Method for manufacturing a structure, an anisotropic conductive member, and a composition for forming a protective layer

Abstract

The present invention provides: a structure which suppresses the influence of chips that are generated by cutting works such as dicing; a method for producing an anisotropic conductive member; and a composition for forming a protective layer. This structure comprises: an insulating film; a plurality of conductors that penetrate through the insulating film in the thickness direction, while being electrically insulated from each other; a resin layer that covers at least one surface of the insulating film in the thickness direction; and a protective layer that is configured from an organic material. The resin layer is arranged between the insulating film and the protective layer; and the protective layer serves as the outermost surface layer.

Description

[Technical Field]

[0001] The present invention relates to a structure comprising a resin layer covering at least one surface in the thickness direction of an insulating film, a protective layer made of organic material as the outermost surface layer, a method for manufacturing an anisotropic conductive member, and a composition for forming a protective layer. [Background technology]

[0002] Structures in which conductive materials such as metals are filled into multiple through-holes provided in an insulating substrate are one of the fields that have attracted attention in nanotechnology in recent years, and are expected to have applications such as anisotropic conductive materials. Anisotropic conductive members are widely used as electrical connection members for electronic components such as semiconductor elements, and as test connectors for functional testing, because they can be inserted between electronic components such as semiconductor elements and circuit boards and an electrical connection between the electronic components and the circuit board can be obtained simply by applying pressure. In particular, electronic components such as semiconductor devices are undergoing significant downsizing. Conventional methods such as wire bonding, which directly connects wiring boards, flip-chip bonding, and thermocompression bonding may not be able to adequately guarantee the stability of the electrical connections of electronic components. Therefore, anisotropic conductive materials are attracting attention as electronic connection materials.

[0003] As an anisotropic conductive member, for example, Patent Document 1 describes an anisotropic conductive bonding member comprising an insulating substrate, a plurality of conductive passages made of a conductive member, and a resin layer provided on the entire surface of the insulating substrate. The resin layer contains a thermosetting resin. The conductive passages are provided penetrating the insulating substrate in the thickness direction while being insulated from each other. The conductive passages have protruding portions that protrude from the surface of the insulating substrate, and the ends of the protruding portions are embedded in the resin layer. [Prior art documents] [Patent Documents]

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] In a configuration in which a resin layer is provided on the entire surface of an insulating base material like the anisotropic conductive joint member of Patent Document 1 described above, when the anisotropic conductive joint member is separated into individual pieces by cutting processes such as dicing, cutting chips are generated from the anisotropic conductive joint member. In the separated anisotropic conductive member, when cutting chips adhere to the resin layer, when the separated anisotropic conductive member is inserted and joined, for example, between a semiconductor element, an electronic component, and a circuit board, the cutting chips become a physical obstacle. For this reason, in the separated anisotropic conductive member, it is necessary to remove the cutting chips from the resin layer. However, it has been found that it is difficult to remove the cutting chips adhering to the resin layer. From this, when separating the anisotropic conductive member into individual pieces by cutting processes such as dicing, it is desired to suppress the influence of the cutting chips.

[0006] An object of the present invention is to provide a structure that suppresses the influence of cutting chips generated by cutting processes such as dicing, a method for manufacturing an anisotropic conductive member, and a composition for forming a protective layer.

Means for Solving the Problems

[0007] To achieve the above object, one aspect of the present invention has an insulating film, a plurality of conductors that penetrate the insulating film in the thickness direction and are provided in a state of being electrically insulated from each other, a resin layer that covers at least one surface in the thickness direction of the insulating film, and a protective layer composed of an organic substance. The resin layer is provided between the insulating film and the protective layer, and the protective layer is the outermost surface layer, and provides a structure.

[0008] The protective layer preferably has oxygen barrier properties. It is preferable that the protective layer and the resin layer are in direct contact. The protective layer preferably has an adhesiveness of 2 to 10 N / 25 mm with respect to other layers in contact therewith. The protective layer is preferably subjected to dissolution and removal with a removal liquid, and the removal liquid contains a solvent having a dissolution rate of the protective layer at 25°C of 1 μm / s or more. The removal liquid preferably contains ethyl acetate. The conductor preferably protrudes from at least one surface in the thickness direction of the insulating film. The conductor preferably protrudes from both surfaces in the thickness direction of the insulating film. The insulating film is preferably composed of an anodic oxidation film.

[0009] Another aspect of the present invention is a method for manufacturing an anisotropic conductive member using a structure having an insulating film, a plurality of conductors penetrating the insulating film in the thickness direction and provided in a state of being electrically insulated from each other, a resin layer covering at least one surface in the thickness direction of the insulating film, and a protective layer made of an organic substance, wherein the resin layer is provided between the insulating film and the protective layer, and the protective layer is the outermost surface layer, and the method includes a removal step of removing the protective layer. The insulating film is preferably composed of an anodic oxidation film. Another aspect of the present invention is a composition for forming a protective layer that constitutes the protective layer of the structure of the present invention, and the composition for forming a protective layer contains a resin.

Advantages of the Invention

[0010] According to the structure of the present invention, the influence of cutting chips during singulation can be suppressed. Further, according to the method for manufacturing an anisotropic conductive member of the present invention, an anisotropic conductive member capable of suppressing the influence of cutting chips during singulation can be obtained. Further, according to the composition for forming a protective layer of the present invention, a protective layer capable of suppressing the influence of cutting chips during singulation can be obtained.

Brief Description of the Drawings

[0011] [Figure 1]This is a schematic cross-sectional view showing an example of a structure according to an embodiment of the present invention. [Figure 2] This is a schematic plan view showing an example of a structure according to an embodiment of the present invention. [Figure 3] This is a schematic cross-sectional view showing an example of a cross-section of a structure according to an embodiment of the present invention. [Figure 4] This is a schematic cross-sectional view showing an example of a cross-section of a structure according to an embodiment of the present invention. [Figure 5] This is a schematic cross-sectional view showing an example of a cross-section of a structure according to an embodiment of the present invention. [Figure 6] This is a schematic cross-sectional view showing one step in an example of a method for manufacturing a structure according to an embodiment of the present invention. [Figure 7] This is a schematic cross-sectional view showing one step in an example of a method for manufacturing a structure according to an embodiment of the present invention. [Figure 8] This is a schematic cross-sectional view showing one step in an example of a method for manufacturing a structure according to an embodiment of the present invention. [Figure 9] This is a schematic cross-sectional view showing one step in an example of a method for manufacturing a structure according to an embodiment of the present invention. [Figure 10] This is a schematic cross-sectional view showing one step in an example of a method for manufacturing a structure according to an embodiment of the present invention. [Figure 11] This is a schematic cross-sectional view showing one step in an example of a method for manufacturing a structure according to an embodiment of the present invention. [Figure 12] This is a schematic cross-sectional view showing one step in an example of a method for manufacturing a structure according to an embodiment of the present invention. [Figure 13] This is a schematic diagram showing an example of a joint according to an embodiment of the present invention. [Modes for carrying out the invention]

[0012] The structure of the present invention, the method for manufacturing an anisotropic conductive member, and the composition for forming a protective layer will be described in detail below based on preferred embodiments shown in the attached drawings. The figures described below are illustrative examples for illustrating the present invention, and the present invention is not limited to the figures shown below. In the following, the symbol "~" indicating a numerical range includes the numerical values described on both sides. For example, ε a is a numerical value α b ~ numerical value β c means that the range of ε a is a range including the numerical value α b and the numerical value β c and, expressed in mathematical symbols, α b ≦ ε a ≦ β c That is. Regarding temperature and time, unless otherwise specified, it includes the error range generally allowed in the relevant technical field.

[0013] [An example of a structure] FIG. 1 is a schematic cross-sectional view showing an example of the detailed structure of an embodiment of the present invention, and FIG. 2 is a schematic plan view showing an example of the detailed structure of an embodiment of the present invention. FIG. 2 is a plan view seen from the surface side of the insulating film of FIG. l, showing a state without the resin layer 20 and the protective layer 22. The structure 10 shown in FIG. 1 has an insulating film 12 having electrical insulation properties, and a plurality of conductors 14 that penetrate the insulating film 12 in the thickness direction Dt and are provided in a state of being electrically insulated from each other.

[0014] The plurality of conductors 14 are arranged in the insulating film 12 in a state of being electrically insulated from each other. In this case, for example, the insulating film 12 has a plurality of pores 13 penetrating in the thickness direction Dt. The conductors 14 are provided in the plurality of pores 13. The conductors 14 protrude from the surface 12a in the thickness direction Dt of the insulating film 12. Further, the conductors 14 protrude from the back surface 12b in the thickness direction Dt of the insulating film 12. Note that the insulating film 12 and the plurality of conductors 14 constitute an anisotropic conductive layer 16.

[0015] The structure 10 has a resin layer 20 that covers at least one surface of the insulating film 12 in the thickness direction Dt. In Figure 1, the resin layer 20 is provided on the entire surface 12a and the entire surface 12b of the insulating film 12, respectively. The insulating film 12 is composed of, for example, an anodic oxide film 15. The resin layer 20 covers the protruding conductor 14. The resin layer 20 covers the protruding portion 14a of the conductor 14, and the protruding portion 14a is embedded in the resin layer 20. Also, the resin layer 20 covers the protruding portion 14b of the conductor 14, and the protruding portion 14b is embedded in the resin layer 20. The structure 10 has a protective layer 22 made of organic material. The resin layer 20 is provided between the insulating film 12 and the protective layer 22. In Figure 1, for example, the protective layer 22 is provided in direct contact with the surface 20a of the resin layer 20. The surface 20a of the resin layer 20 is the surface opposite to the insulating film 12. The protective layer 22 is provided on the front surface 12a and the back surface 12b of the insulating film 12, respectively. The protective layer 22 is the outermost layer of the structure 10.

[0016] The protective layer 22 protects the resin layer 20, preventing cutting debris and other contaminants from adhering to the surface 20a of the resin layer 20. Furthermore, it is preferable that the protective layer 22 has oxygen-blocking properties. By having oxygen-blocking properties, oxidation of the conductor 14 can be suppressed. When the conductor 14 protrudes, the protruding parts 14a and 14b of the conductor 14 are prone to oxidation, so it is particularly effective for the protective layer 22 to have oxygen-blocking properties. It is more preferable that the protective layer 22 has the ability to block gases of elements other than oxygen, in addition to blocking oxygen as described above. Here, "direct contact between the protective layer 22 and the resin layer 20" means that there is no other layer between the protective layer 22 and the resin layer 20, and the protective layer 22 is formed on the surface 20a of the resin layer 20.

[0017] Furthermore, the configuration is not limited to one in which the protective layer 22 and the resin layer 20 are in direct contact; another layer may be provided between the protective layer 22 and the resin layer 20. For example, an intermediate layer (not shown) that facilitates the removal of the protective layer 22 may be provided between the protective layer 22 and the resin layer 20. The intermediate layer may, for example, contain a fluororesin. Fluororesins are, for example, fluoroethylene vinyl ether alternating copolymers. More specifically, fluororesins include Lumiflon® LF200 (trade name, manufactured by AGC Inc.). Furthermore, for example, by providing an intermediate layer made of the aforementioned fluororesin, the adhesion of cutting debris to the surface 20a of the resin layer 20 is suppressed after the protective layer 22 is removed. The resin layer 20, the intermediate layer (not shown), and the protective layer 22 are collectively referred to as the coating layer. A configuration consisting only of the resin layer 20 and the protective layer 22, without the intermediate layer, is also referred to as the coating layer.

[0018] The structure 10 has anisotropic conductivity and is conductive in the thickness direction Dt, but its conductivity in the direction parallel to the surface 12a of the insulating film 12 is sufficiently low. As shown in Figure 2, the structure 10 has, for example, a rectangular shape. However, the shape of the structure 10 is not limited to a rectangle; for example, it may be circular. The shape of the structure 10 can be determined according to its intended use, ease of manufacture, etc. The conductor 14 protrudes from both surfaces of the insulating film 12 in the thickness direction Dt, but it may also protrude from at least one surface of the insulating film 12 in the thickness direction Dt. When the conductor 14 protrudes from at least one surface of the insulating film 12 in the thickness direction Dt, in a configuration where it protrudes from one side, it is preferable that it protrudes from the front surface 12a or the back surface 12b.

[0019] As described above, the structure 10 has a protective layer 22 on the resin layer 20. Because of the protective layer 22, when the structure 10 is cut into individual pieces by cutting processes such as dicing, cutting debris generated from the structure 10 adheres to the protective layer 22 but does not adhere to the resin layer 20. Therefore, by removing the protective layer 22 after cutting, a resin layer 20 free of cutting debris can be obtained. The effects of cutting debris can be suppressed by removing the protective layer 22, for example, to remove cutting debris that adhered during the cutting of the structure 10. As a result, the individualized structure 10 can be inserted and joined, for example, between semiconductor elements, electronic components, and circuit boards, without any physical obstruction.

[0020] Here, Figures 3 to 5 are schematic cross-sectional views showing an example of cutting a structure according to an embodiment of the present invention in order of the process. In Figures 3 to 5, the same reference numerals are used for components identical to those in the structure 10 shown in Figure 1, and their detailed descriptions are omitted. In the structure 10 shown in Figures 3 and 4, a protective layer 22 is provided on the surface 12a of the insulating film 12, on the surface of one of the two resin layers 20. For example, as shown in Figure 3, a support 37 is attached to the resin layer 20 on the back surface 12b side of the insulating film 12 of the structure 10 using a heat release layer 36. By attaching the support 37, the structure 10 can be easily separated into individual pieces. A dicing tape 38 is provided on the opposite side of the heat release layer 36 of the support 37.

[0021] The thermal release layer 36 is not particularly limited in its configuration as long as it can bond the above-described structure 10 and the support 37. For example, Q-chuck® (manufactured by Maruishi Sangyo Co., Ltd.) or Nitto Denko Corporation's double-sided type Riba Alpha® can be used. In order to facilitate handling of the laminated structure in the substrate removal process described above, it is preferable that the support 37 has the same external shape as the laminated structure described above. The support 37 is, for example, a silicon substrate. The support 37 is not limited to a silicon substrate, but can also be a ceramic substrate such as SiC, SiN, GaN, and alumina (Al2O3), a glass substrate, a fiber-reinforced plastic substrate, or a metal substrate. Fiber-reinforced plastic substrates include FR-4 (Flame Retardant Type 4) substrates, which are printed circuit boards. The dicing tape 38 is used to fix the support 37. The dicing tape 38 is not particularly limited, and any known type can be used as appropriate.

[0022] The structure 10, which has the configuration shown in Figure 3, is cut from the surface 22a side of the protective layer 22 on the resin layer 20 on the surface 12a side of the insulating film 12, as shown in Figure 4. At this time, cutting debris 39 is generated, and the cutting debris 39 adheres to the surface 22a of the protective layer 22. Note that the surface 22a of the protective layer 22 is the surface opposite to the insulating film 12, and is the outermost surface of the structure 10. After cutting the structure 10 into individual pieces, the protective layer 22 is removed as shown in Figure 5. By removing the protective layer 22, a resin layer 20 without cutting debris 39 adhering to the surface 20a is exposed. This makes it possible to suppress the influence of cutting debris 39 on the structure 10. Furthermore, the removal of the protective layer 22 can be appropriately carried out according to the composition or physical properties of the protective layer 22. For example, the removal of the protective layer 22 can be done by physical peeling using adhesive tape or by dissolution using a removal solution containing a solvent. For example, if the protective layer 22 is made of PVA (polyvinyl alcohol), hot water can be used as the solvent in the removal solution to dissolve the protective layer 22. Hot water is water with a temperature of 35°C or higher.

[0023] The protective layer removal step, which involves removing the protective layer 22 from the structure 10 described above, yields an anisotropic conductive member 11. Here, the anisotropic conductive member 11 is the structure 10 in a state where the protective layer 22 is absent.

[0024] The structure of the system will be explained in more detail below. [Insulating film] The insulating film 12 is made of a conductive material and electrically insulates multiple conductors 14 from each other. The insulating film has electrical insulating properties. The insulating film 12 also has multiple pores 13 in which the conductors 14 are formed. The insulating film is made of, for example, an inorganic material. 14 Materials with an electrical resistivity of approximately Ω·cm can be used. Furthermore, the phrase "made of inorganic materials" is a provision to distinguish it from polymer materials, and does not limit it to insulating substrates composed solely of inorganic materials, but rather specifies that inorganic materials are the main component (50% by mass or more). As mentioned above, the insulating film is composed of, for example, an anodic oxide film. Furthermore, the insulating film can also be composed of, for example, metal oxides, metal nitrides, glass, ceramics such as silicon carbide and silicon nitride, carbon substrates such as diamond-like carbon, polyimide, or composite materials thereof. Alternatively, the insulating film may be formed by depositing a film of an inorganic material containing 50% or more by mass of ceramic or carbon material on an organic material having through-holes.

[0025] The length of the insulating film 12 in the thickness direction Dt, i.e., the thickness of the insulating film 12, is preferably in the range of 1 to 1000 μm, more preferably in the range of 5 to 500 μm, and even more preferably in the range of 10 to 300 μm. When the thickness of the insulating film 12 is within this range, the handling properties of the insulating film 12 are good. The thickness ht of the insulating film 12 is preferably 30 μm or less, and more preferably 5 to 20 μm, from the viewpoint of ease of winding. The thickness of the anodic oxide film was calculated by cutting the anodic oxide film in the thickness direction Dt using a focused ion beam (FIB), taking surface photographs (magnification 50,000x) of the cross-section using a field emission scanning electron microscope (FE-SEM), and taking the average value of 10 measurements. The spacing between each conductor 14 in the insulating film 12 is preferably 5 nm to 800 nm, more preferably 10 nm to 200 nm, and even more preferably 20 nm to 60 nm. When the spacing between each conductor 14 in the insulating film 12 is within the above range, the insulating film 12 functions sufficiently as an electrically insulating barrier for the conductors 14. Here, the spacing between each conductor refers to the width between adjacent conductors, and is the average value obtained by observing the cross-section of the structure 10 at a magnification of 200,000 times using an electrolytic emission scanning electron microscope and measuring the width between adjacent conductors at 10 points.

[0026] <Average pore diameter> The average diameter of the pores is preferably 1 μm or less, more preferably 5 to 500 nm, even more preferably 20 to 400 nm, even more preferably 40 to 200 nm, and most preferably 50 to 100 nm. When the average diameter d of the pores 13 is 1 μm or less and within the above range, a conductor 14 having the above average diameter can be obtained. The average diameter of the pores 13 is determined by taking images of the surface of the insulating film 12 from directly above using a scanning electron microscope at a magnification of 100 to 10,000 times. In the images, at least 20 pores with a ring-like structure around their periphery are extracted, their diameters are measured and defined as the aperture diameters, and the average of these aperture diameters is calculated as the average diameter of the pores. The magnification can be appropriately selected within the above-mentioned range to obtain an image in which 20 or more pores can be extracted. The aperture diameter is determined by measuring the maximum distance between the ends of the pore portion. That is, the shape of the pore opening is not limited to a roughly circular shape, so if the shape of the opening is not circular, the maximum distance between the ends of the pore portion is taken as the aperture diameter. Therefore, for example, even in the case of a pore with a shape in which two or more pores are integrated, it is treated as a single pore, and the maximum distance between the ends of the pore portion is taken as the aperture diameter.

[0027] 〔conductor〕 As described above, the multiple conductors 14 are provided in an insulating film 12, for example, an anodized film 15, in a state where they are electrically insulated from one another. Multiple conductors 14 are electrically conductive. The conductors are composed of a conductive material. The conductive material is not particularly limited, but metals are an example. Specific examples of metals that are preferably exemplified include gold (Au), silver (Ag), copper (Cu), aluminum (Al), magnesium (Mg), and nickel (Ni). From the viewpoint of electrical conductivity, copper, gold, aluminum, and nickel are preferred, copper and gold are more preferred, and copper is the most preferred. Besides metals, oxide conductive materials can be used. Examples of oxide conductive materials include indium-doped tin oxide (ITO). However, metals are preferable to oxide conductors because they have superior ductility and are easily deformed, and are also easily deformed by compression during joining. Furthermore, the conductor can also be constructed using a conductive resin containing nanoparticles such as Cu or Ag. The height H of the conductor 14 in the thickness direction Dt is preferably 10 to 300 μm, and more preferably 20 to 30 μm.

[0028] <Shape of the conductor> The average diameter d of the conductor 14 is preferably 1 μm or less, more preferably 5 to 500 nm, even more preferably 20 to 400 nm, even more preferably 40 to 200 nm, and most preferably 50 to 100 nm. The density of conductor 14 is 20,000 particles / mm³ 2 Preferably, the density is 2 million pieces / mm². 2 It is more preferable that the number be greater than or equal to 10 million pieces / mm 2 It is even more preferable that the number be 50 million / mm² or higher. 2 It is particularly preferable that the value be 100 million pieces / mm 2 The above is the most preferable. Furthermore, the distance p between the centers of adjacent conductors 14 is preferably 20 nm to 500 nm, more preferably 40 nm to 200 nm, and even more preferably 50 nm to 140 nm. The average diameter of the conductor is determined by taking images of the surface of the anodized film from directly above using a scanning electron microscope at a magnification of 100 to 10,000 times. From the images, at least 20 conductors with a ring-shaped perimeter are extracted, their diameters are measured and defined as the aperture diameter, and the average of these aperture diameters is calculated as the average diameter of the conductor. The magnification can be appropriately selected within the range described above so that an image is obtained in which 20 or more conductors can be extracted. The aperture diameter is determined by measuring the maximum distance between the ends of the conductor portion. That is, the shape of the conductor opening is not limited to a roughly circular shape, so if the shape of the opening is not circular, the maximum distance between the ends of the conductor portion is taken as the aperture diameter. Therefore, for example, even in the case of a conductor with a shape in which two or more conductors are integrated, it is treated as a single conductor, and the maximum distance between the ends of the conductor portion is taken as the aperture diameter.

[0029] <Protrusion> The protruding portion is part of the conductor and is columnar in shape. The protruding portion is preferably cylindrical in shape, as this allows for a larger contact area with the object being joined. The average protrusion length ha of the protrusion portion 14a and the average length hb of the protrusion portion 14b are preferably 30 nm to 500 nm, and more preferably 100 nm or less as the upper limit. The average protrusion length ha of the protrusion 14a and the average length hb of the protrusion 14b are the average values ​​obtained by acquiring cross-sectional images of the protrusions using a field emission scanning electron microscope as described above, and measuring the height of each protrusion at 10 points based on the cross-sectional images.

[0030] [Resin layer] As described above, the resin layer covers at least one of the front and back surfaces of the insulating film, protecting the insulating film and the conductor. If the conductor has a protruding portion, for example, the resin layer embeds the protruding portion. That is, the resin layer covers the end of the conductor that protrudes from the insulating film, protecting the protruding portion. To perform the functions described above, the resin layer is preferably fluid in a temperature range of 50°C to 200°C and hardens at temperatures above 200°C. The resin layer is a thermoplastic layer composed of, for example, a thermoplastic resin, which will be described in detail later.

[0031] The average protruding lengths ha and hb of the conductor 14 are preferably less than the average thickness hm of the resin layer 20. If the average protruding length ha of the protruding portion 14a and the average length hb of the protruding portion 14b of the conductor 14 are both less than the average thickness hm of the resin layer 20, then the protruding portions 14a and 14b are both embedded in the resin layer 20, and the conductor 14 is protected by the resin layer 20. The average thickness hm of the resin layer 20 is the average distance from the surface 12a of the insulating film 12, or the average distance from the back surface 12b of the insulating film 12. The average thickness hm of the resin layer 20 described above is the average of 10 measurements taken by cutting the resin layer in the thickness direction Dt of the structure 10, observing the cross-section of the cut surface using a field emission scanning electron microscope (FE-SEM), and measuring the distance from the surface 12a of the insulating film 12 at 10 locations corresponding to the resin layer. Alternatively, the distance from the back surface 12b of the insulating film 12 at 10 locations corresponding to the resin layer is measured, and the average of 10 measurements taken is the average of 10 measurements. The average thickness hm of the resin layer is preferably 200 to 1000 nm, and more preferably 400 to 600 nm. If the average thickness of the resin layer is 200 to 1000 nm as described above, the effect of protecting the protruding portion of the conductor 14 can be sufficiently achieved.

[0032] [Protective layer] As described above, the protective layer 22 protects the resin layer 20, and the protective layer 22 prevents cutting debris 39 and the like from adhering to the surface 20a of the resin layer 20. The protective layer 22 is composed of organic material, as described above. Furthermore, the protective layer 22 is the outermost layer of the structure 10.

[0033] The protective layer 22 preferably has oxygen-blocking properties as described above. By having oxygen-blocking properties, oxidation of the conductor 14 can be suppressed. When the conductor 14 protrudes from the insulating film 12, the protruding portions 14a and 14b of the conductor 14 are exposed and easily oxidized, so it is particularly effective for the protective layer 22 to have oxygen-blocking properties. The protective layer 22 is said to have oxygen barrier properties if its oxygen permeability coefficient is 1.5 × 10⁻⁶. 17 m 3 (STP)m·m -2 ·s -1 ·kPa -1 The following is what is meant: STP (standard temperature and pressure) indicates the temperature and pressure under standard conditions. STP is 273.15 K (Kelvin) in absolute temperature and 1.01325 × 10⁻¹⁵ pressure. 5 Pa is equivalent to 0°C and 1 atmosphere. The protective layer 22 has an oxygen permeability coefficient of 1.5 × 10⁻⁶. 16 m 3 (STP)m·m -2 ·s -1 ·kPa -1 Preferably, and more preferably, 7.0 × 10 15 m 3 (STP)m·m -2 ·s -1 ·kPa -1 The following applies: The lower limit of the oxygen permeability coefficient is 3 × 10⁻⁶. 15 m 3 (STP)m·m -2 ·s -1 ·kPa -1 That is the case. The oxygen permeability coefficient is a value measured using the differential pressure method. In the differential pressure method, the oxygen permeability coefficient is calculated from the slope after the pressure change on the depressurization side becomes constant with respect to the depressurization time. A protective film with a diameter of 50 mm is used to measure the oxygen permeability coefficient. If the protective layer is a laminate film, the laminate film is cut to a diameter of 50 mm and used for measuring the oxygen permeability coefficient. The thickness is measured separately.

[0034] The protective layer 22 is composed of an organic material, which is, for example, a resin. The protective layer 22 is specifically composed of, for example, PVA (polyvinyl alcohol) or PVDC (polyvinylidene chloride). For PVA, a copolymer with ethylene, EVOH (ethylene vinyl alcohol copolymer), may also be used. Polyacrylonitrile can also be used. For PVDC, a copolymer with acrylonitrile or vinyl chloride may be used. Examples of commercial products include Asahi Kasei Corporation's Saran Resin (trade name, PDVC type) or Mitsubishi Gas Chemical Company's Maxieve (trade name, epoxy type). Alternatively, a protective layer 22 can be formed with epoxy resin. As the laminate film, for example, a PVDC coated film can be used. As the PVDC coated film, for example, V-Barrier (registered trademark, manufactured by Mitsui Chemicals Tohcello Co., Ltd.) or Bonil-K (manufactured by Kojin Film & Chemicals Co., Ltd.) can be used.

[0035] Furthermore, it is preferable that the protective layer 22 has an adhesive strength of 2 to 10 N / 25 mm to the other layers it is in contact with. The above-mentioned adhesive strength of 2 to 10 N / 25 mm is a value obtained by a method in accordance with JIS (Japanese Industrial Standards) K 6854-2 "Adhesives - Test method for peel adhesion strength - Part 2: 180 degree peel". The protective layer 22 maintains its function and is easy to remove because it has an adhesive strength of 2 to 10 N / 25 mm to other layers it is in contact with. Examples of protective layers having an adhesive strength of 2-10 N / 25 mm include PVA and PVDC. Here, "other layers in contact" refers to the layer directly beneath the protective layer 22 in contact with it, and in Figure 1, the resin layer 20 is the other layer in contact. If another layer, such as the intermediate layer described later, is formed between the protective layer 22 and the resin layer 20, then the intermediate layer becomes the other layer in contact with the protective layer 22 if it is in contact with the protective layer 22. Regarding adhesion, for example, if the protective layer 22 is composed of Saran resin, the tackiness can be controlled by adding a small amount of isocyanate-based adhesive.

[0036] Furthermore, the protective layer 22 is subjected to dissolution and removal using a removal solution. It is preferable that the removal solution contains a solvent whose dissolution rate of the protective layer 22 at a temperature of 25°C is 1 μm / s or more. The dissolution rate of the protective layer 22 can be measured by known means. For example, the dissolution rate of the protective layer 22 can be measured using equipment such as the RDA-760 from Lithotech Japan Co., Ltd. The protective layer 22 can be easily removed by using a removal solution that has a dissolution rate of 1 μm / s or more. The removal solution may contain multiple types of solvents, and the solvents may be organic solvents. Preferably, the removal solution contains ethyl acetate. Examples of solvents in the removal solution include methyl ethyl ketone (MEK) or warm water. Alternatively, the removal solution may be a mixed solution of tetrahydrofuran (THF) and toluene (TOL).

[0037] The average thickness hj of the protective layer is preferably 200 to 1000 nm, and more preferably 400 to 600 nm. If the average thickness of the protective layer is 200 to 1000 nm as described above, the adhesion of cutting debris 39 to the resin layer 20 can be suppressed. The average thickness hj of the protective layer 22 is the average distance from the surface 20a of the resin layer 20. The average thickness hj of the protective layer 22 described above is calculated by cutting the protective layer in the thickness direction Dt of the structure 10, observing the cross-section of the cut surface using a field emission scanning electron microscope (FE-SEM), measuring the distance from the surface 20a of the resin layer 20 at 10 locations corresponding to the protective layer, and taking the average of the 10 measured values. Furthermore, when a protective layer is applied as a coating, the boundary of the protective layer may be difficult to discern. In this case, a metal vapor deposition layer was applied to the surface of the resin layer separately, and then the protective layer was coated to confirm its thickness. The protective layer 22 is designed to remove any cutting debris that adheres to it when the structure 10 is divided into individual pieces by cutting processes such as dicing. The protective layer 22 can be removed, for example, by dissolution or peeling. This suppresses the effects of cutting debris, allowing the individualized structure 10 to be inserted and joined, for example, between semiconductor elements, electronic components, and circuit boards, without physical obstruction. Furthermore, if the protective layer 22 is composed of a water-soluble organic material, for example, after dicing, the cutting chips can be removed together with the protective layer 22 by removing the protective layer 22 using hot water.

[0038] <Protective layer forming composition> The protective layer-forming composition forms a protective layer composed of organic matter and includes a resin. The resin is, for example, an epoxy resin. Alternatively, the protective layer-forming composition may be, for example, PVA (polyvinyl alcohol) or PVDC (polyvinylidene chloride). Furthermore, the protective layer-forming composition is one of the specific examples given above for constituting the protective layer 22.

[0039] Unless otherwise specified, the dimensions of each part of the structure 10 are the average values ​​obtained by cutting the structure 10 in the thickness direction Dt, observing the cross-section of the cut surface using a field emission scanning electron microscope (FE-SEM), and measuring 10 points corresponding to each size.

[0040] [An example of a method for manufacturing a structure] The method for manufacturing the structure will now be described. Figures 6 to 12 are schematic cross-sectional views showing an example of a method for manufacturing the structure according to an embodiment of the present invention, in order of steps. In Figures 6 to 12, components identical to those shown in Figures 1 and 2 are denoted by the same reference numerals, and their detailed descriptions are omitted. In one example of a structure manufacturing method, we will explain using the structure 10 shown in Figure 1, in which the insulating film 12 is made of an aluminum anodic oxide film. An aluminum substrate is used to form the aluminum anodic oxide film. Therefore, in this example of a structure manufacturing method, first, an aluminum substrate 30 is prepared as shown in Figure 6. The size and thickness of the aluminum substrate 30 are appropriately determined according to the thickness of the insulating film 12 of the final structure 10 (see Figure 1), the processing equipment, etc. The aluminum substrate 30 is, for example, a rectangular plate. However, it is not limited to an aluminum substrate; any metal substrate capable of forming an electrically insulating insulating film 12 can be used.

[0041] Next, one side surface 30a of the aluminum substrate 30 (see Figure 6) is anodized. As a result, one side surface 30a of the aluminum substrate 30 (see Figure 6) is anodized, and as shown in Figure 7, an insulating film 12 having a plurality of pores 13 extending in the thickness direction Dt of the aluminum substrate 30, i.e., an anodized film 15, is formed. A barrier layer 31 exists at the bottom of each pore 13. The above-described anodizing process is called the anodizing process. As described above, the insulating film 12 having multiple pores 13 has a barrier layer 31 at the bottom of each pore 13. However, the barrier layer 31 shown in Figure 7 is removed. This yields an insulating film 12 having multiple pores 13 without the barrier layer 31 (see Figure 8). The process of removing the barrier layer 31 is called the barrier layer removal process. In the barrier layer removal process, by using an alkaline aqueous solution containing ions of metal M1, which has a higher hydrogen overpotential than aluminum, the barrier layer 31 of the insulating film 12 is removed, and at the same time, a metal layer 35a (see Figure 8) made of metal (metal M1) is formed on the surface 32d (see Figure 8) of the bottom 32c (see Figure 8) of the pore 13. As a result, the aluminum substrate 30 exposed in the pore 13 is covered with the metal layer 35a. This makes it easier for the plating to proceed when filling the pore 13 with metal by plating, suppresses insufficient metal filling of the pore, prevents voids in the pore, and suppresses defects in the formation of the conductor 14. Furthermore, the alkaline aqueous solution containing the above-mentioned metal M1 ions may also contain aluminum ion-containing compounds (such as sodium aluminate, aluminum hydroxide, or aluminum oxide). The content of the aluminum ion-containing compound is preferably 0.1 to 20 g / L, more preferably 0.3 to 12 g / L, and even more preferably 0.5 to 6 g / L, when converted to the amount of aluminum ions.

[0042] Next, plating is performed on the surface 12a of the insulating film 12, which has a plurality of pores 13 extending in the thickness direction Dt. In this case, the metal layer 35a can be used as an electrode for electroplating. Metal 35b is used for plating, and the plating proceeds starting from the metal layer 35a formed on the surface 32d (see Figure 8) of the bottom 32c (see Figure 8) of the pores 13. As a result, as shown in Figure 9, the metal 35b that constitutes the conductor 14 is filled inside the pores 13 of the insulating film 12. By filling the inside of the pores 13 with metal 35b, a conductive conductor 14 is formed. The metal layer 35a and metal 35b together are referred to as metal 35. The process of filling the pores 13 of the insulating film 12 with metal 35b is called the metal filling process. As mentioned above, the conductor 14 is not limited to being made of metal, but can be made of conductive material. Electroplating is used in the metal filling process, and the metal filling process will be explained in detail later. Note that the surface 12a of the insulating film 12 corresponds to one side of the insulating film 12. After the metal filling process, as shown in Figure 10, a portion of the surface 12a of the insulating film 12 on the side where the aluminum substrate 30 is not provided is removed in the thickness direction Dt, causing the metal 35 filled in the metal filling process to protrude beyond the surface 12a of the insulating film 12. In other words, the conductor 14 is made to protrude beyond the surface 12a of the insulating film 12. This results in a protruding portion 14a. The process of making the conductor 14 protrude beyond the surface 12a of the insulating film 12 is called the surface metal protrusion process. After the surface metal protrusion process, the aluminum substrate 30 is removed as shown in Figure 11. The process of removing the aluminum substrate 30 is called the substrate removal process.

[0043] Next, as shown in Figure 12, after the substrate removal process, the side of the insulating film 12 on which the aluminum substrate 30 was provided, i.e., the back surface 12b, is partially removed in the thickness direction Dt, and the metal 35 filled in the metal filling process, i.e., the conductor 14, is made to protrude beyond the back surface 12b of the insulating film 12. This gives rise to the protruding portion 14b. The above-described surface metal protrusion process and back surface metal protrusion process may include both processes, or they may include only one of the two processes. Both the surface metal protrusion process and the back surface metal protrusion process are considered "protrusion processes," and both the surface metal protrusion process and the back surface metal protrusion process are protrusion processes. As shown in Figure 12, the conductor 14 protrudes from the front surface 12a and the back surface 12b of the insulating film 12, respectively, and has protruding portions 14a and 14b.

[0044] Next, a resin layer 20 (see Figure 1) is formed to cover the entire surface 12a and the entire back surface 12b of the insulating film 12 on which the conductor 14 protrudes. The process for forming the resin layer 20 will be described later. A protective layer 22 (see Figure 1) is formed on the surface 20a (see Figure 1) of the resin layer 20. The process for forming the protective layer 22 will be described later. This makes it possible to obtain the structure 10 shown in Figure 1. In the case where the conductor 14 does not protrude from the back surface 12b of the insulating film 12, a resin layer 20 (see Figure 1) is formed to cover the entire surface 12a and the entire back surface 12b of the insulating film 12 in the state shown in Figure 11, and a protective layer 22 (see Figure 1) is formed on the surface 20a (see Figure 1) of the resin layer 20 to obtain the structure 10.

[0045] In the barrier layer removal process described above, by removing the barrier layer using an alkaline aqueous solution containing ions of metal M1, which has a higher hydrogen overpotential than aluminum, not only is the barrier layer 31 removed, but a metal layer 35a of metal M1, which generates less hydrogen gas than aluminum, is formed on the aluminum substrate 30 exposed at the bottom of the pores 13. As a result, the in-plane uniformity of the metal filling is improved. This is thought to be because the generation of hydrogen gas by the plating solution is suppressed, and the metal filling by electroplating proceeds more easily. Furthermore, it has been found that by combining a holding step in the barrier layer removal process, in which a voltage (holding voltage) selected from a range of less than 30% of the voltage in the anodizing process is maintained at 95% to 105% for a total of 5 minutes or more, with the application of an alkaline aqueous solution containing metal M1 ions, the uniformity of metal filling during the plating process is greatly improved. For this reason, it is preferable to have a holding step. Although the detailed mechanism is unknown, it is thought that in the barrier layer removal process, using an alkaline aqueous solution containing metal M1 ions forms a layer of metal M1 beneath the barrier layer. This suppresses damage to the interface between the aluminum substrate and the anodic oxide film, thereby improving the uniformity of the barrier layer dissolution.

[0046] In the barrier layer removal process, a metal layer 35a made of metal (metal M1) was formed at the bottom of the pore 13. However, the process is not limited to this; the barrier layer 31 may be removed, exposing the aluminum substrate 30 at the bottom of the pore 13. With the aluminum substrate 30 exposed, it may be used as an electrode for electroplating.

[0047] [Anodized film] As mentioned above, anodized films are often used, for example, aluminum anodized films, because they form pores with a desired average diameter and facilitate the formation of conductors. However, they are not limited to aluminum anodized films; anodized films of valve metal can also be used. For this reason, valve metal is used as the metal substrate. Here, specific examples of valve metals include, for example, the aforementioned aluminum, as well as tantalum, niobium, titanium, hafnium, zirconium, zinc, tungsten, bismuth, and antimony. Of these, an anodized aluminum film is preferred because it has good dimensional stability and is relatively inexpensive. For this reason, it is preferable to manufacture the structure using an aluminum substrate. The thickness of the anodic oxide film is the same as the thickness ht of the insulating film 12 described above (see Figure 2).

[0048] [Metal substrate] Metal substrates are used in the manufacture of structures and are substrates for forming anodic oxide films. For example, as mentioned above, metal substrates on which anodic oxide films can be formed can be used, and those composed of the aforementioned valve metals can be used. For instance, aluminum substrates are used as metal substrates because, as mentioned above, they readily form anodic oxide films as insulating films.

[0049] [Aluminum substrate] The aluminum substrate used to form the insulating film 12 is not particularly limited, and specific examples include: pure aluminum plates; alloy plates mainly composed of aluminum and containing trace amounts of other elements; substrates in which high-purity aluminum is deposited onto low-purity aluminum (e.g., recycled material); substrates in which high-purity aluminum is coated onto the surface of silicon wafers, quartz, glass, etc. by methods such as deposition and sputtering; and resin substrates laminated with aluminum.

[0050] Of the aluminum substrate, the surface on which the anodic oxide film is formed by anodizing treatment preferably has an aluminum purity of 99.5% by mass or higher, more preferably 99.9% by mass or higher, and even more preferably 99.99% by mass or higher. When the aluminum purity is within the above range, the regularity of the micropore arrangement is sufficient. The aluminum substrate is not particularly limited as long as it can form an anodic oxide film; for example, JIS (Japanese Industrial Standards) 1050 material can be used.

[0051] It is preferable that one side of the aluminum substrate that is to be anodized is pre-treated with heat treatment, degreasing, and mirror finishing. Here, the heat treatment, degreasing treatment, and mirror finishing treatment can be performed in the same manner as described in paragraphs

[0044] to

[0054] of Japanese Patent Application Publication No. 2008-270158. The mirror-finish treatment prior to anodizing is, for example, electropolishing, and for electropolishing, an electropolishing solution containing, for example, phosphoric acid is used.

[0052] [Anodizing process] While conventionally known methods can be used for anodic oxidation, it is preferable to use a self-ordering method or constant voltage treatment from the viewpoint of increasing the regularity of the micropore arrangement and ensuring the anisotropic conductivity of the structure. Here, the self-ordering method and constant voltage treatment for anodic oxidation can be performed in the same manner as the treatments described in paragraphs

[0056] to

[0108] and [Figure 3] of Japanese Patent Application Publication No. 2008-270158.

[0053] [Holding process] The method for manufacturing the structure may include a holding step. The holding step is a step of holding the structure for a total of 5 minutes or more at a voltage of 95% to 105% of a holding voltage selected from a range of 1V or more and less than 30% of the voltage used in the anodizing step, after the anodizing step described above. In other words, the holding step is a step of performing electrolytic treatment for a total of 5 minutes or more at a voltage of 95% to 105% of a holding voltage selected from a range of 1V or more and less than 30% of the voltage used in the anodizing step, after the anodizing step described above. Here, "voltage in anodizing" refers to the voltage applied between the aluminum and the counter electrode. For example, if the electrolysis time for anodizing is 30 minutes, it refers to the average value of the voltage maintained during those 30 minutes.

[0054] From the viewpoint of controlling the thickness of the barrier layer to an appropriate thickness relative to the sidewall thickness of the anodic oxide film, that is, the depth of the pores, it is preferable that the voltage in the holding process be 5% to 25% of the voltage in the anodizing process, and more preferably 5% to 20%.

[0055] Furthermore, for reasons of improved in-plane uniformity, the total holding time in the holding process is preferably 5 minutes or more and 20 minutes or less, more preferably 5 minutes or more and 15 minutes or less, and even more preferably 5 minutes or more and 10 minutes or less. Furthermore, the holding time in the holding process may be 5 minutes or more in total, but it is preferable that it be 5 minutes or more continuously.

[0056] Furthermore, the voltage in the holding process may be set by continuously or stepwise decreasing it from the voltage in the anodizing process to the voltage in the holding process. However, for the reason that in-plane uniformity is further improved, it is preferable to set the voltage to 95% to 105% of the holding voltage within 1 second after the completion of the anodizing process.

[0057] The holding step described above can also be performed in conjunction with the anodic oxidation process by, for example, lowering the electrolytic potential at the end of the anodic oxidation process. The holding process described above can employ the same electrolyte and processing conditions as the conventionally known anodic oxidation treatment described above, except for the electrolytic potential. In particular, when the holding process and the anodizing process are performed consecutively, it is preferable to use the same electrolyte solution for both processes.

[0058] In an anodic oxide film having multiple micropores, a barrier layer (not shown) exists at the bottom of the micropores, as described above. The process includes a barrier layer removal step to remove this barrier layer.

[0059] [Barrier layer removal process] The barrier layer removal process involves removing the barrier layer of the anodic oxide film using, for example, an alkaline aqueous solution containing ions of metal M1, which has a higher hydrogen overpotential than aluminum. As a result of the barrier layer removal process described above, the barrier layer is removed, and a conductive layer made of metal M1 is formed at the bottom of the micropore. Here, hydrogen overvoltage refers to the voltage required for hydrogen to be generated. For example, the hydrogen overvoltage of aluminum (Al) is -1.66V (Journal of the Chemical Society of Japan, 1982, (8), pp. 1305-1313). Examples of metal M1 with a hydrogen overvoltage higher than that of aluminum, and their hydrogen overvoltage values, are shown below. <Metal M1 and hydrogen (1N H2SO4) overpotential> ·Platinum (Pt): 0.00V ·Gold (Au): 0.02V ·Silver (Ag): 0.08V Nickel (Ni): 0.21V ·Copper (Cu): 0.23V ·Tin (Sn): 0.53V Zinc (Zn): 0.70V

[0060] The pores 13 can also be formed by expanding the diameter of the micropores and removing the barrier layer. In this case, pore widening treatment is used to expand the diameter of the micropores. Pore widening treatment is a process in which the anodic oxide film is dissolved by immersing it in an acidic aqueous solution or an alkaline aqueous solution, thereby expanding the diameter of the micropores. For pore widening treatment, aqueous solutions of inorganic acids such as sulfuric acid, phosphoric acid, nitric acid, hydrochloric acid or mixtures thereof, or aqueous solutions of sodium hydroxide, potassium hydroxide and lithium hydroxide can be used. Furthermore, the barrier layer at the bottom of micropores can also be removed by pore-widening treatment. By using an aqueous sodium hydroxide solution in pore-widening treatment, the micropores are enlarged and the barrier layer is removed.

[0061] [Metal filling process] <Metals used in the metal filling process> In the metal filling process, the metal that is filled as a conductor inside the pores 13 and the metal that constitutes the metal layer have an electrical resistivity of 10 3 It is preferable that the material has a density of Ω·cm or less. Specific examples of the above-mentioned metals include gold (Au), silver (Ag), copper (Cu), aluminum (Al), magnesium (Mg), nickel (Ni), and zinc (Zn). Furthermore, from the viewpoint of electrical conductivity and formation by plating, copper (Cu), gold (Au), aluminum (Al), and nickel (Ni) are preferred as conductors, copper (Cu) and gold (Au) are more preferred, and copper (Cu) is even more preferred.

[0062] <Plating Method> For example, electroplating or electroless plating can be used as plating methods for filling the inside of pores with metal. In conventional electroplating methods used for coloring and other purposes, it is difficult to selectively deposit (grow) metal in pores with a high aspect ratio. This is thought to be because the deposited metal is consumed within the pores, and the plating does not grow even if electrolysis is performed for a certain period of time or longer. Therefore, when filling with metal using electroplating, it is necessary to include a pause time during pulse electrolysis or constant potential electrolysis. The pause time should be 10 seconds or more, preferably 30 to 60 seconds. Furthermore, it is desirable to apply ultrasound to promote agitation of the electrolyte.

[0063] Furthermore, the electrolysis voltage is usually 20V or less, preferably 10V or less, but it is preferable to measure the deposition potential of the target metal in the electrolyte used in advance and perform constant potential electrolysis within +1V of that potential. When performing constant potential electrolysis, it is desirable to use a device that can also perform cyclic voltammetry, and potentiostat devices from companies such as Solartron, BAS Corporation, Hokuto Denko Co., Ltd., and IVIUM can be used.

[0064] (Plating solution) Conventional known plating solutions can be used as the plating solution. Specifically, when precipitating copper, an aqueous solution of copper sulfate is generally used, with a copper sulfate concentration of 1 to 300 g / L being preferred, and more preferably 100 to 200 g / L. Furthermore, adding hydrochloric acid to the electrolyte can accelerate precipitation. In this case, a hydrochloric acid concentration of 10 to 20 g / L is preferred. Furthermore, when depositing gold, it is preferable to use a tetrachlorogold sulfuric acid solution and perform the plating by alternating current electrolysis.

[0065] The plating solution preferably contains a surfactant. Any known surfactant can be used. Sodium lauryl sulfate, which is conventionally known as a surfactant added to plating solutions, can be used as is. Both surfactants with ionic (cationic, anionic, or zwitter) and nonionic (nonionic) hydrophilic portions are usable, but cationic surfactants are preferable to avoid the generation of bubbles on the surface of the object to be plated. The concentration of the surfactant in the plating solution composition should preferably be 1% by mass or less. Furthermore, since electroless plating requires a long time to completely fill pores, which consist of pores with a high aspect ratio, it is preferable to fill the pores with metal using electroplating.

[0066] [Substrate removal process] The substrate removal step is a step in which the aforementioned aluminum substrate is removed after the metal filling step. The method for removing the aluminum substrate is not particularly limited, but methods such as removal by dissolution are preferred.

[0067] <Dissolving aluminum substrates> When dissolving the aluminum substrate as described above, it is preferable to use a processing solution that does not easily dissolve the anodic oxide film but easily dissolves aluminum. Such a processing solution preferably has a dissolution rate of 1 μm / min or more for aluminum, more preferably 3 μm / min or more, and even more preferably 5 μm / min or more. Similarly, the dissolution rate for the anodic oxide film preferably has a rate of 0.1 nm / min or less, more preferably 0.05 nm / min or less, and even more preferably 0.01 nm / min or less. Specifically, the treatment solution preferably contains at least one metal compound with a lower ionization tendency than aluminum, and has a pH (hydrogen ion concentration) of 4 or less or 8 or more, more preferably 3 or less or 9 or more, and even more preferably 2 or less or 10 or more.

[0068] The treatment solution for dissolving aluminum is preferably based on an acid or alkaline aqueous solution and contains, for example, compounds of manganese, zinc, chromium, iron, cadmium, cobalt, nickel, tin, lead, antimony, bismuth, copper, mercury, silver, palladium, platinum, or gold (e.g., chloroplatinic acid), their fluorides, or their chlorides. In particular, an acidic aqueous solution base is preferred, and blending with chlorides is preferred. In particular, treatment solutions obtained by blending hydrochloric acid aqueous solution with mercury chloride (hydrochloric acid / mercury chloride) and treatment solutions obtained by blending hydrochloric acid aqueous solution with copper chloride (hydrochloric acid / copper chloride) are preferred from the viewpoint of treatment latitude. The composition of the treatment solution used to dissolve aluminum is not particularly limited; for example, a bromine / methanol mixture, a bromine / ethanol mixture, and aqua regia can be used.

[0069] Furthermore, the acid or alkali concentration of the treatment solution used to dissolve the aluminum is preferably 0.01 to 10 mol / L, and more preferably 0.05 to 5 mol / L. Furthermore, the processing temperature using the aluminum dissolving solution is preferably -10°C to 80°C, and more preferably 0°C to 60°C.

[0070] Furthermore, the dissolution of the aluminum substrate described above is carried out by bringing the aluminum substrate after the plating process described above into contact with the processing solution described above. The method of contact is not particularly limited, and examples include immersion and spraying. Among these, the immersion method is preferred. The contact time at this time is preferably 10 seconds to 5 hours, and more preferably 1 minute to 3 hours.

[0071] Furthermore, a support may be provided on the insulating film 12, for example. It is preferable that the support has the same external shape as the insulating film 12. Attaching the support improves handling.

[0072] [Protrusion process] To partially remove the insulating film 12 as described above, for example, an acidic or alkaline aqueous solution that dissolves the insulating film 12, i.e., aluminum oxide (Al2O3), without dissolving the metal constituting the conductor 14 is used. The insulating film 12 is partially removed by bringing the acidic or alkaline aqueous solution into contact with the insulating film 12 having metal-filled pores 13. The method of bringing the acidic or alkaline aqueous solution into contact with the insulating film 12 is not particularly limited, and examples include immersion and spraying methods. Among these, the immersion method is preferred.

[0073] When using an aqueous acid solution, it is preferable to use an aqueous solution of an inorganic acid such as sulfuric acid, phosphoric acid, nitric acid, and hydrochloric acid, or a mixture thereof. Among these, an aqueous solution that does not contain chromic acid is preferred due to its superior safety. The concentration of the aqueous acid solution is preferably 1 to 10% by mass. The temperature of the aqueous acid solution is preferably 25 to 60°C. Furthermore, when using an alkaline aqueous solution, 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 aqueous phosphoric acid solution at 40°C, a 0.5 g / L aqueous sodium hydroxide solution at 30°C, or a 0.5 g / L aqueous potassium hydroxide solution at 30°C are preferably used.

[0074] The immersion time in the acidic or alkaline aqueous solution is preferably 8 to 120 minutes, more preferably 10 to 90 minutes, and even more preferably 15 to 60 minutes. Here, the immersion time refers to the sum of the individual immersion times when short immersion treatments are repeated. Washing treatments may be performed between each immersion treatment.

[0075] Furthermore, the metal 35, i.e., the conductor 14, is made to protrude from the surface 12a or back surface 12b of the insulating film 12 to the extent described above. It is preferable that the conductor 14 protrudes 30 nm to 500 nm from the surface 12a or back surface 12b of the insulating film 12, and it is more preferable that the upper limit is 100 nm or less. That is, the amount of protrusion of the protruding portion 14a from the surface 12a and the amount of protrusion of the conductor 14 from the back surface 12b of the protruding portion 14b are each preferably 30 nm to 500 nm, and it is more preferable that the upper limit is 100 nm or less.

[0076] When precisely controlling the height of the protruding portion of the conductor 14, it is preferable to fill the inside of the pore 13 with a conductive material such as metal, process the insulating film 12 and the end of the conductive material such as metal so that they are on the same plane, and then selectively remove the insulating film and the anodic oxide film. Furthermore, after the metal filling or after the extrusion process described above, a heat treatment may be applied to reduce the distortion within the conductor 14 that occurs during the metal filling process. The heat treatment is preferably carried out in a reducing atmosphere from the viewpoint of suppressing metal oxidation, and more preferably at an oxygen concentration of 20 Pa or less, and more preferably under vacuum. Here, vacuum refers to a state of space in which at least one of the gas density and atmospheric pressure is lower than that of the atmosphere. Furthermore, it is preferable to perform the heat treatment while applying stress to the insulating film 12 for the purpose of straightening.

[0077] [Process for forming the resin layer] For example, the process of forming the resin layer 20 can be performed using an inkjet method, a transfer method, a spray method, or a screen printing method. The inkjet method is preferred because it simplifies the process of forming the resin layer 20 by directly forming the resin layer 20 on the insulating film 12. The resin layer 20 can also be formed using, for example, a conventionally known surface protection tape application device and laminator. Furthermore, in the resin layer formation process, a resin layer is formed over the entire surface of the insulating film.

[0078] Specific examples of resin materials constituting the resin layer 20 include thermoplastic resins such as ethylene copolymers, polyamide resins, polyester resins, polyurethane resins, polyolefin resins, acrylic resins, acrylonitrile resins, and cellulose resins. From the viewpoint of transportability and ease of use as an anisotropic conductive member, the resin layer 20 is preferably a film with a peelable adhesive layer, and more preferably a film with an adhesive layer whose adhesiveness is weakened by heat treatment or ultraviolet exposure treatment, making it peelable.

[0079] The adhesive film mentioned above is not particularly limited and includes heat-release resin layers and ultraviolet (UV)-release resin layers, among others. In this context, heat-release resin layers are adhesive at room temperature and can be easily removed by simply heating them. These often utilize foamed microcapsules or similar materials. Furthermore, specific examples of adhesives that constitute the adhesive layer include rubber-based adhesives, acrylic-based adhesives, vinyl alkyl ether-based adhesives, silicone-based adhesives, polyester-based adhesives, polyamide-based adhesives, urethane-based adhesives, and styrene-diene block copolymer-based adhesives. Furthermore, UV-peelable resin layers have a UV-curable adhesive layer that loses its adhesive strength upon curing, making them peelable.

[0080] Examples of UV-curable adhesive layers include polymers in which carbon-carbon double bonds are introduced into the polymer side chains, main chain, or main chain ends of the base polymer. It is preferable that the base polymer having carbon-carbon double bonds uses an acrylic polymer as its basic framework. Furthermore, since acrylic polymers are crosslinked, polyfunctional monomers and the like can be included as copolymerization monomer components as needed. The base polymer having a carbon-carbon double bond can be used alone, but UV-curable monomers or oligomers can also be added. For UV-curable adhesive layers, it is preferable to use a photopolymerization initiator in combination to cure them by UV irradiation. Examples of photopolymerization initiators include benzoin ether compounds, ketal compounds, aromatic sulfonyl chloride compounds, photoactive oxime compounds, benzophenone compounds, thioxanthone compounds, camphorquinone, halogenated ketones, acylphosphinoxides, and acylphosphonates.

[0081] Examples of commercially available heat-release resin layers include Intellimar® tapes (manufactured by Nitta Corporation) such as WS5130C02 and WS5130C10; Somatac® TE series (manufactured by Somar Corporation); No.3198, No.3198LS, No.3198M, No.3198MS, No.3198H, No.3195, No.3196, No.3195M, No.3195MS, No.3195H, N Examples include the Riva Alpha® series (manufactured by Nitto Denko Corporation), such as o.3195HS, No.3195V, No.3195VS, No.319Y-4L, No.319Y-4LS, No.319Y-4M, No.319Y-4MS, No.319Y-4H, No.319Y-4HS, No.319Y-4LSC, No.31935MS, No.31935HS, No.3193M, and No.3193MS.

[0082] Commercially available UV-peelable resin layers include, for example, Elep Holder® (manufactured by Nitto Denko Corporation) products such as ELP DU-300, ELP DU-2385KS, ELP DU-2187G, ELP NBD-3190K, and ELP UE-2091J; Adwill D-210, Adwill D-203, Adwill D-202, Adwill D-175, and Adwill D-675 (all manufactured by Lintec Corporation); Sumilight® FLS N8000 series (manufactured by Sumitomo Bakelite Co., Ltd.); and UC353EP-110 (manufactured by Furukawa Electric Co., Ltd.). Other commercially available UV-peelable resin layers include, for example, backgrind tapes such as ELP RF-7232DB and ELP UB-5133D (both manufactured by Nitto Denko Corporation); SP-575B-150, SP-541B-205, SP-537T-160, and SP-537T-230 (all manufactured by Furukawa Electric Co., Ltd.). The aforementioned adhesive-coated film can be applied using a known surface protection tape application device and laminator.

[0083] In addition to the method described above, other methods for forming the resin layer 20 include, for example, applying a resin composition containing an antioxidant material, a polymer material, a solvent (e.g., methyl ethyl ketone), etc., as described later, to the front and back surfaces of the insulating film, drying it, and firing it if necessary. The method of applying the resin composition is not particularly limited, and conventionally known coating methods such as gravure coating, reverse coating, die coating, blade coating, roll coating, air knife coating, screen coating, bar coating, and curtain coating can be used. Furthermore, the drying method after application is not particularly limited. Examples include heating in the atmosphere at a temperature of 0°C to 100°C for several seconds to several tens of minutes, or heating under reduced pressure at a temperature of 0°C to 80°C for several minutes to several hours. Furthermore, the firing method after drying is not particularly limited as it varies depending on the polymer material used. However, when using polyimide resin, for example, a heating process at a temperature of 160°C to 240°C for 2 to 60 minutes may be used, and when using epoxy resin, for example, a heating process at a temperature of 30°C to 80°C for 2 to 60 minutes may be used.

[0084] The resin layer may also use the following composition. The composition of the resin layer will be described below. For example, the resin layer may contain polymer materials and may also contain antioxidant materials.

[0085] <Polymer materials> The polymer material included in the resin layer is not particularly limited, but it is preferably a thermosetting resin because it can efficiently fill the gap between the bonding target, such as a semiconductor chip or semiconductor wafer, and the structure, and because it improves the adhesion between the structure and the semiconductor chip or semiconductor wafer. Examples of thermosetting resins include epoxy resins, phenolic resins, polyimide resins, polyester resins, polyurethane resins, bismaleimide resins, melamine resins, and isocyanate resins. In particular, polyimide resin and / or epoxy resin are preferred because they offer improved insulation reliability and superior chemical resistance.

[0086] <Antioxidant materials> Specifically, antioxidant materials included in the resin layer include, for example, 1,2,3,4-tetrazol, 5-amino-1,2,3,4-tetrazol, 5-methyl-1,2,3,4-tetrazol, 1H-tetrazol-5-acetic acid, 1H-tetrazol-5-succinic acid, 1,2,3-triazole, 4-amino-1,2,3-triazole, 4,5-diamino-1,2,3-triazole, 4-carboxy-1H-1,2,3-triazole, 4,5-dicarboxy-1H-1,2,3-triazole, 1H-1,2,3-triazole-4-acetic acid, 4-carboxy-5-carboxymethyl-1H-1,2,3-triazole, 1,2, Examples include 4-triazole, 3-amino-1,2,4-triazole, 3,5-diamino-1,2,4-triazole, 3-carboxy-1,2,4-triazole, 3,5-dicarboxy-1,2,4-triazole, 1,2,4-triazole-3-acetic acid, 1H-benzotriazole, 1H-benzotriazole-5-carboxylic acid, benzofloxane, 2,1,3-benzothiazole, o-phenylenediamine, m-phenylenediamine, catechol, o-aminophenol, 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, melamine, and derivatives thereof. Of these, benzotriazole and its derivatives are preferred. Examples of benzotriazole derivatives include substituted benzotriazoles having a hydroxyl group, alkoxy group (e.g., methoxy group, ethoxy group, etc.), amino group, nitro group, alkyl group (e.g., methyl group, ethyl group, butyl group, etc.), halogen atom (e.g., fluorine, chlorine, bromine, iodine, etc.) on the benzene ring of benzotriazole. Also, substituted naphthalentriazoles and substituted naphthalenebistriazoles, which are similarly substituted to naphthalentriazoles and naphthalenebistriazoles, can also be mentioned.

[0087] Other examples of antioxidant materials included in the resin layer include common antioxidants such as higher fatty acids, higher fatty acid copper, phenol compounds, alkanolamines, hydroquinones, copper chelating agents, organic amines, and organic ammonium salts.

[0088] The content of the antioxidant material in the resin layer is not particularly limited, but from the viewpoint of corrosion protection, it is preferably 0.0001% by mass or more, and more preferably 0.001% by mass or more, relative to the total mass of the resin layer. Furthermore, in order to obtain appropriate electrical resistance in this bonding process, it is preferably 5.0% by mass or less, and more preferably 2.5% by mass or less.

[0089] <Migration prevention material> The resin layer preferably contains a migration prevention material because trapping metal ions, halogen ions, and metal ions originating from semiconductor chips and semiconductor wafers that may be contained in the resin layer further improves insulation reliability.

[0090] As migration prevention materials, for example, ion exchangers, specifically a mixture of cation exchangers and anion exchangers, or cation exchangers alone can be used. Here, the cation exchanger and the anion exchanger can be appropriately selected from, for example, the inorganic ion exchanger and the organic ion exchanger described later.

[0091] (Inorganic ion exchanger) Examples of inorganic ion exchangers include hydrated metal oxides, such as hydrated zirconium oxide. Examples of metals include zirconium, as well as iron, aluminum, tin, titanium, antimony, magnesium, beryllium, indium, chromium, and bismuth. Among these, zirconium-based ones contain the cation Cu 2+ , Al 3+ It has the ability to exchange with iron. Also, with iron-based substances, Ag + Cu 2+It has exchange capacity. Similarly, tin-based, titanium-based, and antimony-based materials are cation exchangers. On the other hand, bismuth-based substances have the anion Cl - It has the capability to exchange information. Furthermore, zirconium-based materials exhibit anion exchange capacity depending on the manufacturing conditions. The same applies to aluminum-based and tin-based materials. Other known inorganic ion exchangers include acidic salts of polyvalent metals, such as zirconium phosphate, heteropolyates, such as ammonium molybdate, and synthetic compounds of insoluble ferrocyanides. Some of these inorganic ion exchangers are already commercially available; for example, various grades are known under the trade name "IXE" by Toagosei Co., Ltd. In addition to synthetic materials, powders of natural zeolites or inorganic ion exchangers such as montmorillonite can also be used.

[0092] (Organic ion exchanger) Examples of organic ion exchangers include cross-linked polystyrene having sulfonic acid groups as cation exchangers, as well as those having carboxylic acid groups, phosphonic acid groups, or phosphinic acid groups. Furthermore, cross-linked polystyrene having a quaternary ammonium group, a quaternary phosphonium group, or a tertiary sulfonium group can be used as an anion exchanger.

[0093] These inorganic and organic ion exchangers should be selected appropriately, taking into account the type of cations and anions to be captured and their respective exchange capacities. Of course, it goes without saying that inorganic and organic ion exchangers can also be used in mixtures. Since the manufacturing process of electronic devices involves a heating process, inorganic ion exchangers are preferred.

[0094] Furthermore, from the viewpoint of mechanical strength, the mixing ratio of the ion exchanger to the polymer material described above is preferably 10% by mass or less of the ion exchanger, more preferably 5% by mass or less, and even more preferably 2.5% by mass or less. In addition, from the viewpoint of suppressing migration when a semiconductor chip or semiconductor wafer is joined to a structure, it is preferable that the ion exchanger be 0.01% by mass or more.

[0095] <Inorganic fillers> The resin layer preferably contains an inorganic filler. There are no particular restrictions on the inorganic filler, and it can be appropriately selected from known materials. Examples include kaolin, barium sulfate, barium titanate, silicon oxide powder, fine silicon oxide, vapor-phase silica, amorphous silica, crystalline silica, fused silica, spherical silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, mica, aluminum nitride, zirconium oxide, yttrium oxide, silicon carbide, and silicon nitride.

[0096] To prevent inorganic fillers from entering the spaces between the conduits and to further improve conductivity reliability, it is preferable that the average particle size of the inorganic filler is larger than the spacing between each conduit. The average particle size of the inorganic filler is preferably 30 nm to 10 μm, and more preferably 80 nm to 1 μm. Here, the average particle diameter is defined as the primary particle diameter measured by a laser diffraction scattering particle size analyzer (Microtrac MT3300 manufactured by Nikkiso Co., Ltd.).

[0097] <Hardening agent> The resin layer may contain a hardening agent. When a curing agent is included, it is more preferable to use a curing agent that is liquid at room temperature rather than a curing agent that is solid at room temperature, from the viewpoint of suppressing poor bonding with the surface shape of the semiconductor chip or semiconductor wafer to be connected. Here, "solid at room temperature" means a substance that is solid at 25°C, for example, a substance whose melting point is higher than 25°C.

[0098] Examples of curing agents include aromatic amines such as diaminodiphenylmethane and diaminodiphenylsulfone, aliphatic amines, imidazole derivatives such as 4-methylimidazole, dicyandiamide, tetramethylguanidine, thiourea-added amines, carboxylic acid anhydrides such as methylhexahydrophthalic anhydride, carboxylic acid hydrazides, carboxylic acid amides, polyphenol compounds, novolac resins, and polymer captans. From these curing agents, those that are liquid at 25°C can be appropriately selected and used. The curing agent may be used alone or in combination of two or more types.

[0099] The resin layer may contain various additives, such as dispersants, buffers, and viscosity modifiers, which are commonly added to resin insulating films of semiconductor packages, as long as they do not impair its properties.

[0100] In addition to those mentioned above, the resin layer can also contain, for example, a main composition comprising the acrylic polymer, acrylic monomer, and maleimide compound shown below.

[0101] <Acrylic polymer> The acrylic polymer is preferably a polymer containing constituent units derived from (meth)acrylate components, which does not result in excessive tackiness of the resin layer and is less likely to impair workability in the semiconductor mounting process. Examples of (meth)acrylate components that can be used include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, butoxyethyl (meth)acrylate, isoamyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, heptyl (meth)acrylate, octylheptyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, and lauryl (meth)acrylate.

[0102] In addition to the (meth)acrylate component described above, the acrylic polymer may further contain constituent units corresponding to other monomer components copolymerizable with the (meth)acrylate component described above. Examples of other monomer components include carboxyl group-containing monomers (e.g., (meth)acrylic acid), epoxy group-containing monomers (e.g., glycidyl (meth)acrylate), and nitrile group-containing monomers (e.g., acrylonitrile).

[0103] For example, as the acrylic polymer, one can be used that contains constituent units corresponding to butyl acrylate, methyl acrylate, acrylic acid, glycidyl methacrylate, and acrylonitrile.

[0104] Acrylic polymers can be obtained by polymerizing the above-mentioned (meth)acrylate component or other monomer components. Polymerization methods include solution polymerization, emulsion polymerization, bulk polymerization, and suspension polymerization. Examples of polymerization reactions for acrylic polymers include radical polymerization, cationic polymerization, anionic polymerization, living radical polymerization, living cationic polymerization, living anionic polymerization, and coordination polymerization.

[0105] The weight-average molecular weight (Mw) of the acrylic polymer is not particularly limited, but can be, for example, in the range of 100,000 to 1,200,000, or in the range of 500,000 to 1,000,000.

[0106] If we refer to the acrylic polymer, acrylic monomer, and maleimide compound in the resin layer as the main composition, the acrylic polymer is contained in an amount of 10 parts by mass or more and 60 parts by mass or less per 100 parts by mass of the main composition, preferably in an amount of 10 parts by mass or more and 45 parts by mass or less, and more preferably in an amount of 15 parts by mass or more and 40 parts by mass or less. If the acrylic polymer content is less than 10 parts by mass, it tends to be difficult to eliminate voids. Also, if the acrylic polymer content exceeds 60 parts by mass, it tends to be difficult to achieve low-pressure mounting and connectivity tends to deteriorate.

[0107] The acrylic polymer may be included in the main composition by itself as one type of acrylic polymer, or by using two or more types of acrylic polymers in combination. When using two or more types of acrylic polymers in combination, the total content of acrylic polymers in the resin layer is preferably within the range described above.

[0108] <Acrylic monomer> As acrylic monomers, monofunctional (meth)acrylates and (meth)acrylates with two or more functionalities can be used. Examples of acrylic monomers include isocyanuric acid EO-modified diacrylate (manufactured by Toagosei Co., Ltd.), isocyanuric acid EO-modified triacrylate (manufactured by Toagosei Co., Ltd.), dipentaerythritol and tetraacrylate (manufactured by Toagosei Co., Ltd.), 2-hydroxy-3-phenoxypropyl acrylate (manufactured by Toagosei Co., Ltd.), 9,9-bis[4-(2-acryloyloxyethoxy)phenyl]fluorene (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), tricyclodecanedimethanol diacrylate (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), ethoxylated bisphenol A diacrylate (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), and fluorene-based acrylates (e.g., product names: Ogusol EA0200, EA0300, manufactured by Osaka Gas Chemical Co., Ltd.). Among these acrylic monomers, fluorene-based acrylates are preferred when considering heat resistance and other factors.

[0109] The acrylic monomer in the resin layer is contained in an amount of 10 parts by mass or more and 60 parts by mass or less per 100 parts by mass of the main composition, preferably in an amount of 10 parts by mass or more and 55 parts by mass or less, and more preferably in an amount of 10 parts by mass or more and 50 parts by mass or less. If the acrylic monomer content is less than 10 parts by mass, connectivity tends to deteriorate. Also, if the acrylic monomer content exceeds 60 parts by mass, void removal tends to become difficult.

[0110] The acrylic monomer may be a single type of acrylic monomer, or two or more types of acrylic monomers may be used in combination. When two or more types of acrylic monomers are used in combination, the total content of acrylic monomers in the resin layer is preferably within the range described above.

[0111] <Maleimide compounds> As the maleimide compound, for example, a compound having two or more maleimide groups in one molecule can be used, and bismaleimide is preferred. Examples of maleimide compounds include 4-methyl-1,3-phenylenebismaleimide, 4,4-bismaleimidediphenylmethane, m-phenylenebismaleimide, bisphenol A diphenyl etherbismaleimide, and 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethanebismaleimide. Among these, aromatic bismaleimides are preferred, and in particular, considering the workability in the resin layer manufacturing process, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethanebismaleimide, which has good solvent solubility or flowability, is preferred.

[0112] The maleimide compound in the resin layer is contained in an amount of 20 parts by mass or more and 70 parts by mass or less, preferably in the range of 20 parts by mass or more and 60 parts by mass or less, and more preferably in the range of 20 parts by mass or more and 55 parts by mass or less, in 100 parts by mass of the main composition. If the maleimide compound content is less than 20 parts by mass, it tends to be difficult to achieve low-pressure mounting and connectivity tends to deteriorate. Furthermore, if the maleimide compound content exceeds 70 parts by mass, it tends to be difficult to achieve low-pressure mounting and void-free mounting.

[0113] The composition used for the resin layer may further contain other components besides those constituting the main composition described above, depending on the purpose. Examples of other components include phenolic compounds and fillers.

[0114] <Phenol compounds> Phenol compounds can be used as curing agents for the maleimide compounds described above, but the thermosetting reaction can be initiated even without containing phenol. As phenol compounds, for example, allylated bisphenols can be used, specifically 2,2'-diallylbisphenol A (product name: DABPA), 4,4'-(dimethylmethylene)bis[2-(2-propenyl)phenol], 4,4'-methylenebis[2-(2-propenyl)phenol], and 4,4'-(dimethylmethylene)bis[2-(2-propenyl)-6-methylphenol]. Among these, 2,2'-diallylbisphenol A is preferred.

[0115] When a phenolic compound is included, the amount of the phenolic compound can be, for example, 15 parts by mass or less per 100 parts by mass of the total of the acrylic polymer, acrylic monomer, maleimide compound, and phenolic compound. The phenolic compound may be a single type of phenolic compound, or two or more types of phenolic compounds may be included in combination. When two or more types of phenolic compounds are used in combination, the total amount of phenolic compounds in the resin layer is preferably within the range described above.

[0116] <Filler> As fillers, inorganic fillers, organic fillers, conductive particles, etc., can be used. In particular, from the viewpoint of reducing the coefficient of thermal expansion and improving reliability, it is preferable to use inorganic fillers (e.g., silica fillers).

[0117] When a filler is used, the filler content can be, for example, 30 parts by mass or less per 100 parts by mass of the total of the acrylic polymer, acrylic monomer, maleimide compound, and filler. The filler may be a single type of filler or two or more types of fillers may be used in combination. When two or more types of fillers are used in combination, the total filler content in the resin layer is preferably within the range described above.

[0118] [Method for forming a protective layer] For example, the formation process of the protective layer 22 can be performed using an inkjet method, a transfer method, a spray method, or a screen printing method. The inkjet method is preferred because it simplifies the formation process of the protective layer 22 by directly forming the protective layer 22 on the resin layer 20. Alternatively, the protective layer 22 can be formed using, for example, a conventionally known surface protection tape application device and laminator. Another method involves applying the above-mentioned protective layer-forming composition to the surface of a resin film, drying it, and firing it if necessary. The method of applying the protective layer-forming composition is not particularly limited, and conventionally known coating methods such as gravure coating, reverse coating, die coating, blade coating, roll coating, air knife coating, screen coating, bar coating, and curtain coating can be used.

[0119] [An example of a joint] Figure 13 is a schematic diagram showing an example of a joined body according to an embodiment of the present invention. The laminated device 40 shown in Figure 13 is an example of a joined body. The above-described structure 10 (see Figure 1) is used as an anisotropic conductive member 45 exhibiting anisotropic conductivity. The laminated device has a conductive member having a conductive portion and an anisotropic conductive member, and is joined by bringing the conductive portion and the protruding portion of the anisotropic conductive member into contact. The stacked device 40 shown in Figure 13 is formed by, for example, a semiconductor element 42, an anisotropic conductive member 45, and a semiconductor element 44 being joined in this order in the stacking direction Ds and electrically connected. In the anisotropic conductive member 45, the conductor 14 (see Figure 1) is arranged parallel to the stacking direction Ds and has conductivity in the stacking direction Ds. The bonded body 41 is formed by stacked semiconductor elements 42, anisotropic conductive member 45, and semiconductor element 44. The stacked device 40 is configured in which one semiconductor element 44 is bonded to one semiconductor element 42, but is not limited to this configuration. It may also be configured in which three semiconductor elements (not shown) are bonded via anisotropic conductive members 45. The stacked device is composed of three semiconductor elements and two anisotropic conductive members 45. The bonded body 41 is composed of the stacked semiconductor elements 42, anisotropic conductive members 45, semiconductor element 44, anisotropic conductive members 45, and semiconductor element 46. A semiconductor device is a conductive member that has a conductive portion. A conductive member that has a conductive portion is not limited to a semiconductor device, but may also be a substrate having electrodes. Examples of substrates having electrodes are wiring boards and interposers. The form of stacked devices is not particularly limited and includes, for example, SoC (System on a chip), SiP (System in Package), PoP (Package on Package), PiP (Package in Package), CSP (Chip Scale Package), and TSV (Through Silicon Via).

[0120] The stacked device 40 may have semiconductor elements that function as optical sensors. For example, semiconductor elements and a sensor chip (not shown) are stacked in the stacking direction Ds. The sensor chip may be provided with a lens. In this case, the semiconductor element is one on which a logic circuit is formed, and its configuration is not particularly limited as long as it can process the signals obtained from the sensor chip. The sensor chip has an optical sensor that detects light. The optical sensor is not particularly limited as long as it can detect light; for example, a CCD (Charge Coupled Device) image sensor or a CMOS (Complementary Metal Oxide Semiconductor) image sensor can be used. The lens's configuration is not particularly limited as long as it can focus light onto the sensor chip; for example, a type called a microlens can be used. Furthermore, when a conductive member having a conductive part is joined to a structure, it becomes a joined body. However, if the structure is joined to a semiconductor element having electrodes, and the semiconductor element is joined to the structure, the joined object becomes a device.

[0121] [Objects to be joined to a structure] As mentioned above, semiconductor elements are examples of objects to be joined to a structure, but they can also include objects having electrodes or element regions. Examples of objects having electrodes include semiconductor elements that perform a specific function on their own, but also objects where multiple elements come together to perform a specific function. Furthermore, it also includes objects that only transmit electrical signals, such as wiring members, and printed circuit boards are also included as objects having electrodes. An element region is a region in which various element configuration circuits and other components for functioning as an electronic element are formed. Examples of element regions include memory circuits such as flash memory, logic circuits such as microprocessors and FPGAs (field-programmable gate arrays), and communication modules such as wireless tags, as well as wiring. In addition to these, MEMS (Micro Electro Mechanical Systems) may also be formed in the element region. Examples of MEMS include sensors, actuators, and antennas. Sensors include various types such as acceleration, sound, and light sensors. As described above, the element region has element configuration circuits and the like formed within it, and electrodes (not shown) are provided to electrically connect the semiconductor chip to the outside. The element region has electrode regions where electrodes are formed. Note that the electrodes in the element region are, for example, Cu posts. Basically, the electrode region is the region that includes all the formed electrodes. However, if the electrodes are provided discretely, the region where each electrode is provided is also called an electrode region. The structure can take the form of individual components like semiconductor chips, semiconductor wafers, or even wiring layers. Furthermore, the structure is joined to the object to be joined, but the object to be joined is not particularly limited to the semiconductor elements mentioned above. For example, semiconductor elements in wafer form, semiconductor elements in chip form, printed circuit boards, and heat sinks can also be joined.

[0122] [Semiconductor devices] The semiconductor elements 42 and 44 mentioned above include, in addition to those described above, logic LSIs (Large Scale Integration) (e.g., ASICs (Application Specific Integrated Circuits), FPGAs (Field Programmable Gate Arrays), ASSPs (Application Specific Standard Products), etc.), microprocessors (e.g., CPUs (Central Processing Units), GPUs (Graphics Processing Units), etc.), memories (e.g., DRAM (Dynamic Random Access Memory), HMCs (Hybrid Memory Cubes), MRAMs (Magnetic RAMs) and PCMs (Phase-Change Memory), ReRAMs (Resistive RAMs), FeRAMs (Ferroelectric RAMs), flash memories (NAND (Not AND) flash), etc.), LEDs (Light Emitting Diodes) (e.g., microflash in mobile devices, automotive applications, projector light sources, LCD backlights, general lighting, etc.), power devices, and analog ICs (Integrated Circuits, (e.g., DC (Direct Current)-DC (Direct Current) converters, insulated gate bipolar transistors (IGBTs), etc.), MEMS (Micro Electro Mechanical Systems), (e.g., accelerometers, pressure sensors, oscillators, gyroscopes, etc.), wireless (e.g., GPS (Global Positioning System), FM (Frequency Modulation), NFC (Nearfield Communication), RFEM (RF Expansion Module), MMIC (Monolithic Microwave Integrated Circuit), WLAN (Wireless Local Area Network), etc.), discrete elements, BSI (Back Side Illumination), CIS (ContactExamples include image sensors, camera modules, CMOS (Complementary Metal Oxide Semiconductor), passive devices, SAW (Surface Acoustic Wave) filters, RF (Radio Frequency) filters, RFIPD (Radio Frequency Integrated Passive Devices), and BB (Broadband). A semiconductor element is, for example, a self-contained device that performs a specific function, such as a circuit or sensor, on its own. A semiconductor element may also have an interposer function. Furthermore, it is possible to stack multiple devices, such as logic chips with logic circuits and memory chips, on a device with an interposer function. In this case, the devices can be joined even if their electrode sizes differ. Furthermore, the stacked device is not limited to a one-to-many configuration in which multiple semiconductor elements are bonded to a single semiconductor element, but may also be a multiple-to-many configuration in which multiple semiconductor elements are bonded to multiple semiconductor elements.

[0123] The present invention is basically configured as described above. Although the structure of the present invention, the method for manufacturing an anisotropic conductive member, and the composition for forming a protective layer have been described in detail above, the present invention is not limited to the embodiments described above, and various improvements or modifications may be made without departing from the spirit of the present invention. [Examples]

[0124] The features of the present invention will be further described in detail below with reference to examples. The materials, reagents, amounts and proportions of substances, and procedures shown in the following examples can be modified as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the following examples. In this example, structures from Examples 1 to 7 and comparative examples 1 and 2 were fabricated. The degree of oxidation and chip adhesion were evaluated for the structures from Examples 1 to 7 and comparative examples 1 and 2. The evaluation results for the degree of oxidation and chip adhesion are shown in Table 1 below. The evaluation of the degree of oxidation and chip adhesion will be explained below.

[0125] (Degree of oxidation) After fabricating the structure, it was left in the atmosphere for one month. After this period, cross-sections of the structure were cut using FIB (Focused Ion Beam) to obtain ultrathin sections. The thickness of the oxide film in the protruding conductive parts of the ultrathin sections of the structure was measured using TEM (Transmission Electron Microscope). The degree of oxidation was evaluated according to the following evaluation criteria based on the thickness of the oxide film. Evaluation Criteria A: Oxide film thickness ≤ 5 nm B: 5nm < Oxide film thickness ≤ 10nm C: 10nm < Oxide film thickness ≤ 20nm D: 20nm < Oxide film thickness

[0126] (Adhesion of cutting chips) After the structure was divided into individual pieces by dicing, the degree of attachment of cutting chips before cleaning the individual pieces was examined. In the dicing process described above, a structure with a protective layer formed on it was first fixed onto a Si wafer, and then the Si wafer was fixed to the dicing apparatus with dicing tape. The structure was made to the size of 50mm x 50mm. A dicing saw DAD322 (product name) manufactured by DISCO Corporation was used as the dicing device. Next, the structure was processed using a dicing machine, with 20 lines at 2mm intervals, and then rotated 90° to process 11 lines at 4mm intervals. The processing was carried out to obtain 100 individual pieces measuring 2x4mm from the structure. For materials with a protective layer, the degree of debris adhesion to the resin layer after dicing and removal of the protective layer was examined using a scanning electron microscope (SEM) and visual inspection. For materials without a protective layer, the degree of debris adhesion to the resin layer after dicing was also examined using a scanning electron microscope (SEM) and visual inspection. To assess the degree of chip adhesion to the resin layer using SEM, 10 fields of view were observed at the same magnification, the number of chips was counted, and the total amount of chips across the 10 fields of view was calculated. The magnification was set to 20,000x. The degree of debris adhering to the resin layer was assessed by visual inspection, specifically by checking changes around the cutting line. The degree of chip adhesion was evaluated according to the following evaluation criteria. Evaluation Criteria A: SEM observation of 10 fields of view showed a total of 0 cutting chips, and no visible changes were observed around the cutting line. B: Observation of 10 fields of view using SEM showed that the total number of cutting chips was more than 0 but less than 10, and no changes were observed around the cutting line by visual inspection. C: SEM observation of 10 fields of view revealed a total of 10 or more cutting chips, and no visible changes were observed around the cutting line. D: Visual inspection revealed changes around the cutting line, which had turned white.

[0127] Examples 1 to 7 and Comparative Examples 1 and 2 will be described below. (Example 1) The structure of Example 1 will now be described. [Structure] <Fabrication of aluminum substrates> A molten metal was prepared using an aluminum alloy containing Si:0.06 mass%, Fe:0.30 mass%, Cu:0.005 mass%, Mn:0.001 mass%, Mg:0.001 mass%, Zn:0.001 mass%, and Ti:0.03 mass%, with the remainder being Al and unavoidable impurities. After molten metal treatment and filtration, an ingot with a thickness of 500 mm and a width of 1200 mm was produced by DC (Direct Chill) casting. Next, the surface was milled to an average thickness of 10 mm using a milling machine, then it was heated to 550°C for approximately 5 hours until the temperature dropped to 400°C, at which point it was rolled into a 2.7 mm thick sheet using a hot rolling mill. Furthermore, after heat treatment at 500°C using a continuous annealing machine, the material was cold-rolled to a thickness of 1.0 mm to obtain an aluminum substrate conforming to JIS 1050 material. After making this aluminum substrate 1030 mm wide, the following processes were performed on it.

[0128] <Electropolishing Treatment> The above-mentioned aluminum substrate was subjected to electrolytic polishing using an electrolytic polishing solution with the following composition, under the conditions of a voltage of 25V, a liquid temperature of 65°C, and a liquid flow rate of 3.0 m / min. A carbon electrode was used as the cathode, and a GP0110-30R (manufactured by Takasago Seisakusho Co., Ltd.) was used as the power supply. The electrolyte flow rate was measured using a vortex-type flow monitor FLM22-10PCW (manufactured by AS ONE Corporation).

[0129] (Electrolytic polishing liquid composition) • 85% by mass phosphoric acid (reagent manufactured by Wako Pure Chemical Industries, Ltd.) 660 mL ·Pure water 160mL ·Sulfuric acid 150mL • Ethylene glycol 30mL

[0130] <Anodizing process> Next, the aluminum substrate after electropolishing was subjected to anodizing treatment by a self-regulating method according to the procedure described in Japanese Patent Publication No. 2007-204802. After electropolishing, the aluminum substrate was subjected to pre-anodic oxidation treatment for 5 hours using a 0.50 mol / L oxalic acid electrolyte under the conditions of a voltage of 40 V, a liquid temperature of 16 °C, and a liquid flow rate of 3.0 m / min. Subsequently, the aluminum substrate, after pre-anodic oxidation treatment, was subjected to a defilm removal treatment by immersing it for 12 hours in a mixed aqueous solution of 0.2 mol / L chromic anhydride and 0.6 mol / L phosphoric acid (at a temperature of 50°C). Subsequently, a re-anodic oxidation treatment was performed for 3 hours and 45 minutes using a 0.50 mol / L oxalic acid electrolyte under the conditions of a voltage of 40 V, a liquid temperature of 16 °C, and a liquid flow rate of 3.0 m / min, to obtain an anodic oxide film with a thickness of 30 μm. For both the pre-anodic oxidation and re-anodic oxidation processes, a stainless steel electrode was used as the cathode, and a GP0110-30R power supply (manufactured by Takasago Seisakusho Co., Ltd.) was used. A NeoCool BD36 (manufactured by Yamato Scientific Co., Ltd.) was used as the cooling device, and a Pair Stirrer PS-100 (manufactured by EYELA Tokyo Rikakikai Co., Ltd.) was used as the stirring and heating device. Furthermore, the electrolyte flow rate was measured using a vortex flow monitor FLM22-10PCW (manufactured by AS ONE Corporation).

[0131] <Barrier layer removal process> Next, after the anodic oxidation process, an etching treatment was performed by immersing the substrate in an alkaline aqueous solution prepared by dissolving zinc oxide in a sodium hydroxide aqueous solution (50 g / l) to a concentration of 2000 ppm at 30°C for 150 seconds. This removed the barrier layer at the bottom of the micropores of the anodic oxide film and simultaneously deposited zinc on the exposed surface of the aluminum substrate. Furthermore, the average thickness of the anodic oxide film after the barrier layer removal process was 30 μm.

[0132] <Metal filling process> Next, an electroplating process was performed using an aluminum substrate as the cathode and platinum as the cathode. Specifically, metal-filled microstructures with nickel filling the inside of micropores were fabricated by using a copper plating solution with the following composition and applying constant-current electrolysis. Here, constant-current electrolysis was performed using a plating apparatus manufactured by Yamamoto Plating Testing Equipment Co., Ltd. and a power supply (HZ-3000) manufactured by Hokuto Denko Co., Ltd. After confirming the deposition potential by performing cyclic voltammetry in the plating solution, the treatment was carried out under the conditions shown below. (Composition and conditions of copper plating solution) ·Copper sulfate 100g / L ·Sulfuric acid 50g / L Hydrochloric acid 15g / L ·Temperature 25℃ ·Current density 10A / dm 2

[0133] The surface of the anodic oxide film after filling micropores with metal was observed using a field emission scanning electron microscope (FE-SEM). The presence or absence of metal sealing in 1000 micropores was observed, and the sealing rate (number of sealed micropores / 1000 micropores) was calculated to be 98%. Furthermore, after filling the micropores with metal, the anodic oxide film was machined in the thickness direction using a focused ion beam (FIB), and surface images (magnification 50,000x) of the cross-section were taken using a field emission scanning electron microscope (FE-SEM) to examine the inside of the micropores. It was found that in the sealed micropores, the inside was completely filled with metal.

[0134] <Substrate removal process> Next, the aluminum substrate was dissolved and removed by immersion in a mixed solution of copper chloride and hydrochloric acid, thereby fabricating a metal-filled microstructure with an average thickness of 30 μm. In the fabricated metal-filled microstructure, the diameter of the conduits is 60 nm, the pitch between conduits is 100 nm, and the density of conduits is 57.7 million particles / mm². 2 That was the case.

[0135] <Protrusion process> The metal-filled microstructure after the substrate removal process was immersed in an aqueous sodium hydroxide solution (concentration: 5% by mass, liquid temperature: 20°C), and the immersion time was adjusted so that the height of the protruding parts was 300 nm to selectively dissolve the surface of the aluminum anodic oxide film. Then, it was washed with water and dried to expose the copper cylinders that serve as conduits. Similarly, on the back surface of the aluminum anodized film, copper cylinders serving as conductive channels were made to protrude so that the height of the protrusions was 300 nm.

[0136] <Resin layer formation process> A resin layer with a thickness of 0.5 μm was formed on both sides of the anodic oxide film using resin. The resin layer was formed using a solution consisting of 20 g of thermosetting resin BST001A (manufactured by Namics Corporation) and 180 g of diethylene glycol diethyl ether.

[0137] <Protective layer formation process> A protective layer with a thickness of 1 μm was formed on the surface of the resin layer using PVA (Gosenol (trade name), Mitsubishi Chemical Corporation). The oxygen permeability coefficient of the protective layer is shown in Table 1 below. Note that the unit of the oxygen permeability coefficient in Table 1 below is m. 3 (STP)m·m -2 ·s -1 ·kPa -1 In this context, STP indicates the temperature and pressure under standard conditions, as described above. As shown in Table 1 below, the coating layer is a combination of the resin layer, intermediate layer, and protective layer. Even if there is no intermediate layer, the configuration consisting only of the resin layer and protective layer is still considered a coating layer. In Example 1, the protective layer was dissolved and removed using 40°C hot water as the solvent for the removal solution. The dissolution and removal time was 5 minutes.

[0138] (Example 2) Example 2 differed from Example 1 in that a protective layer with a thickness of 2 μm was formed using PVDC (polyvinylidene chloride), but otherwise it was the same as Example 1. Saran Resin F216 (trade name, Asahi Kasei Corporation) was used as the PVDC. In Example 2, a mixed solution of tetrahydrofuran (THF) and toluene (TOL) was used as the solvent for the removal solution to dissolve and remove the protective layer. The mixing ratio of tetrahydrofuran (THF) to toluene (TOL) was 2:1, and the temperature of the mixture was 25°C. The dissolution and removal time was 1 minute. (Example 3) Example 3 differs from Example 1 in that an intermediate layer is provided between the resin layer and the protective layer; otherwise, it is the same as Example 1. In Example 3, the intermediate layer was formed using fluororesin. For the intermediate layer, a fluoroethylene vinyl ether alternating copolymer (Lumiflon® LF200 (product name, manufactured by AGC Inc.)) was further diluted 10 times with xylene and formed on the resin layer by spin coating. In Example 3, the protective layer was dissolved and removed in the same manner as in Example 1.

[0139] (Example 4) Example 4 differs from Example 1 in that an intermediate layer is provided between the resin layer and the protective layer, and the protective layer is formed using PVDC. Otherwise, it is the same as Example 1. In Example 4, the intermediate layer was formed using PVA. The intermediate layer was formed in the same manner as the protective layer in Example 1. The protective layer was formed using Saran Resin F310 (trade name, Asahi Kasei Corporation). In Example 4, the protective layer was dissolved and removed using methyl ethyl ketone (MEK) at 25°C as the solvent for the removal solution. The dissolution and removal time was 1 minute. (Example 5) Example 5 differs from Example 1 in that an intermediate layer is provided between the resin layer and the protective layer, and the protective layer is made of epoxy resin; otherwise, it is the same as Example 1. In Example 5, the intermediate layer was formed using fluororesin. The intermediate layer was formed in the same manner as the protective layer in Example 3. The protective layer was formed to a thickness of 3 μm using Maxive (trade name, manufactured by Mitsubishi Gas Chemical Company, Inc.). In Example 5, the protective layer was removed by delamination, which is a physical peeling process.

[0140] (Example 6) Example 6 differs from Example 1 in that an intermediate layer is provided between the resin layer and the protective layer, and the protective layer is made of a laminate film; otherwise, it is the same as Example 1. In Example 6, a protective layer with a thickness of 1.4 μm was formed using a PVDC coated film (V-Barrier (registered trademark, manufactured by Mitsui Chemicals Tohcello Co., Ltd.)). The base layer of the PVDC coated film served as the intermediate layer. In Example 6, the protective layer was removed by delamination, which is a physical peeling method. In this case, the layer was peeled off between the base layer and the resin layer. (Example 7) Example 7 differs from Example 1 in that an intermediate layer is provided between the resin layer and the protective layer, and the protective layer is made of a laminate film; otherwise, it is the same as Example 1. In Example 7, a protective layer with a thickness of 1.2 μm was formed using a PVDC coated film (Bonel-K PC (Kojin Film & Chemicals Co., Ltd.)). The nylon film (base layer) of the PVDC coated film served as the intermediate layer. In Example 7, the protective layer was removed by delamination, which is a physical peeling method. In this case, the layer was peeled off between the base layer and the resin layer.

[0141] For Examples 1-7, the solubility in ethyl acetate and the adhesion between the protective layer and the layer directly beneath it were investigated. The results are shown in Table 1 below. In Examples 6 and 7, the protective layer was composed of a laminate film, and it was not possible to investigate the adhesion between the protective layer and the layer directly beneath it. Therefore, "Not Measurable" is indicated in the "Adhesion between Protective Layer and Substrate" column of Table 1 below. To assess the solubility in ethyl acetate, a mixed solution of ethyl acetate and hexane was prepared. The ratio of ethyl acetate to hexane in the mixed solution was 50:50 by mass. A protective layer was applied to a Si wafer to a thickness of 10 μm or more. The wafer was then immersed in a mixed solvent at 25°C for 5 seconds. After thoroughly washing off the solvent with ethanol, the wafer was rinsed with running water and dried. The change in thickness before and after treatment was measured using a non-contact film thickness meter, and the dissolution rate was calculated. This calculated dissolution rate indicates the solubility in ethyl acetate. To evaluate the adhesion between the protective layer and the layer directly beneath it, a 25mm wide tape was applied to the protective layer and peeled off at a 180° angle according to the method of JIS K 6854-2.

[0142] (Comparative Example 1) Comparative Example 1 differed from Example 1 in that it lacked a resin layer and a protective layer; otherwise, it was the same as Example 1. (Comparative Example 2) Comparative Example 2 differed from Example 1 in that it lacked a protective layer; otherwise, it was the same as Example 1.

[0143] [Table 1]

[0144] As shown in Table 1, Examples 1 to 7 showed better evaluation of the degree of chip adhesion after removal of the protective layer compared to Comparative Examples 1 and 2. In other words, less chip adhesion to the resin layer after removal of the protective layer. Furthermore, Examples 1-7 showed little oxidation and were of good quality. A lower oxygen permeability coefficient resulted in less oxidation. Comparative Example 1 lacked a resin layer, an intermediate layer, and a protective layer, and after cleaning, a large amount of cutting debris was attached to it. Comparative Example 2 lacked an intermediate layer and a protective layer, consisting only of a resin layer, and after cleaning, a considerable amount of cutting debris was attached to it. From Examples 1 and 2, it was found that PVA was a better protective layer than PVDC in terms of the degree of chip adhesion after removal of the protective layer. Examples 1 and 3 showed that providing an intermediate layer made of fluororesin resulted in a better evaluation of the degree of chip adhesion after removal of the protective layer. [Explanation of Symbols]

[0145] 10 Structure 11 Anisotropic conductive member 12 Insulating film 12a surface 12b Reverse side 13 pores 14 Conductors 14a, 14b protrusion 15 Anodized film 16 Anisotropic conductive layer 20 resin layer 20a, 22a surface 22 Protective layer 30 Aluminum substrate 30a surface 31 Barrier layer 32c bottom 32d surface 35 metal 35a metal layer 35b metal 36 Thermal peeling layer 37 Support 38 Dicing Tapes 40 Stacked Devices 41 Zygote 42, 44 Semiconductor devices 45 Anisotropic conductive member Ds stacking direction Dt thickness direction d average diameter H Height hm, hj average thickness ht thickness p Center distance

Claims

1. insulating film and Multiple conductors are provided, penetrating the insulating film in the thickness direction and electrically insulated from one another. A resin layer covering at least one surface in the thickness direction of the insulating film, It has a protective layer made of organic material, The resin layer is provided between the insulating film and the protective layer, and an intermediate layer containing a fluororesin is provided between the protective layer and the resin layer, with the protective layer being the outermost layer, in a structure.

2. The protective layer has oxygen-blocking properties, as described in claim 1.

3. The structure according to claim 1 or 2, wherein the protective layer has an adhesiveness of 2 to 10 N / 25 mm to other layers in contact with it.

4. The structure according to any one of claims 1 to 3, wherein the protective layer is dissolved and removed using a removal solution containing a solvent, and the dissolution rate of the protective layer by the removal solution at a temperature of 25°C is 1 μm / s or more.

5. The structure according to claim 4, wherein the removal solution contains ethyl acetate.

6. The structure according to any one of claims 1 to 5, wherein the conductor protrudes from at least one surface of the insulating film in the thickness direction.

7. The structure according to any one of claims 1 to 6, wherein the conductor protrudes from both sides of the insulating film in the thickness direction.

8. The structure according to any one of claims 1 to 7, wherein the insulating film is composed of an anodic oxide film.

9. A method for manufacturing an anisotropic conductive member using a structure comprising an insulating film, a plurality of conductors provided in a state where they penetrate the insulating film in the thickness direction and are electrically insulated from one another, a resin layer covering at least one surface of the insulating film in the thickness direction, and a protective layer made of organic material, wherein the resin layer is provided between the insulating film and the protective layer, and the protective layer is the outermost layer, An intermediate layer containing fluororesin is provided between the protective layer and the resin layer. A method for manufacturing an anisotropic conductive member, comprising a removal step of removing the protective layer.

10. The method for manufacturing an anisotropic conductive member according to claim 9, wherein the insulating film is composed of an anodic oxide film.

11. A protective layer forming composition comprising a resin, which constitutes the protective layer of the structure according to any one of claims 1 to 8.

Images