WO2020085137A1

WO2020085137A1 - Layered body, and layered body manufacturing method

Info

Publication number: WO2020085137A1
Application number: PCT/JP2019/040405
Authority: WO
Inventors: 聡健古谷; 白髪　潤; 深澤　憲正
Original assignee: Dic株式会社
Priority date: 2018-10-22
Filing date: 2019-10-15
Publication date: 2020-04-30
Also published as: TW202031935A; JP6892021B2; JPWO2020085137A1

Abstract

The present invention provides a layered body having: an insulating layer (A) that has a surface in which a trench is formed; a metal particulate layer (B) that is layered on the trench; and a metal plating layer (C) that is layered within the trench and on the metal particulate layer (B). The present invention also provides a layered body having a barrier metal plating layer (E) between the metal particulate layer (B) and the metal plating layer (C). The present invention further provides a layered body having a primer layer (D) between the insulating layer (A) and the metal particulate layer (B). These layered bodies can be manufactured according to a simple method without the use of large-scale vacuum equipment or similar, and allow a metal layer to be formed on a trench.

Description

Laminated body and method for manufacturing laminated body

The present invention relates to a laminate and a method for manufacturing the laminate.

In recent years, due to miniaturization of semiconductor elements, high integration of wiring due to high integration, multi-layer wiring, shift to wafer level package (WLP), panel level package (PLP), wiring and rewiring of copper, titanium, etc. There is a demand for miniaturization.

In Non-Patent Document 1, a trench pattern is formed on a high-resolution photosensitive material, a seed layer is formed on the obtained pattern by sputtering, and then electrolytic plating is performed to form a wiring layer. It is disclosed.

However, in the method of forming the seed layer on the insulating resin layer by the sputtering method, a large vacuum facility is required to form the seed layer, and there is a problem that the substrate size is limited due to design.

The present invention has been made in view of the above-described problems, and an object thereof is to provide a laminated body in which a metal layer is formed in a trench, which can be manufactured by a simple method without using large-scale vacuum equipment. . Moreover, this invention is providing the manufacturing method of the said laminated body.

As a result of earnest research to solve the above problems, the present inventors have found that the above problems can be solved by adopting the following configuration, and have completed the present invention.

That is, the laminate according to the present invention,
An insulating layer (A) having a surface in which a trench is formed,
A metal particle layer (B) laminated in the trench,
It has a metal plating layer (C) laminated in the trench and on the metal particle layer (B).

In the laminated body according to the present invention, for example, a trench formed in an insulating layer (A) is coated with a dispersion liquid (b) containing metal particles to form a metal particle layer (B), and then a plating treatment is performed. And forming a metal plating layer (C) on the metal particle layer (B).

As described above, the laminated body according to the present invention can be manufactured by a simple method without using a large vacuum facility for forming the metal layer (metal plating layer) in the trench.

Further, the method for manufacturing a laminate according to the present invention,
A step (1) of preparing an insulating layer (A) having a surface in which a trench is formed,
A step (2) of applying a dispersion liquid (b) containing metal particles to the trench to form a metal particle layer (B), and
The method is characterized by including a step (3) of performing a plating treatment to form a metal plating layer (C) in the trench and on the metal particle layer (B).

According to the method for manufacturing a laminated body of the present invention, the dispersion liquid (b) containing metal particles is applied to the trench to form the metal particle layer (B), and then the metal that is the metal layer is plated. Since the plating layer (C) is formed, it can be manufactured by a simple method without using a large-scale vacuum facility for forming the metal layer (metal plating layer) in the trench. Further, since the metal particle layer (B) is formed by applying the dispersion liquid (b) containing metal particles to the trench, the metal particle layer (having a relatively uniform thickness) is formed on both the bottom surface and the side wall of the trench. B) can be formed. As a result, a uniform metal plating layer (C) can be formed in the trench.

According to the present invention, it is possible to provide a laminate in which a metal layer is formed in a trench, which can be manufactured by a simple method without using a large-scale vacuum facility or the like. Moreover, the manufacturing method of the said laminated body can be provided.

It is a cross-sectional schematic diagram of the laminated body which concerns on one Embodiment of this invention. It is a cross-sectional schematic diagram for demonstrating the manufacturing method of the laminated body which concerns on this embodiment. It is a cross-sectional schematic diagram for demonstrating the manufacturing method of the laminated body which concerns on this embodiment. It is a cross-sectional schematic diagram for demonstrating the manufacturing method of the laminated body which concerns on this embodiment. It is a cross-sectional schematic diagram for demonstrating the manufacturing method of the laminated body which concerns on this embodiment.

Hereinafter, embodiments of the present invention will be described with reference to the drawings. In the following, first, the laminated structure of the laminated body of the present embodiment will be described.

The laminated body according to the present invention includes an insulating layer (A) having a surface in which a trench is formed, a metal particle layer (B) laminated in the trench, and in the trench and on the metal particle layer (B). It has a metal plating layer (C) laminated.

In the present specification, a trench means a line-shaped groove formed on one surface side and not penetrating to the other surface. In the present specification, a through hole (for example, a via hole) penetrating from one surface side to the other surface does not correspond to a trench. That is, the laminated body having the through hole but not the trench does not correspond to the laminated body according to the present invention. The laminated body according to the present invention may include the through holes and the like in addition to the trench.

In the laminated body according to the present invention, the metal plating layer (C) may be formed in at least some of the trenches, and the metal plating layer (C) may not be formed in all the trenches. Further, in the laminated body according to the present invention, the metal plating layer (C) may be formed in all the trenches.

In the present specification, the upper surface of the metal plating layer (C) may be flush with the upper surface of the insulating layer (A), or may be higher than the upper surface of the insulating layer (A). It may be below the upper surface of (A). That is, the metal plating layer (C) may be formed in the entire trench, or may be formed only in a part of the trench. However, from the viewpoint of use as wiring, the upper surface of the metal plating layer (C) is preferably flush with the surface of the insulating layer (A) (see, for example, FIG. 1). In addition, the laminated body according to the present invention may have a plurality of trenches, and may have a location where the plurality of trenches are arranged in parallel (see, for example, FIG. 1). Hereinafter, a specific example will be described.

In the embodiments described below, the laminate has a base material, an insulating layer (A), a primer layer (D), a metal particle layer (B), a barrier metal plating layer (E), and a metal. The case of including the plating layer (C) will be described. If the laminate according to the present invention has at least the insulating layer (A), the metal particle layer (B), and the metal plating layer (C). Good.

FIG. 1 is a schematic sectional view of a laminate according to an embodiment of the present invention. As shown in FIG. 1, the laminated body 10 includes a base material 12, an insulating layer 14, a primer layer 16, a metal particle layer 18, a barrier metal plating layer 20, and a metal plating layer 22. The substrate 12 is not particularly limited, but is preferably a substrate that serves as a support when forming the insulating layer 14, and examples thereof include a silicon wafer and a chip. Moreover, the base material 12 may have flexibility.

A trench 15 is formed on the upper surface 14a of the insulating layer 14. A primer layer 16 is formed on the bottom surface 15 a of the trench 15 and the sidewall 15 b of the trench 15. The thickness of the primer layer 16 on the bottom surface 15a and the thickness of the primer layer 16 on the side wall 15b are substantially the same.

A metal particle layer 18 is formed on the primer layer 16 along the primer layer 16. The thickness of the metal particle layer 18 on the bottom surface 15a and the thickness of the metal particle layer 18 on the side wall 15b are substantially the same.

A barrier metal plating layer 20 is formed on the metal particle layer 18 along the metal particle layer 18. The thickness of the barrier metal plating layer 20 on the bottom surface 15a and the thickness of the barrier metal plating layer 20 on the side wall 15b are substantially the same.

A metal plating layer 22 is formed on the barrier metal plating layer 20 so as to fill the inside of the trench 15. In the present embodiment, the upper surface of the metal plating layer 22 is flush with the upper surface 14 a of the insulating layer 14.

The insulating layer 14 corresponds to the insulating layer (A) of the present invention. The primer layer 16 corresponds to the primer layer (D) of the present invention. The metal particle layer 18 corresponds to the metal particle layer (B) of the present invention. The barrier metal plating layer 20 corresponds to the barrier metal plating layer (E) of the present invention. The metal plating layer 22 corresponds to the metal plating layer (C) of the present invention.

The size of the trench 15 can be appropriately set according to the application of the laminated body. For example, from the viewpoint of highly integrating the plurality of trenches 15 (metal plating layer 22), it is preferable that the trenches 15 are small within a range that can be used as wiring. On the other hand, when it is required to withstand high voltage and high current, a certain size is required.
From the above viewpoint, the depth d of the trench 15 is preferably 0.5 μm or more and 1000 μm or less, more preferably 0.5 μm or more and 500 μm or less, and further preferably 0.5 μm or more and 100 μm or less. The width w of the trench 15 is preferably 0.5 μm or more and 1000 μm or less, more preferably 0.5 μm or more and 500 μm or less, and further preferably 0.5 μm or more and 100 μm or less.

When there are a plurality of trenches 15 as in the laminated body 10, the distance a between the plurality of trenches 15 is not particularly limited, but is preferably 0.5 μm or more and 1000 μm or less, more preferably 0.5 μm or more and 500 μm or less, and 0 It is more preferably 0.5 μm or more and 100 μm or less. In particular, when the barrier metal plating layer 20 is provided as in the present embodiment, the barrier metal plating layer 20 can prevent the metal of the metal plating layer 22 from diffusing into the insulating layer 14. This is also clear from the examples. Therefore, even if the distance a between the trenches 15 is narrowed, the insulation is not destroyed, and a short circuit between the trenches 15 can be prevented. From the above viewpoint, the distance a between the plurality of trenches 15 is preferably 0.5 μm or more and 1000 μm or less, more preferably 0.5 μm or more and 500 μm or less, and further preferably 0.5 μm or more and 100 μm or less. The width w of the trench 15 is preferably 0.5 μm or more and 1000 μm or less, more preferably 0.5 μm or more and 500 μm or less, and further preferably 0.5 μm or more and 100 μm or less.
In this specification, the distance a between the trenches 15 refers to the distance from the side wall 15a of one trench 15 to the side wall 15a of the other trench 15 that is the closest.

The use of the laminated body 10 is not particularly limited, but for example, it can be used as a wiring layer having the metal plating layer 22 as a wiring.

As will be described later, in the laminated body 10, the dispersion liquid (b) containing the metal particles is applied to the trench formed in the insulating layer (A) to form the metal particle layer (B), and then the plating treatment is performed. And forming a metal plating layer (C) on the metal particle layer (B). That is, the stacked body 10 does not require large-scale vacuum equipment for forming the metal layer (metal plating layer (C)) in the trench. Further, it is not necessary to perform the reverse sputtering process before forming the metal layer. Further, since the barrier metal plating layer 20 is provided, it is possible to prevent metal diffusion between the trenches 15 and to prevent a short circuit between the trenches 15 even if the distance a is narrowed. This is also clear from the examples.

The example of the laminated structure of the laminated body of the present embodiment has been described above.

Next, each layer included in the laminated body of the present embodiment will be described.

[Insulating layer (A)]
The insulating layer (A) is made of insulating resin and has a surface in which a trench is formed. The insulating resin is not particularly limited as long as it has electric insulation, and examples thereof include polyimide, polyamide imide, polyamide, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, acrylonitrile-butadiene-styrene (ABS) resin, ABS. Alloys of styrene and polycarbonate, acrylic resins such as poly (meth) acrylate, polytetrafluoroethylene, polyvinylidene fluoride, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polyethylene, polypropylene, polyurethane, liquid crystal polymer (LCP) , Polyetheretherketone (PEEK), polyphenylene sulfide (PPS), polyphenylene sulfone (PPSU), epoxy resin, cellulose nanofiber, etc. That.
Further, the insulating resin may be a photosensitive resin, for example, polybenzoxazole precursor resin, polybenzoxazole resin, polyamide resin, polyimide precursor resin, polyimide resin, novolac resin, resole resin, hydroxystyrene resin. Etc. These photosensitive resins may be positive type or negative type. Further, the patterned insulating layer (A) can be formed by irradiating the photosensitive resin with pattern light. Furthermore, since the insulating layer (A) can be made tougher, it is preferable to heat cure after patterning.

As the insulating layer (A), it is preferable to use a layer having a thickness of about 1 μm or more and 200 μm or less from the viewpoint of realizing weight reduction and thinning of the final product obtained by using the laminate.

[Primer layer (D)]
A primer layer (D) may be provided on the bottom surface of the trench and the sidewall of the trench. The primer layer (D) is a layer provided for the purpose of enhancing the adhesiveness between the insulating layer (A) and the metal particle layer (B).

Examples of the material forming the primer layer (D) include urethane resin, acrylic resin, core-shell type composite resin having urethane resin as a shell and acrylic resin as a core, epoxy resin, imide resin, amide resin, melamine resin. , A phenol resin, a urea formaldehyde resin, a blocked isocyanate obtained by reacting a polyisocyanate with a blocking agent such as phenol, polyvinyl alcohol, polyvinyl pyrrolidone, and the like. The core-shell type composite resin having a urethane resin as a shell and an acrylic resin as a core is obtained, for example, by polymerizing an acrylic monomer in the presence of the urethane resin. These resins may be used alone or in combination of two or more.

The primer layer (D) can be formed by applying and drying the primer composition (d) for forming the primer layer (D).

As the primer composition (d), a composition containing the material and a solvent can be used.

As the solvent, various organic solvents and aqueous media can be used.

Although the primer layer (D) varies depending on the use of the laminate, etc., it preferably has a thickness of 0.01 μm or more and 300 μm or less, and a thickness of 0.01 μm or more and 20 μm or less. More preferable.

[Metal particle layer (B)]
The metal particle layer (B) is laminated directly on the insulating layer (A) or on the insulating layer (A) via the primer layer (D). Examples of the metal forming the metal particle layer (B) include copper, silver, gold, nickel, palladium, platinum, cobalt and the like. Among these, silver is preferable because it is difficult to oxidize the particle surface, has a high activity as an electroless plating catalyst, is a metal having high conductivity, and easily forms the metal plating layer (C).

[Barrier metal plating layer (E)]
A barrier metal plating layer (E) may be provided on the metal particle layer (B). The barrier metal plating layer (E) is a layer provided for the purpose of preventing the metal of the metal plating layer (C) from diffusing. Examples of the metal forming the barrier metal plating layer (E) include nickel, nickel-molybdenum, nickel-molybdenum-boron, nickel-molybdenum-phosphorus, chromium, cobalt, cobalt-phosphorus, molybdenum, cobalt-tungsten-phosphorus, cobalt. -Tungsten-boron and the like.

[Metal plating layer (C)]
The metal plating layer (C) is laminated directly on the metal particle layer (B) or on the metal particle layer (B) via the barrier metal plating layer (E). Examples of the metal forming the metal plating layer (C) include copper, gold, silver, nickel, chromium, cobalt and tin. Among these, when the metal plating layer (C) is used for wiring, copper is preferable because it is relatively inexpensive and has high conductivity.

[Combination of Metal Particle Layer (B) and Primer Layer (D)]
When the structure having the primer layer (D) is used, the combination of the metal particle layer (B) and the primer layer (D) includes a compound (b1) having a basic nitrogen atom-containing group as the metal particle layer (B). And a layer containing the metal particles (b2) and a layer containing the compound (d1) having a functional group [X] as the primer layer (D). With such a structure, the basic nitrogen atom-containing group contained in the compound (b1) contained in the metal particle layer (B) and the functional group contained in the compound (d1) contained in the primer layer (D). The group [X] reacts with each other to form a bond, and the adhesiveness between the insulating layer (A) and the metal plating layer (C) can be further enhanced.

Examples of the basic nitrogen atom-containing group contained in the compound (b1) include imino group, primary amino group, secondary amino group and the like.

When a compound having a plurality of basic nitrogen atom-containing groups in the molecule is used as the compound (b1), one of the basic nitrogen atom-containing groups is a primer when the metal particle layer (B) is formed. Participating in binding to the functional group [X] of the compound (d1) contained in the layer (D), and the other contributing to interaction with the metal particles (b2) such as silver in the metal particle layer (B). It is preferable to improve the adhesion between the metal particle layer (B) and the primer layer (D).

Examples of the metal particles (b2) include copper, silver, gold, nickel, palladium, platinum, cobalt and the like. Further, among these, copper, silver and gold are preferable because they have high conductivity, and further, silver is relatively inexpensive, the particle surface is not easily oxidized, and the activity as an electroless plating catalyst is high. To more preferred.

Examples of the functional group [X] include keto group, epoxy group, carboxylic acid group, carboxylic acid anhydride group, alkylolamide group, isocyanate group, vinyl group, alkyl halide group, acryloyl group, cyanamide group, urea bond, acyl halide. Groups and the like. The keto group refers to a carbonyl group derived from a ketone. The isocyanate group may be blocked with a blocking agent from the viewpoint of preventing the reaction at room temperature.

Among them, as the functional group [X], a keto group, from the viewpoint of preventing the formation of by-products such as halogen, acid and amine when reacted with the basic nitrogen atom-containing group of the compound (b1), It is preferable to use one or more selected from the group consisting of an epoxy group, an acid group, an alkylolamide group and an isocyanate group.

As the compound (d1) having the functional group [X], for example, a resin having the functional group [X] can be used. Specific examples of the resin having the functional group [X] include a urethane resin having the functional group [X], a vinyl resin having the functional group [X], and a urethane-vinyl having the functional group [X]. Composite resin, epoxy resin having the functional group [X], imide resin having the functional group [X], amide resin having the functional group [X], melamine resin having the functional group [X], the functional group A phenol resin having [X], polyvinyl alcohol having the functional group [X], polyvinylpyrrolidone having the functional group [X], and the like can be used. Among them, at least one selected from the group consisting of a urethane resin having the functional group [X], a vinyl resin having the functional group [X], and a urethane-vinyl composite resin having the functional group [X]. Preference is given to using.

The primer layer (D) is present in a coating film formed by applying the primer composition (d) containing the compound (d1) having the functional group [X] to the surface of the support, and drying the composition. The functional group [X] of the compound (d1) reacts with the basic nitrogen atom-containing group of the compound (b1) contained in the metal particle layer (B) to form a bond.

When the primer layer (D) is in contact with the surface of the dispersion (b) containing the compound (b1) having the basic nitrogen atom-containing group and the metal particles (b2), the primer layer (D) may be dried, heated, or the like. By passing through the steps, a basic nitrogen atom-containing group contained in the compound (b1) is reacted with a functional group [X] contained in the compound (d1) contained in the coating film to form a bond. A laminated structure composed of the metal particle layer (B) and the primer layer (D) is formed.

This makes it possible to obtain a laminate having excellent adhesion at the interface between the metal particle layer (B) and the primer layer (D).

The primer layer (D) is formed by applying the primer composition (d) containing the compound (d1) having the functional group [X] and drying it. The compound (d1) contained in the coating film has a functional group [X] that reacts with the basic nitrogen atom-containing group of the compound (b1) contained in the metal particle layer (B).

The combination of the metal particle layer (B) and the primer layer (D) is disclosed in more detail, for example, in International Publication No. 2013/146195.

Next, a method for manufacturing the laminated body 10 (see FIG. 1) according to the present embodiment will be described. 2 to 5 are schematic cross-sectional views for explaining the method for manufacturing the laminate according to the present embodiment.

[Method for manufacturing laminated body]
In the method for manufacturing the laminated body according to the present embodiment, as shown in FIG. 2, first, the insulating layer 14 having the surface 14a in which the trench 15 is formed is prepared (step (1)). The insulating layer 14 to be prepared may have a through hole or the like formed in addition to the trench 15. The insulating layer 14 may be formed on the base material 12 shown in FIG. 2 or may be the insulating layer 14 alone.

The insulating layer 14 in which the trench 15 is formed can be obtained by preparing an insulating layer in which no trench is formed and forming a trench in this insulating layer. As a method of forming the trench in the insulating layer in which the trench is not formed, for example, a nanoimprint method (also referred to as “embossing method”) or a screen printing method can be adopted. When a photosensitive resin is used as the material of the insulating layer (A), the trench is formed by exposing and developing the uncured layer before curing the photosensitive resin through a desired pattern mask, for example. It can be obtained by forming an uncured layer in which a trench is formed and further thermally curing the uncured layer. The photosensitive resin may be positive-type photosensitive or negative-type photosensitive.

Next, if necessary, the primer composition (d) is applied to the insulating layer 14, and the solvent contained in the primer composition (d) is removed by drying or the like, whereby the primer layer 16 (see FIG. 3). Are formed (step (1-1)). Specifically, the insulating layer 14 is formed along the bottom surface 15a and the side wall 15b of the trench 15.
When the specific combination described above is adopted as the metal particle layer 18 and the primer layer 16, the primer layer 16 applies the primer composition (d) to the insulating layer 14 and, if necessary, drying or the like. Thereby, the primer layer 16 is provided, and the dispersion liquid (b) containing the compound (b1) having the basic nitrogen atom-containing group and the metal particles (b2) is applied to the surface of the coating film, followed by baking. It can be manufactured by going through a heating step such as.

Examples of the method of applying the primer composition (d) to the surface of the insulating layer 14 include a gravure method, an offset method, a flexographic method, a pad printing method, a gravure offset method, a letterpress method, a reverse printing method, a screen method, and a micro method. Contact method, reverse method, air doctor coater method, blade coater method, air knife coater method, squeeze coater method, impregnation coater method, transfer roll coater method, kiss coater method, cast coater method, spray coater method, ink jet method, die coater method, Examples thereof include spin coater method, bar coater method, dip coater method and the like.

Next, the dispersion liquid (b) containing metal particles is applied to the trench 15 to form the metal particle layer 18 (see FIG. 4) (step (2)). When the primer layer 16 is formed, the metal particle layer 18 is formed along the primer layer 16. When the primer layer 16 is not formed, the metal particle layer 18 is formed along the insulating layer 14 (the bottom surface 15a and the side wall 15b of the trench 15).

The shape of the metal particles used for forming the metal particle layer 18 is preferably particulate or fibrous. The size of the metal particles is preferably nano size. Specifically, when the metal particles are in the form of particles, a fine pattern can be formed and the resistance value can be further reduced. Therefore, the average particle diameter is preferably 1 nm or more and 100 nm or less, and more preferably 1 nm or more and 50 nm or less. preferable. The "average particle diameter" is a volume average value measured by a dynamic light scattering method after diluting the metal particles with a good dispersion solvent. "Nanotrack UPA-150" manufactured by Microtrac can be used for this measurement.

On the other hand, even when the shape of the metal particles is fibrous, a fine pattern can be formed and the resistance value can be further reduced. Therefore, the fiber diameter is preferably 5 nm or more and 100 nm or less, more preferably 5 nm or more and 50 nm or less. The fiber length is preferably 0.1 μm or more and 100 μm or less, more preferably 0.1 μm or more and 30 μm or less.

The content of the metal particles in the dispersion liquid (b) is preferably 1% by mass or more and 90% by mass or less, more preferably 1% by mass or more and 60% by mass or less, and further preferably 1% by mass or more and 10% by mass or less. preferable.

The components to be added to the dispersion liquid (b) include a dispersant and a solvent for dispersing the metal particles in a solvent, and, if necessary, a surfactant, a leveling agent, a viscosity modifier, and Membrane aids, defoamers, preservatives and the like can be mentioned.

A low molecular weight or high molecular weight dispersant is preferably used to disperse the metal particles in the solvent. Examples of the dispersant include dodecanethiol, 1-octanethiol, triphenylphosphine, dodecylamine, polyethylene glycol, polyvinylpyrrolidone, polyethyleneimine, polyvinylpyrrolidone; fatty acids such as myristic acid, octanoic acid, stearic acid; cholic acid, Examples thereof include polycyclic hydrocarbon compounds having a carboxyl group such as glycyrudic acid and abintic acid. Among these, a polymer dispersant is preferable because it can improve the adhesion between the metal particle layer (B) and the metal plating layer (C). Examples of the polymer dispersant include polyethyleneimine and polypropyleneimine. Examples thereof include polyalkyleneimine, a compound obtained by adding polyoxyalkylene to the above polyalkyleneimine, a urethane resin, an acrylic resin, a compound containing a phosphoric acid group in the urethane resin or the acrylic resin, and the like.

The amount of the dispersant used to disperse the metal particles is preferably 0.01 parts by mass or more and 50 parts by mass or less, and 0.01 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the metal particles. Is more preferable.

As the solvent used in the dispersion liquid (b), an aqueous medium or an organic solvent can be used. Examples of the aqueous medium include distilled water, ion-exchanged water, pure water, and ultrapure water. Examples of the organic solvent include alcohol compounds, ether compounds, ester compounds and ketone compounds.

Examples of the alcohol compound include methanol, ethanol, n-propanol, isopropyl alcohol, n-butanol, isobutyl alcohol, sec-butanol, tert-butanol, heptanol, hexanol, octanol, nonanol, decanol, undecanol, dodecanol, tridecanol, Tetradecanol, pentadecanol, stearyl alcohol, allyl alcohol, cyclohexanol, terpineol, terpineol, dihydroterpineol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol Mo Butyl ether, tetraethylene glycol monobutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, propylene glycol monopropyl ether, dipropylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monobutyl ether, tri Propylene glycol monobutyl ether and the like can be mentioned.

In addition, in the dispersion liquid (b), ethylene glycol, diethylene glycol, 1,3-butanediol, isoprene glycol and the like can be used, if necessary, in addition to the metal particles and the solvent.

As the surfactant, a general surfactant can be used, and examples thereof include di-2-ethylhexylsulfosuccinate, dodecylbenzenesulfonate, alkyldiphenyletherdisulfonate, alkylnaphthalenesulfonate, and hexametaphosphoric acid. Salt etc. are mentioned.

As the leveling agent, a general leveling agent can be used, and examples thereof include silicone compounds, acetylene diol compounds, and fluorine compounds.

As the viscosity modifier, a general thickener can be used. For example, an acrylic polymer or synthetic rubber latex that can be thickened by adjusting the alkalinity, or a urethane that can be thickened by association of molecules. Examples thereof include resins, hydroxyethyl cellulose, carboxymethyl cellulose, methyl cellulose, polyvinyl alcohol, water-added castor oil, amide wax, polyethylene oxide, metal soap, dibenzylidene sorbitol and the like.

As the film forming aid, a general film forming aid can be used, and examples thereof include an anionic surfactant (such as dioctyl sulfosuccinic acid ester soda salt) and a hydrophobic nonionic surfactant (sorbitan monooleate). Etc.), polyether modified siloxane, silicone oil and the like.

As the antifoaming agent, a general antifoaming agent can be used, and examples thereof include a silicone type antifoaming agent, a nonionic surfactant, a polyether, a higher alcohol, and a polymer type surfactant.

As the preservative, it is possible to use a general preservative, for example, isothiazoline preservatives, triazine preservatives, imidazole preservatives, pyridine preservatives, azole preservatives, pyrithione preservatives and the like. Can be mentioned.

The viscosity of the dispersion liquid (b) (value measured at 25 ° C. using a B type viscometer) is preferably 0.1 mPa · s or more and 500,000 mPa · s or less, and 0.2 mPa · s or more and 10,000 mPa · s or more. s or less is more preferable. When the dispersion liquid (b) is applied by a method such as an inkjet printing method or a letterpress reverse printing method described later, its viscosity is preferably 5 mPa · s or more and 20 mPa · s or less.

Examples of the method of applying the dispersion liquid (b) on the primer layer 16 include a gravure method, an offset method, a flexographic method, a pad printing method, a gravure offset method, a letterpress method, a reverse printing method, a screen method, and a microcontact. Method, reverse method, air doctor coater method, blade coater method, air knife coater method, squeeze coater method, impregnation coater method, transfer roll coater method, kiss coater method, cast coater method, spray coater method, inkjet method, die coater method, spin Examples thereof include a coater method, a bar coater method and a dip coater method.

Among these coating methods, in the case of forming the metal particle layer 18 patterned in the form of fine lines of 0.01 to 100 μm, which is required when realizing high density of electronic circuits, an inkjet method, It is preferable to use the reverse printing method.

As the inkjet printing method, what is generally called an inkjet printer can be used. Specific examples thereof include Konica Minolta EB100, XY100 (manufactured by Konica Minolta IJ Co., Ltd.), Dymatics Material Printer DMP-3000, Dymatics Material Printer DMP-2831 (Fuji Film Co., Ltd.) and the like.

Further, as a reverse printing method, a letterpress reverse printing method and an intaglio reverse printing method are known, and for example, the dispersion liquid (b) is applied to the surface of various blankets to form a plate in which a non-image area is projected. By contacting and selectively transferring the dispersion liquid (b) corresponding to the non-image area onto the surface of the plate, the pattern is formed on the surface of the blanket or the like, and then the pattern is supported by the support. Examples thereof include a method of transferring onto the body (A) (surface).

Mass per unit area of the metal particle layer 18 is preferably from 1 mg / ^{m 2} or more 30,000 / ^{m 2} or less, 1 mg / ^{m 2} or more 5,000 mg / ^{m 2} or less. The thickness of the metal particle layer 18 can be adjusted by controlling the treatment time, the current density, the usage amount of the plating additive, and the like in the plating treatment step when forming the metal plating layer 22.

After the step (2), the metal particle layer 18 is subjected to a barrier metal plating treatment, if necessary, to form a barrier metal plating layer 20 (see FIG. 5) (step (2-1)). Specifically, the barrier metal plating layer 20 is formed along the bottom surface and the side wall 1 of the metal particle layer 18.

The barrier metal plating layer 20 can be formed by electroless plating or electrolytic plating. In the electroless plating process, for example, a metal contained in the electroless plating solution is deposited by bringing the metal particle layer 18 into contact with an electroless plating solution such as nickel, chromium, or cobalt, and is formed of a barrier metal metal film. This is a method of forming an electroless plating layer (coating).

By using hypophosphorous acid, sodium hypophosphite, or amine borane as a reducing agent for the barrier metal plating treatment, an alloy film containing phosphorus and boron in the metal such as nickel, chromium and cobalt can be obtained. Further, by using an electroless plating solution in which a salt such as tungsten, molybdenum, rhenium, or ruthenium is further added to the electroless plating solution of the metal, the barrier metal plating layer 20 in which these metals are co-deposited is formed. be able to.

The barrier metal plating treatment may be electrolytic plating treatment as described above. For the electrolytic plating treatment, electrolytic plating of nickel, chromium, cobalt or the like can be used.

Next, a plating process is performed to form a metal plating layer 22 (see FIG. 1) in the trench 15 and on the metal particle layer 18 so as to fill the trench 15 (step (3)). When the barrier metal plating layer 20 is formed, the barrier metal plating layer 20 is plated to form the metal plating layer 22. When the barrier metal plating layer 20 is not formed, the metal particle layer 18 is plated to form the metal plating layer 22.

As a method of forming the metal plating layer 22, a method of forming by a plating process is preferable. Examples of the plating treatment include wet plating methods such as an electrolytic plating method and an electroless plating method that can easily form the metal plating layer 22. Also, these plating methods may be combined. For example, the metal plating layer 22 may be formed by performing electroless plating after performing electroless plating.

In the electroless plating method, for example, a metal such as copper contained in the electroless plating solution is deposited by bringing the electroless plating solution into contact with the metal particle layer 18 or the barrier metal plating layer 20. This is a method of forming an electroless plating layer (coating) made of a coating.

Examples of the electroless plating solution include those containing a metal such as copper, silver, gold, nickel, chromium, cobalt and tin, a reducing agent, and a solvent such as an aqueous medium and an organic solvent. When the metal plating layer 20 is used as the conductive layer, silver, copper, and gold, which are highly conductive metals, are preferable as the metal species of the electroless plating solution, and relatively inexpensive copper is more preferable.

Examples of the reducing agent include dimethylaminoborane, hypophosphorous acid, sodium hypophosphite, hydrazine, formaldehyde, sodium borohydride, phenol and the like.

As the electroless plating solution, if necessary, a monocarboxylic acid such as acetic acid and formic acid; a dicarboxylic acid compound such as malonic acid, succinic acid, adipic acid, maleic acid and fumaric acid; malic acid, lactic acid, glycol Hydroxycarboxylic acid compounds such as acids, gluconic acid and citric acid; amino acid compounds such as glycine, alanine, iminodiacetic acid, arginine, aspartic acid and glutamic acid; iminodiacetic acid, nitrilotriacetic acid, ethylenediaminediacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, etc. Containing an organic acid such as aminopolycarboxylic acid compound, or a soluble salt of these organic acids (sodium salt, potassium salt, ammonium salt, etc.), and a complexing agent such as amine compound such as ethylenediamine, diethylenetriamine, triethylenetetramine, etc. It can be used for.

The electroless plating solution is preferably used at 20 ° C or higher and 98 ° C or lower.

In the electroplating method, for example, the surface of the metal particle layer 18, the electroless plating layer (coating) formed by the electroless treatment, or the barrier metal plating layer 20 is energized in a state of being in contact with an electroplating solution. In this way, a layer in which a metal such as copper contained in the electrolytic plating solution is installed on the cathode (metal particle layer 18, electroless plating layer (coating) formed by the electroless treatment, or barrier metal plating layer) 20) is deposited on the surface to form an electrolytic plating layer (metal coating).

Examples of the electrolytic plating solution include electrolytic plating solutions of copper, silver, gold, nickel, chromium, cobalt, tin and the like. When the metal plating layer 22 is used as a conductive layer, silver, copper, and gold, which are highly conductive metals, are preferable as the metal species of the electrolytic plating solution, and relatively inexpensive copper is more preferable. When the metal plating layer 22 is used as the conductive layer, it is preferable that the plating metal has a high purity and is free of eutectoid substances.

The electrolytic plating solution is preferably used at 20 ° C or higher and 98 ° C or lower.

As a method of forming the metal plating layer 22, an electroless plating method and an electrolytic plating method can be appropriately selected or combined in order to preferably form the metal plating layer 22 in the trench 15. In particular, when filling the whole of the trench with the metal plating layer (C), it is preferable to perform electroless plating and then electrolytic plating. When the metal plating layer 22 is formed, the metal plating layer is formed on the entire surface of the insulating layer (A). In this case, if necessary, the metal plating layer formed on the surface other than the portion where the trench is formed may be removed to expose the insulating layer (A). As a method for removing the metal plating layer, a conventionally known method can be adopted, and examples thereof include chemical mechanical polishing (CMP).

Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded.

[Preparation of dispersion liquid (b) of metal particles]
Metal particles are obtained by dispersing silver particles having an average particle diameter of 30 nm using a compound obtained by adding polyoxyethylene to polyethyleneimine as a dispersant in a mixed solvent of 30 parts by mass of ethylene glycol and 70 parts by mass of ion-exchanged water. And a polymer dispersant having a basic nitrogen atom-containing group as a reactive functional group were prepared. Next, a dispersion liquid (b) of metal particles was prepared by adding ion-exchanged water, ethanol and a surfactant to the obtained metal particle dispersion liquid and adjusting the viscosity thereof to 10 mPa · s.

[Production of Resin for Primer Layer (D)]
Polycarbonate polyol (an acid group equivalent of 1,000 g / equivalent polycarbonate diol obtained by reacting 1,4-cyclohexanedimethanol and a carbonic acid ester in a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen introduction tube, and a thermometer. ) 100 parts by mass, 2,2-dimethylolpropionic acid 9.7 parts by mass, 1,4-cyclohexanedimethanol 5.5 parts by mass, dicyclohexylmethane diisocyanate 51.4 parts by mass in a mixed solvent of methyl ethyl ketone 111 parts by mass. By carrying out the reaction in step 1, an organic solvent solution of a urethane prepolymer having an isocyanate group at the molecular end was obtained.

Then, by adding 7.3 parts by mass of triethylamine to the organic solvent solution of the urethane prepolymer, a part or all of the carboxyl groups of the urethane resin are neutralized, and further 355 parts by mass of water is added and the mixture is sufficiently stirred. By doing so, an aqueous dispersion of the urethane prepolymer was obtained.

Next, 4.3 parts by mass of a 25% by mass aqueous solution of ethylenediamine was added to the aqueous dispersion, and the mixture was stirred to extend the chain of the particulate urethane prepolymer, followed by aging and desolvation to obtain a solid content concentration. An aqueous dispersion of 30% by weight urethane resin was obtained.

140 parts by mass of deionized water in a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen introduction tube, a thermometer, a dropping funnel for dropping a monomer mixture, and a dropping funnel for dropping a polymerization catalyst, and an aqueous dispersion of the urethane resin obtained above. 100 parts by mass of the liquid was added, and the temperature was raised to 80 ° C. while blowing nitrogen. In a reaction vessel heated to 80 ° C., with stirring, a monomer mixture containing 60 parts by mass of methyl methacrylate, 10 parts by mass of n-butyl acrylate, and 30 parts by mass of Nn-butoxymethylacrylamide was added. 20 parts by mass of an aqueous ammonium sulfate solution (concentration: 0.5% by mass) was added dropwise from separate dropping funnels over 120 minutes while maintaining the temperature in the reaction vessel at 80 ± 2 ° C., and polymerization was carried out.

After completion of dropping, the mixture was stirred for 60 minutes at the same temperature, then the temperature in the reaction vessel was cooled to 40 ° C., and then deionized water was added so that the nonvolatile content was 20% by mass, and then 200 mesh By filtering with a filter cloth, a resin for a primer layer (D) containing a carboxyl group and an Nn-butoxymethylacrylamide group as a reactive functional group was obtained.

[Preparation of primer composition (d) containing resin for primer layer (D)]
90 parts by mass of ethanol was stirred and mixed with 10 parts by mass of the resin for primer layer (D) obtained in the production of the resin for primer layer (D), and a fluid containing the resin for primer layer (D) (primer composition The product (d)) was obtained.

[Production of laminated body]
(Example 1)
A non-photosensitive polyimide precursor resin (“Semicofine SP-341” manufactured by Toray Industries, Inc.) was applied on a silicon wafer using a spin coater (“MS-A150” manufactured by Mikasa Co., Ltd.), and then applied on a hot plate. At 95 ° C. for 1 minute 30 seconds and at 125 ° C. for 1 minute 30 seconds to obtain an insulating layer having a thickness of 5 μm.
A positive photosensitive polyimide precursor resin (“Photo Nice LT6300” manufactured by Toray Industries, Inc.) was applied on the insulating layer using a spin coater (“MS-A150” manufactured by Mikasa Corporation), and then a hot plate was applied. At 120 ° C. for 3 minutes to obtain a coating film having a film thickness of 7 μm. Then, exposure was performed through a pattern photomask having a line width of 5 μm, a line interval of 5 μm, and a line length of 1000 μm. The line spacing means the distance a between the trenches, and the length of the insulating layer portion between one line and the other line.
Then, a developing solution of a 2.38 mass% tetramethylammonium hydroxide aqueous solution is sprayed for 180 seconds, and then washed with pure water for 30 seconds, and then, using a clean oven under a nitrogen atmosphere at 50 ° C. for 30 minutes, 110 The insulating layer (A) having a surface in which a trench having a depth of 5 μm was formed was obtained by heating and curing in the order of 30 ° C. for 30 minutes and 200 ° C. for 60 minutes.

On the obtained insulating layer (A) having a trench, the metal particle dispersion liquid (b) prepared above was dried as a metal particle layer by a spin coater (“MS-A150” manufactured by Mikasa Co., Ltd.). It was applied so that the average film thickness afterwards would be 30 nm. That is, the dispersion liquid (b) of metal particles was applied to the bottom surface and the side wall of the insulating layer (A) so that the average film thickness of the metal particle layer after drying was 30 nm. By heating at 80 ° C. for 30 minutes, a metal particle layer (B) was formed on the entire surface of the insulating layer (A).

The metal particle layer (B) formed above is immersed in an electroless copper plating solution ("OIC Copper" manufactured by Okuno Chemical Industries Co., Ltd., pH 12.5) at 45 ° C for 12 minutes to perform electroless copper plating, A copper plating layer (film thickness 0.2 μm) was formed by electroless plating on the entire surface of the insulating layer (A). The copper plating layer formed by this electroless plating corresponds to the metal plating layer (C).

By setting the copper plating layer on the cathode side, setting phosphorus-containing copper on the anode side, and performing electrolytic plating for 10 minutes at a current density of 1.5 A / dm ² using an electrolytic plating solution containing copper sulfate, A copper plating film was formed on the entire surface of the insulating layer (A) to fill the trenches with copper. As the electrolytic plating solution, 70 g / L of copper sulfate, 200 g / L of sulfuric acid, 50 mg / L of chloride ion, and 5 ml / L of additive (“Top Lucina SF-M” manufactured by Okuno Chemical Industries Co., Ltd.) were used. This copper plating layer (electrolytic plating layer) also corresponds to the metal plating layer (C).

The copper layer other than that filled in the trench was removed by subjecting the surface layer of the metal plating layer (C) to chemical mechanical polishing (CMP; Chemical Mechanical Polishing). The CMP was performed using a polishing machine (“18GPAW” manufactured by Speed Fam Co., Ltd.) with a polyurethane independent foaming type polishing pad, a polishing pressure of 30 kPa, a platen rotation speed of 50 rpm, and a polishing agent of a colloidal silica solution.

By the above method, a laminate was obtained in which the metal particle layer (B) and the metal plating layer (C) were sequentially laminated in the trench formed in the insulating layer (A).

(Example 2)
In the same manner as in Example 1, an insulating layer (A) having a surface in which a trench was formed was obtained.

After the primer composition (d) containing the resin for the primer layer (D) was applied onto the insulating layer (A) by a spin coater (“MS-A150” manufactured by Mikasa Co., Ltd.), the primer composition was dried. It was applied so that the film thickness would be 100 nm. Then, it heated at 80 degreeC for 30 minute (s), and formed the primer layer (D) on the whole surface of the said insulating layer (A).

After forming the metal particle layer (B) and the metal plating layer (C) on the surface of the primer layer (D) in the same manner as in Example 1, the inside of the trench is subjected to CMP in the same manner as in Example 1. The copper layers other than the copper filled in were removed.

By the above method, a laminate was obtained in which the primer layer (D), the metal particle layer (B) and the metal plating layer (C) were sequentially laminated in the trench formed in the insulating layer (A).

(Example 3)
Lamination by the same method as in Example 1 except that an electroless nickel-boron plating solution was used instead of the electroless copper plating solution used in Example 1 to form an electroless nickel-boron plating layer. Got the body This electroless nickel-boron plating layer corresponds to the barrier metal plating layer (E). That is, in Example 3, the metal particle layer (B), the barrier metal plating layer (E), and the metal plating layer (C) were sequentially stacked on the insulating layer (A) having the surface where the trench was formed. Got the body As the electroless nickel-boron plating solution, "Top Chemialoy 66-LF" manufactured by Okuno Chemical Industries Co., Ltd. is used and immersed at 65 ° C. for 2 minutes to form a nickel-boron plating layer having a thickness of 0.2 μm. did.

(Example 4)
Laminated body was manufactured in the same manner as in Example 2 except that the electroless nickel-boron plating solution was used in place of the electroless copper plating solution used in Example 2 to form the nickel-boron plating layer. Got This nickel-boron plating layer corresponds to the barrier metal plating layer (E). That is, in Example 4, the primer layer (D), the metal particle layer (B), the barrier metal plating layer (E) and the metal plating layer (C) were formed on the insulating layer (A) having the surface where the trench was formed. A laminated body was obtained by sequentially laminating.

(Example 5)
Instead of the electroless nickel-boron plating solution used in Example 4, a part of silver in the metal particle layer (B) was replaced with palladium, and then the electroless nickel-phosphorus plating solution was used to form a nickel-phosphorus plating layer. A laminate was obtained by the same method as in Example 4 except that the laminate was formed. This nickel-phosphorus plating layer corresponds to the barrier metal plating layer (E). That is, in Example 5, the primer layer (D), the metal particle layer (B), the barrier metal plating layer (E), and the metal plating layer (C) were formed on the insulating layer (A) having the surface where the trench was formed. A laminated body was obtained by sequentially laminating.

As the method for the palladium substitution, 3 parts by mass of palladium chloride and 17 parts by mass of 36 mass% hydrochloric acid are dissolved in 80 parts by mass of ion-exchanged water to prepare an aqueous solution containing palladium ions and an acid, and 45 The temperature is set to 0 ° C., the laminate of the insulating layer (A), the primer layer (D), and the metal particle layer (B) is immersed in this palladium ion aqueous solution, and a part of silver of the metal particle layer (B) Substituted for palladium.

As the electroless nickel-phosphorus plating solution, “elf seed ES-500” manufactured by JCU Co., Ltd. was used and immersed at 40 ° C. for 10 minutes to form a nickel-phosphorus plating layer having a film thickness of 0.2 μm.

(Example 6)
A laminate was obtained in the same manner as in Example 5, except that an electroless cobalt plating solution was used instead of the electroless nickel-phosphorus plating solution used in Example 5 to form the cobalt plating layer. It was This cobalt plating layer corresponds to the barrier metal plating layer (E). That is, in Example 6, the primer layer (D), the metal particle layer (B), the barrier metal plating layer (E) and the metal plating layer (C) were formed on the insulating layer (A) having the surface where the trench was formed. A laminated body was obtained by sequentially laminating.

The electroless cobalt plating solution contains 2 parts by mass of cobalt sulfate, 6 parts by mass of citric acid, 5 parts by mass of tungstic acid, and 0.3 parts by mass of dimethylamine borane, and has a pH value of 9. The liquid adjusted to 5 was used for immersion at 60 ° C. for 35 minutes to form a cobalt plating layer having a thickness of 0.2 μm.

(Example 7)
Instead of the polyimide precursor resin and the positive photosensitive polyimide precursor resin used in Example 2, it has a surface in which a trench having a line width of 5 μm, a line interval of 5 μm, a line length of 1,000 μm, and a depth of 5 μm is formed. A laminate was obtained in the same manner as in Example 2 except that the aliphatic polycarbonate resin base material was used. For the aliphatic polycarbonate resin substrate, a solution of polypropylene carbonate in diethylene glycol monoethyl ether acetate is applied on a silicon wafer by using a spin coater (“MS-A150” manufactured by Mikasa Co., Ltd.), and the hot plate is applied at 150 ° C. It is obtained by drying for 30 minutes to obtain an insulating layer having a film thickness of 5 μm, and then applying a pressure of 5 MPa to press a mold having irregularities at 150 ° C. That is, in Example 7, a laminated body in which the primer layer (D), the metal particle layer (B), and the metal plating layer (C) were sequentially laminated on the insulating layer (A) having the surface where the trench was formed. Obtained.

(Example 8)
A laminate was prepared in the same manner as in Example 4 except that the aliphatic polycarbonate resin substrate was used instead of the polyimide precursor resin and the positive photosensitive polyimide precursor resin used in Example 4. Obtained. That is, in Example 8, the primer layer (D), the metal particle layer (B), the barrier metal plating layer (E) and the metal plating layer (C) were formed on the insulating layer (A) having the surface where the trench was formed. A laminated body was obtained by sequentially laminating.

(Example 9)
A laminate was prepared in the same manner as in Example 6 except that the aliphatic polycarbonate resin substrate was used instead of the polyimide precursor resin and the positive photosensitive polyimide precursor resin used in Example 6. Obtained. That is, in Example 9, the primer layer (D), the metal particle layer (B), the barrier metal plating layer (E), and the metal plating layer (C) were formed on the insulating layer (A) having the surface where the trench was formed. A laminated body was obtained by sequentially laminating.

(Example 10)
Using a spin coater (“MS-A150” manufactured by Mikasa Co., Ltd.) on a silicon wafer so that the film thickness after drying the polyimide precursor resin (“Semicofine, SP-341” manufactured by Toray Co., Ltd.) becomes 10 μm. Applied and dried. The obtained coating film was set on the lower surface stage of a nanoimprint apparatus (“X300” manufactured by SCIVAX Co., Ltd.). A mold made of quartz whose pattern surface was treated with fluorine was set on the upper surface stage of the above apparatus. After the inside of the apparatus was evacuated, the mold was pressure-bonded to the coating film at a pressure of 1.5 atm and heat-cured at 95 ° C. for 1 minute 30 seconds and at 125 ° C. for 1 minute 30 seconds. Then, the mold was peeled off to obtain an insulating layer (A) having a surface in which a trench having a line width of 5 μm, a line interval of 5 μm, a line length of 1000 μm, and a depth of 5 μm was formed.

A laminate was obtained by the same method as in Example 4 except that the insulating layer (A) was used instead of the polyimide precursor resin and the positive photosensitive polyimide precursor resin used in Example 4. It was That is, in Example 10, the primer layer (D), the metal particle layer (B), the barrier metal plating layer (E), and the metal plating layer (C) were formed on the insulating layer (A) having the surface where the trench was formed. A laminated body was obtained by sequentially laminating.

(Example 11)
A 1 mm thick polycarbonate film (Lexan manufactured by Asahi Glass Co., Ltd.) was set on the lower surface stage of a nanoimprint apparatus (“X300” manufactured by SCIVAX Co., Ltd.). A mold made of quartz whose pattern surface was treated with fluorine was set on the upper surface stage of the above apparatus. After the inside of the apparatus was evacuated, the mold was pressed onto the polycarbonate film at 170 ° C. for 30 seconds under a pressure of 2.5 atm. Then, the mold was peeled off to obtain an insulating layer (A) having a surface on which a trench having a line width of 5 μm, a line interval of 5 μm, a line length of 1000 μm, and a depth of 5 μm was formed.

A laminate was obtained by the same method as in Example 4 except that the insulating layer (A) was used instead of the polyimide precursor resin and the positive photosensitive polyimide precursor resin used in Example 4. It was That is, in Example 11, the primer layer (D), the metal particle layer (B), the barrier metal plating layer (E) and the metal plating layer (C) were formed on the insulating layer (A) having the surface where the trench was formed. A laminated body was obtained by sequentially laminating.

(Comparative Example 1)
The surface of the insulating layer (A) having the surface in which the trench was formed, which was manufactured in the same manner as in Example 1, was subjected to reverse sputtering using an RF sputtering device manufactured by Tokuda Manufacturing Co., Ltd., for 5 minutes at an output of 300 W, and the sputtering pressure was The flow rate was 0.5 Pa and the argon gas flow rate was 40 sccm. Next, using the same apparatus, a 0.2 μm titanium film and a 0.2 μm titanium film were formed on the insulating layer (A) by a sputtering method under the conditions of ultimate pressure of 5 × 10 ⁻⁴ Pa, sputtering pressure of 0.2 Pa, and argon gas flow rate of 20 sccm. A 6 μm copper film was formed in this order. This titanium film corresponds to the barrier layer. The copper film is a seed layer for electrolytic plating. Next, electrolytic plating was performed in the same manner as in Example 1 to fill the trenches with copper, and then the copper layer other than copper filled in the trenches was removed by CMP. This copper plating layer corresponds to the metal plating layer.
By the above method, a laminated body was obtained in which the barrier metal layer and the metal plating layer were sequentially laminated on the insulating layer (A) having the surface where the trench was formed.

<Defect evaluation of metal plating layer>
Scanning electron microscope (SEM) was performed on the laminates obtained in Examples 1 to 11 and Comparative Example 1.
(JSM-7800F manufactured by JEOL Ltd.) was used to observe the cross section to confirm the presence or absence of defects in the metal plating layer. The cross section was observed at a magnification of 50,000 times, and 10 points were randomly observed. The defects of the metal plating layer were evaluated according to the following criteria.
◯: Observed at 10 points, no defect was found.
X: There are one or more defects by observing 10 places.

<Diffusion evaluation of metal plating layer>
The laminated bodies obtained in Examples 1 to 11 and Comparative Example 1 were stored in a thermostatic chamber set at 150 ° C. for 168 hours, and then scanned with a scanning electron microscope (SEM) (“JSM-7800F” manufactured by JEOL Ltd.). ) Was used to observe the cross section, and the distance at which the metal of the metal plating layer stacked in the trench diffused into the insulating layer was observed by energy dispersive X-ray (EDS) analysis. The diffusion of the metal plating layer was evaluated according to the following criteria.
◯: Copper diffusion distance is less than 0.05 μm Δ: Copper diffusion distance is 0.05 μm or more and less than 0.10 μm ×: Copper diffusion distance is 0.1 μm or more

From the results shown in Table 1, it was confirmed that the laminates of Examples 1 to 10 had the metal plating layer formed suitably. It was also confirmed that the diffusion of the metal plating layer was suppressed.
On the other hand, the laminate of Comparative Example 1 is an example in which a metal particle layer is not formed, but instead, a barrier layer and a seed layer are formed by sputtering, and a metal plating layer is formed on this seed layer. It was confirmed that the layer had defects and the metal of the metal plating layer diffused into the insulating layer. In the case of sputtering, the thickness of the barrier layer and the seed layer on the bottom surface and side wall of the trench becomes uneven, so that a defect of the metal plating layer is generated especially where the film thickness of the side wall of the trench is thin. It is believed that the metal diffuses into the insulating layer.

10 Laminated body 12 Base material 14 Insulating layer 16 Primer layer 18 Metal particle layer 20 Barrier metal plating layer 22 Metal plating layer

Claims

An insulating layer (A) having a surface in which a trench is formed,
A metal particle layer (B) laminated in the trench,
A laminate having a metal plating layer (C) laminated in the trench and on the metal particle layer (B).
The laminate according to claim 1, further comprising a barrier metal plating layer (E) between the metal particle layer (B) and the metal plating layer (C).
The laminate according to claim 1 or 2, which has a primer layer (D) between the insulating layer (A) and the metal particle layer (B).
A step (1) of preparing an insulating layer (A) having a surface in which a trench is formed,
A step (2) of applying a dispersion liquid (b) containing metal particles to the trench to form a metal particle layer (B), and
A method for manufacturing a laminate, comprising a step (3) of performing a plating treatment to form a metal plating layer (C) in the trench and on the metal particle layer (B).
After the step (2), there is a step (2-1) of performing a barrier metal plating treatment on the metal particle layer (B) to form a barrier metal plating layer (E),
The method for producing a laminate according to claim 4, wherein the step (3) is performed after the step (2-1).
After the step (1), there is a step (1-1) of applying a primer composition (d) to the insulating layer (A) to form a primer layer (D),
The method for producing a laminate according to claim 4 or 5, wherein the step (2) is performed after the step (1-1).