JP6849157B2 - Laminated body and method for manufacturing the laminated body - Google Patents

Description

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

Insulating resins having good electrical properties, mechanical properties and high heat resistance are used as insulating materials for electronic components, passivation films for semiconductor devices, surface protective films, interlayer insulating films and the like. As the insulating resin, a photosensitive resin is used so that a layer structure can be formed through coating, exposure, development, and thermosetting processes. In recent years, the wiring width has decreased due to miniaturization of semiconductor elements, high density wiring due to high integration, multi-layer wiring, wafer level package (WLP), and panel level package (PLP), and wiring such as copper. There is an increasing demand for improving the adhesion between the metal material forming the above and the insulating resin formed by curing the photosensitive resin.

Currently, the method of forming a metal layer on an insulating resin layer by a plating method (vacuum process) is the mainstream, but at present, wiring is performed in order to ensure the adhesion of the metal layer on the insulating resin layer. A metal (for example, chromium, titanium, etc.) that improves the adhesion between the resin and the wiring-forming metal layer and a plating seed metal are sequentially inserted between the metal forming the metal and the insulating resin layer by a sputtering method, and then wiring is performed. A method of forming a metal layer by a plating method is used. However, since this method uses a vacuum process, the manufacturing cost is high, the adhesion is still insufficient, and high-frequency transmission characteristics are deteriorated because a high-resistance metal such as chromium or titanium is inserted into the interface. Since it is a metal that is poorly etched or has poor etching properties, there are problems such as difficulty in forming a fine line pattern.

When the plating seed metal layer is formed on the insulating resin layer by the sputtering method, in order to firmly bond the insulating resin layer and the wiring metal layer, the insulating resin layer is formed before the plating seed metal layer is formed. An inert gas ion impact such as argon is performed under an ultra-high vacuum (see, for example, Patent Document 1). Patent Document 1 discloses that the positive photosensitive resin film and the metal film are firmly adhered to each other by performing this inert gas ion impact treatment called reverse sputtering.

JP-A-2002-289619

However, the method of forming the plating seed metal layer on the insulating resin layer by the sputtering method requires a large-scale vacuum equipment, and has a problem that the substrate size is limited in terms of design.

The present invention has been made in view of the above-mentioned problems, and an object of the present invention is a laminate that can be manufactured by a simple method without using a large-scale vacuum facility and has excellent adhesion between an insulating layer and a metal layer. Is to provide. The present invention also provides a method for producing the laminate.

As a result of diligent 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 is
The insulating layer (A) obtained by curing the photosensitive resin and
The metal particle layer (B) laminated on the insulating layer (A) and
It is characterized by having a metal plating layer (C) laminated on the metal particle layer (B).

The laminate according to the present invention is, for example, a dispersion containing metal particles on an uncured layer (A-1) before curing the photosensitive resin or an insulating layer (A) obtained by curing the photosensitive resin. It can be obtained by applying the liquid (b) to form a metal particle layer (B), and then performing a plating treatment to form a metal plating layer (C) on the metal particle layer (B).

As described above, the laminate according to the present invention does not require a large-scale vacuum facility for forming the plating seed metal layer, and does not need to be reverse-sputtered before forming the plating seed metal layer, but is insulated. Excellent adhesion between the layer (A) and the metal plating layer (C).

Further, the method for producing a laminate according to the present invention is as follows.
Step (1) of preparing an uncured layer (A-1) before curing the photosensitive resin or an insulating layer (A) obtained by curing the photosensitive resin.
A step (2) of applying a dispersion liquid (b) containing metal particles on the uncured layer (A-1) or the insulating layer (A) to form a metal particle layer (B), and
It is characterized by having a step (3) of performing a plating process and forming a metal plating layer (C) on the metal particle layer (B). When the dispersion liquid (b) is applied onto the uncured layer (A-1), the uncured layer (A-) is simultaneously formed in the step (2) or the like for forming the metal particle layer (B). 1) is cured to obtain the insulating layer (A).

According to the method for producing a laminate according to the present invention, since the plating seed metal layer is formed by the coating method, a large-scale vacuum facility is not required. Further, even if the reverse sputtering treatment is not performed before forming the plating seed metal layer, the laminate obtained by the method for producing a laminate according to the present invention includes an insulating layer (A) and a metal plating layer (C). Excellent adhesion between.

According to the present invention, it is possible to provide a laminate having excellent adhesion between an insulating layer and a metal layer, which can be manufactured by a simple method without using a large-scale vacuum facility or the like. Further, it is possible to provide a method for producing the laminated body.

It is sectional drawing of the laminated body which concerns on one Embodiment of this invention. It is sectional drawing of the laminated body which concerns on other embodiment of this invention. It is sectional drawing of the laminated body which concerns on other embodiment of this invention.

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

The laminate according to the present invention has, at least a part thereof, a portion in which an insulating layer (A) obtained by curing a photosensitive resin, a metal particle layer (B), and a metal plating layer (C) are laminated. Just do it. For example, even if the metal particle layer (B) and the metal plating layer (C) are patterned and have a portion in which the metal particle layer (B) and the metal plating layer (C) do not exist in a plan view. Good. Further, for example, it may have a portion where the insulating layer (A) does not exist in a plan view (for example, a portion where the electrode 31 shown in FIG. 2 is arranged). In the laminated body in the present invention, the insulating layer (A), the metal particle layer (B), and the metal plating layer (C) may be laminated as a whole in a plan view. For example, a metal layer (metal particle layer (B) and metal plating layer (C)) may be laminated on the entire surface of the insulating layer (A), such as a copper-clad laminate. A specific example will be described below.

In the embodiment described below, the laminate is 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. A case where the plating layer (C) is provided will be described. As described above, the laminate according to the present invention includes at least an insulating layer (A) obtained by curing a photosensitive resin, a metal particle layer (B), and the like. It may have a metal plating layer (C).

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

The insulating layer 14 corresponds to the insulating layer (A) obtained by curing the photosensitive resin 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.

FIG. 2 is a schematic cross-sectional view of a laminated body according to another embodiment of the present invention. The laminate 30 includes a silicon wafer 32, a passivation layer 33, an insulating layer 34 obtained by curing a photosensitive resin, a primer layer 36, a metal particle layer 38, a barrier metal plating layer 40, and a metal plating layer 42. Has a laminated portion in this order.

The insulating layer 34 corresponds to the insulating layer (A) obtained by curing the photosensitive resin of the present invention. The primer layer 36 corresponds to the primer layer (D) of the present invention. The metal particle layer 38 corresponds to the metal particle layer (B) of the present invention. The barrier metal plating layer 40 corresponds to the barrier metal plating layer (E) of the present invention. The metal plating layer 42 corresponds to the metal plating layer (C) of the present invention.

As shown in FIG. 2, an electrode 31 is formed on a silicon wafer 32 as a base material. In the silicon wafer 32, the portion other than the electrode 31 is covered with the passivation layer 33.

The insulating layer 34 and the primer layer 36 do not exist at the location where the electrode 31 is formed in a plan view, but exist at other locations.

The primer layer 36, the metal particle layer 38, the barrier metal plating layer 40, and the metal plating layer 42 are patterned and formed on a part of the insulating layer 34. Further, the metal particle layer 38, the barrier metal plating layer 40, and the metal plating layer 42 are also formed on the electrode 31.

In the laminate 30 shown in FIG. 2, a case where the patterned metal plating layer 42 is formed on the surface of the insulating layer 34 has been described. However, the present invention is not limited to this example, and a trench may be formed in the insulating layer 34, and a metal plating layer 42 may be formed in the trench. As used herein, the term "trench" refers to a linear groove formed on one surface side and not penetrating to the other surface.

FIG. 3 is a schematic cross-sectional view of the laminated body according to another embodiment of the present invention. The laminate 50 includes a silicon wafer 32, an insulating layer 34 obtained by curing a photosensitive resin, a primer layer 36, a metal particle layer 38, a barrier metal plating layer 40, a metal plating layer 42, and a second insulating layer. 52 has a portion laminated in this order. The silicon wafer 32, the insulating layer 34, the primer layer 36, the metal particle layer 38, the barrier metal plating layer 40, and the metal plating layer 42 have the same configuration as the laminate 30 shown in FIG. The reference numerals are given, and the description thereof is omitted here.

A contact plug 54 is formed in the second insulating layer 52 in the vertical direction, and the lower side of the contact plug 54 is in contact with the metal plating layer 42. Further, the upper side of the contact plug 54 is exposed on the surface of the second insulating layer 52, and the second electrode 56 is formed so as to be in contact with the upper surface of the second insulating layer 52 and the upper side of the contact plug 54.

The use of the laminated body 10, the laminated body 30, and the laminated body 50 is not particularly limited, but can be used as, for example, a rewiring layer (RDL: Redistribution Layer). More specifically, it can be used as a rewiring layer for drawing out wiring from an electrode or the like formed on a base material or the like.

As will be described later, the laminates 10, 30 and 50 have metal particles on the uncured layer (A-1) before the photosensitive resin is cured or the insulating layer (A) on which the photosensitive resin is cured. Obtained by applying the contained dispersion liquid (b) to form a metal particle layer (B), and then performing a plating treatment to form a metal plating layer (C) on the metal particle layer (B). Can be done. That is, the laminated body 10 does not require a large-scale vacuum equipment for forming the metal layer (metal plating layer (C)). Further, it is not necessary to perform a reverse sputtering treatment before forming the metal layer. Further, according to the laminated bodies 10, 30 and 50, the adhesion between the insulating layer (A) and the metal particle layer (B) is excellent.

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

Next, each layer provided in the laminated body of this embodiment will be described.

[Insulation layer (A)]
The insulating layer (A) is obtained by curing the uncured layer (A-1) formed of the photosensitive resin. Examples of the photosensitive resin include polybenzoxazole precursor resin, polybenzoxazole resin, polyamide resin, polyimide precursor resin, polyimide resin, novolak resin, resol resin, hydroxystyrene resin and the like. These photosensitive resins may be positive type or negative type. Further, the patterned insulating layer (A) can be formed by irradiating with the photosensitive resin pattern light. Further, since the insulating layer (A) can be made tougher, it is preferable to heat-cure it 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 laminated body.

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

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

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

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

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

The primer layer (D) varies depending on the intended use of the laminate, but is preferably 0.01 μm or more and 300 μm or less, and preferably 0.01 μm or more and 20 μm or less. More preferred.

The portion where the primer layer (D) is unnecessary, for example, the portion on the electrode 31 of FIGS. 2 and 3 is not applied when applied on the insulating layer (A), or the primer layer (D) is formed. It can be formed later by removing only the unnecessary portion with a laser or the like.

[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 constituting the metal particle layer (B) include copper, silver, gold, nickel, palladium, platinum, cobalt and the like. Among these, silver is preferable because the particle surface is not easily oxidized, the activity as an electroless plating catalyst is high, the metal has high conductivity, and the metal plating layer (C) is easily formed. The metal particle layer (B) is a plating seed metal layer of a barrier metal plating layer (E) or a metal plating layer (C), which will be described later.

[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 into the insulating layer (A). Examples of the metal constituting the barrier metal plating layer (E) include nickel, nickel-molybdenum, nickel-molybdenum-boron, nickel-molybdenum-phosphorus, chromium, cobalt, cobalt-phosphorus, molybdenum, cobalt-tungsten-phosphorus, and cobalt. -Tungsten-Bobalt 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 constituting the metal plating layer (C) include copper, gold, silver, nickel, chromium, cobalt, tin and the like. Among these, when the metal plating layer (C) is used for wiring, copper is preferable because of its relatively low cost and high conductivity.

[Combination of metal particle layer (B) and primer layer (D)]
In the case of a configuration having a primer layer (D), the combination of the metal particle layer (B) and the primer layer (D) is a compound (b1) having a basic nitrogen atom-containing group as the metal particle layer (B). It is preferable to adopt 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 configuration, the basic nitrogen atom-containing group contained in the compound (b1) contained in the metal particle layer (B) and the functionality possessed by the compound (d1) contained in the primer layer (D). The group [X] reacts to form a bond, and the adhesion 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 an imino group, a primary amino group, a 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. It participates in the binding of the compound (d1) contained in the layer (D) to the functional group [X], and the other contributes to the interaction with the metal particles (b2) such as silver in the metal particle layer (B). This is preferable in order 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. Among these, copper, silver and gold are preferable because they have high conductivity, and silver is relatively inexpensive, the particle surface is not easily oxidized, and the activity as an electroless plating catalyst is high. More preferred.

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

Among them, the functional group [X] is a keto group from the viewpoint of preventing the formation of by-products such as halogen, acid and amine when it reacts 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], a polyvinyl alcohol having the functional group [X], polyvinylpyrrolidone having the functional group [X], and the like can be used. Among them, one or more 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]. It is preferable to use it.

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

When the surface of the primer layer (D) comes into contact with the dispersion liquid (b) containing the compound (b1) having a basic nitrogen atom-containing group and the metal particles (b2), the primer layer (D) is dried, heated, etc. By going through the steps, the basic nitrogen atom-containing group contained in the compound (b1) is reacted with the 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.

As a result, it is 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 a primer composition (d) containing a compound (d1) having a functional group [X] and drying or the like. 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 in, for example, International Publication No. 2013/146195.

Next, a method for manufacturing the laminate according to the present embodiment will be described.

[Manufacturing method of laminate]
In the method for producing a laminate according to the present embodiment, first, an uncured layer (A-1) before curing the photosensitive resin or an insulating layer (A) obtained by curing the photosensitive resin is prepared ( Step (1)). The uncured layer (A-1) or the insulating layer (A) to be prepared may have through holes or recesses (for example, the insulating layer 34 in FIG. 2). The through holes and the recesses are formed by, for example, exposing and developing the uncured layer (A-1) having a flat surface on which the through holes and the recesses are not formed through a desired pattern mask to develop the through holes and the recesses. The uncured layer (A-1) on which is formed can be obtained. The insulating layer (A) in which the through holes and recesses are formed can be obtained by further thermosetting the uncured layer (A-1) in which the through holes and recesses are formed. The photosensitive resin may be positive-type photosensitive or negative-type photosensitive.

Next, if necessary, the primer composition (d) is applied to the uncured layer (A-1) or the insulating layer (A), and the solvent contained in the primer composition (d) is dried or the like. By removing it, a primer layer (D) is formed (step (1-1)).
When the specific combination described above is adopted as the metal particle layer (B) and the primer layer (D), the primer layer (D) is the uncured layer (A-1) or the insulating layer (A). The primer composition (d) is applied to the primer composition (d) and dried as necessary to provide the primer layer (D), and the basic nitrogen atom-containing group is provided on a part or all of the surface of the coating film. It can be produced by applying a dispersion liquid (b) containing the compound (b1) having the above metal particles (b2) and then undergoing a heating step such as firing.

The uncured layer (A-1) of the photosensitive resin is a step of forming a primer layer (D) (1-1), and a drying and heating step in a step of forming the metal particle layer (B) (2). Hardens in and forms an insulating layer (A).

Examples of the method of applying the primer composition (d) to the surface of the uncured layer (A-1) or the insulating layer (A) include a gravure method, an offset method, a flexographic method, a pad printing method, and a gravure offset. Method, letterpress method, reverse printing method, screen method, 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 Examples thereof include a method, a spray coater method, an inkjet method, a die coater method, a spin coater method, a bar coater method, and a dip coater method.

Next, the dispersion liquid (b) containing metal particles is applied to the uncured layer (A-1) or the insulating layer (A) to form the metal particle layer (B) (step (2)). ..

The shape of the metal particles used for forming the metal particle layer (B) is preferably particle-like or fibrous. Further, the size of the metal particles is preferably nano-sized. 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 size" 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 Microtrack Co., Ltd. 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 diameter of the fiber is preferably 5 nm or more and 100 nm or less, and 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, and 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 blended in 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 a compound described later. Membrane aids, antifoaming agents, preservatives and the like can be mentioned.

In order to disperse the metal particles in a solvent, it is preferable to use a low molecular weight or high molecular weight dispersant. Examples of the dispersant include dodecanethiol, 1-octanethiol, triphenylphosphine, dodecylamine, polyethylene glycol, polyvinylpyrrolidone, polyethyleneimine, polyvinylpyrrolidone; fatty acids such as myristic acid, octanoic acid and stearic acid; Examples thereof include polycyclic hydrocarbon compounds having a carboxyl group such as glycyrrhizic acid and avintic acid. Among these, a polymer dispersant is preferable because the adhesion between the metal particle layer (B) and the metal plating layer (C) can be improved. Examples of the polymer dispersant include polyethyleneimine and polypropyleneimine. Examples thereof include polyalkyleneimine, a compound in which polyoxyalkylene is added to the polyalkyleneimine, a urethane resin, an acrylic resin, the urethane resin, a compound containing a phosphoric acid group in the acrylic resin, and the like.

The amount of the dispersant required 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 for 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, ultrapure water, and the like. Examples of the organic solvent include alcohol compounds, ether compounds, ester compounds, ketone compounds and the like.

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, and the like. Tetradecanol, pentadecanol, stearyl alcohol, allyl alcohol, cyclohexanol, terpineol, turpineol, dihydroterpineol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol Monobutyl 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, Examples thereof include tripropylene glycol monobutyl ether.

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

As the surfactant, a general surfactant can be used, for example, di-2-ethylhexyl sulfosuccinate, dodecylbenzene sulfonate, alkyldiphenyl ether disulfonate, alkylnaphthalene sulfonate, hexametaphosphate. Examples include salt.

As the leveling agent, a general leveling agent can be used, and examples thereof include silicone-based compounds, acetylenediol-based compounds, and fluorine-based 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 to alkaline, or a urethane that can be thickened by associating molecules. Examples thereof include resins, hydroxyethyl cellulose, carboxymethyl cellulose, methyl cellulose, polyvinyl alcohol, water-added castor oil, amido wax, polyethylene oxide, metal soap, dibenzylidene sorbitol and the like.

As the film-forming auxiliary, a general film-forming auxiliary can be used, for example, an anionic surfactant (such as dioctylsulfosuccinate sodium salt) and a hydrophobic nonionic surfactant (sorbitan monooleate). Etc.), polyether-modified siloxane, silicone oil, etc.

As the defoaming agent, a general defoaming agent can be used, and examples thereof include silicone-based defoaming agents, nonionic-based surfactants, polyethers, higher alcohols, and polymer-based surfactants.

As the preservative, general preservatives can be used. Can be mentioned.

The viscosity of the dispersion liquid (b) (value measured using a B-type viscometer at 25 ° C.) 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. More preferably, it is s or less. When the dispersion liquid (b) is applied by a method such as an inkjet printing method or letterpress reversal printing 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 (D) 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, and a screen method. , Micro 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, inkjet method, die coater method. Methods such as the method, the spin coater method, the bar coater method, and the dip coater method can be mentioned.

By applying the dispersion liquid (b) in a pattern on the primer layer (D), the metal plating layer (C) and the like, which will be described later, can be patterned.

Among these coating methods, when the metal particle layer (B) patterned in a fine line shape of about 0.01 μm or more and 100 μm or less, which is required to realize high density of electronic circuits or the like, is formed, It is preferable to use an inkjet printing method or a 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.), Dimatics Material Printer DMP-3000, and Dimatics Material Printer DMP-2831 (manufactured by Fuji Film Co., Ltd.).

Further, as the reverse printing method, a letterpress reverse printing method and an intaglio reverse printing method are known. For example, a plate in which the dispersion liquid (b) is coated on the surface of various blankets and a non-image portion is projected. The pattern is formed on the surface of the blanket or the like by contacting and selectively transferring the dispersion liquid (b) corresponding to the non-image area to the surface of the plate, and then the pattern is supported by the support. A method of transferring onto the body (A) (surface) can be mentioned.

Further, a pad printing method is known for printing a pattern on a three-dimensional molded product. This involves placing ink on the intaglio and writing it down with a squeegee to evenly fill the recesses with ink, press a pad made of silicone rubber or urethane rubber onto the plate on which the ink is placed, and place the pattern on the pad. This is a method of transferring and transferring to a three-dimensional molded product.

The mass per unit area of the metal particle layer (B) 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 (B) is adjusted by controlling the treatment time, current density, amount of plating additive used, etc. in the plating treatment step when the metal plating layer (C) is formed. Can be done.

After the step (2), if necessary, the metal particle layer (B) is subjected to a barrier metal plating treatment to form the barrier metal plating layer (E) (step (2-1)).

The barrier metal plating layer (E) can be formed by an electroless plating treatment or an electrolytic plating treatment. In the electroless plating treatment, for example, the metal particle layer (B) is brought into contact with an electroless plating solution such as nickel, chromium, or cobalt to precipitate the metal contained in the electroless plating solution, and the barrier metal metal. This is a method of forming an electroless plating layer (film) composed of a film.

By using hypophosphoric 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 salts such as tungsten, molybdenum, rhenium, and ruthenium are further added to the electroless plating solution of the metal, a barrier metal plating layer (E) in which these metals are co-deposited can be obtained. Can be formed.

As described above, the barrier metal plating treatment may be an electrolytic plating treatment. 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 (C) on the metal particle layer (B) (step (3)). When the barrier metal plating layer (E) is formed, the barrier metal plating layer (E) is subjected to a plating treatment to form the metal plating layer (C). When the barrier metal plating layer (E) is not formed, the metal particle layer (B) is plated to form the metal plating layer (C).

As a method for forming the metal plating layer (C), a method of forming the metal plating layer (C) by a plating treatment is preferable. Examples of this plating treatment include wet plating methods such as an electroplating method and an electroless plating method that can easily form the metal plating layer (C). Moreover, you may combine these plating methods. For example, the metal plating layer (C) may be formed by performing electroless plating and then electrolytic plating.

In the above electroless plating method, for example, copper or the like contained in the electroless plating solution is formed by bringing the electroless plating solution into contact with the metal particle layer (B) or the barrier metal plating layer (E). This is a method of forming an electroless plating layer (film) composed of a metal film by precipitating the metal of.

Examples of the electroless plating solution include those containing metals 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 (C) is used as the conductive layer, the metal type of the electroless plating solution is preferably silver, copper, or gold, which are highly conductive metals, and relatively inexpensive copper is more preferable. preferable.

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

The electroless plating solution includes, if necessary, monocarboxylic acids such as acetic acid and formic acid; dicarboxylic acid compounds such as malonic acid, succinic acid, adipic acid, maleic acid and fumaric acid; malic acid, lactic acid and glycol. Hydroxycarboxylic acid compounds such as acids, gluconic acids and citric acids; amino acid compounds such as glycine, alanine, iminodiacetic acid, arginine, aspartic acid and glutamate; Contains an organic acid such as an aminopolycarboxylic acid compound, or a complexing agent such as a soluble salt of these organic acids (sodium salt, potassium salt, ammonium salt, etc.), an amine compound such as ethylenediamine, diethylenetriamine, triethylenetetramine, etc. Can be used.

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

In the electrolytic plating method, for example, an electroless plating solution is applied to the surface of the metal particle layer (B), the electroless plating layer (film) formed by the electroless treatment, or the barrier metal plating layer (E). By energizing in contact with each other, a metal such as copper contained in the electrolytic plating solution is placed on the cathode (the metal particle layer (B), the electroless plating layer formed by the electroless treatment (electroless plating layer). This is a method of forming an electrolytic plating layer (metal film) by precipitating it on the surface of the film) or the barrier metal plating layer (E).

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 (C) is used as the conductive layer, the metal type of the electrolytic plating solution is preferably silver, copper, or gold, which are highly conductive metals, and more preferably copper, which is relatively inexpensive. .. When the metal plating layer (C) is used as the conductive layer, the plating metal preferably has no eutectoid and has high purity.

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

As a method for forming the metal plating layer (C), an electroless plating method and an electrolytic plating method can be appropriately selected or combined in order to obtain a desired film thickness of the metal plating layer (C). In particular, when the film thickness of the metal plating layer (C) is a thick film, a method of performing electroless plating and then electrolytic plating is preferable.

The film thickness of the metal plating layer (C) is preferably 1 μm or more and 50 μm or less. The film thickness of the metal plating layer (D) can be controlled by adjusting the treatment conditions in the plating treatment step when forming the metal plating layer (C).

As a method of forming the metal plating layer (C) by patterning, for example, the above-mentioned metal particle layer (B) is applied as a pattern on the insulating layer (A), and the metal particle layer (B) is formed. A method of forming the metal plating layer (C) only in an existing portion, a method of forming the metal particle layer (B), and then removing only a non-patterned portion with a laser or the like to pattern the metal particle layer (B). A method of forming the metal plating layer (C) only in a portion where the metal particle layer (B) is present, and a method of forming the metal plating layer (C) and then patterning the metal plating layer by a subtractive method. Method of forming (C), before forming the metal plating layer (C), a patterned resist layer is formed on the metal particle layer (B) or the barrier metal plating layer (E), and the resist layer exists. Examples thereof include a method in which the metal plating layer (C) is formed only on the portion not to be formed, and then the resist layer, the metal particle layer (B), the barrier metal plating layer (E) and the like are removed by etching.

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 of the present invention is not exceeded.

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

[Manufacturing of resin for primer layer (D)]
A polycarbonate diol having an acid group equivalent of 1,000 g / equivalent obtained by reacting a polycarbonate polyol (1,4-cyclohexanedimethanol and a carbonic acid ester) in a reaction vessel equipped with a stirrer, a reflux cooling tube, a nitrogen introduction tube, and a thermometer. ) 100 parts by mass, 9.7 parts by mass of 2,2-dimethylolpropionic acid, 5.5 parts by mass of 1,4-cyclohexanedimethanol, 51.4 parts by mass of dicyclohexylmethanediisocyanate in a mixed solvent of 111 parts by mass of methyl ethyl ketone. To obtain an organic solvent solution of a urethane prepolymer having an isocyanate group at the molecular terminal.

Next, 7.3 parts by mass of triethylamine is added to the organic solvent solution of the urethane prepolymer to neutralize a part or all of the carboxyl groups of the urethane resin, and 355 parts by mass of water is further added and sufficiently stirred. As a result, an aqueous dispersion of urethane prepolymer was obtained.

Next, 4.3 parts by mass of a 25% by mass ethylenediamine aqueous solution was added to the aqueous dispersion, and the mixture was stirred to extend the chain of the particulate urethane prepolymer, and then the solid content was concentrated by aging and removing the solvent. An aqueous dispersion of 30% by mass urethane resin was obtained.

140 parts by mass of deionized water and aqueous dispersion of the urethane resin obtained above 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. 100 parts by mass of the liquid was added, and the temperature was raised to 80 ° C. while blowing nitrogen. 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 under stirring in a reaction vessel heated to 80 ° C. 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 inside the reaction vessel at 80 ± 2 ° C. for polymerization.

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

[Preparation of Primer Composition (d) Containing Resin for Primer Layer (D)]
90 parts by mass of ethanol is stirred and mixed with 10 parts by mass of the resin for the primer layer (D) obtained in the production of the resin for the primer layer (D), and a fluid containing the resin for the primer layer (D) (primer composition). Object (d)) Obtained.

[Preparation of laminate]
(Example 1)
A positive photosensitive polyimide precursor resin (“Photonice LT6300” manufactured by Toray Industries, Inc.) is applied onto a silicon wafer using a spin coater, and then dried on a hot plate at 120 ° C. for 3 minutes to obtain a coating film. It was. Then, after immersing it in a developing solution of 2.38% by mass tetramethylammonium hydroxide aqueous solution for 40 seconds, washing it with pure water for 30 seconds, and drying it on a hot plate at 120 ° C. for 3 minutes, it is photosensitive with a film thickness of 10 μm. An uncured layer (A-1) of resin was obtained.

On the surface of the uncured layer (A-1), the dispersion liquid (b) of the metal particles prepared above was applied as a metal particle layer (B) by a spin coating device (“MS-A150” manufactured by Mikasa Sports Co., Ltd.). Was applied so that the film thickness after drying was 150 nm. The metal particle layer (B) is formed by heating at 50 ° C. for 30 minutes, 110 ° C. for 30 minutes, and 200 ° C. for 60 minutes, and the uncured layer (A-1) is cured to form an insulating layer (A-1). A). The surface resistance value of this metal particle layer (B) was 4 Ω / □.

The metal particle layer (B) is set on the cathode side, phosphorus-containing copper is set on the anode side, and electrolytic plating is performed for 30 minutes at ^{a current density of 2.5 A / dm 2 using an electrolytic plating solution containing copper sulfate.} As a result, a copper plating layer (thickness 15 μm) by electrolytic copper plating was formed on the surface of the metal particle layer (B). This copper plating layer corresponds to the metal plating layer (C). As the electrolytic plating solution, 70 g / L of copper sulfate, 200 g / L of sulfuric acid, 50 mg / L of chlorine ions, and 5 ml / L of an additive (“Top Lucina SF-M” manufactured by Okuno Pharmaceutical Co., Ltd.) were used.

By the above method, a laminated body in which the metal particle layer (B) and the metal plating layer (C) were sequentially laminated on the insulating layer (A) obtained by curing the photosensitive resin was obtained.

(Example 2)
A positive photosensitive polyimide precursor resin (“Photonice, LT6300” manufactured by Toray Industries, Inc.) was applied onto a silicon wafer using a spin coater, and then dried on a hot plate at 120 ° C. for 3 minutes to obtain a coating film. It was. Then, after immersing in a developing solution of 2.38% by mass tetramethylammonium hydroxide aqueous solution for 40 seconds, washing with pure water for 30 seconds, and then using a clean oven in a nitrogen atmosphere at 50 ° C. for 30 minutes at 110 ° C. The insulating layer (A) having a film thickness of 10 μm was obtained by heating and curing in this order for 30 minutes at 200 ° C. for 60 minutes.

On the surface of the insulating layer (A), the metal particle dispersion liquid (b) prepared above is applied to the surface of the insulating layer (A) with a spin coating device (“MS-A150” manufactured by Mikasa Sports Co., Ltd.) to form a metal particle layer with a film thickness after drying. Was applied so that the thickness was 150 nm. The metal particle layer (B) was formed by heating at 180 ° C. for 30 minutes. The surface resistance value of this metal particle layer (B) was 4 Ω / □.

A copper plating layer was formed on the surface of the metal particle layer (B) in the same manner as in Example 1.

By the above method, a laminated body in which the metal particle layer (B) and the metal plating layer (C) were sequentially laminated on the insulating layer (A) obtained by curing the photosensitive resin was obtained.

(Example 3)
An uncured layer (A-1) of a photosensitive resin having a film thickness of 10 μm was obtained in the same manner as in Example 1.

On the surface of the uncured layer (A-1), the dispersion liquid (b) of the metal particles prepared above was applied as a metal particle layer (B) by a spin coating device (“MS-A150” manufactured by Mikasa Sports Co., Ltd.). Was applied so that the film thickness after drying was 30 nm. The metal particle layer (B) is formed by heating at 50 ° C. for 30 minutes, 110 ° C. for 30 minutes, and 200 ° C. for 60 minutes, and the uncured layer (A-1) is cured to form an insulating layer (A-1). A).

The metal particle layer (B) formed above was immersed in an electroless copper plating solution (“OIC Copper” manufactured by Okuno Pharmaceutical Co., Ltd., pH 12.5) at 45 ° C. for 12 minutes to perform electroless copper plating. A copper plating layer (thickness 0.2 μm) was formed by electrolytic plating. The copper plating layer by electroless plating corresponds to the metal plating layer (C).

The electroless copper plating layer was set as a cathode, and a copper plating layer (electroplating layer) was formed on the electroless copper plating layer in the same manner as in Example 1. This copper plating layer (electrolytic plating layer) also corresponds to the metal plating layer (C).

By the above method, a laminated body in which the metal particle layer (B) and the metal plating layer (C) were sequentially laminated on the insulating layer (A) obtained by curing the photosensitive resin was obtained.

(Example 4)
Except that the insulating layer (A) obtained by curing the photosensitive resin was prepared and used in the same manner as in Example 2 instead of the uncured layer (A-1) prepared in Example 3, the same as in Example 3. A laminate was obtained by the same method.

(Example 5)
A laminate was obtained by the same method as in Example 3 except that an electroless nickel solution was used instead of the electroless copper plating solution used in Example 3 to form an electroless nickel layer. This electroless nickel layer corresponds to the barrier metal plating layer (E). That is, in Example 5, a laminated body in which a metal particle layer (B), a barrier metal plating layer (E), and a metal plating layer (C) are sequentially laminated on an insulating layer (A) obtained by curing a photosensitive resin. Got As the electroless nickel solution, "Top Chemialoy 66-LF" manufactured by Okuno Pharmaceutical Co., Ltd. was used and immersed at 65 ° C. for 2 minutes to form a nickel-boron plated layer having a film thickness of 0.2 μm.

(Example 6)
Except that the insulating layer (A) obtained by curing the photosensitive resin was prepared and used in the same manner as in Example 2 instead of the uncured layer (A-1) prepared in Example 5, the same as in Example 5. A laminate was obtained by the same method.

(Example 7)
An uncured layer (A-1) of a photosensitive resin having a film thickness of 10 μm was obtained in the same manner as in Example 1.

A primer composition (d) containing a resin for a primer layer (D) is applied to the surface of the uncured layer (A-1) as a primer layer by a spin coating device (“MS-A150” manufactured by Mikasa Sports Co., Ltd.). Was applied so that the film thickness after drying was 100 nm. Then, it was heated at 150 ° C. for 10 minutes to form a primer layer (D).

A dispersion liquid (b) of metal particles was applied to the surface of the primer layer (D) in the same manner as in Example 1. The metal particle layer (B) is formed by heating at 50 ° C. for 30 minutes, 110 ° C. for 30 minutes, and 200 ° C. for 60 minutes, and the uncured layer (A-1) is cured to form an insulating layer (A-1). A). Then, the copper plating layer was formed in the same manner as in Example 1.

By the above method, a laminate in which a primer layer (D), a metal particle layer (B), and a metal plating layer (C) were sequentially laminated on an insulating layer (A) obtained by curing a photosensitive resin was obtained.

(Example 8)
In the same manner as in Example 7, a primer layer (D) was formed on the surface of the uncured layer (A-1) of the photosensitive resin having a film thickness of 10 μm.

A dispersion liquid (b) of metal particles was applied to the surface of the primer layer (D) in the same manner as in Example 3. The metal particle layer (B) is formed by heating at 50 ° C. for 30 minutes, 110 ° C. for 30 minutes, and 200 ° C. for 60 minutes, and the uncured layer (A-1) is cured to form an insulating layer (A-1). A). Then, the copper plating layer was formed in the same manner as in Example 3.

By the above method, a laminate in which a primer layer (D), a metal particle layer (B), and a metal plating layer (C) were sequentially laminated on an insulating layer (A) obtained by curing a photosensitive resin was obtained.

(Example 9)
Similar to Example 7 except that an insulating layer (A) obtained by curing a photosensitive resin was prepared and used in the same manner as in Example 2 instead of the uncured layer (A-1) prepared in Example 7. A laminate was obtained by the method of.

(Example 10)
Similar to Example 8 except that an insulating layer (A) obtained by curing a photosensitive resin was prepared and used in the same manner as in Example 2 instead of the uncured layer (A-1) prepared in Example 8. A laminate was obtained by the method of.

(Comparative Example 1)
The surface of the insulating layer (A) produced in the same manner as in Example 2 was subjected to reverse sputtering treatment using an RF sputtering apparatus manufactured by Tokuda Seisakusho at an output of 300 W for 5 minutes, a sputtering pressure of 0.5 Pa, and an argon gas flow rate of 40 sccm. It was. Next, using the same device, a 0.2 μm titanium sputtering film and 0 were applied on the insulating layer (A) by a sputtering method under the conditions of an ultimate pressure of 5 × 10 ^{-4 Pa, a sputtering pressure of 0.2 Pa, and an argon gas flow rate of 20 sccm.} A copper sputtered film of .6 μm was formed.

The copper sputtered film was set as a cathode, and a copper plating layer (electroplating layer) was formed on the copper sputtered film in the same manner as in Example 1 to obtain a laminate produced by a sputtering method.

<Measurement of peel strength>
With respect to the laminates obtained in Examples 1 to 10 and Comparative Example 1, the peel strength between the insulating layer (A) and the metal plating layer (C) using "Bond Tester SS-30WD" manufactured by Seishin Shoji Co., Ltd. Was measured (peel strength before heating). The temperature at the time of measurement was 25 ° C., the lead width used for the measurement was 5 mm, and the peel angle was 90 °. The peel strength was measured based on the measured value at a thickness of the metal film of 15 μm. The results are shown in Table 1.

<Evaluation of adhesion>
From the peel strength values measured above, the adhesion was evaluated according to the following criteria.
A: The value of peel strength is 750 N / m or more.
B: The value of peel strength is 600 N / m or more and less than 750 N / m.
C: The value of peel strength is 450 N / m or more and less than 600 N / m.
D: The value of peel strength is less than 450 N / m.
The results are shown in Table 1.

<Measurement of peel strength after heating>
The laminates obtained in Examples 1 to 10 and Comparative Example 1 were heated in a constant temperature bath set at 150 ° C. for 168 hours, and then stored at room temperature (25 ° C.) for 1 hour. The peel strength of the heated laminate was measured by the same method as described above. The results are shown in Table 1.

<Evaluation of heat resistance>
From the peel strength values before and after heating measured above, the peel strength value after heating was divided by the peel strength value before heating to calculate the retention rate, and the heat resistance was evaluated according to the following criteria.
A: The retention rate is 85% or more.
B: The retention rate is 75% or more and less than 85%.
C: The retention rate is 70% or more and less than 75%.
D: The retention rate is less than 70%.
The results are shown in Table 1.

From the results shown in Table 1, in the laminates of Examples 1 to 10, the peel strength between the insulating layer (A) and the metal plating layer (C) was high, and the peel strength after heating was slightly reduced. It was confirmed that the retention rate of peel strength after heating was high and that it had excellent heat resistance.
On the other hand, the laminate of Comparative Example 1 was an example in which a metal layer was formed by a sputtering method and then metal-plated, and it was confirmed that the peel strength was low both before and after heating.

10, 30, 50 Laminated body 12 Base material 14, 34 Insulation layer 16, 36 Primer layer 18, 38 Metal particle layer 20, 40 Barrier metal plating layer 22, 42 Metal plating layer 31 Electrode 32 Silicon wafer 33 Passivation layer 52 Second Insulation layer 54 Contact plug 56 Second electrode

Claims (6)

With the insulating layer (A) obtained by thermally curing a photosensitive resin selected from polybenzoxazole precursor resin, polybenzoxazole resin, polyamide resin, polyimide precursor resin, polyimide resin, novolak resin, resole resin, and hydroxystyrene resin. ,
The metal particle layer (B) laminated on the insulating layer (A) and
A laminated body having a metal plating layer (C) laminated on the metal particle layer (B). The laminate according to claim 1, wherein a primer layer (D) is provided between the insulating layer (A) and the metal particle layer (B). The laminate according to claim 1 or 2, wherein a barrier metal plating layer (E) is provided between the metal particle layer (B) and the metal plating layer (C). Uncured layer before which the photosensitive resin is thermally cured (A-1), or a step of preparing a photosensitive resin insulating layer was thermally cured (A) (1),
A step (2) of applying a dispersion liquid (b) containing metal particles on the uncured layer (A-1) or the insulating layer (A) to form a metal particle layer (B), and
A method for producing a laminate, which comprises a step (3) of performing a plating treatment and forming a metal plating layer (C) on the metal particle layer (B). After the step (1), the primer composition (d) is applied onto the uncured layer (A-1) or the insulating layer (A) to form the primer layer (D) (1-1). )
The method for producing a laminate according to claim 4, wherein the step (2) is performed after the step (1-1). 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 or 5, wherein the step (3) is performed after the step (2-1).

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