain the insulating substrate, and (3) obtained after the penetration treatment step. A conductive material filling step for obtaining the anisotropic conductive member by filling a conductive material into the perforated holes in the insulating base material,
Is a manufacturing method.
Next, the aluminum substrate to be used and each processing step applied to the aluminum substrate will be described in detail.

[Aluminum substrate]
The aluminum substrate used in the production method of the present invention is not particularly limited, and specific examples thereof include a pure aluminum plate; an alloy plate containing aluminum as a main component and a trace amount of foreign elements; low-purity aluminum (for example, recycled material) ) On which the surface of high-purity aluminum is vapor-deposited; a substrate on which the surface of silicon wafer, quartz, glass or the like is coated with high-purity aluminum by a method such as vapor deposition or sputtering; a resin substrate on which aluminum is laminated;

  In the production method of the present invention, in the aluminum substrate, the surface on which the anodized film is provided by an anodizing treatment step described later preferably has an aluminum purity of 95.0% by mass or more, and 99.5% by mass or more. It is more preferable that it is 99.99% by mass or more. It is preferable for the aluminum purity to be in the above range since the regularity of the arrangement of micropores is improved.

  Moreover, in the manufacturing method of this invention, it is preferable that the surface which performs the anodic oxidation process mentioned later among aluminum substrates performs a degreasing process and a mirror surface finishing process previously.

<Heat treatment>
When heat treatment is performed, it is preferably performed at 200 to 350 ° C. for about 30 seconds to 2 minutes. Thereby, the regularity of the arrangement | sequence of the micropore produced | generated by the anodizing process mentioned later is improved.
The aluminum substrate after the heat treatment is preferably cooled rapidly. As a method of cooling, for example, a method of directly feeding into water or the like can be mentioned.

<Degreasing treatment>
The degreasing treatment uses acid, alkali, organic solvent, etc. to dissolve and remove the organic components such as dust, fat, and resin adhered to the surface of the aluminum substrate, and in each treatment described later due to the organic components. This is done for the purpose of preventing the occurrence of defects.

Specifically, as the degreasing treatment, for example, a method in which an organic solvent such as various alcohols (for example, methanol), various ketones (for example, methyl ethyl ketone), benzine, volatile oil or the like is brought into contact with the aluminum substrate surface at room temperature (organic Solvent method); a method of bringing a liquid containing a surfactant such as soap or neutral detergent into contact with the aluminum substrate surface at a temperature from room temperature to 80 ° C., and then washing with water (surfactant method); concentration of 10 to 200 g A method in which an aqueous solution of sulfuric acid / L is brought into contact with the aluminum substrate surface at a temperature from room temperature to 70 ° C. for 30 to 80 seconds and then washed with water; while contacting about seconds, the aluminum substrate surface and the electrolyte by passing a direct current of a current density of 1 to 10 a / dm ² in the cathode, the , A method of neutralizing by bringing a nitric acid aqueous solution having a concentration of 100 to 500 g / L into contact; while bringing various known anodizing electrolytes into contact with the aluminum substrate surface at room temperature, the aluminum substrate surface is used as a cathode and a current density of 1 to A method in which a 10 A / dm ² direct current is applied or an alternating current is applied for electrolysis; an alkaline aqueous solution having a concentration of 10 to 200 g / L is brought into contact with the aluminum substrate surface at 40 to 50 ° C. for 15 to 60 seconds; A method of neutralizing by bringing a nitric acid aqueous solution having a concentration of 100 to 500 g / L into contact; an emulsion obtained by mixing light oil, kerosene, etc. with a surfactant, water, etc. is brought into contact with the aluminum substrate surface at a temperature from room temperature to 50 ° C. Then, a method of washing with water (emulsification and degreasing method); a mixed solution of sodium carbonate, phosphates, surfactant and the like on the surface of the aluminum substrate at a temperature from room temperature to 50 ° C. Contacting 0-180 seconds, then, a method of washing with water (phosphate method); and the like.

  Among these, the organic solvent method, the surfactant method, the emulsion degreasing method, and the phosphate method are preferable from the viewpoint that the fat content on the aluminum surface can be removed while the aluminum hardly dissolves.

  Moreover, a conventionally well-known degreasing agent can be used for a degreasing process. Specifically, for example, various commercially available degreasing agents can be used by a predetermined method.

<Mirror finish processing>
The mirror finishing process is performed to eliminate unevenness on the surface of the aluminum substrate and improve the uniformity and reproducibility of the particle forming process by an electrodeposition method or the like. Examples of the irregularities on the surface of the aluminum substrate include rolling stripes generated during rolling in the case where the aluminum substrate is manufactured through rolling.
In the present invention, the mirror finish is not particularly limited, and a conventionally known method can be used. Examples thereof include mechanical polishing, chemical polishing, and electrolytic polishing.

  Examples of the mechanical polishing include a method of polishing with various commercially available polishing cloths, a method of combining various commercially available abrasives (for example, diamond, alumina) and a buff. Specifically, when an abrasive is used, a method in which the abrasive used is changed from coarse particles to fine particles over time is preferably exemplified. In this case, the final polishing agent is preferably # 1500. Thereby, the glossiness can be 50% or more (in the case of rolled aluminum, both the rolling direction and the width direction are 50% or more).

As chemical polishing, for example, “Aluminum Handbook”, 6th edition, edited by Japan Aluminum Association, 2001, p. Examples thereof include various methods described in 164 to 165.
Further, the phosphoric acid-nitric acid method, the Alupol I method, the Alupol V method, the Alcoa R5 method, the H ₃ PO ₄ —CH ₃ COOH—Cu method, and the H ₃ PO ₄ —HNO ₃ —CH ₃ COOH method are preferably exemplified. . Among these, the phosphoric acid-nitric acid method, the H ₃ PO ₄ —CH ₃ COOH—Cu method, and the H ₃ PO ₄ —HNO ₃ —CH ₃ COOH method are preferable.
By chemical polishing, the glossiness can be made 70% or more (in the case of rolled aluminum, both the rolling direction and the width direction are 70% or more).

As electrolytic polishing, for example, “Aluminum Handbook”, 6th edition, edited by Japan Aluminum Association, 2001, p. 164-165; various methods described in US Pat. No. 2,708,655; “Practical Surface Technology”, vol. 33, no. 3, 1986, p. The method described in 32-38;
By electropolishing, the gloss can be 70% or more (in the case of rolled aluminum, both the rolling direction and the width direction are 70% or more).

  These methods can be used in appropriate combination. Specifically, for example, a method of performing mechanical polishing in which the abrasive is changed from coarse particles to fine particles with time, and then performing electrolytic polishing is preferable.

By mirror finishing, for example, a surface having an average surface roughness Ra of 0.1 μm or less and a glossiness of 50% or more can be obtained. The average surface roughness Ra is preferably 0.03 μm or less, and more preferably 0.02 μm or less. Further, the glossiness is preferably 70% or more, and more preferably 80% or more.
The glossiness is a regular reflectance obtained in accordance with JIS Z8741-1997 “Method 3 60 ° Specular Gloss” in the direction perpendicular to the rolling direction. Specifically, using a variable angle gloss meter (for example, VG-1D, manufactured by Nippon Denshoku Industries Co., Ltd.), when the regular reflectance is 70% or less, the incident reflection angle is 60 degrees and the regular reflectance is 70%. In the case of exceeding, the incident / reflection angle is 20 degrees.

[(1) Anodizing treatment step]
The anodic oxidation step is a step of forming an oxide film having micropores on the surface of the aluminum substrate by subjecting the aluminum substrate to an anodic oxidation treatment.
In the present invention, a conventionally known method can be used as the anodic oxidation treatment, but the insulating base material is excellent in the degree of ordering defined by the above formula (i), preferably the degree of ordering. Is an anodized film of an aluminum substrate having micropores arranged so as to be 50% or more, it is preferable to use the self-ordering method described later.
The anodizing treatment is preferably performed as a constant voltage treatment.

The self-ordering method is a method for improving the regularity by utilizing the property that the micropores of the anodic oxide film are regularly arranged and removing the factors that disturb the regular arrangement. Specifically, high-purity aluminum is used, and an anodized film is formed at a low speed over a long period of time (for example, several hours to several tens of hours) at a voltage corresponding to the type of the electrolytic solution.
In this method, since the pore diameter depends on the voltage, a desired pore diameter can be obtained to some extent by controlling the voltage.

In order to form micropores by the self-ordering method, at least anodizing treatment (A) described later may be performed, but it is preferable to form the micropores by self-ordering method I or self-ordering method II described later.
Next, self-ordering method I and self-ordering method II, which are preferred embodiments, will be described in detail.

[(1-a) Self-ordering method I]
In the self-ordering method I, after the anodic oxidation treatment (anodic oxidation treatment (A)) is performed, the anodic oxidation film is completely dissolved (defilming treatment ( After B)), anodization (re-anodization treatment (C)) is performed again.
Next, each process of the self-ordering method I will be described in detail.

<Anodizing treatment (A)>
The average flow rate of the electrolytic solution in the anodizing treatment (A) is preferably 0.5 to 20.0 m / min, more preferably 1.0 to 15.0 m / min, and 2.0 to 10 More preferably, it is 0.0 m / min. By performing the anodizing treatment (A) at a flow rate in the above range, uniform and high regularity can be obtained.
Moreover, the method of flowing the electrolytic solution under the above-mentioned conditions is not particularly limited, but, for example, a method using a general stirring device such as a stirrer is used. In particular, it is preferable to use a stirrer that can control the stirring speed by digital display because the average flow velocity can be controlled. Examples of such a stirring apparatus include “Magnetic Stirrer HS-50D (manufactured by AS ONE)” and the like.

For the anodizing treatment (A), for example, a method of energizing an aluminum substrate as an anode in a solution having an acid concentration of 1 to 10% by mass can be used.
The solution used for the anodizing treatment (A) is preferably an acid solution, and sulfuric acid, phosphoric acid, chromic acid, oxalic acid, sulfamic acid, benzenesulfonic acid, amidosulfonic acid, glycolic acid, tartaric acid, malic acid Citric acid and the like are more preferable, and sulfuric acid, phosphoric acid, and oxalic acid are particularly preferable. These acids can be used alone or in combination of two or more.

The conditions of the anodizing treatment (A) vary depending on the electrolytic solution used, and thus cannot be determined unconditionally. The current density is 0.01 to 20 A / dm ² , the voltage is 3 to 300 V, and the electrolysis time is preferably 0.5 to 30 hours, the electrolyte concentration is 0.5 to 15 mass%, the liquid temperature is −5 to 25 ° C., More preferably, the current density is 0.05 to 15 A / dm ² , the voltage is 5 to 250 V, the electrolysis time is 1 to 25 hours, the electrolyte concentration is 1 to 10% by mass, the solution temperature is 0 to 20 ° C., and the current density is 0.1. More preferably, it is 10A / dm < ² >, voltage 10-200V, and electrolysis time 2-20 hours.

  The treatment time for the anodizing treatment (A) is preferably 0.5 minutes to 16 hours, more preferably 1 minute to 12 hours, and even more preferably 2 minutes to 8 hours.

  The anodizing treatment (A) can be performed by changing the voltage intermittently or continuously in addition to being performed under a constant voltage. In this case, it is preferable to decrease the voltage sequentially. This makes it possible to reduce the resistance of the anodized film, and fine micropores are formed in the anodized film, which is preferable in terms of improving uniformity, particularly when sealing treatment is performed by electrodeposition. .

  In the production method of the present invention, the film thickness of the anodized film formed by such anodizing treatment (A) is preferably 1 to 300 μm, more preferably 5 to 150 μm, More preferably, it is 100 μm.

In the production method of the present invention, the average pore density of micropores of the anodized film formed by such anodizing treatment (A) is preferably 1 to 1000 × 10 ⁶ / μm ^2, more preferably 3 to 300. × 10 ⁶ / μm ²
The area ratio occupied by the micropores is preferably 20 to 50%.
Here, the area ratio occupied by the micropore is defined by the ratio of the total area of the opening of the micropore to the area of the aluminum surface.

<Film removal treatment (B)>
The film removal process (B) is a process for dissolving and removing the anodized film formed on the surface of the aluminum substrate by the anodizing process (A).
After forming an anodic oxide film on the surface of the aluminum substrate by the anodizing treatment (A), a penetration treatment step described later may be performed immediately. ) And re-anodizing treatment (C) described later are preferably performed in this order, and then a penetration treatment step described later is performed.

  Since the anodized film becomes more regular as it gets closer to the aluminum substrate, the bottom part of the anodized film remaining on the surface of the aluminum substrate is removed once by this film removal treatment (B). Can be exposed to the surface to obtain regular depressions. Therefore, in the film removal treatment (B), aluminum is not dissolved, but only the anodized film made of alumina (aluminum oxide) is dissolved.

  Alumina solution can be used without limitation to those conventionally known, but chromium compound, nitric acid, phosphoric acid, zirconium compound, titanium compound, lithium salt, cerium salt, magnesium salt, sodium silicofluoride, zinc fluoride. An aqueous solution containing at least one selected from the group consisting of manganese compounds, molybdenum compounds, magnesium compounds, barium compounds and halogen alone is preferred.

Specific examples of the chromium compound include chromium (III) oxide and chromium (VI) anhydride.
Examples of the zirconium-based compound include zircon ammonium fluoride, zirconium fluoride, and zirconium chloride.
Examples of the titanium compound include titanium oxide and titanium sulfide.
Examples of the lithium salt include lithium fluoride and lithium chloride.
Examples of the cerium salt include cerium fluoride and cerium chloride.
Examples of magnesium salts include magnesium sulfide.
Examples of the manganese compound include sodium permanganate and calcium permanganate.
As a molybdenum compound, sodium molybdate is mentioned, for example.
Examples of the magnesium compound include magnesium fluoride pentahydrate.
Examples of barium compounds include barium oxide, barium acetate, barium carbonate, barium chlorate, barium chloride, barium fluoride, barium iodide, barium lactate, barium oxalate, barium perchlorate, barium selenate, selenite. Examples thereof include barium, barium stearate, barium sulfite, barium titanate, barium hydroxide, barium nitrate, and hydrates thereof.
Among the barium compounds, barium oxide, barium acetate, and barium carbonate are preferable, and barium oxide is particularly preferable.
Examples of the halogen alone include chlorine, fluorine, and bromine.

Among them, the alumina solution is preferably an aqueous solution containing an acid. Examples of the acid include sulfuric acid, phosphoric acid, nitric acid, hydrochloric acid, and the like, and a mixture of two or more acids may be used.
The acid concentration is preferably 0.01 mol / L or more, more preferably 0.05 mol / L or more, and still more preferably 0.1 mol / L or more. There is no particular upper limit, but generally it is preferably 10 mol / L or less, more preferably 5 mol / L or less. An unnecessarily high concentration is not economical, and if it is higher, the aluminum substrate may be dissolved.

  The alumina solution is preferably −10 ° C. or higher, more preferably −5 ° C. or higher, and still more preferably 0 ° C. or higher. In addition, since the starting point of ordering will be destroyed and disturbed if it processes using the boiling alumina solution, it is preferable to use it without boiling.

  The alumina solution dissolves alumina and does not dissolve aluminum. Here, the alumina solution may not dissolve aluminum substantially or may dissolve it slightly.

  The film removal treatment (B) is performed by bringing the aluminum substrate on which the anodized film is formed into contact with the above-described alumina solution. The method of making it contact is not specifically limited, For example, the immersion method and the spray method are mentioned. Of these, the dipping method is preferred.

The dipping method is a treatment in which an aluminum substrate on which an anodized film is formed is dipped in the above-described alumina solution. Stirring during the dipping process is preferable because a uniform process is performed.
The time for the dipping treatment is preferably 10 minutes or more, more preferably 1 hour or more, and further preferably 3 hours or more and 5 hours or more.

<Re-anodizing treatment (C)>
After removing the anodic oxide film by the film removal treatment (B) and forming regular depressions on the surface of the aluminum substrate, the anodic oxidation treatment is performed again, so that the degree of ordering of the micropores is higher. A film can be formed.
The anodizing treatment in the re-anodizing treatment (C) can be performed by a conventionally known method, but is preferably performed under the same conditions as the above-described anodizing treatment (A).
Also, a method of repeatedly turning on and off the current intermittently while keeping the DC voltage constant, and a method of repeatedly turning on and off the current while intermittently changing the DC voltage can be suitably used. According to these methods, fine micropores are generated in the anodic oxide film, which is preferable in that uniformity is improved particularly when sealing treatment is performed by electrodeposition.

When the re-anodizing treatment (C) is performed at a low temperature, the arrangement of micropores becomes regular and the pore diameter becomes uniform.
On the other hand, by performing the re-anodizing treatment (C) at a relatively high temperature, the arrangement of the micropores can be disturbed, and the pore diameter variation can be within a predetermined range. Also, the pore diameter variation can be controlled by the processing time.

  In the production method of the present invention, the film thickness of the anodized film formed by such re-anodizing treatment (C) is preferably 10 to 200 μm, more preferably 20 to 150 μm, 30 More preferably, it is ˜100 μm.

In the production method of the present invention, the pore diameter of the micropores of the anodized film formed by such anodizing treatment (C) is preferably 20 to 200 nm, more preferably 30 to 190 nm. 60 to 180 nm is more preferable. More preferably, the pore diameter is enlarged by chemical dissolution treatment and adjusted to be within a preferable range of the conduction path.
The average pore density is preferably 1 to 1000 × 10 ⁶ pieces / μm ^2, more preferably 3 to 300 × 10 ⁶ pieces / μm ² .

[(1-b) Self-ordering method II]
In the self-ordering method II, the surface of the aluminum substrate is anodized (anodic oxidation (D)), and the anodized film is partially dissolved using an acid or alkali (oxide film dissolution treatment (E)). Then, after anodizing again to grow the micropore in the depth direction, the anodized film above the inflection point of the cross-sectional shape of the micropore is removed.
Next, each process of the self-ordering method II will be described in detail.

<Anodizing treatment (D)>
For the anodizing treatment (D), a conventionally known electrolytic solution can be used. When the film formation rate A is energized and the film dissolution rate B is non-energized under a direct current constant voltage condition, When the parameter R represented by the general formula (ii) is 160 ≦ R ≦ 200, preferably 170 ≦ R ≦ 190, and particularly preferably 175 ≦ R ≦ 185, the treatment is performed using an electrolytic solution. The regular arrangement can be greatly improved.

  R = A [nm / s] ÷ (B [nm / s] × applied voltage [V]) (ii)

The average flow rate of the electrolytic solution in the anodizing treatment (D) is preferably 0.5 to 20.0 m / min, similarly to the above-described anodizing treatment (A), and is 1.0 to 15.0 m / min. More preferably, it is 2.0 to 10.0 m / min. By performing anodization treatment (D) at a flow rate in the above range, uniform and high regularity can be obtained.
Moreover, the method of flowing the electrolytic solution under the above-mentioned conditions is not particularly limited as in the case of the above-described anodic oxidation treatment (A). For example, a method using a general stirring device such as a stirrer is used. In particular, it is preferable to use a stirrer that can control the stirring speed with a digital display because the average flow rate can be controlled. Examples of such a stirring apparatus include “Magnetic Stirrer HS-50D (manufactured by AS ONE)” and the like.
The viscosity of the anodizing solution is preferably 0.0001 to 100.0 Pa · s, more preferably 0.0005 to 80.0 Pa · s at 25 ° C. under 1 atm. By performing the anodic oxidation treatment (D) with an electrolytic solution having a viscosity in the above range, uniform and high regularity can be obtained.

Although both acidic and alkaline can be used for the electrolytic solution used in the anodizing treatment (D), an acidic electrolytic solution is preferably used from the viewpoint of enhancing the roundness of the holes.
Specifically, hydrochloric acid, sulfuric acid, phosphoric acid, chromic acid, oxalic acid, glycolic acid, tartaric acid, malic acid, citric acid, sulfamic acid, benzenesulfonic acid, amidosulfonic acid, as in the above-described anodizing treatment (A) , Glycolic acid, tartaric acid, malic acid, citric acid, and the like are more preferable, and sulfuric acid, phosphoric acid, and oxalic acid are particularly preferable. These acids can be used singly or in combination of two or more, adjusted to the desired parameters from the calculation formula of the above general formula (ii).

The conditions for the anodizing treatment (D) vary depending on the electrolyte used, and cannot be determined unconditionally. However, as with the above-described anodizing treatment (A), generally, the concentration of the electrolyte is 0.1 to It is preferably 20% by mass, a liquid temperature of −10 to 30 ° C., a current density of 0.01 to 20 A / dm ² , a voltage of 3 to 500 V, an electrolysis time of 0.5 to 30 hours, and an electrolyte concentration of 0.5 to 15 It is more preferable that the mass%, the liquid temperature −5 to 25 ° C., the current density 0.05 to 15 A / dm ² , the voltage 5 to 250 V, the electrolysis time 1 to 25 hours, and the electrolyte concentration 1 to 10 mass%, the liquid More preferably, the temperature is 0 to 20 ° C., the current density is 0.1 to 10 A / dm ² , the voltage is 10 to 200 V, and the electrolysis time is 2 to 20 hours.

  By this anodizing treatment (D), an anodized film 14a having micropores 16a is formed on the surface of the aluminum substrate 12, as shown in FIG. 3A. A barrier layer 18a is present on the aluminum substrate 12 side of the anodized film 14a.

<Oxide film dissolution treatment (E)>
The oxide film dissolution treatment (E) is a treatment (pore diameter enlargement treatment) for enlarging the micropores (pore diameter) present in the anodized film formed by the anodization treatment (D).

  The oxide film dissolution treatment (E) is performed by bringing the aluminum substrate after the anodization treatment (D) into contact with an acid aqueous solution or an alkali aqueous solution. The method of making it contact is not specifically limited, For example, the immersion method and the spray method are mentioned. Of these, the dipping method is preferred.

In the oxide film dissolution treatment (E), when an acid aqueous solution is used, it is preferable to use an aqueous solution of an inorganic acid such as sulfuric acid, phosphoric acid, nitric acid, hydrochloric acid, or a mixture thereof. Especially, the aqueous solution which does not contain chromic acid is preferable at the point which is excellent in safety | security. The concentration of the acid aqueous solution is preferably 1 to 10% by mass. The temperature of the acid aqueous solution is preferably 25 to 60 ° C.
On the other hand, when an alkaline aqueous solution is used in the oxide film dissolution treatment (E), 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, 50 g / L, 40 ° C. phosphoric acid aqueous solution, 0.5 g / L, 30 ° C. sodium hydroxide aqueous solution or 0.5 g / L, 30 ° C. potassium hydroxide aqueous solution is preferably used. .
The immersion time in the acid aqueous solution or alkali aqueous solution is preferably 8 to 120 minutes, more preferably 10 to 90 minutes, and still more preferably 15 to 60 minutes.

  Further, in the oxide film dissolution treatment (E), the amount of enlargement of the pore diameter varies depending on the conditions of the anodization treatment (D), but the enlargement ratio before and after the treatment is preferably 1.05 times to 100 times, and 1.1 times to 75 times is more preferable, and 1.2 times to 50 times is particularly preferable.

  By this oxide film dissolution treatment (E), as shown in FIG. 3B, the surface of the anodic oxide film 14a and the inside of the micropores 16a (barrier layer 18a and porous layer) shown in FIG. An aluminum member having an anodized film 14b having a micropore 16b on the surface 12 is obtained. As in FIG. 3A, a barrier layer 18b is present on the aluminum substrate 12 side of the anodized film 14b.

  In the self-ordering method II, the anodic oxidation treatment (D) is preferably performed again after the oxide film dissolution treatment (E).

  By the second anodic oxidation process (D), as shown in FIG. 3C, the oxidation reaction of the aluminum substrate 12 shown in FIG. 3B proceeds, and the micropores 16c deeper than the micropores 16b are formed on the aluminum substrate 12. An aluminum member having the anodic oxide film 14c having the above is obtained. As in FIG. 3A, a barrier layer 18c is present on the aluminum substrate 12 side of the anodized film 14c.

  Further, in the self-ordering method II, after the anodic oxidation treatment (D), the oxide film dissolution treatment (E) and the anodic oxidation treatment (D) are performed in this order, the oxide film dissolution treatment (E) is further performed. It is preferable to apply.

By this treatment, since the treatment liquid enters the micropore, all the anodized film formed in the second anodizing treatment (D) is dissolved, and the micropore formed in the second anodizing treatment (D) is dissolved. The pore diameter can be expanded.
That is, as shown in FIG. 3D, the inside of the micropore 16c on the surface side from the inflection point of the anodic oxide film 14c shown in FIG. The anodized film 14c above the inflection point of the cross-sectional shape of the pore 16c is removed, and an aluminum member having an anodized film 14d having a straight tubular micropore 16d on the aluminum substrate 12 is obtained. As in FIG. 3A, a barrier layer 18d is present on the aluminum substrate 12 side of the anodized film 14d.

  Here, the enlargement amount of the pore diameter of the micropore varies depending on the treatment conditions of the second anodizing treatment (D), but the enlargement ratio before and after the treatment is preferably 1.05 times to 100 times, and 1.1 times to 75 times. Double is more preferable, and 1.2 times to 50 times is particularly preferable.

In the self-ordering method II, the above-described cycle of the anodic oxidation treatment (D) and the oxide film dissolution treatment (E) is performed one or more times. The greater the number of repetitions, the higher the regularity of the pore arrangement described above.
In addition, by completely dissolving the anodized film formed by the last anodizing treatment (D) by the oxide film dissolving treatment (E), the roundness of the micropores viewed from the surface of the film is dramatically improved. The above cycle is preferably repeated twice or more, more preferably 3 times or more, and even more preferably 4 times or more.
In addition, when the above cycle is repeated twice or more, the conditions of each oxide film dissolution treatment and anodization treatment may be the same or different, respectively, and the last treatment is anodization treatment. You can finish it.

  In the production method of the present invention, a method using an imprint process described below can be preferably used as the anodizing process.

[(1-c): Method using imprint processing]
In the method using the imprint process, before the anodizing process for forming an anodized film having micropores on the surface of the aluminum substrate, a plurality of depressions that are the starting points for the generation of micropores in the anodizing process are formed on the aluminum substrate. Are formed at a predetermined interval and arrangement on the surface. By forming such depressions, it becomes easy to control the arrangement of the micropores and the roundness of the pore diameter within a desired range.

The method for forming the depression is not particularly limited, and examples thereof include a physical method including an imprint (transfer) method, a particle beam method, a block copolymer method, and a resist pattern / exposure / etching method. In the imprint process, in order to form the depression, a procedure for forming the depression by performing the anodizing step (A) and the film removal treatment (B) in this order in the self-ordering method (I), An electrochemical method such as a procedure for forming a recess by chemical roughening is not used.
By forming a plurality of depressions that are the starting points for the generation of micropores in the anodizing treatment at predetermined intervals and arrangement, the starting points of the micropores formed by anodizing can be set to any desired arrangement. Thus, the roundness of the resulting structure can be increased.

<Physical method>
For example, a method using an imprint method (a transfer method or press patterning method in which a substrate or a roll having a protrusion is pressed against an aluminum substrate to form a recess) can be used. Specifically, a method of forming a depression by pressing a substrate having a plurality of protrusions on the surface thereof against the surface of the aluminum substrate can be mentioned. For example, a method described in JP-A-10-121292 can be used.
In addition, a method in which polystyrene spheres are arranged in a dense state on the surface of an aluminum substrate, SiO ₂ is deposited thereon, and then the polystyrene spheres are removed, and the substrate is etched using the deposited SiO ₂ as a mask to form a recess. Also mentioned.

<Particle beam method>
The particle beam method is a method in which a depression is formed by irradiating the surface of an aluminum substrate with a particle beam. The particle beam method has an advantage that the position of the depression can be freely controlled.
Examples of the particle beam include a charged particle beam, a focused ion beam (FIB), and an electron beam.
As the particle beam method, for example, a method described in JP-A-2001-105400 can be used.

<Block copolymer method>
The block copolymer method is a method in which a block copolymer layer is formed on the surface of an aluminum substrate, a sea island structure is formed in the block copolymer layer by thermal annealing, and then island portions are removed to form depressions.
As a block copolymer method, the method described in Unexamined-Japanese-Patent No. 2003-129288 can be used, for example.

<Resist pattern, exposure, etching method>
In the resist pattern / exposure / etching method, the resist film formed on the surface of the aluminum substrate is exposed and developed by photolithography or electron beam lithography to form a resist pattern, which is then etched. In this method, a resist is provided and etched to form a recess penetrating to the surface of the aluminum substrate.

  Among the above-described methods for forming various depressions, a physical method, an FIB method, and a resist pattern / exposure / etching method are desirable.

In the imprint process, when forming a plurality of depressions on the surface of an aluminum substrate with a predetermined interval and arrangement, especially when forming fine depressions with an interval of around 0.1 μm, the fine depressions are artificially formed on the surface of the aluminum plate. In order to form regularly regularly, it is not economical to apply a high-resolution microfabrication technique using electron beam lithography or X-ray lithography every time. An imprint (transfer) method of pressing on the substrate surface is preferred.
Specifically, it can be carried out by bringing a substrate or roll having protrusions into close contact with the aluminum substrate surface and applying pressure using a hydraulic press or the like. The arrangement (pattern) of protrusions provided on the substrate is made to correspond to the arrangement of micropores in the anodized film formed by anodizing treatment, not to mention the regular arrangement of regular hexagons, but one of the periodic arrangements. An arbitrary pattern that lacks a portion may be used. Further, it is desirable that the substrate on which the protrusion is formed has a mirror surface and has a strength and a hardness that prevents the protrusion from being destroyed or the arrangement of the protrusion from being deformed by the pressing pressure. For this purpose, it is possible to use a general-purpose silicon substrate that is easy to finely process, including a metal substrate such as aluminum or tantalum. However, a substrate composed of diamond or silicon carbide with high strength is repeatedly Since the number of times of use can be increased, it is more desirable. Thus, if one substrate or roll having protrusions is prepared, a regular array of depressions can be efficiently formed on a large number of aluminum plates by repeatedly using this.

The pressure when using the above imprint method is preferably 0.001 to 100 tons / cm ² , more preferably 0.01 to 75 tons / cm ² , although depending on the type of substrate. ˜50 ton / cm ² is particularly preferred.
Moreover, as temperature at the time of press, 0-300 degreeC is preferable, 5-200 degreeC is more preferable, 10-100 degreeC is especially preferable, As time of a press, 2 seconds-30 minutes are preferable, and 5 seconds-15 Minute is more preferable, and 10 seconds to 5 minutes is particularly preferable.
Further, from the viewpoint of fixing the surface shape after pressing, a method for cooling the surface of the aluminum substrate can be added as a post-treatment.

In the method using the imprint process, after forming a depression on the surface of the aluminum substrate as described above, the surface of the aluminum substrate is subjected to an anodic oxidation process.
At this time, a conventionally known method can be used for the anodizing treatment, a method of treating with a constant voltage, a method of intermittently turning on and off the current while keeping the DC voltage constant, and intermittently applying the DC voltage. It is also possible to suitably use a method of repeatedly turning on and off the current while changing the current.

Further, when the anodizing treatment is performed at a low temperature, the arrangement of micropores becomes regular and the pore diameter becomes uniform.
On the other hand, by performing the anodizing process at a relatively high temperature, the arrangement of the micropores can be disturbed, and the variation in the pore diameter can be made within a predetermined range. Also, the pore diameter variation can be controlled by the processing time.

  In the production method of the present invention, it is preferable to perform any one of the above treatments (1-a) to (1-c) in the anodizing treatment step.

[(2) Penetration processing step]
The penetrating treatment step is a step of obtaining the insulating base material by penetrating holes by the micropores generated by the anodizing after the anodizing treatment step.
In the penetration process step, it is preferable to perform the following process (2-a) or (2-b).
(2-a) A process of dissolving an aluminum substrate having an anodized film using acid or alkali and penetrating the pores by micropores (chemical dissolution process).
(2-b) A process of mechanically polishing an aluminum substrate having an anodized film so as to pierce holes by micropores (mechanical polishing process).
Hereinafter, the processes (2-a) and (2-b) will be described in detail.

[(2-a) Chemical dissolution treatment]
In the chemical dissolution treatment, specifically, for example, after the anodizing treatment step, an aluminum substrate (portion denoted by reference numeral 12 in FIG. 3D) is melted, and further, the bottom of the anodized film (in FIG. 3D). ) Is removed, and the holes by the micropores are made to penetrate.

<Dissolution of aluminum substrate>
For the dissolution of the aluminum substrate after the anodizing treatment step, a treatment solution in which the anodized film (alumina) is difficult to dissolve and aluminum is easily dissolved is used.
That is, the aluminum dissolution rate is 1 μm / min or more, preferably 3 μm / min or more, more preferably 5 μm / min or more, and the anodic oxide film dissolution rate is 0.1 nm / min or less, preferably 0.05 nm / min or less, more preferably Uses a treatment liquid having a condition of 0.01 nm / min or less.
Specifically, a treatment liquid containing at least one metal compound having a lower ionization tendency than aluminum and having a pH of 4 or less and 8 or more, preferably 3 or less and 9 or more, more preferably 2 or less and 10 or more is used. Immerse treatment.

Such treatment liquid is based on an acid or alkaline aqueous solution, for example, manganese, zinc, chromium, iron, cadmium, cobalt, nickel, tin, lead, antimony, bismuth, copper, mercury, silver, palladium, platinum, A gold compound (for example, chloroplatinic acid), a fluoride thereof, a chloride thereof, or the like is preferably used.
Among them, an acid aqueous solution base is preferable, and it is preferable to blend a chloride.
In particular, a treatment liquid (hydrochloric acid / mercury chloride) in which mercury chloride is blended with an aqueous hydrochloric acid solution and a treatment liquid (hydrochloric acid / copper chloride) in which copper chloride is blended with an aqueous hydrochloric acid solution 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 and the like can be used.

Moreover, 0.01-10 mol / L is preferable and, as for the acid or alkali concentration of such a processing liquid, 0.05-5 mol / L is more preferable.

  Furthermore, the treatment temperature using such a treatment liquid is preferably −10 ° C. to 80 ° C., and preferably 0 ° C. to 60 ° C.

  In the production method of the present invention, the aluminum substrate is dissolved by bringing the aluminum substrate after the anodizing treatment step into contact with the treatment liquid described above. The method of making it contact is not specifically limited, For example, the immersion method and the spray method are mentioned. Of these, the dipping method is preferred. The contact time at this time is preferably 10 seconds to 5 hours, and more preferably 1 minute to 3 hours.

<Removal of the bottom of the anodized film>
The bottom part of the anodized film after the aluminum substrate is dissolved is removed by dipping in an acid aqueous solution or an alkali aqueous solution. By removing the bottom anodic oxide film, the pores by the micropores penetrate.

  The bottom of the anodized film is removed by pre-soaking in a pH buffer solution and filling the hole with the pH buffer solution from the opening side of the micropore, and then on the opposite side of the opening, that is, on the bottom of the anodized film. It is preferably carried out by a method of contacting with an acid aqueous solution or an alkali aqueous solution.

In the case of using an acid aqueous solution, it is preferable to use an aqueous solution of an inorganic acid such as sulfuric acid, phosphoric acid, nitric acid, hydrochloric acid or a mixture thereof. The concentration of the acid aqueous solution is preferably 1 to 10% by mass. The temperature of the acid aqueous solution is preferably 25 to 40 ° C.
On the other hand, when an alkaline aqueous solution is used, it is preferable to use an aqueous solution of at least one alkali 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 suitably used. It is done.

The immersion time in the acid aqueous solution or alkali aqueous solution is preferably 8 to 120 minutes, more preferably 10 to 90 minutes, and still more preferably 15 to 60 minutes.
Moreover, when immersing in a pH buffer solution beforehand, the buffer solution corresponding to the acid / alkali mentioned above is used appropriately.

[(2-b) Mechanical polishing treatment]
In the mechanical polishing treatment, specifically, for example, after the anodizing treatment step, an aluminum substrate (portion represented by reference numeral 12 in FIG. 3D) and an anodized film in the vicinity of the aluminum substrate (reference numeral in FIG. 3D). The portion represented by 18d) is mechanically polished and removed, thereby penetrating the holes by the micropores.
In the mechanical polishing treatment, known mechanical polishing treatment methods can be widely used. For example, the mechanical polishing exemplified for the mirror finish processing can be used. However, since the precision polishing rate is high, it is preferable to perform chemical mechanical polishing (CMP). For the CMP treatment, CMP slurry such as PANANERLITE-7000 manufactured by Fujimi Incorporated, GPX HSC800 manufactured by Hitachi Chemical Co., Ltd., CL-1000 manufactured by Asahi Glass (Seimi Chemical Co., Ltd.), or the like can be used.

  By these penetration processing steps, the structure in which the aluminum substrate 12 and the barrier layer 18d shown in FIG. 3D are eliminated, that is, the insulating base material 20 shown in FIG. 4A is obtained.

Instead of performing (1) anodizing treatment step to (2) penetrating treatment step, a commercially available product name: Anodisc (Whatman Japan Co., Ltd.) or the like can be used as appropriate.

[(3) Conductive material filling step]
The conductive material filling step is a step of obtaining the anisotropic conductive material by filling the inside of the penetrated hole in the obtained insulating base material with the conductive material after the penetrating treatment step.
In the conductive material filling step, it is preferable to perform any of the following treatments (3-a) to (3-c).
(3-a) A process (immersion process) of immersing the insulating base material having the penetrated holes in a liquid having a conductive material and filling the holes with the conductive material.
(3-b) A process (electrolytic plating process) of filling the through hole with a conductive material by electrolytic plating.
(3-c) A process (vapor deposition process) for filling a conductive material into the through-holes formed by vapor deposition.
Here, the conductive material to be filled constitutes a conduction path of the anisotropic conductive member, and is the same as that described in the anisotropic conductive member of the present invention.
Hereinafter, the processes (3-a) to (3-c) will be described in detail.

[(3-a) Immersion treatment]
The process of immersing the insulating base material having the perforated holes in the liquid containing the conductive material and filling the holes with the conductive material includes electroless plating, high-viscosity molten metal immersion, conductive Although a known method such as a conductive polymer solution immersion treatment can be used, an electroless plating treatment and a molten metal immersion treatment are preferred because a preferable material as a conductive material is a metal. Electroless plating treatment is preferred.

As a method of electroless plating, known methods and treatment solutions can be used, but are not particularly limited, but a metal nucleus to be deposited is provided in advance, and then a compound and a reducing agent that are soluble in a solvent containing the metal are dissolved in the solution, A method in which a metal is filled in the penetrated holes by immersing the insulating base material in the liquid is preferable.
Moreover, you may process together with the electroplating process mentioned later.

[(3-b) Electroplating treatment]
In the production method of the present invention, when a conductive material is filled in the penetrated holes by electrolytic plating, it is also desirable to apply ultrasonic waves to promote stirring of the electrolytic solution.
Furthermore, the electrolysis voltage is usually −20V or less, preferably −10V or less. When performing constant potential electrolysis or potential scanning electrolysis, it is desirable that cyclic voltammetry can be used in combination, and a potentiostat device such as Solartron, BAS, Hokuto Denko, and IVIUM can be used.
As the electrolysis method, a potential scanning method in which the potential is increased or decreased at a constant rate with time is preferable, and constant current electrolysis in which electrolysis is performed with a constant current regardless of the time is also preferable. In the case of potential scanning, it is preferable to scan at a scanning speed of 0.1 to 50 mV / sec with 0 V as the potential scanning start point, more preferably 0.3 to 30 mV / sec, and 0.5 to It is more preferable to scan to the negative side in the range of 5 mV / sec. The preferred amount of electricity varies depending on the pore diameter, pore density, metal type, and thickness of the anodic oxide film. For example, in the case of copper plating, the required precipitation amount W [g] can be calculated by the following equation.
Formula Pore area [μm ² ] × target filling height [μm] × electrolytic area [cm ² ] × pore density [piece / μm ² ] × metal density [g / cm ³ ] = W × 10 ^-4 [g]
When the precipitation amount W is converted into the number of moles and multiplied by the Faraday constant, the required number of Coulombs can be calculated.
By measuring the amount of electricity with a coulomb meter and reaching the required number of coulombs, it is possible to obtain the necessary and sufficient plating filling height by stopping the electrolysis.
The preferable range of the current density when performing constant current electrolysis varies depending on the electrolyte concentration, pore diameter, pore density, and metal type, but in the case of copper plating, 0.5 to 10 A / dm ² is preferable, and 1 to 5 A. More preferred is / dm ² . In the case of gold plating, 0.05 to 3 A / dm ² is preferable, and 0.22 to 1 A / dm ² is more preferable. In the case of nickel plating, 0.05 to 5 A / dm ² is preferable, and 0.2 to 1.5 A / dm ² is more preferable.
The electrolysis can be stopped by measuring the number of coulombs.
For example, in the case of Cu, assuming that the current efficiency is 100%, the amount of electricity per 1 μm of the anodized film can be calculated as 46 C / dm ² / μm.
When it is desired to fill with 50 μm, the electrolysis is stopped at 2300 C / dm ² , and the filling height can be confirmed with a SEM or an optical microscope from the direction of the fracture surface.

A conventionally well-known plating solution can be used for a plating solution.
Specifically, when copper is deposited, an aqueous copper sulfate solution is generally used. The concentration of copper sulfate is preferably 0.1 mol / l or more, and more preferably 0.4 mol / l or more. Saturated solutions can also be suitably used. When using copper pyrophosphate, a range of 0.05 mol / L to 1 mol / L is preferable, and a range of 0.1 mol / L to 0.5 mol / L is more preferable. It is preferable to add an excess of potassium pyrophosphate, preferably 0.5 mol / L or more, and more preferably 0.7 mol / L or more. Moreover, precipitation can be promoted by adding hydrochloric acid to the electrolytic solution. In this case, the hydrochloric acid concentration is preferably 10 to 20 g / L.
In addition, when gold is deposited, a preferable range of tetrachlorogold is 0.0005% to 1 wt%, and potassium carbonate and hydrochloric acid can be appropriately added. The range of preferable pH is 0.1-10, and pH can be adjusted with the addition amount of an additive.
When nickel is deposited, a known electrolytic solution such as a sulfuric acid bath, a watt bath, a chloride bath, or a nickel sulfamate bath can be used. The preferable range of the liquid temperature is 25 ° C. to 95 ° C., the more preferable range is 30 ° C. to 70 ° C., the preferable range of the current density is 0.5 to 10 A / dm ² , and further 0.8 to 8 A / dm. Within the range of ² .

[(3-c) Deposition treatment]
When the conductive material is filled in the holes penetrated by vapor deposition, a known vapor deposition process such as physical vapor deposition (PVD) or chemical vapor deposition (CVD) can be used. Conditions for performing the vapor deposition process vary depending on the target substance, but a temperature of −40 ° C. to 80 ° C. and a vacuum degree of 10 ⁻³ Pa or less are preferable from the viewpoint of the vapor deposition rate, −20 ° C. to 60 ° C., and a vacuum degree of 10 ^-4 Pa or less is more preferable.

Moreover, in order to perform filling uniformly, a method of performing vapor deposition from an oblique direction by appropriately tilting the surface of the insulating substrate with respect to the vapor deposition direction can be suitably used.
By these conductive material filling steps, the anisotropic conductive member 21 shown in FIG. 4B is obtained.

[(4) Surface smoothing process]
In the manufacturing method of this invention, it is preferable to comprise the surface smoothing process process which smoothes the surface and back surface of the said insulating base material after the said electrically-conductive material filling process. By performing the surface smoothing treatment step, it is possible to smooth the front and back surfaces of the insulating base material after being filled with the conductive material, and to remove excess conductive material attached to the front and back surfaces.
In the surface smoothing process, it is preferable to carry out any of the following processes (4-a) to (4-c).
Hereinafter, the processes (4-a) to (4-c) will be described in detail.
(4-a) Treatment by chemical mechanical polishing (CMP).
(4-b) Treatment by electropolishing.
(4-c) Ion milling treatment.

[(4-a) Treatment by chemical mechanical polishing (CMP)]
For the CMP treatment, CMP slurry such as PANANERLITE-7000 manufactured by Fujimi Incorporated, GPX HSC800 manufactured by Hitachi Chemical Co., Ltd., CL-1000 manufactured by Asahi Glass (Seimi Chemical Co., Ltd.), or the like can be used.
Ordinary mechanical polishing without using a chemical polishing solution is also suitable. In that case, lapping is performed using a polishing cloth having a particle size of # 800 to # 1500, the thickness is adjusted, and then the particle size is 1 to 3 μm. Polishing with a diamond slurry and further polishing with a diamond slurry having a particle diameter of 0.1 to 0.5 μm can provide a mirror state. The preferable range of the polishing thickness of the electrode surface is 0 μm to 20 μm, and the preferable range of the polishing thickness of the opening surface is 10 μm to 50 μm.
Polishing conditions: The rotation speed is preferably in the range of 10 rpm to 100 rpm, more preferably in the range of 20 to 60 rpm. A preferable range of the load is 0.01 to 0.1 kgf / cm ² , and a range of 0.02 to 0.08 kgf / cm ² is more preferable.
Typical polishing conditions

[(4-b) Treatment by electropolishing]
As electrolytic polishing, for example, “Aluminum Handbook”, 6th edition, edited by Japan Aluminum Association, 2001, p. 164-165; various methods described in US Pat. No. 2,708,655; “Practical Surface Technology”, vol. 33, no. 3, 1986, p. The method described in 32-38;

[(4-c) Ion milling treatment]
The ion milling process is performed when more precise polishing is required than the above-described CMP process or electrolytic polishing process, and a known technique can be used. It is preferable to use general argon ions as the ion species.

[(5) Conducting path protruding step]
In the manufacturing method of this invention, it is preferable to comprise the conduction path protrusion process which forms the structure where the said electrically-conductive material protruded from the surface and the back surface of the said insulating base material after the said surface smoothing process.
In the conduction path projecting step, it is preferable to carry out the following processing (5-a) or (5-b).
(5-a) The process which forms the structure where the electrically-conductive material protruded from the surface and back surface of the said insulating base material by removing a part of surface and back surface of the said insulating base material.
(5-b) The process which forms the structure which the electrically-conductive material protruded from the surface and back surface of the said insulating base material by depositing an electrically conductive material on the surface of the said conduction path.

In the (5-a) treatment, only the insulating base material on the surface of the anisotropic conductive member is partially dissolved by bringing the anisotropic conductive member after the surface smoothing treatment step into contact with an acid aqueous solution or an alkali aqueous solution. And the conductive path protrudes (FIG. 4C).
The treatment (5-a) can be performed under the same treatment conditions as the oxide film dissolution treatment (E) described above as long as the conductive material constituting the conduction path is not dissolved. In particular, it is preferable to use an acid aqueous solution or an alkali aqueous solution that can easily control the dissolution rate.

  In the process (5-b), the conductive path is protruded by depositing a conductive material only on the surface of the conductive path 3 shown in FIG. 4B (FIG. 4D). The conductive material can be deposited by electroless plating or electrodeposition. The conductive material to be deposited may be the same as or different from the conductive material filled in the conductive material filling step.

[Protective film formation treatment]
In the production method of the present invention, since the insulating base material formed of alumina changes its pore diameter over time due to hydration with moisture in the air, before the conductive material filling step, the protective film It is preferable to perform a forming process.

  Examples of the protective film include an inorganic protective film containing Zr element and / or Si element, or an organic protective film containing a water-insoluble polymer.

  The method for forming the protective film containing the Zr element is not particularly limited, but, for example, a method in which the protective film is directly immersed in an aqueous solution in which a zirconium compound is dissolved is generally used. Further, from the viewpoint of the robustness and stability of the protective film, it is preferable to use an aqueous solution in which a phosphorus compound is dissolved together.

Here, specific examples of the zirconium compound include zirconium, zirconium fluoride, sodium fluoride zirconate, calcium fluoride zirconate, zirconium fluoride, zirconium chloride, zirconium oxychloride, zirconium oxynitrate, zirconium sulfate. , Zirconium ethoxide, zirconium propoxide, zirconium butoxide, zirconium acetylacetonate, tetrachlorobis (tetrahydrofuran) zirconium, bis (methylcyclopentadienyl) zirconium dichloride, dicyclopentadienylzirconium dichloride, ethylenebis (indenyl) zirconium (IV) Dichloride and the like can be mentioned, among which sodium fluorinated zirconate is preferable.
Moreover, as a density | concentration of the zirconium compound in aqueous solution, 0.01-10 wt% is preferable from a viewpoint of the uniformity of a protective film thickness, and 0.05-5 wt% is more preferable.

Examples of the phosphorus compound include phosphoric acid, sodium phosphate, calcium phosphate, sodium hydrogen phosphate, and calcium hydrogen phosphate. Among them, sodium hydrogen phosphate is preferable.
Moreover, as a density | concentration of the zirconium compound in aqueous solution, 0.1-20 wt% is preferable from a viewpoint of the uniformity of a protective film thickness, and 0.5-10 wt% is more preferable. Moreover, as processing temperature, 0-120 degreeC is preferable and 20-100 degreeC is more preferable.

On the other hand, the method for forming the protective film containing Si element is not particularly limited. For example, a method in which the protective film is directly immersed in an aqueous solution in which an alkali metal silicate is dissolved is generally used.
The aqueous solution of alkali metal silicate has a ratio of silicon oxide SiO ₂ and alkali metal oxide M ₂ O which is a component of silicate (generally expressed as a molar ratio of [SiO ₂ ] / [M ₂ O]). The protective film thickness can be adjusted by the concentration.
Here, as M, sodium and potassium are particularly preferably used.
The molar ratio of [SiO ₂ ] / [M ₂ O] is preferably 0.1 to 5.0, and more preferably 0.5 to 3.0.
Furthermore, the content of SiO ₂ is preferably 0.1 to 20% by mass, and more preferably 0.5 to 10% by mass.

As the organic protective film, a method in which only the solvent is volatilized by heat treatment after being directly immersed in an organic solvent in which a water-insoluble polymer is dissolved is preferable.
Examples of the water-insoluble polymer include polyvinylidene chloride, poly (meth) acrylonitrile, polysulfone, polyvinyl chloride, polyethylene, polycarbonate, polystyrene, polyamide, cellophane and the like.
Examples of organic solvents include ethylene dichloride, cyclohexanone, methyl ethyl ketone, methanol, ethanol, propanol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-methoxyethyl acetate, 1-methoxy-2-propyl acetate, dimethoxyethane. , Methyl lactate, ethyl lactate, N, N-dimethylacetamide, N, N-dimethylformamide, tetramethylurea, N-methylpyrrolidone, dimethyl sulfoxide, sulfolane, γ-butyrolactone, toluene and the like.
As a density | concentration, 0.1-50 wt% is preferable and 1-30 wt% is more preferable.
Moreover, as heating temperature at the time of solvent volatilization, 30-300 degreeC is preferable and 50-200 degreeC is more preferable.

  After the protective film formation treatment, the thickness of the anodized film including the protective film is preferably 0.1 to 1000 μm, and more preferably 1 to 500 μm.

(5) Protective layer The conductive material of the present invention can be further provided with a protective layer 62 shown in FIG. 7C if necessary. Examples of the protective layer include a bump protective layer 62 that protects the bumps of the anisotropic conductive member and a protective layer that protects the surface of the conductive layer 56.
Commercially available films such as Toyoflon manufactured by Toray Film Processing Co., Ltd. can be used as appropriate for commercial release protective sheets. When providing the photosensitive resin layer, it can also laminate simultaneously.

(6) Photosensitive resin layer <Photosensitive resin layer>
The photosensitive resin layer of the present invention comprises a binder, a polymerizable compound, a photopolymerization initiator, and a sensitizer, and further contains other components as necessary. You may contain at least 2 types of sensitizers whose maximum absorption wavelength is 340-500 nm.
As the photosensitive resin layer, at least one of the sensitizers has a maximum absorption wavelength in a wavelength region of less than 405 nm, and at least one other has a maximum absorption wavelength in a wavelength region of 405 nm or more. Is preferred.
The sensitizer includes at least two kinds of sensitizers having a maximum absorption wavelength in a wavelength range of 340 nm to less than 405 nm and sensitizers having a maximum absorption wavelength in a wavelength range of 405 nm to 500 nm. Is preferred.

The photosensitive resin layer has a maximum spectral sensitivity in a wavelength range of 380 to 420 nm, and a minimum exposure amount S that allows pattern formation in a region of 400 to 410 nm is 50 mJ / cm ² or less, and It is preferable that the maximum value Smax of the minimum exposure amount in the wavelength region and the minimum value Smin of the minimum exposure amount satisfy the following formula, Smax / Smin ≦ 1.2, and the following formula, Smax / Smin ≦ 1.1. It is more preferable to satisfy.
When the Smax / Smin exceeds 1.2, a uniform pattern cannot be obtained due to a sensitivity change caused by a variation in wavelength of each semiconductor element when an exposure apparatus using several semiconductor elements is used. There is.

The minimum exposure amount patterning in 400 to 410 nm S is preferably at 50 mJ / cm ² or less, more preferably 30 mJ / cm ^2, and particularly preferably 20 mJ / cm ^2.
If the minimum exposure amount S at which the pattern can be formed is more than 50 mJ / cm ² , the time required for exposure becomes long, and productivity may be reduced.

  The spectral sensitivity is determined by, for example, a photosensitivity obtained by laminating a pattern forming material on a substrate to be processed by a method described in Photopolymer Technology (Ao Yamaoka, published by Nikkan Kogyo Shimbun, 1988, page 262). The photosensitive composition of the conductive laminate is measured using a spectral sensitivity measuring device. Specifically, the light dispersed from a light source such as a xenon lamp or a tungsten lamp is adjusted so that the exposure wavelength changes linearly in the horizontal axis direction and the exposure intensity changes logarithmically in the vertical axis direction. After setting, irradiating and exposing, a development process is performed to form a pattern for each exposure wavelength sensitivity. The exposure energy capable of pattern formation is calculated from the height of the obtained pattern, and the maximum peak in the spectral sensitivity curve created by plotting the wavelength on the horizontal axis and the reciprocal of the exposure energy on the vertical axis is taken as the spectral sensitivity.

The minimum exposure amount at which the pattern can be formed is obtained as the exposure energy at which the image can be formed, which is calculated from the height of the pattern formed in the spectral sensitivity measurement described above. The minimum exposure amount at which the pattern can be formed is determined by changing the development conditions such as the type of developer, the development temperature, the development time, etc., and the minimum exposure amount at which the pattern can be formed under the optimum development conditions. means.
The optimum development conditions are not particularly limited and may be appropriately selected depending on the purpose. For example, a developer having a pH of 8 to 12 is sprayed at a pressure of 25 to 40 ° C. and a pressure of 0.05 to 0.5 MPa. Thus, a condition for completely removing the uncured region is adopted.

(7) Forming method of photosensitive resin layer When the photosensitive resin layer is provided, the type is not particularly limited, but since the flatness is good, it is possible to use a dry film that is easier to handle than a liquid material. Although there are negative resists and positive resists, negative resists that are generally used commercially are preferred.

  On the conductive layer or anisotropic conductive member of the present invention, at least two kinds of a binder, a polymerizable compound, a photopolymerization initiator, and a sensitizer having a maximum absorption wavelength of 340 to 500 nm are included. You may have the photosensitive resin layer obtained using the photosensitive composition containing the selected other component.

The photosensitive composition solution is prepared by dissolving, emulsifying, or dispersing the material contained in the photosensitive resin layer in water or a solvent.
There is no restriction | limiting in particular as said photosensitive composition solution, According to the objective, it can select suitably, For example, methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, n-hexanol etc. Alcohols; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diisobutyl ketone; ethyl acetate, butyl acetate, n-amyl acetate, methyl sulfate, ethyl propionate, dimethyl phthalate, ethyl benzoate and methoxypropyl acetate Esters such as: Aromatic hydrocarbons such as toluene, xylene, benzene, ethylbenzene; Halo such as carbon tetrachloride, trichloroethylene, chloroform, 1,1,1-trichloroethane, methylene chloride, monochlorobenzene Emissions of hydrocarbons; tetrahydrofuran, diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethers such as 1-methoxy-2-propanol; dimethylformamide, dimethylacetamide, dimethyl sulfoxide, sulfolane and the like. These may be used alone or in combination of two or more. Moreover, you may add a well-known surfactant.

  Next, the photosensitive composition solution is applied on the conductive layer or the anisotropic conductive member and dried to form a photosensitive resin layer, thereby producing the conductive material according to the second aspect of the present invention. be able to.

The method for applying the photosensitive composition solution is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a spray method, a roll coating method, a spin coating method, a slit coating method, an extrusion coating method, Examples of the coating method include a curtain coating method, a die coating method, a gravure coating method, a wire bar coating method, and a knife coating method.
The drying conditions vary depending on each component, the type of solvent, the use ratio, and the like, but are usually about 60 to 110 ° C. for about 30 seconds to 15 minutes.

  Since the photosensitive resin layer has a substantially constant sensitivity distribution in the wavelength range of 400 to 410 nm, it is used for forming various patterns exposed to light in the range of 400 to 410 nm and for forming permanent patterns such as wiring patterns. , Etc., and particularly suitable for forming a circuit board for a probe card for semiconductor inspection.

  As another method, the photosensitive resin layer of the present invention may be laminated on the conductive layer while heating or pressurizing the photosensitive resin layer in the form of a film or the like. There is no restriction | limiting in particular as said heating temperature and pressurization, According to the objective, it can select suitably, For example, 15-180 degreeC is preferable and 60-140 degreeC is more preferable. There is no restriction | limiting in particular as said pressurization pressure, According to the objective, it can select suitably, For example, 0.1-1.0 MPa is preferable and 0.2-0.8 MPa is more preferable.

  There is no restriction | limiting in particular as an apparatus which performs at least any one of the said heating, According to the objective, it can select suitably, For example, a laminator (For example, Taisei Laminator company make, VP-II) etc. are mentioned suitably.

(8) A method of manufacturing a wiring circuit by forming a pattern on a conductive layer When patterning by laser ablation, before filling a metal inside the pore, dye it with a dye such as alizarin red. The anodic oxide film itself generates heat by laser irradiation, and it is possible to remove a portion near the surface in an ablation manner to give the ACF an uneven structure. By making the laser absorption rate higher than that of the conductive layer, the conductive layer can be rooted and removed uniformly.
Patterning by exposure and development can be performed by appropriately using the recommended conditions provided by the photosensitive resin manufacturer. By changing the wiring pattern on both sides, a pitch conversion connector with an arbitrary pitch can be created. An example of the pattern forming method will be described below.

  The pattern forming method includes at least an exposure step and includes other steps appropriately selected. The said exposure process is a process of exposing with respect to the photosensitive resin layer in the electroconductive material of this invention. Although digital exposure, analog exposure, etc. are mentioned, Digital exposure is preferable among these.

  The digital exposure is not particularly limited and can be appropriately selected depending on the purpose. For example, a control signal is generated based on pattern formation information to be formed, and light modulated in accordance with the control signal is used. It is preferable to carry out.

  Examples of the digital exposure means include a light irradiation means for irradiating light, a light modulation means for modulating light emitted from the light irradiation means based on pattern information to be formed, and the like.

  In addition, after forming the pattern, a photosensitive resin is further provided, and exposure and development are performed with a different pattern, followed by second patterning, and formation on the conductive layer by a known method such as electrolytic deposition or electroless plating. A contact can be formed in contact with the formed electrode. The conductive material of the present invention having such contacts can be used as a probe card having the circuit board 26 of the present invention as shown in FIG. 8B. The circuit board for a probe card for semiconductor inspection of the present invention is not limited to that shown in the figure.

[Contact formation method]
The contacts 70 and 72 illustrated in FIG. 8B are made of a conductive material such as a single metal material or an alloy, and can also function as electrodes. Furthermore, functionality can be enhanced by laminating contacts or coating with different materials.
As the contact material, for example, as described in the electric and electronic material handbook (1987, first edition Asakura Shoten) p634 to 637, contact consumption and transfer to the inspection object are considered. Generally, the amount of consumption is lower when the mechanical strength is higher, the boiling point is higher, and the vapor pressure is lower. Fe, Ni, Cu, Zn, Mo, Pb, Ag, W, Pt, Au, or alloys thereof are preferable from the relationship between the minimum arc voltage and the minimum arc current.
Pt, Au-based material is preferably Pt, Au-Ag-Pt alloy, and Pt-Ir alloy, and tungsten-based contact material is preferably Ag or Cu sintered alloy or AgWC sintered alloy. In addition, a carbon nanotube needle, a carbon fiber needle, and the like are more preferable because they have conductivity and flexibility.
Carbon fiber electrodes are commercially available from, for example, BAS Corporation. Moreover, since the kit is also marketed, an electrode can be created easily.

  As illustrated in FIG. 9A, a conductive layer is laminated on both surfaces of the anisotropic conductive member 21, and a photosensitive resin layer is further laminated thereon, for example, and this photosensitive resin layer is patterned by the above-described method. Thus, patterned conductive layers 82 and 84 can be obtained. Such a laminate can be used as the signal extraction wiring circuit 26. For example, the carbon fiber can be fixed on the contact 70 with the conductive adhesive 88 as a carbon fiber electrode 90. A metal that is difficult to oxidize may be used as the material of the contact 70. It is also preferable to coat the Cu contact with Ni, Au, W, Pt, an Au—Ag—Pt alloy, a Pt—Ir alloy, an Ag or Cu alloy, AgWC, or the like that is difficult to oxidize.

As the elastic material, carbon fiber also has elasticity, but rubber-based materials can be used as described in the electric and electronic material handbook (1987 first edition Asakura Shoten) p115-129. Of these, silicon rubber and fluororubber which are excellent in heat resistance are preferable.
Conductive fine particles and fillers can be dispersed inside these elastic materials to form a pressurized conductor structure, or the surface can be coated with a conductive material to impart conductivity.
As shown in FIG. 9B, the contact 70 can be provided with a contact 92 made of a conductive elastic material.
The signal extraction electrodes 74, 76, 78, 80 and wiring can be installed at the same position on the opposite side of the contact point of the laminate on which the circuit pattern is formed to contact the object to be inspected and used as a probe card. .

<Probe card>
In wafer testing, the chip is connected to a test device (also called a prober or TEG), voltage is applied to the terminals (electrode pads, bonding pads) on the chip according to the test pattern, the output is measured and compared with the expected value. Determine the quality of the chip. At that time, it is necessary to accurately apply a needle called a probe (probe) to the terminal on the chip. There are several tens to hundreds of micrometers of terminals and intervals of several to several hundred terminals per chip. More needles are needed to test multiple chips simultaneously to reduce test time. In order to apply these needles to the chip quickly and accurately, the probe card is a set of necessary needles arranged in accordance with the terminal pattern on the chip for easy handling. With the miniaturization of the integrated circuit, the size and interval of the terminals are reduced (minimum 30 to 50 μm), and the number of terminals tends to increase. It can handle ~ 1000 needles, and more than 5000 needles.
The shape of the card is often circular (there are other shapes such as a rectangle), and a connection terminal for a test device is attached to the periphery of the card, and a needle connected to a chip is attached to the center.
The needle has a structure called a cantilever type (or horizontal type) that is mounted horizontally (diagonally below) from the periphery toward the center, and a vertical type (or spring type) in which the needle is mounted vertically from the top to the bottom, or the center of the needle is a spring. There are two structures that are said to produce pressure at the time of contact. The vertical type has a higher degree of freedom in needle layout than the cantilever type, and has the advantage that the needles can be arranged in an array instead of a row.
The probe card is attached to a test device called a prober (or probe tester). When used as a probe card, the shape of the contact is preferably a needle shape, and the tip of the needle is preferably made of a hard metal coated or joined with a noble metal or a noble metal alloy.
Furthermore, a conductive polymer material and a pressurized conductive rubber can be used as the contact.
Dense carbon nanotubes can be formed as probe inspection needles.
A method for forming dense carbon nanotubes (described in JP 2000-31462 A).

  According to such a probe card and probe inspection apparatus using the signal extraction wiring circuit 24 of the present invention, in order to electrically connect the inspection circuit board and the probe inspection needle formed of the carbon fiber electrode 90, 1 and FIGS. 5 to 7, the conductive material 100 of the present invention can be used.

  Therefore, the electrical connection between the inspection electrode of the inspection circuit board and the probe inspection needle is reliably achieved with a small applied pressure.

  As a result, it is not necessary to use large pressurizing means. In addition, since the distance between the inspection circuit board and the probe inspection needle is short, the dimension in the height direction of the probe inspection apparatus can be reduced. Accordingly, it is possible to reduce the size of the entire probe inspection apparatus.

  In addition, since the pressure applied to the inspection electrode of the inspection circuit board is small, the inspection electrode is not damaged, and the service life of the inspection circuit board is not shortened. Further, the inspection electrodes of the inspection circuit board are electrically connected by the specific conductive material 100, so that the inspection electrodes 70 and 72 can be arranged at a high density. Since the electrodes can be formed, it is possible to inspect a large number of electrodes to be inspected at once.

In addition, the electrical connection using the conductive material has low contact resistance and can achieve a stable connection state, so that good electrical characteristics can be obtained.
In addition, since the inspection electrode of the inspection circuit board and the probe inspection needle are electrically connected via the conductive material, the distance of the signal transmission system is short, and therefore high speed that requires high-speed processing is required. It is also possible to cope with the electrical inspection of the function integrated circuit.

[Inspection needle]
In general, commercially available probe inspection needles can be used as appropriate. For example, there are probe pins manufactured by Nippon Dennee Co., Ltd. and Tulip Corporation. Furthermore, a microcontact probe formed by the LIGA process is described in SEI Technical Review No. 161-p87-90.
Japanese Patent Application Laid-Open No. 11-190748 discloses a rod-like single crystal probe pin prepared by the VLS method.
By controlling the position by the VLS method, a large number of rod-shaped single crystals can be grown substantially perpendicular to the contacts, and the rod-shaped single crystals can be used as probe pins.

  That is, for example, gold bumps are provided as contacts. Next, for example, silicon is supplied by a method of introducing a gas such as silicon tetrachloride and hydrogen under heating conditions, and a silicon rod-like single crystal is grown substantially perpendicularly to the substrate at the position of the gold bump. A contact having a rod-like single crystal is manufactured by the VLS method.

  Next, the length of the rod-like single crystal is made uniform by polishing, and further, the surface of each of the rod-like single crystal and the single crystal circuit is made conductive by a method such as covering with a conductive material to obtain an inspection needle. The inspection needle obtained by the above method has high density and high integration since the position accuracy of the probe pin is high and the characteristics such as the thermal expansion coefficient are made of the same Si single crystal as the semiconductor element. It is suitable as an inspection needle for a semiconductor probe card.

1. An anisotropic conductive member was manufactured.
(Anisotropic conductive member 1)
(A) Mirror finish (electropolishing)
A high-purity aluminum substrate (manufactured by Sumitomo Light Metal Co., Ltd., purity 99.99 mass%, thickness 0.4 mm) is cut so that it can be anodized in an area of 10 cm square, using an electropolishing liquid having the following composition, voltage 25 V, liquid The electropolishing treatment was performed under conditions of a temperature of 65 ° C. and a liquid flow rate of 3.0 m / min.
The cathode was a carbon electrode, and GP0110-30R (manufactured by Takasago Seisakusho) was used as the power source. The flow rate of the electrolytic solution was measured using a vortex flow monitor FLM22-10PCW (manufactured by AS ONE).

(Electrolytic polishing liquid composition)
-660 mL of 85% phosphoric acid (reagent manufactured by Wako Pure Chemical Industries, Ltd.)
・ Pure water 160mL
・ Sulfuric acid 150mL
・ Ethylene glycol 30mL

(B) Anodizing treatment process (self-ordering method I)
Next, the aluminum substrate after the electropolishing treatment was subjected to a pre-anodizing treatment for 12 hours under the conditions of 0.3 mol / L sulfuric acid voltage 25 V 16 ° C. and liquid flow rate 3.0 m / min.
Thereafter, a film removal treatment was performed in which the aluminum substrate after the pre-anodizing treatment was immersed in a mixed aqueous solution (liquid temperature: 50 ° C.) of 0.2 mol / L chromic anhydride and 0.6 mol / L phosphoric acid for 12 hours.
Thereafter, re-anodizing treatment was performed for 10 hours under the conditions of 0.3 mol / L sulfuric acid voltage 25 V 16 ° C. and liquid flow rate 3.0 m / min.
In both the pre-anodizing treatment and the re-anodizing treatment, the cathode was a stainless electrode, and the power source was GP0110-30R (manufactured by Takasago Seisakusho). Moreover, NeoCool BD36 (made by Yamato Kagaku) was used for the cooling device, and Pear Stirrer PS-100 (made by EYELA) was used for the stirring and heating device. Furthermore, the flow rate of the electrolyte was measured using a vortex flow monitor FLM22-10PCW (manufactured by AS ONE).

(C) Penetration treatment step Next, the aluminum substrate was dissolved by immersion (visually) until the aluminum was removed at a temperature of 15 ° C. and 0.1 M copper chloride + 20% hydrochloric acid, and further to 5% by mass phosphoric acid. By immersing at 30 ° C. for 30 minutes, the bottom of the anodized film was removed, and at the same time, the pores were enlarged to produce a structure (insulating base material) comprising an anodized film having micropores.

(D) Heat treatment Next, the structure obtained above was subjected to a heat treatment at a temperature of 400 ° C for 1 hour.

(E) Conductive material filling step Next, a gold electrode formed by an electroless plating method is brought into close contact with one surface of the structure after the heat treatment, and the gold electrode is used as a cathode and electrolytic plating is performed using a copper plate as a positive electrode. It was.
A mixed solution of 600 g / L of copper sulfate was used as an electrolyte while maintaining a temperature of 60 ° C., and Cu was scanned from 0.337 V to the negative side at a scanning speed of 1 mV / sec. The amount of electricity became 4000 C / dm ² . The electrolysis was stopped at that time. An anisotropic conductive member made of an anodized film having a conduction path filled with copper in holes made of micropores was manufactured. When the fracture surface was observed with an optical microscope, it was filled with about 70 μm.
Here, a potentiostat / galvanostat Model 7060 manufactured by AMEL was used as the electrolyzer. The standard electrode was an Ag / AgCl type.
When the surface after filling with copper was observed with an optical microscope, it was in the form that copper partially overflowed from the surface of the insulating substrate (anodized film).

(F) Surface smoothing process Next, the grinding | polishing process was performed to the surface and back surface of the structure with which copper was filled.
Polishing conditions: The rotation speed is 50 rpm.
After lapping polishing, polishing polishing was further performed with an abrasive particle size of 2 μm, and polishing was further performed with a particle size of 0.25 μm by changing the polishing cloth.

  Next, after rinsing with water and drying, observation with an FE-SEM confirmed that the diameter of the conductive path, which is the size of the electrode portion, was 60 nm, and the thickness of the member was 50 μm.

(Anisotropic conductive member 2)
A method similar to Example 1 was performed except that nickel filling was performed instead of copper filling, and the anisotropic conductive member after the obtained conductive path projecting step was washed with water and dried, and then subjected to FE-SEM. Observed.
As a result, it was confirmed that the diameter of the conductive path, which is the electrode part size, was 60 nm, and the thickness of the member was 50 μm.
In the Ni bath, a plating cathode is formed by Au sputtering on one of the anisotropic conductive members, a sulfuric acid bath, (nickel sulfate 0.99 M, boric acid 0.5 M) temperature 30 ° C., current density 0.3 A / dm ² , Coulomb number 4000C / dm ²

(Anisotropic conductive member 3)
The above (B) anodizing treatment step (pre-anodizing and re-anodizing treatment in (self-regulating method I)) of 0.5 mol / L oxalic acid voltage 40 v, liquid temperature 16 ° C., liquid flow rate 3.0 m / min. Then, the structure after the surface smoothing treatment was immersed in 0.1N-KOH for 1 minute to selectively dissolve the anodic oxide film, thereby projecting a copper cylinder as a conduction path ( Conduction path protrusion process).
After rinsing with water and drying, when observed with FE-SEM, it was confirmed that the bump height was 40 nm, the diameter of the conductive path as the electrode part size was 60 nm, and the thickness of the member was 50 μm.

(Anisotropic conductive member 4)
In the same manner as the anisotropic conductive member 3, except that the processing time of the (G) conductive path protruding step was 1 minute, and both surfaces of the anodized film were further processed to protrude conductive paths on both surfaces. .
When observed by FE-SEM, it was confirmed that the bump height was 40 nm on both sides, the diameter of the conductive path as the electrode part size was 60 nm, and the thickness of the member was 50 μm.

2. Formation of conductive layer (Example 1)
Using the anisotropic conductive member 1, Au was vapor-deposited by a sputtering method, a conductive layer 56 was laminated, and the conductive material of the present invention shown in FIG. 1A was manufactured. Au was vapor deposited by placing a 6 mm length of 0.5 mmφ Au wire on a tungsten boat.
Specifically, the applied current was applied at an increasing rate of 1 A / sec from 0 to 40 A and held at 40 A for 10 seconds.
The vapor deposition thickness was measured by measuring a step generated by peeling with a commercially available roughness meter after a commercially available instantaneous adhesive was dropped and a part thereof was peeled off. The thickness was 0.13 μm.
(Example 1-2)
Using the anisotropic conductive member 2, Au was vapor-deposited in the same manner as in Example 1 to produce the conductive material shown in FIG. 1A.
(Example 2)
A graphite sheet was bonded to the anisotropic conductive member 1 with an anisotropic conductive adhesive 58 to produce the conductive material 100 of the present invention shown in FIG. 1B. A commercially available anisotropic conductive adhesive, Anisotropic conductive adhesive 3373C manufactured by Three Bond Co., Ltd. was used. An anisotropic conductive adhesive layer was provided on the anisotropic conductive member 1 by screen printing. Mesh type: stainless steel screen 80 mesh, emulsion thickness: 10 μm, squeegee: urethane rubber, angle 60 °, drying: 100 ° C. for 15 minutes. The graphite sheet was a graphite sheet product name: PERMA-FOIL ^(R) product name: PF-UHP manufactured by Toyo Tanso Co., Ltd.

(Example 3)
A copper foil sheet was joined to the projecting surface of the conductive path of the anisotropic conductive member 3 by a thermocompression bonding method to produce the conductive material 100 of the present invention having the conductive bumps 60 shown in FIG. 1C. The conductive layer 56 is made of 99.9% pure Cu foil (thickness 30 μm) and manufactured by Kitagawa Seiki Co., Ltd. under the thermocompression bonding method (high heat resistance, narrow pitch possible). Crimped using a machine. The pressure was set at 300 ° C. for 5 minutes. The anisotropic conductive member 3 has a high heat resistance and a narrow pitch, and was sufficiently thermocompression bonded.

Example 4
An anisotropic conductive member 3 was used, and an Al foil was bonded to the projecting surface of the conduction path with an anisotropic conductive adhesive to produce a conductive material 100 having conductive bumps 60 shown in FIG. 5A.
The adhesive used was manufactured by Nihon Solder Co., Ltd. Trade name: Dodent Model No. NH-070A (L), and an aluminum foil (Niraco Co., Ltd.) was laminated on the anisotropic conductive member 3 with a laminator. The Al foil was AL-013261 (0.05 × 100 × 100 mm and 99 +% purity).

(Example 5)
Using the anisotropic conductive member 3, Cu was vapor-deposited on the surface opposite to the surface on which the conduction path projecting step was performed, and the conductive layer 56 was laminated to manufacture the conductive material of the present invention shown in FIG. 5B. Cu was deposited in the same manner as in Example 1.

(Example 6)
A base layer 56a was formed by Ni vapor deposition using the anisotropic conductive member 4, and a commercially available Au substitution plating was performed using the base layer 56a as a production nucleus to deposit a gold plating layer 56b. The conductive material 100 of the present invention shown in FIG. 5C having two conductive layers (56a and 56b) was produced.
Ni was vapor-deposited by placing a 0.5 mmφ Ni wire length of 6 cm on a tungsten boat.
Specifically, the applied current was applied at an increasing rate of 1 A / sec from 0 to 40 A and held at 40 A for 10 seconds. The vapor deposition thickness was measured by measuring a step generated by peeling with a commercially available roughness meter after a commercially available instantaneous adhesive was dropped and a part thereof was peeled off. The thickness was 0.13 μm.
The gold plating process was performed by a substitution reaction on nickel. A Melplate AU-6630 thickness: 40 nm manufactured by Meltex Co., Ltd. was used.

(Example 7)
Using the anisotropic conductive member 3, a tungsten foil was stuck with an anisotropic conductive adhesive 58 on the surface opposite to the surface on which the conduction path protruding step was performed, and the conductive material of the present invention shown in FIG. 6A was manufactured. . As the anisotropic conductive adhesive, the same adhesive as in Example 4 was used. The tungsten foil had a Nilaco tungsten foil thickness of 50 μm and was W-463261, 0.05 × 100 × 100 mm, 99.95%.

(Example 8)
Using the anisotropic conductive member 4, the copper foil was bonded as the conductive layer 56 with the anisotropic conductive adhesive used in Example 4, and the conductive material 100 of this invention shown to FIG. 6B was manufactured. The copper foil is the same as that used in Example 3.

Example 9
Using the anisotropic conductive member 1, as shown in FIG. 6C, Cu was vapor-deposited and the conductive layers 56 and 56 were laminated on both surfaces to manufacture the conductive material of the present invention. Cu was deposited in the same manner as in Example 5, and the deposition thickness was 0.13 μm.

(Example 10)
Using the anisotropic conductive member 1, using the anisotropic conductive adhesive as in Example 2 on both sides of the anisotropic conductive member with graphite sheets as the conductive layers 56, 56 with the anisotropic conductive adhesive. The conductive material 100 of the present invention shown in FIG. The graphite sheet is the same as that used in Example 2.

(Example 11)
Using the anisotropic conductive member 4, as shown in FIG. 7A, Cu was vapor-deposited and the conductive layers 56 and 56 were laminated on both surfaces to manufacture the conductive material of the present invention. The deposition of Cu was performed in the same manner as in Example 5, and the deposition thickness was 0.13 μm.

Example 12
As shown in FIG. 7B, the anisotropic conductive member 4 is used, and an anisotropic conductive adhesive is used to form graphite sheets as conductive layers 56 and 56 on both sides of the anisotropic conductive member. Bonding was performed using the conductive adhesives 58 and 58 to manufacture the conductive material 100 of the present invention shown in FIG. 7B. The graphite sheet is the same as that used in Example 2.

(Example 13)
Although the anisotropic conductive member 4 was used, the protective film formation process was performed by immersing the anodized alumina film in an alkali metal silicate aqueous solution before the step of filling the conductive material.
As shown in FIG. 7C, one surface of the anisotropic conductive member was bonded using an anisotropic conductive adhesive 58 with a graphite sheet as the conductive layer 56 in the same manner as in Example 2. A film of the photosensitive resin layer 64 was laminated thereon.
The photosensitive resin layer was a film-like photosensitive film FRA063 manufactured by DuPont MRC Dry Film Co., Ltd.
On the other hand, the film of the bump protective layer 62 was laminated and bonded to one surface of the anisotropic conductive member in the same process as the photosensitive resin layer. The protective layer 62 was Toray Film Processing Co., Ltd. product name: therapy, product number: MD (# 38, thickness 50 μm).
For laminator adhesion, TOLAMI DX-700 was used, and the laminating conditions were 100 ° C. and 0.6 m / min.

(Example 14)
In the same manner as in Example 13, except that graphite sheets are attached to both sides of the anisotropic conductive member 4 as conductive layers 56 and 56 using anisotropic conductive adhesives 58 and 58 in the same manner as in Example 12. In addition, the conductive material of the present invention having the conductive layers 56 and 56 and the photosensitive resin layers 64 and 64 shown in FIG. 7D was manufactured.

Example 15 Preparation of Probe Card Circuit Board A dot pattern mask having a period of 200 μm and a 70 μm square pattern corresponding to the position of the probe needle is prepared on the photosensitive resin layer 64 of the conductive material of the present invention manufactured in Example 14. Then, both surfaces of the anisotropic conductive printed wiring board having the photosensitive resin produced in Example 14 were exposed and developed with a mercury lamp under the manufacturer's recommended conditions.
A dot pattern having a period of 200 μm and a 70 μm square pattern could be formed on both surfaces of the anisotropic conductive member.
Using a wire bonding apparatus (Model 7400D ultrasonic / ultrasonic thermocompression wedge wire bonder manufactured by Hisol Co., Ltd.), Cu wiring was connected and formed, and a wiring circuit was produced on the surface. As shown in FIG. 8A, signal extraction wirings 24 were formed at the end portions. A pitch of 500 μm for the signal extraction portion 28 and a pitch of 200 μm for the contact connection portion 29 were produced. FIG. 8B shows a cross-sectional view of the probe card of the present invention. The position of the probe needle is indicated by contacts 70 and 72, and the signal extraction wiring circuit 26 having a pattern corresponding to the position of the probe needle having the signal extraction electrodes 74, 76, 78, and 80 is provided on both surfaces of the anisotropic conductive member 21. Has been created.

1A, 1B and 1C are schematic end views illustrating the configuration of the conductive material of the present invention. 2A and 2B are simplified views showing an example of a preferred embodiment of the anisotropically conductive member, FIG. 2A is a front view, and FIG. 2B is a cross-sectional view taken along the section line IB-IB in FIG. 2A. 3A to 3D are schematic end views for explaining an example of the anodizing treatment. 4A to 4D are schematic end views for explaining an example of the conductive material filling step and the like. 5A to 5C are schematic end views illustrating the configuration of the conductive material of the present invention. 6A to 6D are schematic end views illustrating the configuration of the conductive material of the present invention. 7A to 7D are schematic end views illustrating the configuration of the conductive material of the present invention. FIG. 8A is a diagram showing a pattern of lead electrodes. FIG. 8B is a schematic diagram of a probe card using the conductive material of the present invention as a circuit board. 9A and 9B are schematic diagrams of a probe card using the conductive material of the present invention as a circuit board.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Anisotropic conductive member 2 Insulating base material 3 Conducting path 4a, 4b Protruding part 5 In-base material conducting part 6 Insulating base material thickness 7 Width between conducting paths 8 Diameter of conducting path 9 Distance between centers of conducting paths (pitch)
12 Aluminum substrate 14a, 14b, 14c, 14d Anodized film 16a, 16b, 16c, 16d Micropore 18a, 18b, 18c, 18d Barrier layer 20 Insulating substrate 21 Anisotropic conductive member 24 Signal extraction wiring 26 Wiring circuit 28 Signal Extraction Section 29 Contact Connection Section 52 Conductive Path 54 Anodized Film 56 Conductive Layer 56a Underlayer 56b Plating Layer 58 Conductive Adhesive 60 Conductive Bump 62 Protective Layer 64 Photosensitive Resin Layer 70, 72 Contacts 74, 76, 78, 80 Signal extraction electrode 82, 84 Patterned conductive layer 88 Conductive adhesive 90 Carbon fiber electrode 92 Contact made of conductive elastic material 100 Conductive material

Claims (4)

  An anisotropic conductive member having an anodic oxide film of aluminum and a conductive material penetrating in the thickness direction of the oxide film, and a conductive layer are stacked, and the conductive material is electrically connected to the conductive layer. material.   The conductive material according to claim 1, further comprising a photosensitive resin layer on the conductive layer and / or the anisotropic conductive member.   The conductive material according to claim 1, wherein the conductive layer has a wiring circuit pattern.   A circuit board for a probe card for semiconductor inspection, comprising the conductive material according to claim 1.

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