WO2019106809A1 - Sheet-form laminate, and laminated article - Google Patents

Abstract

Provided is a sheet-form laminate having exceptional magnetic characteristics and filling properties. A sheet-form laminate body 10 is provided with a metal foil 12, and a resin layer 11 laminated on the metal foil 12. The resin layer 11 includes a resin composition and a metallic-element-containing powder. The resin composition contains an epoxy resin, a phenol resin, and an acrylic resin. The expression MA/(ME + MP) equals at least 1/9 and less than 7/3, where ME is the mass of the epoxy resin, MP is the mass of the phenol resin, and MA is the mass of the acrylic resin.

Description

Sheet-like laminate and laminate

The present invention relates to a sheet-like laminate and a laminate.

A mixture of a metal powder and a resin composition is used, for example, as a raw material of an industrial product such as an inductor or a bonded magnet (see Patent Documents 1 and 2 below). Moreover, metal foil (for example, aluminum foil or copper foil) to which the adhesive agent was apply | coated is marketed as an electromagnetic wave shield.

JP 2004-31786 A Unexamined-Japanese-Patent No. 8-273916

A metal foil composed of a soft magnetic material such as an Fe-based alloy is used as an electromagnetic wave shield that shields an electromagnetic wave generated inside and outside the electronic device. In the manufacturing process of industrial products using such metal foils, for example, processing and handling of the metal foils such as molding, cutting, lamination, transfer, conveyance, etc. are required, so the mechanical strength and flexibility of the sheet Sex is required. Even when the metal foil itself is used as an industrial product such as an electromagnetic wave shield, mechanical strength and flexibility of the sheet are required to prevent breakage.

However, since the metal foil is brittle and does not have sufficient mechanical strength and flexibility, it is easily damaged during processing and handling. Therefore, contrary to conventional common sense, the present inventors laminated a resin layer on a metal foil used for an electromagnetic wave shield or the like to improve the sheet-like laminate having improved mechanical strength and flexibility of the metal foil. It succeeded in producing. However, since the magnetic properties (for example, relative permeability) of the resin layer itself are significantly inferior to the metal foil, the magnetic properties of the entire sheet-like laminate including the resin layer are also inferior to the magnetic properties of the metal foil alone. In order to solve this problem, the present inventors succeeded in improving the magnetic characteristics of the resin layer by adding metal element-containing powder such as an Fe-based alloy to the resin layer.

When manufacturing an industrial product using the sheet-like laminate as described above, the resin layer of the sheet-like laminate is crimped to the surface of another component for industrial product (hereinafter referred to as "base material"). Steps are assumed. Since the recess or cavity is formed in the substrate depending on the function and use of the substrate, it is desired that the resin layer of the sheet-like laminate be packed without defects (without gaps) inside the recess or cavity. . However, since the resin layer containing the metal element-containing powder is inferior in flexibility and fluidity as compared with the resin layer not containing the metal element-containing powder, it hardly adheres to the surface of the substrate without gaps, and filling in the recess or cavity It is hard to be done. For example, a void tends to be generated between the resin layer containing the metal element-containing powder and the inner wall of the recess or cavity. In the following, the property that the resin layer is likely to be filled into the recess or cavity formed in the substrate is referred to as "fillability". The filling property may be reworded as the property (embedding property) that the resin layer is easily embedded in the recess or cavity formed in the substrate.

An object of the present invention is to provide a sheet-like laminate excellent in magnetic properties and filling properties, and a laminate comprising the sheet-like laminate.

The sheet-like laminate according to one aspect of the present invention includes a metal foil and a resin layer laminated on the metal foil, the resin layer includes a resin composition and a powder containing a metal element, and the resin composition includes Containing epoxy resin, phenolic resin and acrylic resin, the mass of epoxy resin is represented as ME, the mass of phenolic resin is represented as MP, the mass of acrylic resin is represented as MA, MA / (ME + MP) Is 1/9 to less than 7/3.

In one aspect of the present invention, the polystyrene equivalent weight average molecular weight of the acrylic resin may be 500,000 or more and 1.5 million or less.

In one aspect of the present invention, the content of the metal element-containing powder in the resin layer may be 70% by volume or more and less than 100% by volume.

In one aspect of the invention, the metal foil may comprise a Fe-based alloy.

In one aspect of the present invention, the Fe-based alloy may contain Fe and Nb.

In one aspect of the present invention, the Fe-based alloy may contain Fe, Nb, Cu, Si and B.

In one aspect of the present invention, the metal foil may contain a Fe-based alloy crystal having a crystal grain size of 10 nm or less.

In one aspect of the present invention, the metal element-containing powder may contain an Fe-based alloy.

In one aspect of the present invention, the Fe-based alloy contained in the metal element-containing powder may contain Fe, Nb, Cu, Si and B.

In one aspect of the present invention, the metal element-containing powder may contain metal element-containing particles having a particle diameter of 10 nm or less.

In one aspect of the present invention, the resin layer may contain a semi-cured product of the resin composition.

The layered product concerning one side of the present invention is provided with the above-mentioned sheet-like layered product, and the substrate on which the sheet-like layered product was piled up.

In the laminate according to one aspect of the present invention, at least a part of the resin layer may be filled in a recess or a cavity formed in the substrate.

In the laminate according to one aspect of the present invention, the resin layer may include at least one of a semi-cured product of the resin composition and a cured product of the resin composition.

According to the present invention, a sheet-like laminate excellent in magnetic properties and filling properties, and a laminate comprising the sheet-like laminate are provided.

(A) in FIG. 1 is a schematic view of a cross section parallel to the stacking direction of the sheet-like laminate according to one embodiment of the present invention, and (b) in FIG. 1 corresponds to one embodiment of the present invention It is a schematic diagram of the cross section parallel to the lamination direction of the laminated body which concerns, and (c) in FIG. 1 is a schematic diagram of a cross section parallel to the lamination direction of the laminated body which concerns on one Embodiment of this invention. It is a schematic diagram of a cross section parallel to the lamination direction of the laminated body which concerns on one Embodiment of this invention.

Hereinafter, preferred embodiments of the present invention will be described with reference to the drawings as needed. However, the present invention is not limited to the following embodiment.

As shown in (a) in FIG. 1, the sheet-like laminate 10 according to the present embodiment includes a metal foil 12 and a resin layer 11 laminated on the metal foil 12. By laminating the resin layer 11 on the metal foil 12, the flexibility of the metal foil 12 is reinforced. In other words, the mechanical strength of the originally brittle metal foil 12 is reinforced by the resin layer 11. As a result, the sheet-like laminate 10 can have superior flexibility as compared to the metal foil 12 alone. The resin layer 11 provided in the sheet-like laminate 10 excellent in mechanical strength and flexibility is easily deformed according to the shape of the recess or cavity formed in the substrate, and the recess or recess formed in the substrate It is easy to be in close contact with the inside of the cavity without any gap. When the sheet-like laminate 10 is laminated on another member (for example, a base described later), the resin layer 11 functions as an adhesive. The resin layer 11 may cover at least a part or the whole of the surface of the metal foil 12. The resin layer 11 may be laminated directly on the surface of the metal foil 12. The thickness of the metal foil 12 is not particularly limited, but may be, for example, preferably 100 μm or less, more preferably 50 μm or less, and further preferably 20 μm or less. The thickness of the metal foil 12 may be 2 μm or more. The thickness of the resin layer 11 is not particularly limited, but may be, for example, 20 μm to 500 μm, or 20 μm to 200 μm. The dimensions of the metal foil 12 may be changed depending on the application of the sheet-like laminate 10 and is not particularly limited. For example, when the sheet-like laminate 10 is a square, the longitudinal width of the sheet-like laminate 10 may be 10 mm or more and 500 mm or less, and the width of the sheet-like laminate 10 may be 10 mm or more and 500 mm or less. The shape of the entire sheet-like laminate 10 may be changed depending on the application of the sheet-like laminate 10 and is not particularly limited. The shape of the sheet-like laminate 10 may be, for example, a polygon, a circle, or an ellipse. Each side of the sheet-like laminate 10 may be, for example, linear or curved.

The metal foil 12 is not particularly limited, but a group consisting of iron foil, iron alloy foil, copper foil, copper alloy foil, aluminum foil, aluminum alloy foil, silver foil, silver alloy foil, gold foil and gold alloy foil It may be at least one selected from the group consisting of The metal foil 12 is, for example, an Fe-Cr alloy, Fe-Ni-Cr alloy, Fe-Si alloy, Fe-Si-Al alloy, Fe-Ni alloy, Fe-Cu-Ni alloy, Fe -Co alloys, Fe-Cr-Si alloys, Nd-Fe-B alloys, Nd-Fe-B alloys, Sm-Co alloys, Sm-Fe-N alloys, Al-Ni-Co alloys And at least one selected from the group consisting of Cu-Sn alloys, Cu-Sn-P alloys, Cu-Ni alloys, and Cu-Be alloys. The metal foil 12 may be a soft magnetic material or a hard magnetic material.

The metal foil 12 may include an Fe-based alloy (that is, an alloy containing Fe). The metal foil 12 may be made of only an Fe-based alloy. The metal foil 12 may contain one or more Fe-based alloys. The metal foil 12 may include other components (for example, a metal or an alloy) in addition to the Fe-based alloy as long as the relative permeability of the metal foil 12 is not excessively reduced.

The Fe-based alloy may contain Fe and Nb. The Fe-based alloy may contain Fe, Nb, Cu, Si and B. In an Fe-based alloy containing Fe and Nb, or an Fe-based alloy containing Fe, Nb, Cu, Si and B, a high saturation magnetic flux density and a high relative magnetic permeability are easily compatible.

The Fe-based alloy may be represented, for example, by the following chemical formula (1). In the Fe-based alloy represented by the following chemical formula (1), a high saturation magnetic flux density and a high relative permeability are easily compatible.
(Fe _1-a M _a ) _{100-x-y-z-α-β-γ} Cu _x Si _y B _z M ' _α M'' _β X _γ (1)
In the chemical formula (1), M is one or both of Co and Ni. M ′ is at least one selected from the group consisting of Nb, Mo, Ta, Ti, Zr, Hf, V, Cr, Mn and W. M ′ ′ is at least one selected from the group consisting of Al, a platinum group element, Sc, a rare earth element, Au, Zn, Sn and Re. X is at least one selected from the group consisting of C, Ge, P, Ga, Sb, In, Be and As. a, x, y, z, α, β and γ are respectively 0 ≦ a ≦ 0.5, 0.1 ≦ x ≦ 3, 0 ≦ y ≦ 30, 0 ≦ z ≦ 25, 5 ≦ y + z ≦ 30, 0 ≦ α ≦ 20, 0 ≦ β ≦ 20 and 0 ≦ γ ≦ 20 are satisfied.

The metal foil 12 may contain a crystal of an Fe-based alloy having a crystal grain size of 10 nm or less. When the crystal grain size of the Fe-based alloy contained in the metal foil 12 is 10 nm or less, the whole of the metal foil 12 and the sheet-like laminate 10 is superior in magnetism to the metal foil made of the conventional Fe-based alloy. It can have properties (e.g. soft magnetic properties). For example, when the crystal grain size of the Fe-based alloy contained in the metal foil 12 is 10 nm or less, both a high saturation magnetic flux density and a high relative magnetic permeability can be achieved as compared with a conventional metal foil made of amorphous Fe-based alloy. It becomes possible. The crystal grain size (for example, the average value of the crystal grain sizes) of the crystals of the Fe-based alloy contained in the metal foil 12 may be 5 nm or more and 10 nm or less. The means for measuring the crystal grain size of the Fe-based alloy contained in the metal foil 12 is not particularly limited, but may be, for example, a scanning electron microscope (SEM) or a transmission electron microscope (TEM). The grain size of the Fe-based alloy contained in the metal foil 12 may be identified using Scherrer's equation based on powder X-ray diffraction.

The metal foil 12 containing crystals of an Fe-based alloy having a crystal grain size of 10 nm or less can be manufactured, for example, by the following method. A raw material of an Fe-based alloy having the same composition as the target metal foil 12 is produced as a raw material. For example, the material of the Fe-based alloy may be an alloy containing Fe as a main component and further containing Si, B, Cu and Nb as additive elements. By heating the material of the Fe-based alloy at a high temperature, a melt of the alloy is obtained. The melt is quenched and solidified at about 1,000,000 ° C./sec to obtain a thin strip made of an amorphous (non-crystalline) Fe-based alloy. The thin strip is heat treated at a temperature above the crystallization temperature of the Fe-based alloy. By the above method, the crystal grain size of the Fe-based alloy is refined, and the metal foil 12 containing crystals of the Fe-based alloy having a crystal grain size of 10 nm or less is obtained.

As a commercial item of the Fe-based alloy, for example, “FINEMET” (registered trademark) which is a nanocrystalline soft magnetic material manufactured by Hitachi Metals, Ltd. is preferable. The finemet contains, for example, a crystal containing Fe, Nb, Cu, Si and B and having a crystal grain size of 10 nm or less.

The resin layer 11 contains a resin composition and metal element-containing powder. The resin layer 11 may be composed of a resin composition and metal element-containing powder. The resin layer 11 containing the metal element-containing powder can have magnetic properties derived from the metal element-containing powder. The resin composition contains at least an epoxy resin, a phenol resin and an acrylic resin. Epoxy resins are relatively excellent in fluidity among thermosetting resins. Therefore, at least a part of the resin layer 11 containing the epoxy resin is easily softened or liquefied by heating at a temperature lower than the curing temperature, and easily flows into the inside of the recess or cavity formed in the substrate. , It is easy to be filled in a recess or a cavity without a gap (without a gap). Phenolic resins may, for example, function as curing agents for epoxy resins. Since the molecular weight of the acrylic resin is larger than that of the epoxy resin, the acrylic resin has higher viscosity than the epoxy resin. Therefore, the flexibility (flexibility) of the resin layer 11 is improved by the inclusion of the acrylic resin, and the flexibility of the sheet-like laminate 10 is also improved. The sheet-like laminate 10 excellent in flexibility is easily deformed according to the shape of the recess or the cavity formed in the base material, and is not easily broken with the deformation.

The mass of the epoxy resin contained in the resin composition is represented as ME. The mass of the phenolic resin contained in the resin composition is represented as MP. The mass of the acrylic resin contained in the resin composition is represented as MA. MA / (ME + MP) is at least 1/9 and less than 7/3. MA / (ME + MP) may be preferably 2/8 or more and 5/5 or less. When MA / (ME + MP) is less than 1/9, the flexibility (handling property) of the resin layer 11 is reduced, and the resin layer 11 after curing is fragile and easily broken. When MA / (ME + MP) is 7/3 or more, the fluidity of the resin layer 11 is reduced, and the filling property (embedding property) of the resin layer 11 is impaired. When MA / (ME + MP) is 7/3 or more, the magnetic properties (for example, relative permeability) of the resin layer 11 are also impaired.

The content of the metal element-containing powder in the resin layer 11 may be preferably 70% by volume or more and less than 100% by volume, more preferably 70% by volume or more and 85% by volume or less. When the content of the metal element-containing powder in the resin layer 11 is 70% by volume or more, the magnetic properties (for example, relative permeability) of the resin layer 11 and the flexibility of the resin layer 11 can be easily achieved. As a result, the excellent magnetic properties and the excellent flexibility of the sheet-like laminate 10 are easily compatible. If the content of the metal element-containing powder in the resin layer 11 is too small, the magnetic properties (for example, relative permeability) of the resin layer 11 derived from the metal element-containing powder are easily impaired, and the magnetic properties of the sheet laminate 10 as a whole Properties are also easily impaired. When the content of the metal element-containing powder in the resin layer 11 is too large, the flexibility of the resin layer 11 derived from the resin composition is easily impaired, and the flexibility of the sheet-like laminate 10 as a whole is also easily impaired. The content of the resin composition in the resin layer 11 is preferably more than 0% by volume and 30% by volume or less, more preferably 15% by volume or more and 30% by volume or less. However, even if the content of the metal element-containing powder in the resin layer 11 is out of the above range, the effect of the present invention is exhibited.

The content of the metal element-containing powder in the resin layer 11 is preferably 65% by mass or more and 90% by mass or less, more preferably 68% by mass or more, from the viewpoint of easily achieving both the magnetic properties and flexibility of the sheet-like laminate 10 It may be 84 mass% or less. For the same reason, the content of the resin composition in the resin layer 11 may be preferably 10% by mass to 35% by mass, and more preferably 16% by mass to 32% by mass.

The metal element-containing powder contained in the resin layer 11 may contain, for example, at least one selected from the group consisting of simple metals, alloys, and metal compounds. The metal element-containing powder may be made of, for example, at least one selected from the group consisting of simple metals, alloys, and metal compounds. The alloy may include at least one selected from the group consisting of solid solution, eutectic and intermetallic compounds. The alloy may be, for example, stainless steel (Fe-Cr based alloy, Fe-Ni-Cr based alloy, etc.). The metal compound may be, for example, an oxide such as ferrite. The metal element-containing powder may contain one metal element or a plurality of metal elements. The metal element contained in the metal element-containing powder may be, for example, a base metal element, a noble metal element, a transition metal element, or a rare earth element. The compound powder may contain one kind of metal element-containing powder, and may contain plural kinds of metal element-containing particles.

The metal element contained in the metal element-containing powder is, for example, iron (Fe), copper (Cu), titanium (Ti), manganese (Mn), cobalt (Co), nickel (Ni), zinc (Zn), aluminum ( Al), tin (Sn), chromium (Cr), barium (Ba), strontium (Sr), lead (Pb), silver (Ag), praseodymium (Pr), neodymium (Nd), samarium (Sm) and dysprosium ( It may be at least one selected from the group consisting of Dy). The metal element-containing powder may contain an element other than the metal element. The metal element-containing powder may contain, for example, oxygen (O), beryllium (Be), phosphorus (P), boron (B), or silicon (Si). The metal element-containing powder may be magnetic powder. The metal element-containing powder may be a soft magnetic alloy or a hard magnetic alloy. Metallic element-containing powders include, for example, Fe-Si alloys, Fe-Si-Al alloys (Sendust), Fe-Ni alloys (Permalloy), Fe-Cu-Ni alloys (Permalloy), Fe-Co alloys (Permendur), Fe-Cr-Si alloy (electromagnetic stainless steel), Nd-Fe-B alloy (rare earth magnet), Sm-Co alloy (rare earth magnet), Sm-Fe-N alloy (rare earth) The magnetic powder may be at least one selected from the group consisting of magnets), Al-Ni-Co alloys (Alnico magnets), and ferrites. The ferrite may be, for example, spinel ferrite, hexagonal ferrite, or garnet ferrite. The metal element-containing powder may be a copper alloy such as a Cu-Sn alloy, a Cu-Sn-P alloy, a Cu-Ni alloy, or a Cu-Be alloy. The metal-element-containing powder may contain one of the above-described elements and compositions, and may contain two or more of the above-described elements and compositions.

The metal element-containing powder may be Fe alone. The metal element-containing powder may be an Fe-based alloy. The Fe-based alloy may be, for example, an Fe-Si-Cr-based alloy or an Nd-Fe-B-based alloy. The metal element-containing powder may be at least one of amorphous iron powder and carbonyl iron powder. When the metal element-containing powder contains at least one of Fe and Fe-based alloy, it is easy to produce the resin layer 11 having a high space factor and excellent in magnetic characteristics. The metal element-containing powder may be a Fe amorphous alloy. Commercial products of Fe amorphous alloy powder include, for example, AW2-08, KUAMET-6B2 (all trade names of Epson Atomics Co., Ltd., DAP MS3, DAP MS7, DAP MSA10, DAP PB, DAP PC, DAP MKV 49). , DAP 410L, DAP 430L, DAP HYB series (all trade names of Daido Steel Co., Ltd.), MH45D, MH28D, MH25D, and MH20D (all trade names of Kobe Steel Co., Ltd.) At least one may be used.

The Fe-based alloy contained in the metal element-containing powder may preferably contain Fe and Nb, and more preferably may contain Fe, Nb, Cu, Si and B. When the metal element-containing powder contains an Fe-based alloy containing Fe and Nb, or Fe, Nb, Cu, Si and B, the saturation magnetic flux density and relative permeability of the resin layer 11 can be easily improved. As a result, the magnetic properties of the sheet-like laminate 10 can be easily improved.

The Fe-based alloy contained in the metal element-containing powder may be represented by the above chemical formula (1). When the metal element-containing powder contains the Fe-based alloy represented by the chemical formula (1), the saturation magnetic flux density and relative permeability of the resin layer 11 can be easily improved, and the magnetic properties of the sheet-like laminate 10 are also improved. Easy to do. As a result, the magnetic properties of the sheet-like laminate 10 can be easily improved.

The average particle size of the metal element-containing powder may be, for example, 1 μm or more and 300 μm or less. The median diameter D50 of the metal element-containing powder may be 1 μm or more and 90 μm or less. The metal element-containing powder may contain metal element-containing particles having a particle diameter of 10 nm or less. The metal element-containing powder may contain metal element-containing particles having a particle diameter of 5 nm or more and 10 nm or less. As the particle size of the metal element-containing particle is smaller, more metal element-containing particles are more easily densely packed in the resin layer 11, and the density of the entire resin layer 11 is easily improved. As a result, the saturation magnetic flux density and the relative magnetic permeability of the resin layer 11 are easily improved, and the decrease in mechanical strength and flexibility of the resin layer 11 caused by the inclusion of the metal element-containing powder is easily suppressed. Therefore, the magnetic properties and flexibility of the sheet-like laminate 10 can be easily improved. The particle size of the metal element-containing particle may be measured, for example, using a laser diffraction / scattering type particle size distribution measuring device. The metal element-containing particle having a particle diameter of 10 nm or less may be produced by using the above-mentioned metal foil containing a crystal of an Fe-based alloy having a crystal particle diameter of 10 nm or less as a raw material. For example, a metal element-containing particle having a particle diameter of 10 nm or less can be prepared by pulverizing the above-mentioned metal foil containing a crystal of an Fe-based alloy having a crystal particle size of 10 nm or less. From the viewpoint of improving the magnetic properties of the sheet-like laminate 10, each metal element-containing particle constituting the metal element-containing powder may contain a crystal of an Fe-based alloy having a crystal grain size of 10 nm or less.

The shape of the individual metal element-containing particles contained in the metal element-containing powder is not particularly limited. The individual metal element-containing particles may be, for example, spherical, flat, prismatic or needle-like. The resin layer 11 may contain plural types of metal element-containing particles having different average particle sizes. The composition of the metal foil 12 may be the same as the composition of the metal element-containing powder contained in the resin layer 11. The composition of the metal foil 12 may be different from the composition of the metal element-containing powder contained in the resin layer 11. The metal element-containing powder and the resin composition may be dispersed in the resin layer 11. That is, in the resin layer 11, the resin composition and the metal element-containing powder may be mixed uniformly.

The resin layer 11 may contain an uncured resin composition. When the resin layer 11 contains an uncured resin composition, it is easy to soften or liquefy a part of the resin composition in the resin layer 11 in a timely process of manufacturing an industrial product using the sheet-like laminate 10 The fluidity of the composition is likely to be improved. As a result, the resin layer 11 can be easily adhered to the surface of the substrate, and the resin layer 11 can be easily filled into the recess or cavity formed in the substrate. The resin layer 11 may contain a semi-cured product of the resin composition (B-stage resin composition). The resin layer 11 containing the semi-cured product of the resin composition is superior in mechanical strength to the case where the resin composition is not cured at all, and therefore, the filling of the sheet-like laminate 10 provided with such a resin layer 11 Improves the quality. When the resin layer 11 contains a semi-cured product of a resin composition, the resin layer 11 may be completely cured in a timely process of manufacturing an industrial product using the sheet-like laminate 10. The resin layer 11 may contain an uncured resin composition and a semi-cured product of the resin composition. The semi-cured product of the resin composition corresponds to the component excluding the metal element-containing powder among the solid content residue remaining after the resin layer 11 is dissolved in the ketone solvent (methyl ethyl ketone etc.).

The layered product concerning this embodiment may be provided with the above-mentioned sheet-like layered product, and a substrate on which a sheet-like layered product was piled up, and a resin layer may be in contact with a substrate. The resin layer may be in close contact with the substrate. The cured product of the resin layer may be in contact with the substrate. For example, as shown in (c) in FIG. 1, the laminate 30 according to one aspect of the present embodiment includes the first metal foil 31 and the second metal foil 33, the first metal foil 31 and the first metal foil 31 and The resin layer 32 sandwiched by the second metal foil 33 and the base 34 embedded in the resin layer 32 are provided. The laminate 30 is produced from the pair of sheet- like laminates 10 a and 10 b and the base material 34. The resin layer 32a of one sheet-like laminate 10a and the resin layer 32b of the other sheet-like laminate 10b face each other, and the base material 34 is sandwiched between the pair of resin layers 32a and 32b to form resin layers 32a and 32b. In close contact with each other. By heating the resin layers 32a and 32b at a temperature lower than the curing temperature of the resin composition, the resin compositions contained in the resin layers 32a and 32b soften or liquefy. As a result, the surfaces of the resin layers 32 a and 32 b are mixed and integrated, and the surface of the base material 34 is covered with the resin layer 32 without unevenness. Subsequently, the resin layer 32 may be cured. When the substrate 34 is a coil, for example, the resin layers 32a and 32b wrap the coil and are filled without gaps into the inside of the coil (the cavity surrounded by the coil). That is, the resin layers 32a and 32b become the core of the coil. The resin layer 32 included in the laminate 30 may include at least one of a semi-cured product of the resin composition and a cured product of the resin composition. That is, the resin layer 32 of the laminate 30 may not be completely cured, but may be completely cured.

When a laminate is formed from a pair of sheet-like laminates, the compositions of the pair of overlapping resin layers may be the same as or different from each other. The composition of the metal foil of one sheet-like laminate may be the same as the composition of the other metal foil. The composition of the metal foil of one sheet-like laminate may be different from the composition of the other metal foil.

As shown in FIG. 2, a laminate 40 according to another aspect of the present embodiment includes a sheet-like laminate 10 c and a base material 43 on which the sheet-like laminate 10 c is superimposed. At least a part of the resin layer 42 of the sheet-like laminate 10 c is filled in a recess formed on the surface of the base 43. Since the sheet-like laminate 10 c is excellent in the filling property, it is difficult to form a void in the recess of the base 43 filled with the resin layer 11.

As described above, the resin composition contained in the resin layer 11 is a component that contains at least an epoxy resin, a phenol resin and an acrylic resin, and can further contain a curing agent, a curing accelerator and an additive, and an organic solvent It may be the remaining component (nonvolatile component) excluding the metal element-containing powder. The additive is a component of the resin composition except the resin, the curing agent and the curing accelerator. The additive is, for example, a coupling agent or a flame retardant. The resin composition may contain a wax as an additive. When the resin composition contains a wax, the releasability of the resin layer 11 is improved, or the flowability of the heated resin layer 11 is improved. The wax may be, for example, at least one of fatty acids such as higher fatty acids and fatty acid esters.

The resin composition has a function as a binder (binder) of the metal element-containing granular powder, and imparts mechanical strength to the resin layer 11. For example, when the resin composition in the resin layer 11 is pressurized and brought into contact with a member (for example, the base 34), it is filled in between the metal element-containing powders and binds the metal element-containing powders to each other. By curing the resin composition in the resin layer 11, the cured product of the resin composition binds the metal element-containing powders more firmly, and the resin layer 11, the sheet-like laminate 10 and the laminates Mechanical strength is improved.

The resin composition contained in the resin layer 11 may further contain another thermosetting resin (for example, a polyamideimide resin) in addition to the epoxy resin and the phenol resin. The resin composition may further contain another thermoplastic resin in addition to the acrylic resin. The thermoplastic resin may be, for example, at least one selected from the group consisting of polyethylene, polypropylene, polystyrene, polyvinyl chloride, and polyethylene terephthalate. The resin composition may contain a silicone resin.

The epoxy resin may be, for example, a resin having two or more epoxy groups in one molecule. Among epoxy resins, crystalline epoxy resins are preferred. Although the molecular weight of the crystalline epoxy resin is relatively low, the crystalline epoxy resin has a relatively high melting point and is excellent in fluidity.

The epoxy resin is, for example, stilbene epoxy resin, diphenylmethane epoxy resin, sulfur atom-containing epoxy resin, novolak epoxy resin, dicyclopentadiene epoxy resin, salicylaldehyde epoxy resin, copolymerization of naphthols and phenols Type epoxy resin, epoxy compound of aralkyl type phenol resin, bisphenol type epoxy resin, glycidyl ether type epoxy resin of alcohol, glycidyl ether type epoxy resin of paraxylylene and / or metaxylylene modified phenolic resin, glycidyl ether type epoxy of terpene modified phenolic resin Resin, cyclopentadiene type epoxy resin, glycidyl ether type epoxy resin of polycyclic aromatic ring modified phenolic resin, naphthalene ring containing phenolic resin Sidyl ether epoxy resin, glycidyl ester epoxy resin, glycidyl or methyl glycidyl epoxy resin, alicyclic epoxy resin, halogenated phenol novolak epoxy resin, hydroquinone epoxy resin, trimethylolpropane epoxy resin, and olefin It may be at least one selected from the group consisting of linear aliphatic epoxy resins obtained by oxidizing a bond with a peracid such as peracetic acid.

From the viewpoint of excellent fluidity, the epoxy resin is selected from the group consisting of biphenyl epoxy resin, ortho cresol novolac epoxy resin, phenol novolac epoxy resin, salicylaldehyde novolac epoxy resin, and naphthol novolac epoxy resin. It may be at least one type.

The epoxy resin may be a crystalline epoxy resin. Although the molecular weight of the crystalline epoxy resin is relatively low, the crystalline epoxy resin has a relatively high melting point and is excellent in fluidity. The crystalline epoxy resin (highly crystalline epoxy resin) may be, for example, at least one selected from the group consisting of a hydroquinone epoxy resin, a bisphenol epoxy resin, a thioether epoxy resin, and a biphenyl epoxy resin. Commercial products of crystalline epoxy resin include, for example, Epiclon 860, Epiclon 1050, Epiclon 1055, Epiclon 2050, Epiclon 3050, Epiclon 4050, Epiclon 7050, Epiclon HM-091, Epiclon HM-101, Epiclon N-730A, Epiclon N -740, Epiclon N-770, Epiclon N-775, Epiclon N-865, Epiclon HP-4032D, Epiclon HP-7200L, Epiclon HP-7200, Epiclon HP-7200H, Epiclon HP-7200HH, Epiclon HP-7200HHH, Epiclon HP -4700, Epiclon HP-4710, Epiclon HP-4770, Epiclon HP-5000, Epiclon HP-6000, and N500P-2 (above, Product name made by IC Co., Ltd.), NC-3000, NC-3000-L, NC-3000-H, NC-3100, CER-3000-L, NC-2000-L, XD-1000, NC-7000-L , NC-7300-L, EPPN-501H, EPPN-501HY, EPPN-502H, EOCN-1020, EOCN-102S, EOCN-103S, EOCN-104S, CER-1020, EPPN-201, BREN-S, BREN-10S (Above, trade name of Nippon Kayaku Co., Ltd.), YX-4000, YX-4000H, YL4121H, and YX-8800 (all of which are trade names of Mitsubishi Chemical Co., Ltd.) You may

The resin composition may contain one of the above epoxy resins. The resin composition may contain a plurality of epoxy resins among the above.

The curing agent is classified into a curing agent which cures an epoxy resin in a range from low temperature to room temperature, and a heat curing type curing agent which cures an epoxy resin with heating. Examples of curing agents that cure epoxy resins in the range from low temperature to room temperature include aliphatic polyamines, polyaminoamides, polymercaptans and the like. The heat-curable curing agent is, for example, an aromatic polyamine, an acid anhydride, a phenol novolac resin, and dicyandiamide (DICY).

When a curing agent for curing the epoxy resin in the range from low temperature to room temperature is used, the glass transition point of the cured product of the epoxy resin is low, and the cured product of the epoxy resin tends to be soft. As a result, the resin layer 11 also tends to be soft. On the other hand, from the viewpoint of improving the heat resistance of the resin layer 11, the curing agent may preferably be a heat curing type curing agent, more preferably a phenol resin, and still more preferably a phenol novolac resin. In particular, by using a phenol novolac resin as a curing agent, a cured product of an epoxy resin having a high glass transition temperature can be easily obtained. As a result, the heat resistance and mechanical strength of the molded body can be easily improved.

The phenolic resin is, for example, an aralkyl type phenolic resin, a dicyclopentadiene type phenolic resin, a salicylaldehyde type phenolic resin, a novolak type phenolic resin, a copolymer type phenolic resin of benzaldehyde type phenol and an aralkyl type phenol, paraxylylene and / or metaxylylene modified From the group consisting of phenolic resin, melamine modified phenolic resin, terpene modified phenolic resin, dicyclopentadiene type naphthol resin, cyclopentadiene modified phenolic resin, polycyclic aromatic ring modified phenolic resin, biphenyl type phenolic resin, and triphenylmethane type phenolic resin It may be at least one selected. The phenolic resin may be a copolymer composed of two or more of the above. As a commercial product of a phenol resin, for example, Tamanor 758 manufactured by Arakawa Chemical Industries, Ltd., HP-850N manufactured by Hitachi Chemical Co., Ltd., or the like may be used.

The phenol novolac resin may be, for example, a resin obtained by condensation or cocondensation of phenols and / or naphthols with aldehydes under an acidic catalyst. The phenols constituting the phenol novolac resin may be, for example, at least one selected from the group consisting of phenol, cresol, xylenol, resorcin, catechol, bisphenol A, bisphenol F, phenylphenol and aminophenol. The naphthols constituting the phenol novolac resin may be, for example, at least one selected from the group consisting of α-naphthol, β-naphthol and dihydroxynaphthalene. The aldehydes constituting the phenol novolac resin may be, for example, at least one selected from the group consisting of formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde and salicylaldehyde.

The curing agent may be, for example, a compound having two phenolic hydroxyl groups in one molecule. The compound having two phenolic hydroxyl groups in one molecule may be, for example, at least one selected from the group consisting of resorcin, catechol, bisphenol A, bisphenol F, and substituted or unsubstituted biphenol.

The resin composition may contain one of the above phenolic resins. The resin composition may comprise a plurality of phenolic resins of the above. The resin composition may contain one of the above curing agents. The resin composition may contain a plurality of curing agents among the above.

The ratio of the active group (phenolic OH group) in the curing agent that reacts with the epoxy group in the epoxy resin is preferably 0.5 to 1.5 equivalents, more preferably one equivalent to the epoxy group in the epoxy resin. May be 0.9 to 1.4 equivalents, more preferably 1.0 to 1.2 equivalents. When the ratio of active groups in the curing agent is less than 0.5 equivalent, the amount of OH per unit weight of the epoxy resin after curing decreases, and the curing rate of the resin composition (epoxy resin) decreases. If the ratio of active groups in the curing agent is less than 0.5 equivalent, the glass transition temperature of the resulting cured product may be lowered, or a sufficient elastic modulus of the cured product may not be obtained. On the other hand, when the ratio of active groups in the curing agent exceeds 1.5 equivalents, the mechanical strength after curing of the resin layer 11 tends to decrease. However, even if the ratio of the active group in the curing agent is outside the above range, the effect according to the present invention can be obtained.

The acrylic resin is a polymer or copolymer having at least one of a structural unit derived from acrylic acid (acrylic monomer) and a structural unit derived from methacrylic acid (methacrylic monomer). The acrylic resin may be formed, for example, by radical polymerization or living polymerization. From the viewpoint of improving the flexibility (flexibility) of the sheet-like laminate 10, the polystyrene equivalent weight average molecular weight of the acrylic resin is preferably 500,000 to 1,500,000, and more preferably 600,000 to 1,000,000. You may The acrylic monomer may be, for example, at least one selected from the group consisting of acrylonitrile, ethyl acrylate, and butyl acrylate. The methacrylic monomer may be, for example, glycidyl methacrylate. The acrylic resin may have a glycidyl group. The resin composition may include one of the above acrylic resins, and the resin composition may include a plurality of the above acrylic resins.

The curing accelerator is not limited as long as it is, for example, a composition that reacts with the epoxy resin to accelerate the curing of the epoxy resin. The resin composition may comprise one type of curing accelerator. The resin composition may be provided with a plurality of curing accelerators. When the resin composition contains a curing accelerator, the moldability and releasability of the resin layer 11 can be easily improved. In addition, the resin composition contains a curing accelerator to improve the mechanical strength of a laminate (for example, an electronic component) manufactured using the sheet-like laminate 10, or in a high temperature / high humidity environment. The storage stability of the resin layer 11 is improved. The curing accelerator may be, for example, an alkyl group-substituted imidazole or an imidazole such as benzimidazole. Examples of commercially available imidazole-based curing accelerators include 2MZ-H, C11Z, C17Z, 1,2DMZ, 2E4MZ, 2PZ-PW, 2P4MZ, 1B2MZ, 1B2PZ, 2MZ-CN, C11Z-CN, 2E4MZ-CN and 2PZ At least one selected from the group consisting of -CN, C11Z-CNS, 2P4MHZ, TPZ, and SFZ (all trade names of Shikoku Kasei Kogyo Co., Ltd.) may be used. Among these, curing agents having a long chain alkyl group are preferable, and, for example, C11Z-CN (1-cyanoethyl-2-undecylimidazole) is preferable.

The compounding quantity of a hardening accelerator should just be an quantity which the hardening acceleration effect is acquired, and is not specifically limited. However, from the viewpoint of improving the curability and fluidity of the resin composition during moisture absorption, the compounding amount of the curing accelerator is preferably 0.1 to 30 parts by mass, relative to 100 parts by mass of the epoxy resin. Preferably, it may be 1 to 15 parts by mass. It is preferable that content of a hardening accelerator is 0.001 mass part or more and 5 mass parts or less with respect to the sum total of the mass of an epoxy resin and a hardening agent (for example, phenol resin). When the compounding quantity of a hardening accelerator is less than 0.1 mass part, sufficient hardening acceleration effect is hard to be acquired. When the compounding quantity of a hardening accelerator exceeds 30 mass parts, the storage stability of the resin layer 11 falls easily. However, even if the compounding amount and content of the curing accelerator are out of the above range, the effects according to the present invention can be obtained.

The coupling agent improves the adhesion between the resin composition and the metal element-containing powder, and improves the flexibility and mechanical strength of each of the resin layer 11 and the sheet-like laminate 10. The coupling agent may be, for example, at least one selected from the group consisting of silane compounds (silane coupling agents), titanium compounds, aluminum compounds (aluminum chelates), and aluminum / zirconium compounds. The silane coupling agent may be, for example, at least one selected from the group consisting of epoxysilane, mercaptosilane, aminosilane, alkylsilane, ureidosilane, acid anhydride silane and vinylsilane. In particular, aminophenyl-based silane coupling agents are preferred. The compound powder may include one of the above coupling agents, and may include two or more of the above coupling agents.

The resin composition may contain a flame retardant because of the environmental safety, recyclability, moldability and low cost of the resin layer 11. The flame retardant is, for example, at least one selected from the group consisting of bromine flame retardants, stalk flame retardants, hydrated metal compound flame retardants, silicone flame retardants, nitrogen containing compounds, hindered amine compounds, organic metal compounds and aromatic engineering plastics It may be. The compound powder may include one of the above-described flame retardants, and may include a plurality of the above-described flame retardants.

The application of the sheet-like laminate 10 is not limited. Depending on the composition of the metal foil 12, the composition of each of the metal element-containing powder resin compositions contained in the resin layer 11, and the combination thereof, various physical properties such as electromagnetic properties or thermal conductivity of the sheet-like laminate 10 It is controlled freely. Therefore, the sheet-like laminate 10 can be used for various industrial products or their materials. Industrial products manufactured using the sheet-like laminate 10 may be, for example, automobile-related equipment, medical equipment, electronic equipment, electrical equipment, information communication equipment, home appliances, audio equipment, and general industrial equipment. For example, when the resin layer 11 contains soft magnetic powder such as an Fe-based alloy or ferrite as the metal element-containing powder, the sheet-like laminate 10 may be used as a material of an inductor (for example, an EMI filter) or a transformer. When the resin layer 11 contains a permanent magnet as the metal element-containing powder, the sheet-like laminate 10 may be used as a material of a bond magnet. When the resin layer 11 contains iron and copper as the metal element-containing powder, the sheet-like laminate 10 may be used as an electromagnetic wave shield.

The manufacturing method of a sheet-like layered product may comprise the 1st process and the 2nd process. The method for producing a sheet-like laminate may further include a third step following the second step, as necessary. Below, the detail of each process is demonstrated.

In the first step, a paste is prepared by uniformly mixing the above-mentioned resin composition, metal element-containing powder and organic solvent. In other words, a paste is prepared by mixing the above-mentioned resin composition, metal element-containing powder and an organic solvent. The paste may contain a curing agent and a curing accelerator. The paste may contain additives such as a silane coupling agent and a flame retardant. The organic solvent is not particularly limited as long as it is a liquid that dissolves the components of the resin layer described above. The organic solvent may be, for example, at least one selected from the group consisting of acetone, methyl ethyl ketone, methyl isobutyl ketone, benzene, toluene, carbitol acetate, butyl carbitol acetate, cyclohexanone and xylene. From the viewpoint of workability, the organic solvent is preferably liquid at normal temperature, and the boiling point of the organic solvent is preferably 60 ° C. or more and 150 ° C. or less.

In the second step, the paste is applied to the surface of the metal foil. Then, the paste applied to the metal foil is dried to remove the organic solvent, thereby forming a B-stage resin layer on the surface of the metal foil. The B-stage resin layer may be rephrased as a resin layer containing a semi-cured product of the resin composition. A laminate including a B-stage resin layer and a metal foil on which the resin layer is laminated may be used as a finished product of a sheet-like laminate. The paste application method may be, for example, a bar coater, a comma coater, or a dip coater.

The drying temperature of the paste applied to the substrate may be appropriately adjusted according to the type of the organic solvent. The drying temperature may be, for example, 60 ° C. or more and 160 ° C. or less, preferably 70 ° C. or more and 140 ° C. or less, and more preferably 80 ° C. or more and 130 ° C. or less. When the drying temperature is less than 60 ° C., drying takes a long time. When the drying temperature is less than 60 ° C., the organic solvent remains in the resin layer, the mechanical strength of the resin layer is impaired, wrinkles occur in the resin layer, or voids occur in the third step. On the other hand, when the drying temperature exceeds 160 ° C., voids are generated in the second step due to rapid volatilization of the organic solvent, or curing of the resin composition proceeds too much.

In the third step, the resin layer (resin layer of B-stage) may be further cured by heat treatment to obtain a resin layer of C-stage. The C-stage resin layer may be rephrased as a resin layer containing a cured product of a resin composition. A sheet-like laminate having a C-stage resin layer may be used as a finished product. The temperature of the heat treatment may be a temperature at which the resin composition in the resin layer is sufficiently cured. The temperature of the heat treatment may be, for example, preferably 150 ° C. or more and 300 ° C. or less, more preferably 175 ° C. or more and 250 ° C. or less. In order to suppress the oxidation of the metal element-containing powder in the resin layer, the heat treatment is preferably performed in an inert atmosphere. When the heat treatment temperature exceeds 300 ° C., the metal element-containing powder is oxidized or the cured resin product is degraded by a trace amount of oxygen inevitably contained in the atmosphere of the heat treatment. In order to cure the resin composition sufficiently while suppressing the oxidation of the metal element-containing powder and the deterioration of the cured resin, the holding time of the heat treatment temperature is preferably several minutes to 4 hours, more preferably 5 minutes. It may be one hour or less.

As mentioned above, although the suitable embodiment of the present invention was described, the present invention is not limited to the above-mentioned embodiment.

For example, the sheet-like laminate may include a pair of metal foils and a resin layer sandwiched between the pair of metal foils. That is, metal foils may be laminated on both surfaces of the resin layer.

By directly laminating the resin layer of one sheet-like laminate on the resin layer of another sheet-like laminate, a laminate 20 as shown in (b) in FIG. 1 may be produced. The laminate 20 includes a first metal foil 23, a resin layer 22 laminated on the first metal foil 23, and a second metal foil 21 laminated on the resin layer 22. The resin layer 22 may contain a semi-cured product of the resin composition, and may contain a cured product of the resin composition.

Hereinafter, the present invention will be described in more detail by way of examples and comparative examples, but the present invention is not limited by these examples.

Example 1
219.6 g of cyclohexanone solution of acrylic resin, 39.84 g of methyl ethyl ketone solution of epoxy resin, 17.32 g of methyl ethyl ketone solution of phenol novolac resin, 2.00 g of methyl ethyl ketone solution of curing accelerator and 4.5 g of silane coupling agent are measured. Ingredients were placed in a 650 ml ointment container.

As the acrylic resin, “HTR-860-P3” manufactured by Nagase ChemteX Co., Ltd. was used. The NV (nonvolatile content) of the cyclohexanone solution of the acrylic resin was 12.5% by mass. The polystyrene equivalent weight average molecular weight of the acrylic resin was 500,000.

As the epoxy resin, “NC3000-H” manufactured by Nippon Kayaku Co., Ltd. was used. The NV (nonvolatile content) of the methyl ethyl ketone solution of the epoxy resin was 50.2% by mass.

As a phenol novolac resin (hardening agent), "HP-850N" manufactured by Hitachi Chemical Co., Ltd. was used. The NV (nonvolatile content) of the methyl ethyl ketone solution of phenol novolac resin was 43.0% by mass.

As a curing accelerator, “2PZ-CN” manufactured by Shikoku Kasei Kogyo Co., Ltd. was used. The NV (nonvolatile content) of the methyl ethyl ketone solution of the curing accelerator was 10% by mass.

As a silane coupling agent, “KBM-573” manufactured by Shin-Etsu Chemical Co., Ltd. was used.

The resin composition varnish was obtained by stirring and mixing all the raw materials in an ointment container with a revolution stirrer. As a revolution-revolution stirrer, "ARE-500" made by Shinky Co., Ltd. was used. In the stirring and mixing process, the revolution speed of the revolution / revolution stirrer was maintained at 1000 rpm for 5 minutes, and then the revolution speed was maintained at 2000 rpm for 1 minute.

8.85 g of the above resin composition varnish and 100 g of metal element-containing powder were weighed and placed in a 150 ml ointment container. The material in the ointment container was stirred at a revolution speed of 1000 rpm for 40 seconds using a revolution-revolution stirrer. The raw material in the ointment container was stirred a total of five times with a revolution-revolution stirrer to obtain a paste for a resin layer.

100 g of the metal element-containing powder was prepared by mixing 80 g of the first alloy powder with 20 g of the second alloy powder.

The first alloy powder was produced by grinding a metal foil of an Fe-based alloy. As a metal foil, a product "FINEMET" manufactured by Hitachi Metals, Ltd. was used. The first alloy powder was a powder of an Fe-based alloy containing Fe, Nb, Cu, Si and B. The particle diameter D50 of the first alloy powder was 25 μm. In Table 1 below, the first alloy powder is referred to as "FINEMET 1".

The second alloy powder was produced by grinding a metal foil of an Fe-based alloy. As a metal foil, a product "FINEMET" manufactured by Hitachi Metals, Ltd. was used. The second alloy powder was a powder of an Fe-based alloy containing Fe, Nb, Cu, Si and B. The particle diameter D50 of the second alloy powder was 4 μm. In Table 1 below, the second alloy powder is referred to as "FINEMET 2".

The metal foil was placed on a glass plate and the above paste was applied to the surface of the metal foil using a bar coater. The paste applied to the metal foil was dried at 110 ° C. for 12 minutes to obtain a sheet-like laminate of Example 1 including the metal foil and the resin layer laminated on the metal foil. The thickness of the resin layer after drying was 100 μm. A hot air circulating dryer made by Tabai Espec Corp. was used to dry the paste. The resin layer of Example 1 contained a semi-cured product of the above resin composition (B-stage resin composition).

As the metal foil, a product "FINEMET FT-3M" manufactured by Hitachi Metals, Ltd. was used. The thickness of the metal foil was 18 μm. This metal foil consisted of an Fe-based alloy containing Fe, Nb, Cu, Si and B. The metal foil of Example 1 was an amorphous metal foil before heat treatment (before crystallization).

The content (unit: mass%) of the metal element-containing powder in the resin layer of Example 1 is shown in Table 1 below. The content (unit: volume%) of the metal element-containing powder in the resin layer of Example 1 is shown in Table 1 below. MA / (ME + MP) of Example 1 is shown in Table 1 below. As described above, ME is the mass of the epoxy resin contained in the resin composition, MP is the mass of the phenolic resin contained in the resin composition, and MA is the acrylic resin contained in the resin composition Mass of The numerical values described in the column of each component in Tables 1 and 2 below are the relative mass (unit: g) of each component with respect to 100 g of metal powder. The numerical values described in the columns of acrylic resin, epoxy resin, phenol resin and curing accelerator in Tables 1 and 2 below are the mass of the solution of each component.

(Examples 2 to 11 and Comparative Example 1)
In the preparation of sheet-like laminates of Examples 2 to 11 and Comparative Example 1 respectively, acrylic resin, epoxy resin, phenol resin, curing accelerator shown in Table 1 or Table 2 below as components constituting the resin layer , A coupling agent and metal powder (metal element) were used. The mass of each component used for preparation of each of the resin layers of Examples 2 to 11 and Comparative Example 1 is shown in Table 1 or Table 2 below. The content (unit: mass%) of the metal element-containing powder in each of the resin layers of Examples 2 to 11 and Comparative Example 1 is shown in Table 1 or Table 2 below. The content (unit: volume%) of the metal element-containing powder in each of the resin layers of Examples 2 to 11 and Comparative Example 1 is shown in Table 1 or Table 2 below. In preparation of sheet-like laminates of Examples 2 to 11 and Comparative Example 1, metal foils shown in Table 1 or Table 2 below were used. The MA / (ME + MP) of each of Examples 2 to 11 and Comparative Example 1 are shown in Table 1 below.

“HTR-860-P3 ′” described in Tables 1 and 2 below is an acrylic resin manufactured by Nagase ChemteX Co., Ltd. The NV (nonvolatile content) of the cyclohexanone solution of HTR-860-P3 ′ was 12.5% by mass. The polystyrene equivalent weight average molecular weight of HTR-860-P3 'was 800,000.
“JER 828” described in Tables 1 and 2 below is a bisphenol A epoxy resin manufactured by Mitsubishi Chemical Corporation. The NV (nonvolatile content) of the methyl ethyl ketone solution of JER 828 was 60.2% by mass.
“YX4000” described in Tables 1 and 2 below is a biphenyl type epoxy resin manufactured by Mitsubishi Chemical Corporation. The NV (nonvolatile content) of the methyl ethyl ketone solution of YX4000 was 50.8% by mass.
“Type A” described in Tables 1 and 2 below is a powder average particle diameter of 2 μm) made of FeSiCr manufactured by Shinto Kogyo Co., Ltd.
“MT18SD-H” described in Tables 1 and 2 below is a copper foil manufactured by Mitsui Mining & Smelting Co., Ltd. (copper foil with carrier foil, thickness: 3 μm).
“3EC-M3-VLP” described in Tables 1 and 2 below is a copper foil manufactured by Mitsui Mining & Smelting Co., Ltd. (low-profile electrodeposited copper foil, thickness: 12 μm).
“MW-P-VSP” described in Tables 1 and 2 below is a copper foil (thickness: 18 μm) manufactured by Mitsui Mining & Smelting Co., Ltd.
“1085” described in Tables 1 and 2 below is an aluminum foil (thickness: 12 μm) manufactured by UACJ Co., Ltd.

Sheet-like laminates of Examples 2 to 11 and Comparative Example 1 were produced in the same manner as in Example 1 except for the above matters. In any of Examples 2 to 11 and Comparative Example 1, the resin layer of the sheet-like laminate contained a semi-cured product of the resin composition.

[Evaluation of fillability]
The filling properties of the sheet-like laminates of Examples 1 to 11 and Comparative Example 1 were individually evaluated by the following methods.

For the evaluation of the filling property, three types of copper-clad laminates (substrates) for printed wiring boards having different thicknesses of copper foil were used. As a substrate, a product "MCL" series manufactured by Hitachi Chemical Co., Ltd. was used. The thicknesses of the copper foils of the three types of substrates were 12 μm, 18 μm, and 35 μm. A so-called line-and-space linear pattern was formed on the copper foil of each substrate by etching the copper foil of each substrate. The width of each line (L) / space (S) formed on each substrate is 05 mm / 0.5 mm, 0.3 mm / 0.3 mm, 0.2 mm / 0.2 mm, and 0.1 mm / 0.1. It was 1 mm. The space located between the lines is a recess (groove), and the depth of the space is approximately equal to the thickness of each copper foil. The sheet-like laminate was disposed such that the resin layer of the sheet-like laminate directly overlapped with the linear pattern of the copper foil. Then, the sheet laminate was pressure-bonded to the surface of each substrate while heating at 180 ° C. for 30 minutes to form three types of laminates for each of Examples 1 to 11 and Comparative Example 1. Crimping was done by a vacuum press. The pressure applied to the sheet laminate was 5 MPa. Subsequently, each laminate was cut perpendicularly to the surface of the substrate to which the sheet-like laminate was pressure-bonded, and a cross section of each laminate was observed.

Similar to FIG. 2, in the cross section of any of the laminates of Examples 1 to 11, the resin layer of the sheet-like laminate was filled into the space (concave portion) of the linear pattern without any gap. On the other hand, in the cross section of the laminate of Comparative Example 1, the resin layer of the sheet-like laminate is not sufficiently filled in the space of the linear pattern, and a void is formed between the resin layer of the sheet-like laminate and the space of the linear pattern. Was formed.

[Evaluation of magnetic properties]
The relative magnetic permeability μ ′ of each of the resin layers of Examples 1 to 11 was individually measured by an impedance analyzer. The measurement results are shown in Table 1 or Table 2 below. For measurement of the relative magnetic permeability μ ′, a resin layer before being laminated to a metal foil was used. As a measuring device, a measuring device "F9049A" (trade name) manufactured by Keysight Technologies, Inc. was used. In the case of Comparative Example 1, since the mechanical strength of the resin layer itself was extremely low, the relative magnetic permeability μ ′ of the resin layer could not be measured.

The sheet-like laminate according to the present invention is excellent in magnetic properties and filling properties, and has high industrial value.

DESCRIPTION OF SYMBOLS 10, 10a, 10b, 10c ... Sheet-like laminated body, 12, 21, 23, 23, 33, 41 ... Metal foil, 11, 22, 32, 32, 32a, 32b, 42 ... Resin layer, 34, 43 ... Base material, 20, 30, 40 ... laminates.

Claims (14)

1. With metal foil,
   A resin layer laminated on the metal foil;
   Equipped with
   The resin layer contains a resin composition and metal element-containing powder,
   The resin composition contains an epoxy resin, a phenol resin and an acrylic resin,
   The mass of the epoxy resin is represented as ME,
   The mass of the phenolic resin is represented as MP,
   The mass of the acrylic resin is represented as MA,
   MA / (ME + MP) is at least 1/9 and less than 7/3,
   Sheet-like laminate.
2. The polystyrene equivalent weight average molecular weight of the acrylic resin is not less than 500,000 and not more than 1.5 million.
   The sheet-like laminate according to claim 1.
3. The content of the metal element-containing powder in the resin layer is 70% by volume or more and less than 100% by volume.
   The sheet-like laminate according to claim 1 or 2.
4. The metal foil contains an Fe-based alloy,
   The sheet-like laminate according to any one of claims 1 to 3.
5. The Fe-based alloy contains Fe and Nb.
   The sheet-like laminate according to claim 4.
6. The Fe-based alloy contains Fe, Nb, Cu, Si and B.
   The sheet-like laminate according to claim 4 or 5.
7. The metal foil contains crystals of the Fe-based alloy having a crystal grain size of 10 nm or less.
   A sheet-like laminate according to any one of claims 4 to 6.
8. The metal element-containing powder contains an Fe-based alloy,
   The sheet-like laminate according to any one of claims 1 to 7.
9. The Fe-based alloy contained in the metal element-containing powder contains Fe, Nb, Cu, Si and B.
   The sheet-like laminate according to claim 8.
10. The metal element-containing powder contains metal element-containing particles having a particle diameter of 10 nm or less.
    The sheet-like laminate according to claim 8 or 9.
11. The resin layer contains a semi-cured product of the resin composition,
    A sheet-like laminate according to any one of claims 1 to 10.
12. The sheet-like laminate according to any one of claims 1 to 11,
    A substrate on which the sheet-like laminate is stacked;
    Equipped with
    The resin layer is in contact with the substrate,
    Stacks.
13. At least a portion of the resin layer is filled in a recess or a cavity formed in the substrate,
    A laminate according to claim 12.
14. The resin layer contains at least one of a semi-cured product of the resin composition and a cured product of the resin composition.
    The laminate according to claim 12 or 13.

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