JP2022154716A - Electromagnetic shield laminate, manufacturing method of electromagnetic shield laminate, shield printed wiring board, manufacturing method of shield printed wiring board, semiconductor package, and electronic device - Google Patents

Abstract

To provide an electromagnetic shielding laminate or the like that is less susceptible to delamination when a shield printed wiring board is manufactured.SOLUTION: An electromagnetic shielding laminate according to an embodiment of the present invention includes a shield layer, and at least one of an adhesive layer and an insulating layer bonded to the shield layer via a compound α, and the compound α is one of a compound α1 having, in one molecule, a benzene ring, an alkoxysilyl group, and one or more groups selected from the group consisting of an azide group, an azidosulfonyl group, and a diazomethyl group, and a compound α2 obtained by hydrolytic condensation of a hydrolyzable silane compound containing the compound α1.SELECTED DRAWING: Figure 1

Description

The present invention relates to an electromagnetic shield laminate, a method for manufacturing an electromagnetic shield laminate, a shield printed wiring board, a method for manufacturing a shield printed wiring board, a semiconductor package, and an electronic device.

2. Description of the Related Art Conventionally, electromagnetic wave shielding laminates have been attached to printed wiring boards such as flexible printed wiring boards (FPC) to shield electromagnetic waves from the outside.

An electromagnetic wave shield laminate usually has a configuration in which a conductive adhesive layer, a shield layer made of a metal thin film or the like, and an insulating layer are laminated in this order. By heat-pressing the electromagnetic wave shielding laminate while superposed on the printed wiring board, the electromagnetic wave shielding laminate is adhered to the printed wiring board by the conductive adhesive layer, and the shield printed wiring board is produced. After this bonding, the components are usually mounted on the printed wiring board by solder reflow. Also, printed wiring boards generally have a structure in which a printed circuit on a base film is covered with an insulating film.

When a shield printed wiring board is manufactured by heating the shield printed wiring board by hot pressing, solder reflow, or the like, gas is generated from the conductive adhesive layer of the electromagnetic wave shield laminate, the insulating film of the printed wiring board, and the like. Further, when the base film of the printed wiring board is made of a highly hygroscopic resin such as polyimide, the heat may generate water vapor from the base film. These volatile components generated from the conductive adhesive layer, the insulating film, the base film, etc. cannot smoothly pass through the shield layer, so they accumulate between the shield layer and the conductive adhesive layer. Therefore, if rapid heating is performed during the solder reflow process, etc., the volatile components that accumulate between the shield layer and the conductive adhesive layer will destroy the interlayer adhesion between the shield layer and the conductive adhesive layer, resulting in poor shielding performance. may decrease.

In order to solve such problems, Patent Literature 1 describes an electromagnetic wave shield laminate in which a shield layer (metal thin film) is provided with a plurality of openings to improve air permeability. Providing a plurality of openings in the shield layer allows volatile components to pass through the shield layer through the openings. Therefore, it is said that it is possible to prevent volatile components from accumulating between the shield layer and the conductive adhesive layer, and to prevent deterioration of the shielding performance due to destruction of interlayer adhesion.

WO2014/192494

In the electromagnetic wave shield laminate described in Patent Document 1, the strength of the shield layer is weak because the opening is formed in the shield layer. Therefore, when the electromagnetic wave shield laminate described in Patent Document 1 is used for a flexible printed wiring board, the following problems arise. Flexible printed wiring boards are repeatedly bent during use. Therefore, the electromagnetic shield laminate used for such a flexible printed wiring board and the shield layer constituting the electromagnetic shield laminate are also repeatedly bent. As described above, the strength of the shield layer of the electromagnetic wave shield laminate described in Patent Document 1 is weak, and therefore repeated bending may break the shield layer, resulting in a decrease in shield performance. Also, a semiconductor package or the like may be provided with a shield layer for shielding electromagnetic waves, and the adhesion between the shield layer and other layers such as an insulating layer is important.

The present invention has been made based on the circumstances as described above, and an object of the present invention is to provide an electromagnetic shielding laminate in which delamination is unlikely to occur when manufacturing a shield printed wiring board, and such an electromagnetic shielding laminate. It is an object of the present invention to provide a manufacturing method, a shield printed wiring board using such an electromagnetic wave shield laminate, a method for manufacturing a shield printed wiring board, a semiconductor package, and an electronic device.

One embodiment of the present invention comprises a shield layer and at least one of an adhesive layer and an insulating layer bonded to the shield layer via a compound α, wherein the compound α contains a benzene ring and a benzene ring in one molecule. , a compound α1 having an alkoxysilyl group and one or more groups selected from the group consisting of an azide group, an azidosulfonyl group and a diazomethyl group, and a hydrolyzable silane compound containing the compound α1, obtained by hydrolytic condensation. It is an electromagnetic wave shield laminate, which is at least one of the compounds α2 obtained.

Another embodiment of the present invention comprises a step of bonding a shield layer and at least one of an adhesive layer and an insulating layer via a compound α, wherein the compound α contains a benzene ring and an alkoxy A compound obtained by hydrolytic condensation of a compound α1 having a silyl group and one or more groups selected from the group consisting of an azide group, an azidosulfonyl group and a diazomethyl group, and a hydrolyzable silane compound containing the compound α1 A method for manufacturing an electromagnetic wave shield laminate, which is at least one of α2.

Another aspect of the present invention is a shield printed wiring board comprising a printed wiring board and the electromagnetic wave shielding laminate adhered to the printed wiring board.

Another aspect of the present invention is a method for manufacturing a shield printed wiring board, comprising a step of adhering the electromagnetic shield laminate or the electromagnetic shield laminate obtained by the method for manufacturing the electromagnetic shield laminate to a printed wiring board. .

Another aspect of the present invention is a semiconductor package comprising the electromagnetic wave shield laminate.

Another aspect of the present invention is an electronic device including the shield printed wiring board or the semiconductor package.

According to one aspect of the present invention, an electromagnetic shield laminate in which delamination is unlikely to occur when manufacturing a shield printed wiring board, a method for manufacturing such an electromagnetic shield laminate, and such an electromagnetic shield laminate is used. It is possible to provide a shield printed wiring board, a method for manufacturing a shield printed wiring board, and an electronic device.

FIG. 1 is a schematic cross-sectional view showing an electromagnetic wave shield laminate according to one embodiment of the present invention. FIG. 2 is a schematic cross-sectional view showing an electromagnetic wave shield laminate according to an embodiment different from that of FIG. FIG. 3 is a flow diagram of electroless plating treatment in a reference example. FIG. 4 is a flow diagram of thermocompression bonding in a reference example.

<Electromagnetic wave shield laminate>
An electromagnetic wave shield laminate according to one embodiment of the present invention includes a shield layer and at least one of an adhesive layer and an insulating layer bonded to the shield layer via a predetermined compound α. Examples of the electromagnetic wave shield laminate according to the present invention include a mode comprising a shield layer and an adhesive layer, a mode comprising a shield layer and an insulating layer, and a mode comprising an adhesive layer, a shield layer and an insulating layer in this order. be done. When an adhesive layer, a shield layer and an insulating layer are provided, at least one between the adhesive layer and the shield layer and between the shield layer and the insulating layer may be bonded via the compound α. In the electromagnetic wave shield laminate according to one embodiment of the present invention, at least one of the adhesive layer and the shield layer and the shield layer and the insulating layer is bonded via the compound α. Separation between layers is difficult to occur, and bending resistance is sufficiently high. Hereinafter, a specific description will be given centering on the form of an electromagnetic wave shield laminate in which an adhesive layer, a shield layer, and an insulating layer are provided in this order, and the respective layers are bonded via a compound α.

An electromagnetic wave shield laminate 10 according to one embodiment of the present invention shown in FIG. 1 is a laminate including an adhesive layer 11, a shield layer 12 and an insulating layer 13 in this order. The adhesive layer 11 and the shield layer 12 are bonded via the compound α, and the first compound α layer 14a exists between these layers. The shield layer 12 and the insulating layer 13 are also bonded via the compound α, and the second compound α layer 14b exists between these layers. The first compound α-layer 14a and the second compound α-layer 14b may exist as a continuous layer or intermittent layers. Since the first compound α layer 14a and the second compound α layer 14b are usually very thin layers, it may not be possible to confirm that they are layers with an optical microscope or the like. 12 and between the shield layer 12 and the insulating layer 13.

In the electromagnetic wave shield laminate 10, the adhesive layer 11 and the shield layer 12 and the shield layer 12 and the insulating layer 13 are chemically interface-bonded by the compound α. Therefore, when the electromagnetic wave shield laminate 10 is used to manufacture a shield printed wiring board, delamination is unlikely to occur, and the bending resistance is sufficiently high. Specifically, for example, when the electromagnetic wave shield laminate 10 is used to manufacture a shield printed wiring board, heat press, solder reflow, etc. are performed, and volatilization occurs between the adhesive layer 11 and the shield layer 12. Even if a component is generated and permeates the interface, peeling of the interface is unlikely to occur. As a result, it is possible to suppress the interlayer adhesion from being destroyed, thereby improving the electromagnetic wave shielding performance. Furthermore, even when the electromagnetic wave shield laminate 10 is used for a flexible printed wiring board or the like, disconnection or the like hardly occurs because the bending resistance is sufficiently high.

As another embodiment, one of the adhesive layer 11 and the shield layer 12 and the shield layer 12 and the insulating layer 13 may be joined by other means. At least one between the adhesive layer 11 and the shield layer 12 and between the shield layer 12 and the insulating layer 13 is bonded via the compound α, so that the interlayer Peeling is unlikely to occur, and bending resistance is sufficiently high. However, since volatile components tend to accumulate, it is preferable that at least the adhesive layer 11 and the shield layer 12 are bonded via the compound α. More preferably, both the agent layer 11 and the shield layer 12 and the shield layer 12 and the insulating layer 13 are bonded via the compound α.

(adhesive layer)
The adhesive layer 11 is usually the innermost layer of the electromagnetic shield laminate 10, and is a layer for bonding the electromagnetic shield laminate 10 to a printed wiring board or the like.

The adhesive layer 11 usually contains a resin (adhesive resin) that functions as an adhesive. As this resin, conventionally known resins used as adhesives can be used. Resins include thermoplastic resins such as polyamide resins, polyester resins, acrylic resins, polyolefin resins (polyethylene resins, polypropylene resins, etc.), polyimide resins, polystyrene resins, polyvinyl acetate resins, epoxy resins, polyurethane resins, polyurethane urea resins, Thermosetting resins such as melamine resins, alkyd resins and phenol resins, active energy ray-curable resins such as resins having a plurality of (meth)acryloyloxy groups, and the like can be used. These resins may be homopolymers, copolymers, or variously modified resins. 1 type(s) or 2 or more types can be used for resin. The adhesive layer 11 contains at least one resin selected from the group consisting of polyamide resins, polyester resins, acrylic resins, epoxy resins, polyurethane resins, and polyurethane urea resins in order to exhibit good adhesiveness. preferably included. Also, the resin contained in the adhesive layer 11 is preferably a thermosetting resin, more preferably an epoxy resin. The resin contained in the adhesive layer 11 exists in an adhesive state (for example, in an uncured state).

The lower limit of the resin content in the adhesive layer 11 is preferably 50% by mass, more preferably 60% by mass, and even more preferably 70% by mass. The adhesiveness of the adhesive layer 11 can be enhanced by setting the content of the resin in the adhesive layer to the above lower limit or more. On the other hand, the upper limit of the resin content in the adhesive layer 11 is preferably 99% by mass, more preferably 95% by mass, and even more preferably 90% by mass.

The adhesive layer 11 preferably has conductivity. The conductive adhesive layer 11 also functions as a layer for shielding electromagnetic waves. Therefore, the electromagnetic shield laminate 10 having such an adhesive layer 11 can be used more preferably as an electromagnetic shield laminate such as a printed wiring board. For this reason, the adhesive layer 11 preferably contains conductive particles.

The shape of the conductive particles is not particularly limited, but may be spherical, flat, scale-like, dendrite-like, rod-like, fibrous, or the like.

Examples of the conductive particles include metal particles and carbon particles, and metal particles are preferred. Metal particles (metal powder) include silver powder, copper powder, nickel powder, solder powder, aluminum powder, silver-coated copper powder obtained by plating copper powder with silver, and fine particles obtained by coating polymer fine particles and glass beads with metal. can be mentioned. Among these, copper powder and silver-coated copper powder are preferable from the viewpoint of economy and the like.

The average particle size of the conductive particles is preferably 0.5 μm or more and 15 μm or less. When the average particle size of the conductive particles is within the above range, the adhesiveness of the adhesive layer 11, the shielding performance, and the like are improved. Further, by setting the average particle size of the conductive particles to be equal to or less than the above upper limit, it is possible to reduce the thickness of the adhesive layer 11 . In this specification, the "average particle diameter" means the volume average value measured by the dynamic light scattering method after dispersing the particles of the specific object in a dispersion medium.

The lower limit of the content of the conductive particles in the adhesive layer 11 is preferably 5% by mass, more preferably 10% by mass, and even more preferably 15% by mass. By making the content of the conductive particles equal to or higher than the above lower limit, the shielding performance of the adhesive layer 11 and the like can be enhanced. On the other hand, the upper limit of the content of the conductive particles in the adhesive layer is preferably 80% by mass, more preferably 60% by mass, and even more preferably 40% by mass. Sufficient adhesiveness of the adhesive layer 11 can be ensured by setting the content of the conductive particles to the above upper limit or less.

The adhesive layer 11 preferably has anisotropic conductivity. When the adhesive layer 11 has anisotropic conductivity, for example, the transmission characteristics of high-frequency signals transmitted in the signal circuit of the printed wiring board are improved as compared with the case of having isotropic conductivity.

The adhesive layer 11 may contain a curing accelerator, a tackifier, an antioxidant, a pigment, a dye, a plasticizer, an ultraviolet absorber, an antifoaming agent, a leveling agent, a filler, a flame retardant, a viscosity Modulators and the like may also be included.

The average thickness of the adhesive layer 11 is not particularly limited and can be appropriately set as necessary, but the lower limit is preferably 0.2 μm, more preferably 1 μm, and even more preferably 5 μm. By setting the average thickness of the adhesive layer 11 to the above lower limit or more, sufficient adhesiveness and sufficient shielding performance when containing conductive particles are exhibited. On the other hand, the upper limit of the average thickness of the adhesive layer 11 is preferably 40 µm, more preferably 30 µm, and even more preferably 20 µm. By making the average thickness of the adhesive layer 11 equal to or less than the above upper limit, it is possible to reduce the thickness of the entire electromagnetic wave shield laminate 10 .

(shield layer)
The shield layer 12 may be made of any material as long as it has shielding performance against electromagnetic waves, but is preferably made mainly of metal. In particular, shield layer 12 is preferably a metal layer. The metal content in the shield layer 12 is preferably 70% by mass or more, more preferably 90% by mass or more, and even more preferably 99% by mass or more. When the metal content in the shield layer 12 is high, good shield performance can be exhibited. The shield layer 12 preferably contains at least one metal selected from the group consisting of nickel, copper, silver, tin, gold, palladium, aluminum, chromium, titanium and zinc, and at least one metal of copper and silver. It is more preferable to include The content of these metals in the shield layer 12 is preferably 90% by mass or more, more preferably 99% by mass or more. By forming the shield layer 12 from such a metal, it is possible to exhibit good shield performance.

As a material for forming the shield layer 12, for example, metal nano-ink can be used. Metal nanoinks described in JP-A-2018-184553, JP-A-5833540, and JP-A-6029721 can be used. These descriptions are included herein.

Such metal nanoink is usually applied by a screen printing method or an inkjet method. In the case of the inkjet method, it is necessary to adjust the viscosity of the solution to suit the inkjet ejection. Metal nano-inks with well-adjusted solution viscosities often do not contain polymers, and generally when they do not contain polymers, the formed shield layer may have low adhesion to other layers. Therefore, the surface of the other layer is treated with the compound α, that is, the compound α is provided on the surface of the other layer, and then the metal nanoink is applied to the surface of the other layer to form a shield layer with excellent adhesion. can do. In addition, it is also possible to form a shield layer specifically on a part of the surface of another layer by inkjet coating or the like. For example, partial shield layer formation is preferably performed in the manufacture of semiconductor packages.

In addition, the shield layer 12 may be a layer formed of a material other than metal nanoink, such as a layer formed by plating, vapor deposition, or the like, a layer made of metal foil, or the like.

The shield layer 12 may be a layer containing a single metal or a layer containing multiple metals. Also, the shield layer 12 may be a single layer or multiple layers. As the shield layer 12 has a multilayer form, the shield layer preferably has a layer containing copper and a layer containing silver. Such a form will be explained in detail later.

The lower limit of the average thickness of the shield layer 12 is preferably 0.2 μm, more preferably 0.5 μm, even more preferably 1 μm. By making the average thickness of the shield layer 12 equal to or greater than the above lower limit, the shield performance is enhanced. In particular, when the shield layer 12 has an average thickness of 1 μm or more, good transmission characteristics are obtained in a signal transmission system for transmitting high-frequency signals having a frequency of 0.01 to 10 GHz. On the other hand, in the conventional electromagnetic wave shield laminate, when the average thickness of the shield layer is 1 μm or more, separation between layers tends to occur easily when the laminate is repeatedly bent. However, since the electromagnetic wave shield laminate 10 has sufficiently high bending resistance, separation between the layers is unlikely to occur even when the shield layer 12 is thick, and good shielding performance can be maintained. On the other hand, the upper limit of the average thickness of the shield layer 12 is preferably 10 µm, more preferably 5 µm. By making the average thickness of the shield layer 12 equal to or less than the above upper limit, the bending resistance can be enhanced.

Preferably, the shield layer 12 does not have openings. Since the shield layer 12 does not have openings, good shield performance is exhibited, and the strength of the shield layer 12 is increased, thereby improving bending resistance.

(insulating layer)
The insulating layer 13 is a layer having insulating properties. The insulating layer 13 is not particularly limited as long as it has sufficient insulating properties and is preferably a layer capable of protecting the shield layer 12 and the like, but is preferably a resin layer.

Examples of the resin forming the insulating layer 13 include thermoplastic resins, thermosetting resins, active energy ray-curable resins, and the like. Specific examples of these resins include the resins exemplified for the adhesive layer 11 .

The insulating layer 13 may contain a curing accelerator, a tackifier, an antioxidant, a pigment, a dye, a plasticizer, an ultraviolet absorber, an antifoaming agent, a leveling agent, a filler, a flame retardant, and a viscosity adjuster, if necessary. agents, anti-blocking agents and the like may also be included.

The average thickness of the insulating layer 13 is not particularly limited and can be appropriately set as necessary, but the lower limit is preferably 1 μm, more preferably 3 μm. By making the average thickness of the insulating layer 13 equal to or greater than the above lower limit, it is possible to exhibit sufficient insulating properties, protective properties, and the like. On the other hand, the upper limit of the average thickness of the insulating layer 13 is preferably 15 μm, more preferably 10 μm. By making the average thickness of the insulating layer 13 equal to or less than the above upper limit, it becomes easier to bend, and the insulating layer 13 is less likely to break when bent. That is, by setting the average thickness of the insulating layer 13 to the above upper limit or less, the bending resistance can be enhanced.

(Compound α)
The compound α for bonding between the adhesive layer 11 and the shield layer 12 and between the shield layer 12 and the insulating layer 13 will be described below. The compound α forms a first compound α layer 14a and a second compound α layer 14b. The first compound α layer 14a and the second compound α layer 14b may contain components other than the compound α. The compound α bonding between the adhesive layer 11 and the shield layer 12 and the compound α bonding between the shield layer 12 and the insulating layer 13 may be the same or different. The compound α is a material for forming a conjugate (bond) of two substances by interfacial molecular bonding. Interfacial molecular bonding means intervening a certain compound at the interface of two substances and chemically bonding each substance and the compound by chemical reaction to bond the two substances, or a bond resulting therefrom. .

The compound α includes a compound α1 having a benzene ring, an alkoxysilyl group, and one or more groups selected from the group consisting of an azide group, an azidosulfonyl group, and a diazomethyl group in one molecule, and the above compound α1. It is at least one compound α2 obtained by hydrolytic condensation of a hydrolyzable silane compound. Two or more kinds of compounds α can be used, and compound α1 and compound α2 can also be used in combination.

An alkoxysilyl group refers to a group in which an alkoxy group (oxyhydrocarbon group) is bonded to a silicon atom. An alkoxy group refers to a group in which a hydrocarbon group is bonded to an oxygen atom, and examples thereof include a methoxy group, an ethoxy group, a propoxy group, a vinyloxy group, a phenoxy group, and a benzyloxy group. The number of alkoxy groups attached to the silicon atom may be 1, 2 or 3, with 3 being preferred. In the alkoxysilyl group, a group other than an alkoxy group may be bonded to the silicon atom, and examples of such groups include an alkyl group, a phenyl group, a hydroxy group, and a hydrogen atom. As the alkoxy group, an alkoxy group having 1 to 3 carbon atoms is preferable, and a methoxy group, an ethoxy group and a propoxy group are more preferable. Examples of alkoxysilyl groups include trimethoxysilyl groups, triethoxysilyl groups, tribenzyloxysilyl groups, and the like.

The alkoxysilyl group possessed by the compound α can mainly form a “—Si—OM—type” chemical bond with an inorganic material M such as a metal through a chemical reaction. Further, the azide group, azidosulfonyl group or diazomethyl group possessed by the compound α can mainly form a chemical bond such as "-NC-type" with an organic substance such as a resin through a chemical reaction. Here, the chemical bond means covalent bond, ionic bond, bond by intermolecular force, etc., preferably covalent bond or ionic bond. Therefore, the compound α can strongly bond (bond) the shield layer 12, which is usually made of metal, and the adhesive layer 11 and insulating layer 13, which are usually made of resin.

Compound α is preferably a compound in which one or more groups selected from the group consisting of an azide group, an azidosulfonyl group and a diazomethyl group are directly bonded to a benzene ring. When the azide group or the like is directly bonded to the benzene ring, the reaction rate of the reaction in which the nitrogen molecule (N ₂ ) is eliminated from the azide group or the like by ultraviolet irradiation treatment or heat treatment increases compared to the case where it is not. . In addition, an azide group or the like directly bonded to a benzene ring is characterized in that the reaction rate of photodecomposition reaction is sufficiently high even with long-wavelength ultraviolet rays, compared to, for example, an azide group or the like directly bonded to a triazine ring. That is, in the case of the triazine ring, the reaction rate of the photolysis reaction has a peak with a certain wavelength width centered on a specific wavelength of short-wave ultraviolet light, whereas in the case of the benzene ring, the photolysis reaction rate The reaction rate of has a peak of similar wavelength width centered on a specific wavelength of longer wavelength ultraviolet light. Therefore, by using the compound α in which an azide group or the like is directly bonded to the benzene ring, it becomes possible to perform the treatment efficiently even when the substance to be surface-treated is irradiated with long-wavelength ultraviolet rays that do not deteriorate the substance so much. In addition, heat treatment can be efficiently performed at a relatively low temperature for a short period of time.

(Compound α1)
Compound α1 is preferably a compound represented by the following formula (1) or (2).

In formula (1), R ¹ is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a phenyl group, an alkoxy group having 1 to 12 carbon atoms, or a hydroxy group. A plurality of R ² are each independently a hydrogen atom, a halogen, or a monovalent organic group. X ¹ is an azide group, an azidosulfonyl group, or a diazomethyl group. Y ¹ is a single bond, an ester group, an ether group, a thioether group, an amide group, a urethane group, a urea group, a group represented by —NHR ³ —, or a group represented by the following formula (3a) or (3b) is. R ³ is an alkyl group having 1 to 6 carbon atoms. Z ¹ is a single bond, a methylene group, an alkylene group having 2 to 12 carbon atoms, or -NH-, -O-, -S- and - at the end of an alkylene group having 2 to 12 carbon atoms or between the carbon-carbon bonds; A group containing one or more groups of S(O)—. m is an integer from 1 to 3; When each of R ¹ , X ¹ , Y ¹ and Z ¹ is plural, each independently satisfies the above definition. However, at least one of one or more R ¹ is an alkoxy group having 1 to 12 carbon atoms.

In formula (2), a plurality of R ⁴ , R ⁵ and R ⁶ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a phenyl group, an alkoxy group having 1 to 12 carbon atoms, or a hydroxy group. and at least one of the plurality of R ⁴ , R ⁵ and R ⁶ is an alkoxy group having 1 to 12 carbon atoms. A plurality of R ⁷ are each independently a hydrogen atom, a halogen, or a monovalent organic group. X2 is an azide group, an ^{azidosulfonyl} group, or a diazomethyl group. A plurality of Z ² are each independently a single bond, a methylene group, an alkylene group having 2 to 12 carbon atoms, or —NH—, —O between the terminal of an alkylene group having 2 to 12 carbon atoms or a carbon-carbon bond. A group containing one or more of -, -S- and -S(O)-.

^In formula (3a), R8 is a hydrogen atom or a methyl group.

Examples of alkyl groups having 1 to 12 carbon atoms represented by R ¹ , R ⁴ , R ⁵ and R ⁶ include methyl group, ethyl group, propyl group, butyl group and octyl group.
Examples of the alkoxy group having 1 to 12 carbon atoms represented by R ¹ , R ⁴ , R ⁵ and R ⁶ include the alkoxy groups described above.
Halogen represented by R ² and R ⁷ includes a fluorine atom, a chlorine atom, a bromine atom and the like.
The monovalent organic group represented by R ² and R ⁷ includes a ^monovalent hydrocarbon group, an alkoxy group, and -Y ¹ -Z ¹ -Si-R ¹³ (Y ₁ , Z ¹ and R ¹ are are the same as Y ¹ , Z ¹ and R ¹ in formula (1)), a group represented by —COO—N—(—Z ² —SiR ⁴ R ⁵ R ⁶ ) ₂ (Z ² , R ⁴ , R ⁵ and R ⁶ have the same meanings as Z ² , R ⁴ , R ⁵ and R ⁶ in formula (2), respectively.), groups represented by formula (14) described later, and the like.
Examples of the alkyl group having 1 to 6 carbon atoms represented by R ³ include methyl group, ethyl group, propyl group and butyl group.

Preferred forms of the compound represented by formula (1) are as follows.
R ¹ is preferably an alkoxy group having 1 to 12 carbon atoms, more preferably an alkoxy group having 1 to 6 carbon atoms, and still more preferably an alkoxy group having 1 to 3 carbon atoms.
A hydrogen atom is preferred as R ² .
X ¹ is preferably an azide group or an azidosulfonyl group. X ¹ is preferably bonded to the group containing Y ¹ and the like at the para-position or meta-position.
Y ¹ is preferably an amide group, more preferably an amide group represented by *-CONH- (* indicates a bonding site with a benzene ring).
Z ¹ is preferably an alkylene group having 2 to 12 carbon atoms, more preferably an alkylene group having 2 to 6 carbon atoms.
m is preferably 3.

Preferred forms of the compound represented by formula (2) are as follows.
R ⁴ , R ⁵ and R ⁶ are preferably alkoxy groups having 1 to 12 carbon atoms, more preferably alkoxy groups having 1 to 6 carbon atoms, and even more preferably alkoxy groups having 1 to 3 carbon atoms.
A hydrogen atom is preferred as ^R7 .
X2 is preferably an azide group or an ^{azidosulfonyl} group. X ² is preferably bonded to the group represented by -COO-N-(-Z ² -SiR ⁴ R ⁵ R ⁶ ) ₂ at the para- or meta-position.
Z ² is preferably an alkylene group having 2 to 12 carbon atoms, more preferably an alkylene group having 2 to 6 carbon atoms.

Compound α1 is also preferably a compound represented by the following formula (11), (12) or (13).

In formulas (11) to (14), X ¹⁰ , X ¹¹ and X ¹² are each independently an azide group, an azidosulfonyl group or a diazomethyl group. E ¹¹ and E ¹² are each independently >C═O, a methylene group or an alkylene group having 2 to 12 carbon atoms. Y ¹¹ , Y ¹² , Y ¹³ and Y ¹⁴ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or —J ¹³ —Si(OA ¹⁰ ) _3-k (R ¹⁰ ) _k It is a group that is J ¹¹ , J ¹² and J ¹³ are each independently a methylene group, an alkylene group having 2 to 12 carbon atoms, or an oxygen atom (—O—) between the carbon-carbon bonds of an alkylene group having 2 to 12 carbon atoms. is a group containing Y ¹⁵ is a group represented by -R ¹⁵ or -OA ¹⁵ ; Y ¹⁶ is a group represented by -R ¹⁶ or -OA ¹⁶ ; A ¹⁰ , A ¹⁵ and A ¹⁶ are each independently an alkyl group having 1 to 4 carbon atoms, a benzyl group or a hydrogen atom. R ¹⁰ , R ¹⁵ and R ¹⁶ are each independently an alkyl group having 1 to 4 carbon atoms or a benzyl group. k is an integer of 0 or more and 2 or less. ^Q10 is a hydrogen atom or an organic group represented by formula (4). In formulas (11) and (12), at least one of Y ¹¹ and Y ¹² contains an oxygen atom. In formula (13), at least one of Y ¹⁵ and Y ¹⁶ contains an oxygen atom. In formula (13), the groups X ¹¹ and X ¹² attached to the benzene ring are each independently attached to the para or meta position.

(Method for synthesizing compound α1)
The method for synthesizing the compound α1 is not particularly limited. b, and a compound B having a benzene ring and one or more groups selected from the group consisting of an azide group, an azidosulfonyl group and a diazomethyl group, by a known method. Examples of the combination of the reactive group a and the reactive group b include a combination of an isocyanate group, an epoxy group, an amino group, etc., and a carboxy group.

Examples of the silane coupling agent A include 3-isocyanatopropyltriethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltrimethoxysilane, 2-( 3,4-epoxycyclohexyl)ethyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, N-2-( aminoethyl)-3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, bis(3-triethoxysilylpropyl)amine, bis(3-trimethoxysilylpropyl)amine, bis(3-aminopropyl)diethoxysilane, bis(3-aminopropyl)dimethoxysilane and the like.

Compound B includes azidobenzoic acid, azidosulfonylbenzoic acid, diazomethylbenzoic acid, 3-(4-azidophenyl)propionic acid, chlorides of these carboxylic acids, azidoaniline, azidophenol and the like.

(Compound α2)
In compound α2, an unreacted alkoxysilyl group usually remains. That is, compound α2 also usually has a benzene ring, an alkoxysilyl group, and one or more groups selected from the group consisting of an azide group, an azidosulfonyl group and a diazomethyl group in one molecule.

A compound α2 obtained by hydrolyzing and condensing a hydrolyzable silane compound containing the compound α1 has a structural unit A derived from the compound α1. The compound α2 may be obtained by other synthetic methods as long as the structure is the same as that of a compound obtained by hydrolytic condensation of a hydrolyzable silane compound including the compound α1. Compound α2 is preferably a silsesquioxane compound. Compound α2 preferably has at least one of an alkoxysilyl group and a hydroxysilyl group, more preferably a hydroxysilyl group.

Structural unit A includes structural units represented by the following formula (4). The structural unit represented by the following formula (4) is a structural unit derived from the compound α1 represented by the formula (1) in which m is 3.

In formula (4), R ¹ , R ² , X ¹ , Y ¹ and Z ¹ are synonymous with R ¹ , R ² , X ¹ , Y ¹ and Z ¹ in formula (1). a is an integer from 0 to 2;

Specific examples of R ¹ , R ² , X ¹ , Y ¹ and Z ¹ in formula (4) are the same as specific examples of R ¹ , R ² , X ¹ , Y ¹ and Z ¹ in formula (1) is. From the viewpoint of reactivity, etc., R ¹ in formula (4) is preferably a hydroxy group or an alkoxy group, more preferably a hydroxy group. As for a, 1 is preferable.

The lower limit of the content of structural unit A relative to all structural units in compound α2 is preferably 10 mol%, more preferably 20 mol%, and even more preferably 30 mol%. On the other hand, the upper limit of this content is preferably 90 mol%, more preferably 80 mol%, and even more preferably 70 mol%.

Compound α2 preferably has a structural unit B containing an amino group (—NH ₂ ). When the compound α2 has the structural unit B, there are advantages such as improved water solubility of the compound α2. Hydrolyzable silane compounds that provide the structural unit B include 3-aminopropyltrimethoxysilane and 3-aminopropyltriethoxysilane.

The lower limit of the content of structural unit B relative to all structural units in compound α2 is preferably 10 mol%, more preferably 20 mol%, and even more preferably 30 mol%. On the other hand, the upper limit of this content is preferably 90 mol%, more preferably 80 mol%, and even more preferably 70 mol%.

Compound α2 may have structural unit C other than structural unit A and structural unit B. Examples of the hydrolyzable silane compound that provides the structural unit C include compounds represented by the following formula (C).

In formula (C), R ^d is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 15 carbon atoms, or an organic group having a reactive group. , a plurality of R ^d may be the same or different. R ^e is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an acyl group having 2 to 6 carbon atoms, or an aryl group having 6 to 15 carbon atoms, and a plurality of R ^e may be the same or different. . x represents an integer of 0 to 3; Further, these alkyl groups, alkenyl groups and aryl groups may be either unsubstituted or substituted, and can be selected depending on the properties.

Specific examples of alkyl groups represented by R ^d and R ^e include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, n-hexyl group and n-decyl group. , trifluoromethyl group, 3,3,3-trifluoropropyl group, 3-glycidoxypropyl group, 2-(3,4-epoxycyclohexyl)ethyl group, [(3-ethyl-3-oxetanyl)methoxy] A propyl group, a 3-mercaptopropyl group, a 3-isocyanatopropyl group and the like can be mentioned. Specific examples of the alkenyl group represented by R ^d include vinyl group, 3-acryloxypropyl group, 3-methacryloxypropyl group and the like. Specific examples of the aryl group represented by R ^d and R ^e include a phenyl group, a tolyl group, a p-hydroxyphenyl group, a p-methoxyphenyl group, a 1-(p-hydroxyphenyl)ethyl group, a 2-(p -hydroxyphenyl)ethyl group, 4-hydroxy-5-(p-hydroxyphenylcarbonyloxy)pentyl group, naphthyl group and the like. Examples of the organic group having a reactive group represented by ^Rd include an isocyanate group, a group having an isocyanurate structure and an alkoxysilyl group, and the like. The number of carbon atoms in the organic group having a reactive group represented by ^Rd is preferably 1 or more and 40 or less. A specific example of the ^acyl group represented by Re is an acetyl group.

In formula (C), tetrafunctional silane when x=0, trifunctional silane when x=1, bifunctional silane when x=2, and monofunctional silane when x=3. be.

Specific examples of hydrolyzable silane compounds represented by formula (C) include tetrafunctional silanes such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraacetoxysilane and tetraphenoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltri-n-butoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltri-n-butoxysilane, n-propyltrimethoxysilane, n-propyltri ethoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, decyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-methacryloxysilane propyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, p-hydroxyphenyltrimethoxysilane, p-methoxyphenyltrimethoxysilane, 1 -(p-hydroxyphenyl)ethyltrimethoxysilane, 2-(p-hydroxyphenyl)ethyltrimethoxysilane, 4-hydroxy-5-(p-hydroxyphenylcarbonyloxy)pentyltrimethoxysilane, 1-naphthyltrimethoxysilane , 2-naphthyltrimethoxysilane, trifluoromethyltrimethoxysilane, trifluoromethyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane , 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane , [(3-ethyl-3-oxetanyl)methoxy]propyltrimethoxysilane, [(3-ethyl-3-oxetanyl)methoxy]propyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-trimethoxysilylpropylsuccinate Trifunctional silanes such as acids, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldiacetoxysilane, di-n-butyldimethoxysilane , diphenyldimethoxysilane, (3-glycidoxypropyl)methyldimethoxysilane, (3-glycidoxypropyl)methyldiethoxysilane, trimethylmethoxysilane, tri-n-butylethoxysilane, (3- monofunctional silanes such as glycidoxypropyl)dimethylmethoxysilane, (3-glycidoxypropyl)dimethylethoxysilane, and the like.

Further, the hydrolyzable silane compound represented by the formula (C) has 5 or more silicon-bonded alkoxy groups such as 1,3,5-tris[3-(trimethoxysilyl)propyl]isocyanurate. Also included are compounds having

A hydrolyzable silane compound may be used individually by 1 type, or may be used in combination of 2 or more type.

The weight average molecular weight (Mw) of compound α2 is not particularly limited, but is preferably 1,000 to 100,000, more preferably 2,000 to 50,000 in terms of polystyrene measured by GPC (gel permeation chromatography).

(Method for synthesizing compound α2)
The compound α2 is obtained by (i) a method of hydrolyzing and condensing a hydrolyzable silane compound containing the compound α1, and (ii) a hydrolytic condensate of a hydrolyzable silane compound having a structural unit B. "Compound X having a reactive group capable of binding reaction with an amino group, a benzene ring, and one or more groups selected from the group consisting of an azide group, an azidosulfonyl group and a diazomethyl group" (azidobenzoic acid, azidosulfonylbenzoic acid, diazomethylbenzoic acid, etc.). In (ii) above, the amino group in structural unit B reacts with compound X to form structural unit A.

General methods can be used for hydrolytic condensation to obtain compound α2. For example, a solvent, water, and optionally a catalyst are added to a hydrolyzable silane compound, and the mixture is heated and stirred at 30 to 150° C. for about 0.5 to 100 hours. During stirring, if necessary, hydrolysis by-products (alcohol such as methanol) and condensation by-products (water) may be removed by distillation.

Although there are no particular restrictions on the catalyst added as necessary, acid catalysts and base catalysts are preferably used. Specific examples of acid catalysts include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid, acetic acid, trifluoroacetic acid, formic acid, polyvalent carboxylic acids or their anhydrides, and ion exchange resins. Specific examples of basic catalysts include triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, diethylamine, triethanolamine, diethanolamine, sodium hydroxide, potassium hydroxide, amino alkoxysilanes having groups, ion-exchange resins, and the like. The amount of the catalyst to be added is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the hydrolyzable silane compound.

From the viewpoint of storage stability of the solution containing compound α2, the solution after hydrolytic condensation preferably does not contain a catalyst, and the catalyst can be removed as necessary. The removal method is not particularly limited, but preferably includes water washing and/or ion exchange resin treatment. Washing with water is a method of diluting a solution with a suitable hydrophobic solvent, washing with water several times, and concentrating the obtained organic layer with an evaporator. Ion exchange resin treatment is a method of contacting a solution with a suitable ion exchange resin.

The solvent used in the hydrolytic condensation reaction is not particularly limited, but compounds having an alcoholic hydroxyl group are preferably used. Although the compound having an alcoholic hydroxyl group is not particularly limited, it is preferably a compound having a boiling point of 110 to 250°C under atmospheric pressure.

Specific examples of compounds having an alcoholic hydroxyl group include acetol, 3-hydroxy-3-methyl-2-butanone, 4-hydroxy-3-methyl-2-butanone, 5-hydroxy-2-pentanone, 4-hydroxy- 4-methyl-2-pentanone (diacetone alcohol), ethyl lactate, butyl lactate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, propylene glycol mono-t- Butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methyl-1-butanol and the like. These alcoholic hydroxyl-containing compounds may be used alone or in combination of two or more.

Moreover, as a solvent, you may use another solvent with the compound which has an alcoholic hydroxyl group. Other solvents include ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, propylene glycol monomethyl ether acetate, 3-methoxy-1-butyl acetate, 3-methyl-3-methoxy-1- Esters such as butyl acetate and ethyl acetoacetate, ketones such as methyl isobutyl ketone, diisopropyl ketone, diisobutyl ketone and acetylacetone, diethyl ether, diisopropyl ether, di-n-butyl ether, diphenyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dimethyl ether, etc. Ethers, γ-butyrolactone, γ-valerolactone, δ-valerolactone, propylene carbonate, N-methylpyrrolidone, cyclopentanone, cyclohexanone, cycloheptanone and the like.

(Specific example of compound α)
Compound α can more specifically include compounds represented by the following formulas (15), (16), (17), (18a), (18b), (18c) or (19).

The compound represented by the formula (19) is a silsesquioxane compound composed of 1, m, and n of the three types of structural units shown in the formula (19) bonded together, X is an azide group, l is any integer of 0 or more, m is any integer of 1 or more, and n is any integer of 0 or more. R ^a , R ^b and R ^c are each independently a hydrogen atom, a hydroxy group, an alkoxy group or —O—. R ^f is a hydrogen atom, a hydroxy group, an alkoxy group, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 15 carbon atoms, or an organic group having a reactive group; , a plurality of R ^f may be the same or different. These alkyl groups, alkenyl groups, and aryl groups may be either unsubstituted or substituted, and can be selected depending on the properties. The compound represented by formula (19) (“IMB-4KP”) is water-soluble, for example, when l:m:n=1:1:0. In general, the compounds are water soluble except when the value of the ratio l/(m+n) is close to 0 (eg, less than 0.2 or less than 0.1). That is, the lower limit of the ratio l/(m+n) is preferably 0.2, more preferably 0.5, and even more preferably 1, from the viewpoint of water solubility. The upper limit of the ratio l/(m+n) is preferably 5, more preferably 2.

The first compound α layer 14a and the second compound α layer 14b may contain components other than the compound α. Other components include unreacted substances and side reaction products when synthesizing compound α. However, the lower limit of the content of the compound α in the first compound α layer 14a and the second compound α layer 14b is preferably 50% by mass, more preferably 70% by mass, and even more preferably 90% by mass. As described above, the high content ratio of the compound α in the first compound α layer 14a and the second compound α layer 14b can further enhance the bondability (cohesion) between the layers.

(Other embodiments)
The electromagnetic shield laminate 20 shown in FIG. 2 is an electromagnetic shield laminate in which the shield layer 22 has a two-layer structure having a copper layer 22a (a layer containing copper) and a silver layer 22b (a layer containing silver). . The electromagnetic shield laminate 20 is the same as the electromagnetic shield laminate 10 in FIG. 1 except that the shield layer 22 has a two-layer structure. description is omitted.

In the two-layered shield layer 22, the copper layer 22a is arranged on the adhesive layer 11 side. The content of copper in the copper layer 22a is preferably 90% by mass or more, more preferably 99% by mass or more. The copper layer 22a may be a layer formed from a copper alloy, and may contain components other than metals.

The copper layer 22a can be effectively formed by plating copper, for example. The lower limit of the average thickness of the copper layer 22a is preferably 0.1 μm, more preferably 0.4 μm. On the other hand, the upper limit of this average thickness is preferably 10 μm, more preferably 4 μm.

In the two-layer shield layer 22, the silver layer 22b is arranged on the insulating layer 13 side. The silver content in the silver layer 22a is preferably 90% by mass or more, more preferably 99% by mass or more. The silver layer 22a may be a layer formed from a silver alloy, and may contain components other than metals.

The silver layer 22b can be formed, for example, by applying a silver paste. That is, the silver layer 22b preferably contains silver particles. The shape of the silver particles contained in the silver layer 22b, or the silver particles contained in the silver paste when the silver layer 22b is formed from the silver paste, may be spherical, flake-like, dendritic, needle-like, fibrous, or the like, and is not particularly limited. not. Moreover, as a minimum of the average particle diameter of a silver particle, 1 nm is preferable and 10 nm is more preferable. On the other hand, the upper limit of the average particle size is preferably 100 nm, more preferably 50 nm. By using silver particles having such an average particle diameter, it is possible to form a highly homogeneous silver layer 22b.

The average thickness of the silver layer 22a is preferably 5 nm or more and 500 nm or less.

The electromagnetic wave shield laminate of the present invention may not have an adhesive layer. That is, an electromagnetic wave shielding laminate including a shield layer and an insulating layer, wherein the shield layer and the insulating layer are bonded via the compound α is also one aspect of the present invention. Specific forms and preferred forms of the shield layer, the insulating layer and the compound α in the electromagnetic shield laminate having such a form are the shield layer, the insulating layer and the compound α in the electromagnetic shield laminate 10 and the electromagnetic shield laminate 20 described above. It is the same. The electromagnetic wave shield laminate of this embodiment is also resistant to delamination and exhibits sufficient shielding performance, and is particularly suitable for semiconductor packages. For example, a sealing material or the like in a semiconductor package corresponds to an insulating layer, and an electromagnetic wave shield laminate is formed by providing a shield layer on this insulating layer via a compound α. In this manner, the insulating layer and the like may not be in the shape of a thin film.

(other configuration)
The electromagnetic wave shield laminate according to one embodiment of the present invention may have layers other than the adhesive layer, the shield layer, the insulating layer and the compound α layer. For example, an anchor coat layer may be provided on the shield layer side surface of the insulating layer. An anchor coat layer may be provided on the surface of a layer other than the insulating layer. Materials for the anchor coat layer include urethane resin, acrylic resin, core-shell type composite resin with urethane resin as the shell and acrylic resin as the core, epoxy resin, imide resin, amide resin, melamine resin, phenol resin, and urea-formaldehyde resin. , blocked isocyanate obtained by reacting polyisocyanate with a blocking agent such as phenol, polyvinyl alcohol, polyvinylpyrrolidone, and the like.

Further, in the electromagnetic wave shield laminate according to one embodiment of the present invention, a support film may be laminated on the side of the insulating layer opposite to the shield layer, and the adhesive layer may be laminated on the side opposite to the shield layer. A peelable film may be laminated on the surface. When the electromagnetic shielding laminate has at least one of a support film and a peelable film, transportation of the electromagnetic shielding laminate and production of shield printed wiring boards using the electromagnetic shielding laminate In operation, the electromagnetic wave shielding laminate can be easily handled. When the electromagnetic wave shield laminate is arranged on a shield printed wiring board or the like, the support film and the peelable film are peeled off.

(Usage, etc.)
The electromagnetic shield laminate according to one embodiment of the present invention preferably has an electromagnetic shielding characteristic of 85 dB or more at 200 MHz measured by the KEC method. Such an electromagnetic wave shield laminate has sufficiently high shield performance.

The electromagnetic wave shield laminate according to one embodiment of the present invention may be used for any purpose as long as it is for the purpose of blocking electromagnetic waves. The electromagnetic shield laminate may be an electromagnetic shield film. The electromagnetic wave shield laminate is preferably used for a printed wiring board, particularly a flexible printed wiring board. The electromagnetic wave shield laminate is resistant to delamination when manufacturing a shield printed wiring board, and has sufficiently high bending resistance. Therefore, the electromagnetic wave shield laminate is used in a flexible printed wiring board, and even if it is repeatedly bent, it is less likely to be damaged. Therefore, the electromagnetic shield laminate can be suitably used as an electromagnetic shield laminate for a flexible printed wiring board. Moreover, the electromagnetic shield laminate according to one embodiment of the present invention is also suitable as an electromagnetic shield laminate for semiconductor packages.

The electromagnetic wave shield laminate according to one embodiment of the present invention is preferably used in a signal transmission system that transmits signals with a frequency of 0.01 GHz or more and 10 GHz or less.

<Method for manufacturing electromagnetic wave shield laminate>
A method for manufacturing an electromagnetic wave shield laminate according to one embodiment of the present invention includes a step of bonding a shield layer and at least one of an adhesive layer and an insulating layer via a compound α, wherein the compound α is the It is at least one of the compound α1 and the compound α2.

According to this manufacturing method, it is possible to manufacture an electromagnetic wave shielding laminate in which delamination is unlikely to occur when a shield printed wiring board is manufactured, and which has sufficiently high bending resistance.

When manufacturing an electromagnetic shielding laminate comprising an adhesive layer, a shield layer and an insulating layer in this order, the step of joining the insulating layer and the shield layer (step 1) and the step of joining the shield layer and the adhesive layer (step 2), wherein in at least one of the two bonding steps (step 1 and step 2), the compound α is placed between the layers (between the insulating layer and the shield layer or between the shield layer and the adhesive layer). are joined through The order of Step 1 and Step 2 in the manufacturing method is not particularly limited, and either may be performed first or may be performed simultaneously. However, it is preferable to perform step 1 and step 2 in this order. Further, when manufacturing an electromagnetic wave shielding laminate that does not have one of the adhesive layer and the insulating layer, only one of the above steps 1 and 2 may be performed.

(Method for manufacturing electromagnetic wave shield laminate: first mode)
As a specific first embodiment of the method for manufacturing an electromagnetic wave shield laminate comprising an adhesive layer, a shield layer and an insulating layer in this order, an insulating layer is formed on one surface of the shield layer and an adhesive layer is formed on the other surface. A method for forming the The manufacturing method of the present embodiment includes a step of providing a compound α on at least one surface of the shield layer (step A), a step of providing an insulating layer on one surface of the shield layer (step B), and the other surface of the shield layer. Preferably, a step of providing an adhesive layer (step C) is provided. In this embodiment, the process B is the process 1 (the process of bonding the insulating layer and the shield layer), and the process C is the process 2 (the process of bonding the shield layer and the adhesive layer). In addition, the process B and the process C are usually performed after the process A. However, when an insulating layer or an adhesive layer is provided without providing the compound α on one surface of the shield layer, Step B or Step C may be performed prior to Step A. Although the order of the step B and the step C is not particularly limited, it is preferable to perform the step B and the step C in the order.

(Step A)
In the step of providing the compound α on at least one surface of the shield layer (step A), at least one surface of the shield layer is coated with a solution containing the compound α, and at least one of light irradiation and heat drying is performed to obtain the compound α. is chemically immobilized on the surface of the shield layer. In this embodiment, a metal foil or the like can be used as the shield layer. In this step, it is preferable to provide the compound α on both sides of the shield layer.

The solution containing compound α contains a solvent. Solvents include alcohols such as methanol, ethanol, isopropanol, ethylene glycol, propylene glycol, cellosolve, carbitol and 3-methoxy-3-methyl-1-butanol, ketones such as acetone, methyl ethyl ketone and cyclohexanone, benzene, toluene and xylene. etc., aliphatic hydrocarbons such as hexane, octane, decane, dodecane, octadecane, esters such as ethyl acetate, methyl propionate, methyl phthalate, tetrahydrofuran (THF), ethyl butyl ether, anisole, propylene glycol monomethyl Ethers such as ether acetate (PGMEA), water, and the like can be used. Moreover, the solvent illustrated as a solvent used for hydrolytic condensation can also be used. Among these, alcohol, ether and water are preferred. Solvents can be used singly or in combination of two or more.

The concentration of the compound α in the solution containing the compound α is preferably 0.05% by mass or more and 5% by mass or less. By setting the concentration of the compound α within the above range, it is possible to effectively form a layer of the compound α having an appropriate thickness, thereby enhancing the bondability (adhesiveness) between the layers.

The solution containing compound α may contain components other than compound α and the solvent. Surfactant etc. can be mentioned as another component. However, the content of compound α relative to the total solid content (all components other than the solvent) in the solution is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 90% by mass or more. The content of compound α with respect to the total solid content in the solution may be 100% by mass.

As a method for coating the solution containing the compound α, conventionally known coating methods such as gravure coating, kiss coating, die coating, lip coating, comma coating, blade coating, roll coating, knife coating, A spray coating method, a bar coating method, a spin coating method, a dip coating method, and the like can be mentioned. The thickness (wet thickness) of the coating film when the solution containing the compound α is coated is preferably, for example, 1 μm or more and 100 μm or less.

The heat drying conditions after coating with the solution containing the compound α are preferably, for example, 80° C. or more and 120° C. or less and 1 minute or more and 30 minutes or less. Moreover, it is preferable to irradiate an ultraviolet-ray containing the wavelength range of 230 nm - 300 nm, for example.

(Step B)
In the step of providing an insulating layer (step B), one surface of the shield layer is coated with an insulating layer forming material and cured to form an insulating layer. A compound α (compound α layer) is preferably provided on one surface of the shield layer. Examples of the method of coating the insulating layer forming material include the method exemplified as the method of coating the solution containing the compound α in step A. As a method for curing the insulating layer forming material, various conventionally known methods can be employed depending on the type of the insulating layer forming material.

(Process C)
In the step of providing an adhesive layer (step C), the other surface of the shield layer is coated with an adhesive layer-forming material to form an adhesive layer. A compound α (compound α layer) is preferably provided on the other surface of the shield layer. Examples of the method of coating the adhesive layer-forming material include the method exemplified as the method of coating the solution containing the compound α in step A.

(Method for producing electromagnetic wave shield laminate: second form)
As a second specific embodiment of the method for manufacturing an electromagnetic shield laminate comprising an adhesive layer, a shield layer and an insulating layer in this order, manufacture of an electromagnetic shield laminate in which the shield layer has a two-layer structure of a copper layer and a silver layer. An example method is described. The manufacturing method of the present embodiment includes a step of providing a compound α on one surface of an insulating layer (step i), a step of providing a silver layer on the surface of the insulating layer provided with the compound α (step ii), A step of providing a copper layer (step iii), a step of providing a compound α on the surface of the copper layer (step iv), and a step of providing an adhesive layer on the surface of the copper layer provided with the compound α (step v). is preferred. In this embodiment, steps ii and iii are step 1 (step of bonding the insulating layer and the shield layer), and step v is step 2 (step of bonding the shield layer and the adhesive layer).

(Step i)
In the step of providing the compound α on one surface of the insulating layer (step i), one surface of the insulating layer is coated with a solution containing the compound α, and at least one of light irradiation and heat drying is performed to remove the compound α chemically. effectively immobilized on the surface of the insulating layer. In this embodiment, a resin film or the like prepared by a conventionally known method can be used as the insulating layer. The specific form of the solution containing the compound α, coating method, light irradiation and heat drying in step i can be the same as in step A above.

(Step ii)
In the step (step ii) of providing a silver layer on the surface of the insulating layer provided with the compound α (or the compound α layer), the surface of the insulating layer provided with the compound α is coated with, for example, silver paste or silver ink as a plating catalyst. print as Examples of methods for printing the silver paste include intaglio printing such as gravure printing, letterpress printing such as flexography, screen printing, offset printing, and inkjet printing. A silver paste or silver ink usually contains silver particles and a dispersion medium, and may contain various additives such as a dispersant, a thickener, a leveling agent, and an antifoaming agent.

(Step iii)
In the step of providing a copper layer on the surface of the silver layer (step iii), a copper layer is provided on the surface of the silver layer by, for example, copper plating. The method of plating copper is not particularly limited, and conventional electroless plating, electrolytic plating, or the like can be used. When plating copper by electroless plating, it is preferable to use a plating solution containing copper sulfate, a reducing agent, and a solvent such as an aqueous medium or an organic solvent. When plating copper by electroplating, it is preferable to use a plating solution containing copper sulfate, sulfuric acid, and an aqueous medium. In addition, it is preferable to control the plating treatment time, the current density, the amount of the plating additive used, etc. so as to obtain the desired thickness of the copper layer.

A shield layer having a two-layer structure of a copper layer and a silver layer can be formed by steps ii and iii.

(Step iv)
In the step of providing the compound α on the surface of the copper layer (step iv), the surface of the copper layer is coated with a solution containing the compound α, and at least one of light irradiation and heat drying is performed to chemically remove the compound α from the copper layer. (Shield layer) Immobilize on the surface. The specific form of the solution containing compound α, coating method, light irradiation and heat drying in step iv can be the same as in step A above.

(Step v)
In the step (step v) of providing an adhesive layer on the surface of the copper layer provided with the compound α (or the compound α layer), an adhesive layer is formed on the surface of the copper layer (shield layer) provided with the compound α. material to form an adhesive layer. Examples of the method of coating the adhesive layer-forming material include the method exemplified as the method of coating the solution containing the compound α in step A.

<Shield printed wiring board>
A shield printed wiring board according to one embodiment of the present invention includes a printed wiring board and an electromagnetic wave shield laminate. The electromagnetic shield laminate provided in this shield printed wiring board is the electromagnetic shield laminate according to one embodiment of the present invention. An electromagnetic wave shield laminate used for a shield printed wiring board usually has an adhesive layer, and is adhered to the printed wiring board by this adhesive layer.

The printed wiring board may have a conventionally known structure. A printed wiring board has, for example, a base member (base film or the like) having a printed circuit formed thereon, and an insulating film provided on the base member so as to cover the printed circuit. The printed wiring board is preferably a flexible printed wiring board. A shield printed wiring board according to an embodiment of the present invention includes an electromagnetic shield laminate having sufficient bending resistance. Therefore, the shield printed wiring board also has sufficient bending resistance.

<Method for manufacturing shield printed wiring board>
A method for manufacturing a shield printed wiring board according to an embodiment of the present invention is an electromagnetic shielding laminate according to an embodiment of the present invention, or obtained by a method for manufacturing an electromagnetic shielding laminate according to an embodiment of the present invention. A step of adhering the electromagnetic wave shield laminate to the printed wiring board is provided. An electromagnetic wave shield laminate used in a method for manufacturing a shield printed wiring board usually includes an adhesive layer.

As a method for bonding the electromagnetic wave shield laminate and the printed wiring board, a conventionally known method can be used. For example, the printed wiring board and the electromagnetic shielding laminate are superimposed so that the adhesive layer of the electromagnetic shielding laminate is in contact with the surface of the printed wiring board, and the printed wiring board and the electromagnetic shielding laminate are heat-pressed in this state.

Further, the method for manufacturing the shield printed wiring board may include a step of mounting components by solder reflow after the bonding step.

According to the manufacturing method of the shield printed wiring board, even when volatile components are accumulated between the layers of the electromagnetic wave shielding laminate due to hot press, solder reflow, etc., a high bonding state between the layers is maintained, and delamination is unlikely to occur. In addition, the shield printed wiring board obtained by the manufacturing method has sufficiently high bending resistance.

<Semiconductor package>
A semiconductor package according to one embodiment of the present invention includes an electromagnetic wave shield laminate according to one embodiment of the present invention. For example, a shield layer can be partially formed by providing compound α on an insulating layer (sealing material, etc.) of a semiconductor package, and then applying metal nano-ink by screen printing, an ink jet method, or the like. Among metal nano-inks, by using silver nano-particle-containing inks in particular, it is possible to form a shield layer excellent in adhesion, electrical conductivity, electromagnetic wave shielding performance, and the like. Therefore, according to the semiconductor package according to one embodiment of the present invention, it is possible to improve the functionality of the semiconductor package.

<Electronic equipment>
An electronic device according to one embodiment of the present invention includes a shield printed wiring board according to one embodiment of the present invention or a semiconductor package according to one embodiment of the present invention. A shield printed wiring board according to an embodiment of the present invention has strong bonding between layers and sufficient bending resistance. Therefore, even when the shield printed wiring board is assembled in an electronic device in a bent state, damage or the like is unlikely to occur. Therefore, the electronic device according to one embodiment of the present invention can narrow the space for arranging the shield printed wiring board. Therefore, the electronic device can be made thinner and smaller. In addition, the semiconductor package according to one embodiment of the present invention has a highly adhesive shield layer formed thereon, and an electronic device provided with such a semiconductor package can achieve high functionality.

<Other embodiments>
It should be understood that the present invention is not limited to the above-described embodiments, but includes various modifications implemented within the scope of the present invention.

For example, when the electromagnetic wave shield laminate of the present invention has an adhesive layer, a shield layer and an insulating layer in this order, one of the adhesive layer and the shield layer and the shield layer and the insulating layer is It does not have to be conjugated via compound α. Examples of such a form include a form in which they are bonded via another compound, a form in which they are directly bonded without via a compound α or the like, and the like.

EXAMPLES The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the embodiments of these examples.

[Preparation Example 1] Preparation of Compound α Solution 1 5.5 g of 4-azidobenzoic acid, 400 g of THF (tetrahydrofuran), and 74 g of 3-aminopropyltriethoxysilane were weighed into a 2 L flask. While stirring, 5.4 g of 1,1-carbonylimidazole dissolved in 50 g of THF was successively added and allowed to react with continued stirring for 24 hours. After completion of the reaction, THF was distilled off using a rotary evaporator, and 12 g of reaction mixture A containing N-(3-triethoxysilylpropyl)-4-azidobenzamide (IMB-4K) represented by the above formula (15) got To 1 g of reaction mixture A was added 500 g of 3-methoxy-3-methyl-1-butanol to obtain compound α solution 1.

[Preparation Example 2] Preparation of Compound α Solution 2 10 g of reaction mixture A, 860 g of 3-methoxy-3-methyl-1-butanol, 27 g of water, and 3.3 g of 3-aminopropyltriethoxysilane were added to a 2 L flask. and stirred at 40°C for 24 hours to obtain a reaction mixture B. 50 g of reaction mixture B and 450 g of 3-methoxy-3-methyl-1-butanol were mixed to obtain compound α solution 2.

[Preparation Example 3] Preparation of Compound α Solution 3 3.3 g of 3-aminopropyltriethoxysilane was replaced with 9.2 g of 1,3,5-tris[3-(trimethoxysilyl)propyl]isocyanurate. Compound α Solution 3 was prepared in the same manner as in Preparation Example 2 except for the above.

[Preparation Example 4] Preparation of silver paste Silver particles having an average particle size of 30 nm were dispersed in a mixed dispersion medium of 35 parts by mass of ethanol and 65 parts by mass of ion-exchanged water using a polyethyleneimine compound as a dispersant. A silver paste with a concentration of 15% by weight was obtained.

[Example 1] Manufacture of electromagnetic wave shield laminate (step i)
An insulating layer (epoxy resin film) made of epoxy resin and having an average thickness of 5 μm was prepared. On one side of this insulating layer, compound α solution 1 obtained in Preparation Example 1 was applied with a bar coater (ROD No. #10; wet thickness: 22.9 μm) and dried by heating at 100° C. for 10 minutes. gone.

(Step ii)
Next, the silver paste obtained in Preparation Example 4 was screen-printed on the surface of the insulating layer provided with the compound α, and baked at 120° C. for 2 hours to provide a silver layer with an average thickness of 100 nm.

(Step iii)
Next, the insulating layer provided with the silver layer via the compound α was immersed in an electroless copper plating solution (“ARG Copper” manufactured by Okuno Pharmaceutical Co., Ltd., pH 12.5) at 55° C. for 20 minutes to remove the silver layer. An electroless copper plating film (average thickness 0.5 μm) was provided on the surface. Then, the surface of the electroless copper plating film obtained above was placed on the cathode, the phosphorous copper was placed on the anode, and an electroplating solution containing copper sulfate was used at a current density of 2.5 A/dm ² for 30 minutes. Electroplating was performed. As a result, a copper layer (copper plating layer) having a total average thickness of 1 μm including the electroless copper plating film was formed on the surface of the silver layer. As an electroplating solution, a solution containing 70 g/liter of copper sulfate, 200 g/liter of sulfuric acid, 50 mg/liter of chloride ion, and 5 g/liter of Top Lucina SF (brightener manufactured by Okuno Chemical Industry Co., Ltd.) was used.

(Step iv)
Next, the compound α solution 1 obtained in Preparation Example 1 was applied to the surface of the copper layer with a bar coater (ROD No. #10; wet thickness: 22.9 μm) and dried by heating at 100° C. for 10 minutes. rice field.

(Step v)
Then, on the surface of the copper layer provided with the compound α, an adhesive forming material (conductive adhesive) to provide an adhesive layer. A lip coating method was used as a coating method. An electromagnetic wave shield laminate of Example 1 was obtained through the above steps.

[Examples 2 and 3]
Each electromagnetic shield laminate of Examples 2 and 3 was obtained in the same manner as in Example 1, except that each compound α solution listed in Table 1 was used instead of Compound α solution 1 in Step i and Step iv. rice field.

[Comparative Example 1]
Same as Example 1 except that step i and step iv were not performed, i.e., step ii provided a silver layer directly on the surface of the insulating layer, and step v provided an adhesive layer directly on the surface of the copper layer. Then, an electromagnetic wave shield laminate of Comparative Example 1 was obtained.

[evaluation]
(delamination)
Delamination of each electromagnetic wave shield laminate was evaluated by the following method. First, the electromagnetic wave shield laminate was adhered onto a printed wiring board by hot pressing to obtain a shield printed wiring board. Next, this shield printed wiring board was left in a clean room at 23° C. and 63% RH for 7 days, and then exposed to the temperature conditions during reflow for 30 seconds to evaluate the presence or absence of delamination. As for the temperature conditions during reflow, a maximum temperature profile of 265° C. was set assuming lead-free soldering.
A sample without delamination was evaluated as "A", and a sample with delamination was evaluated as "B". Table 1 shows the evaluation results.

(bending resistance)
The bending resistance of each electromagnetic shield laminate was evaluated by the following method. The electromagnetic wave shield laminate was attached to both sides of a polyimide film having an average thickness of 50 μm by hot pressing, and cut into a size of 130 mm long and 15 mm wide to obtain a test piece. For this test piece, using an MIT folding endurance tester (manufactured by Yasuda Seiki Co., Ltd., No. 307 MIT folding endurance tester), JIS P8115: 2001 and JIS C 6471: Based on the method specified in 1995 The bending resistance (folding resistance) was measured. The test conditions were as follows.
Bending clamp tip R: 0.38 mm
Bending angle: ±135°
Bending speed: 175 cpm
Load: 500gf
Detection method: Detecting disconnection of the electromagnetic wave shield laminate with the built-in electric current device "A" when the number of times of bending is 600 times and no disconnection occurs, "B" when the number of times of bending is less than 600 times and disconnection occurs evaluated. Table 1 shows the evaluation results.

(Electromagnetic shielding characteristics)
The electromagnetic shielding characteristics of each electromagnetic shielding laminate were evaluated by the following method. Cut the electromagnetic shield laminate into a 15 cm square, and use an electromagnetic shield effect measuring device developed by the KEC Kansai Electronics Industry Promotion Center to measure the electromagnetic shield at 200 MHz under the conditions of a temperature of 25 ° C and a relative humidity of 30 to 50%. Properties were measured.
Those having electromagnetic wave shielding properties of 85 dB or more at 200 MHz measured by the KEC method were evaluated as "A", and those having less than 85 dB were evaluated as "B". Table 1 shows the evaluation results.

As shown in Table 1, each of the electromagnetic wave shield laminates of Examples 1 to 3, in which the adhesive layer and the shield layer and the shield layer and the insulating layer were bonded via a predetermined compound α, Delamination hardly occurred even after the heating step, the bending resistance was sufficiently high, and the electromagnetic wave shielding property was also good.

[Reference example]
<Synthesis of Compound α>
For identification of the compound, a Fourier transform infrared spectrophotometer IRTracer-100 manufactured by Shimadzu Corporation, a nuclear magnetic resonance spectrometer NMR spectrometer Z manufactured by JEOL Ltd., and a gas chromator manufactured by Shimadzu Corporation A tograph mass spectrometer GCMS-QP2020 NX was used.

塩化メチレン（ＣＨ_２Ｃｌ_２）３０ｍＬとＤＭＦ（Ｎ，Ｎ－ジメチルホルムアミドＣ_３Ｈ_７ＮＯ）０．３ｍＬとの混合溶媒に、４－アジド安息香酸（Ｎ_３Ｃ_６Ｈ_４ＣＯＯＨ）２．６ｇを溶解させた。窒素ガスの雰囲気下、撹拌しながら、塩化メチレン２０ｍＬに溶かした塩化チオニル（ＳＯＣｌ_２）７．３ｇを、室温で滴下した。反応を完結させるためさらに２ｈｒ撹拌を続けた。反応終了後、塩化メチレンを含む低沸点物を留去し、４－アジド安息香酸クロリド（Ｎ_３Ｃ_６Ｈ_４ＣＯＣｌ）を含む黄色油状物を得た。この油状物は、更に精製することなく、直接に次の反応に供した。 (1) Synthesis of 4-azidobenzoyl chloride (manufacture of raw material)

2.6 g of 4-azidobenzoic acid (N ₃ C ₆ H ₄ COOH) was added to a mixed solvent of 30 mL of methylene chloride (CH ₂ Cl ₂ ) and 0.3 mL of DMF (N,N-dimethylformamide C ₃ H ₇ NO). was dissolved. Under a nitrogen gas atmosphere, 7.3 g of thionyl chloride (SOCl ₂ ) dissolved in 20 mL of methylene chloride was added dropwise at room temperature while stirring. Stirring was continued for an additional 2 hours to complete the reaction. After completion of the reaction, low boilers containing methylene chloride were distilled off to obtain a yellow oily substance containing 4-azidobenzoyl chloride (N ₃ C ₆ H ₄ COCl). This oil was taken directly to the next reaction without further purification.

(2) Synthesis of N-(3-triethoxysilylpropyl)-4-azidobenzamide (IMB-4K)

1.8 g of 4-azidobenzoyl chloride (N ₃ C ₆ H ₄ COCl) was dissolved in 15 mL of THF (tetrahydrofuran). Under a nitrogen gas atmosphere, 3.6 g of 3-triethoxysilylpropylamine and 2.1 g of TEA (triethylamine) were dissolved in 20 mL of THF and added dropwise at room temperature while stirring. Stirring was continued for an additional 2 hours to complete the reaction. After completion of the reaction, the solution containing THF was distilled off, and the resulting crude product was purified by column chromatography (eluent: acetone/hexane = 85/15) to give a pale yellow oil with a yield of 66% (2.4 g). got
IR, NMR and QCMS analysis confirmed that the product was N-(3-triethoxysilylpropyl)-4-azidobenzamide.

(3) Synthesis of N-(3-triethoxysilylpropyl)-3-azidobenzamide (IMB-3K)

1.8 g of 3-azidobenzoyl chloride (N ₃ C ₆ H ₄ COCl) was dissolved in 15 mL of THF. Under a nitrogen gas atmosphere, 3.6 g of 3-triethoxysilylpropylamine (H ₂ N(CH ₂ ) ₂ Si(OC ₂ H ₅ ) ₃ ) and 2.1 g of TEA were dissolved in 20 mL of THF and added dropwise at room temperature while stirring. did. Stirring was continued for an additional 2 hours to complete the reaction. After completion of the reaction, the solution containing THF was distilled off, and the resulting crude product was purified by column chromatography (eluent: acetone/hexane = 85/15) to yield 62% (2.2 g) of pale yellow oil. got From spectra and the like, the product was confirmed to be N-(3-triethoxysilylpropyl)-3-azidobenzamide.

(4) Synthesis of N,N-bis(3-triethoxysilylpropyl)-4-azidobenzamide (IMB-4KB)

1.8 g of 4-azidobenzoyl chloride (N ₃ C ₆ H ₄ COCl) was dissolved in 15 mL of THF. Under an atmosphere of nitrogen gas, 6 g of bis(3-triethoxysilylpropyl)amine (HN((CH ₂ ) ₃ Si(OC ₂ H ₅ ) ₃ ) ₂ ) and 2.1 g of TEA were dissolved in 20 mL of THF and stirred at room temperature. dripped with Stirring was continued for an additional 2 hours to complete the reaction. After completion of the reaction, the solution containing THF was distilled off, and the obtained crude product was purified by column chromatography (eluent: acetone/hexane=85/15) to obtain a pale yellow oil with a yield of 61%. From spectra and the like, the product was confirmed to be N,N-bis(3-triethoxysilylpropyl)-4-azidobenzamide.

(5) Synthesis of N,N-bis(3-triethoxysilylpropyl)-3-azidobenzamide (IMB-3KB)

1.8 g of 3-azidobenzoyl chloride (N ₃ C ₆ H ₄ COCl) was dissolved in 15 mL of THF. Under an atmosphere of nitrogen gas, 6 g of bis(3-triethoxysilylpropyl)amine (HN((CH ₂ ) ₃ Si(OC ₂ H ₅ ) ₃ ) ₂ ) and 2.1 g of TEA were dissolved in 20 mL of THF and stirred at room temperature. dripped with Stirring was continued for an additional 2 hours to complete the reaction. After completion of the reaction, the solution containing THF was distilled off, and the obtained crude product was purified by column chromatography (eluent: acetone/hexane=85/15) to obtain a pale yellow oil with a yield of 62%. From spectra and the like, the product was confirmed to be N,N-bis(3-triethoxysilylpropyl)-3-azidobenzamide.

(6) Synthesis of N,N'-((diethoxysilanediyl)bis(3-propyl-3,1-diyl)bis(4-azidobenzamide)

2.8 g of 4-azidobenzoyl chloride (N ₃ C ₆ H ₄ COCl) was dissolved in 30 mL of THF. Under a nitrogen gas atmosphere, bis(3-aminopropyl)diethoxysilane (2.3 mL) and TEA 2.1 g were dissolved in THF 20 mL and added dropwise at room temperature while stirring. Stir overnight at room temperature. Stirring was continued for an additional 2 hours to complete the reaction. After completion of the reaction, the solution containing THF was distilled off, and the obtained crude product was purified by column chromatography (eluent: acetone/hexane=85/15) to obtain a pale yellow oil with a yield of 50%. The spectrum confirmed that the product was N,N'-((diethoxysilanediyl)bis(3-propyl-3,1-diyl)bis(4-azidobenzamide).

(7) Preparation of Silsesquioxane Compound (IMB-4KP) Represented by Formula (19) 3-Azidobenzoyl chloride (N ₃ C ₆ H ₄ COCl) was dissolved in THF. In an atmosphere of nitrogen gas, a starting oligomer (manufactured by Gelest, USA), which is a hydrolytic condensate of 3-aminopropyltriethoxysilane, and TEA were dissolved in THF and added dropwise at room temperature while stirring. Stirring was continued to complete the reaction. After completion of the reaction, the solution containing THF was distilled off, and the resulting crude product was purified to obtain the desired product. The target product was the silsesquioxane compound represented by formula (19). From the spectrum, it was confirmed that l, m and n in formula (19) were l:m:n=1:1:0 in the product.

<1. Effect of IMB-K in electroless plating on various resin substrates>
For each resin substrate shown in Table 2, according to the flowchart shown in FIG. 3, a copper coating having a thickness of 20 μm was formed and the adhesion was tested. As shown in Table 2, acetone or ethanol was used in the degreasing step S1 depending on the resin base material. In the pretreatment step S2, corona discharge treatment or oxygen plasma treatment (100 mL/min, 5 minutes, 200 W) was applied to the resin substrate. In the IMB (compound α) supporting treatment S3, the substrate was immersed in an ethanol solution of IMB-4K for 30 seconds. In the post-treatment step S4, the sample was irradiated with ultraviolet rays from a UV-LED irradiator at an irradiation energy of 200 mJ/cm ² . Steps S3 and S4 were repeated twice. In the post-IMB heat treatment step S6, the resin substrate was held at 80° C., 110° C. or 125° C. for 10 minutes. A copper coating with a thickness of 20 μm was obtained through the electroless plating process S7 and the electrolytic plating process S8. Annealing was performed at 150° C. for 10 minutes in order to relax the residual stress of the plating. After electroless plating, after electrolytic plating, and after annealing, the appearance of the copper coating formed on each resin substrate was observed. Also, the peel strength of the copper coating was measured for each resin substrate. A force gauge ZTA-50N was attached to a vertical electric measuring stand MX2-500N (manufactured by Imada Co., Ltd.) to configure a peel strength tester for 90° peeling. The peeling speed was 50 mm/min. Three samples were prepared for each resin base material, and the front and back surfaces were measured, and the average values of the maximum and average peel strength values were obtained.

All of these resin substrates are resins in which an electroless plated copper coating is not formed without IMB supporting treatment, or even if formed, the adhesion strength of the copper coating is extremely weak. The treatment produced a copper coating with good appearance and adhesion. In addition, for the fluorine-based composite resin substrate of sample #9, we have conventionally carried out IMB support treatment using 2,4-diazido-6-(3-triethoxysilylpropyl)amino-1,3,5-triazine. The maximum peel strength of 6.82 N/cm was obtained by a process that combined electroless plating with IMB-4K, but the IMB supporting treatment using IMB-4K and electroless plating can achieve a peel strength that greatly exceeds that. I found out.

<2. Effect of various compounds α in electroless plating of cycloolefin polymer (COP) sheet>
A 20 μm thick copper coating was formed on a COP sheet (0.1 mm thick, sample #41) according to the flow diagram shown in FIG. 3, and the adhesion was tested. Acetone was used in the degreasing cleaning step S1. In the pretreatment step S2, oxygen plasma treatment (100 mL/min, 2 min, 200 W) was performed. In the IMB supporting treatment S3, the substrate was immersed in an ethanol solution of IMB-4K for 30 seconds. In the post-treatment step S4, the sample was irradiated with ultraviolet rays from a UV-LED irradiator at an irradiation energy of 200 mJ/cm ² . Then, heat treatment was performed at 125° C. for 15 minutes. Steps S3 and S4 were repeated and performed a total of two times. The post-IMB heat treatment step S6 was not performed. A copper coating with a thickness of 20 μm was obtained through the electroless plating process S7 and the electrolytic plating process S8. In the electroless plating process S7, an annealing process S75 was performed at 110° C. for 60 minutes. After electroplating, the peel strength of the copper coating was measured. Three samples were prepared for each sample and measured for each, and the average value of the peel strength was obtained. Peel strength was 6.09 N/cm.

Regarding the COP sheets (samples #42 to #45) having the same material and thickness as sample #41, the type of compound α used in the IMB supporting treatment S3 and whether only heat treatment is performed in the post-treatment step S4 (represented by "H") Alternatively, a copper coating with a thickness of 20 μm was formed in the same process as sample #41, except that both ultraviolet irradiation treatment and heat treatment were performed (represented as “UV + H”), and the peel strength was determined. . The results are shown below. The conditions for ultraviolet irradiation in the post-treatment step S4 were the same as those for the sample #41, and the conditions for the heat treatment in the post-treatment step S4 were 125° C. and 15 minutes.
Sample Compound α Post-treatment Peel strength (N/cm)
#41 IMB-4K UV+H 6.09
#42 IMB-3K UV+H 4.78
#43 IMB-3KB UV+H 4.23
#44 IMB-4KH 4.92
#45 IMB-3KBH 4.91

<3. Effect of Various Compounds α of Composite Formed by Thermocompression Bonding of Sheet-like Substances>
A polytetrafluoroethylene (PTFE) sheet (sample #110) was prepared by thermocompression bonding a metal foil along the flow diagram shown in FIG. 4, and the peel strength was examined. A PTFE sheet manufactured by Nitto Denko (defluorinated, thickness 0.18 mm) was used. A rolled copper foil having a thickness of 18 μm was used as the metal foil. The surface treatment step Sst for the PTFE sheet was performed along the surface treatment step Sst of FIG. A 1% by mass ethanol solution was applied to a wet thickness of 20 μm. Furthermore, in the post-treatment step S4, ultraviolet irradiation was performed with an irradiation energy of 100 mJ/cm ² . The post-IMB heat treatment step S6 was not performed. Next, in the thermocompression bonding process Shp, the rolled copper foil was thermocompression bonded to the surface of the PTFE sheet at a pressing temperature of 180° C., a pressing pressure of 8 MPa, and a pressing time of 10 minutes. After natural cooling, a peel strength test was performed to obtain a peel strength of 8.0 N/cm.

A bonded body was formed by thermocompression bonding of two substances in the same manner as sample #110 except for the two substances to be thermocompressed and the type of compound α used in the IBM supporting treatment step, and a peel strength test was performed. The results are shown below. The thickness of each material is 20 μm or 18 μm. Also, the solvent for IMB-4KP is water, and the solvent for other compounds α is ethanol.
Sample Substance 1 Substance 2 Compound α Peel strength (N/cm)
#110 PTFE Cu IMB-4K 8.0
#111 PTFE Cu IMB-3K 7.8
#112 PTFE Cu IMB-4KB 8.0
#113 PTFE Al IMB-4KP 6.5
#114 PI PI IMB-4K 7.2
#115 PI PTFE IMB-4K 8.9
#116 PI Cu IMB-4K 3.9
#117 PI Al IMB-4K 2.1
#118 PI Al None 0.0

From the results of the above Reference Examples, compound α1 having, in one molecule, a benzene ring, an alkoxysilyl group, and one or more groups selected from the group consisting of an azide group, an azidosulfonyl group and a diazomethyl group, and the above compound It can be seen that the use of the compound α, which is at least one of the compounds α2 obtained by hydrolytic condensation of the hydrolyzable silane compound containing α1, enables strong bonding between the metal and the resin. Therefore, when such a compound α is used for bonding between layers of an electromagnetic shielding laminate, as in Example 1 etc., delamination is unlikely to occur when manufacturing a shield printed wiring board, and bending resistance is sufficient. It is clear that a high electromagnetic shielding laminate can be obtained.

Reference Signs List 10, 20 electromagnetic wave shield laminate 11 adhesive layer 12, 22 shield layer 13 insulating layer 14a first compound α layer 14b second compound α layer 22a copper layer 22b silver layer

Claims (14)

a shield layer;
At least one of an adhesive layer and an insulating layer bonded to the shield layer via a compound α,
The compound α is
in one molecule,
a benzene ring;
an alkoxysilyl group;
a compound α1 having one or more groups selected from the group consisting of an azide group, an azidosulfonyl group and a diazomethyl group; and a compound α2 obtained by hydrolytic condensation of a hydrolyzable silane compound containing the compound α1.
An electromagnetic wave shield laminate, which is at least one of The electromagnetic wave shield laminate according to claim 1, wherein the compound α is a compound in which one or more groups selected from the group consisting of the azide group, the azidosulfonyl group and the diazomethyl group are directly bonded to the benzene ring. . 3. The electromagnetic wave shield laminate according to claim 1, wherein the compound α1 is a compound represented by the following formula (1) or (2).

In formula (1), R ¹ is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a phenyl group, an alkoxy group having 1 to 12 carbon atoms, or a hydroxy group. A plurality of R ² are each independently a hydrogen atom, a halogen, or a monovalent organic group. X ¹ is an azide group, an azidosulfonyl group, or a diazomethyl group. Y ¹ is a single bond, an ester group, an ether group, a thioether group, an amide group, a urethane group, a urea group, a group represented by —NHR ³ —, or a group represented by the following formula (3a) or (3b) is. R ³ is an alkyl group having 1 to 6 carbon atoms. Z ¹ is a single bond, a methylene group, an alkylene group having 2 to 12 carbon atoms, or -NH-, -O-, -S- and - at the end of an alkylene group having 2 to 12 carbon atoms or between the carbon-carbon bonds; A group containing one or more groups of S(O)—. m is an integer from 1 to 3; When each of R ¹ , X ¹ , Y ¹ and Z ¹ is plural, each independently satisfies the above definition. However, at least one of one or more R ¹ is an alkoxy group having 1 to 12 carbon atoms.
In formula (2), a plurality of R ⁴ , R ⁵ and R ⁶ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a phenyl group, an alkoxy group having 1 to 12 carbon atoms, or a hydroxy group. and at least one of the plurality of R ⁴ , R ⁵ and R ⁶ is an alkoxy group having 1 to 12 carbon atoms. A plurality of R ⁷ are each independently a hydrogen atom, a halogen, or a monovalent organic group. X2 is an azide group, an ^{azidosulfonyl} group, or a diazomethyl group. A plurality of Z ² are each independently a single bond, a methylene group, an alkylene group having 2 to 12 carbon atoms, or —NH—, —O between the terminal of an alkylene group having 2 to 12 carbon atoms or a carbon-carbon bond. A group containing one or more of -, -S- and -S(O)-.

^In formula (3a), R8 is a hydrogen atom or a methyl group. comprising the adhesive layer,
4. The adhesive layer according to claim 1, 2 or 3, wherein the adhesive layer contains at least one resin selected from the group consisting of polyamide resins, polyester resins, acrylic resins, epoxy resins, polyurethane resins and polyurethane urea resins. electromagnetic wave shielding laminate. comprising the adhesive layer,
4. The electromagnetic wave shield laminate according to claim 1, wherein the adhesive layer has electrical conductivity. Equipped with the above shield layer,
6. The shield layer according to any one of claims 1 to 5, wherein the shield layer contains at least one metal selected from the group consisting of nickel, copper, silver, tin, gold, palladium, aluminum, chromium, titanium and zinc. An electromagnetic wave shield laminate as described. Equipped with the above shield layer,
The electromagnetic wave shield laminate according to any one of claims 1 to 5, wherein the shield layer has a layer containing copper and a layer containing silver. The electromagnetic wave shield laminate according to any one of claims 1 to 7, which is for a flexible printed wiring board. The electromagnetic wave shield laminate according to any one of claims 1 to 7, which is for a semiconductor package. A step of bonding the shield layer and at least one of the adhesive layer and the insulating layer via the compound α,
The compound α is
in one molecule,
a benzene ring;
an alkoxysilyl group;
a compound α1 having at least one group selected from the group consisting of an azide group, an azidosulfonyl group and a diazomethyl group; and a compound α2 obtained by hydrolytic condensation of a hydrolyzable silane compound containing the compound α1.
A method for manufacturing an electromagnetic shielding laminate, which is at least one of a printed wiring board;
A shield printed wiring board comprising: the electromagnetic wave shield laminate according to any one of claims 1 to 8, which is adhered to the printed wiring board. A step of adhering the electromagnetic shield laminate according to any one of claims 1 to 8 or the electromagnetic shield laminate obtained by the method for manufacturing the electromagnetic shield laminate according to claim 9 to a printed wiring board. A method for manufacturing a shield printed wiring board comprising: A semiconductor package comprising the electromagnetic wave shield laminate according to claim 9 . An electronic device comprising the shield printed wiring board according to claim 11 or the semiconductor package according to claim 13.

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