JP4838606B2 - Copper foil with resin - Google Patents

Description

  The present invention relates to a resin-coated copper foil, and more particularly to a resin-coated copper foil capable of producing a multilayer wiring board by laminating a plurality of resin-coated copper foils.

  In the field of infrastructure network equipment such as base stations, servers, and routers, and in the field of semiconductor packages and the like where the demand for high-density mounting is increasing, a high-density, high-multilayer, all-layer IVH (interstitial via hole) substrate is required. It has been. In response to such market demand, Non-Patent Document 1 describes the following three wiring boards.

(1) High multi-layer printed wiring board Connection between vias and adhesion between multiple multi-layer (6 to 8 layers) printed wiring boards are directly connected with a prepreg filled with conductive paste of ALIVH (Any Layer IVH) technology. Printed wiring board. By adopting this method, it becomes easy to reduce the diameter of the via of the high multilayer printed wiring board, which has been difficult until now. Furthermore, by stacking via holes in the multilayer printed wiring board and copper plating, a stacked via of a high multilayer (20 to 40 layers) printed wiring board can be easily realized. The “stack via” refers to a via in which three or more layers are vertically formed.

(2) All-layer filled via high multi-layer printed wiring board A plurality of multilayer (6-layer to 8-layer) printed wiring boards having an all-layer filled via structure. By the same method as described above, a high-layer printed wiring board having an all-layer filled via structure that can be freely connected between all the layers exceeding 12 layers becomes possible. “Filled via” refers to a via filled with a conductor.

(3) Batch lamination build-up wiring board Prepare the required number of double-sided printed wiring boards with a filled via structure, and laminate and press the prepreg filled with conductive paste of ALIVH technology alternately, and then laminate the entire layer filled via structure. Build-up wiring board can be realized. By batch stacking, the manufacturing process can be reduced and the delivery time can be shortened.

  Further, in Patent Document 1, a step of forming an active energy ray-curable resin composition layer between a metal foil and an inner panel having a conductor circuit, the metal foil leaving a position portion for forming a via hole. The step of removing the metal foil, the step of irradiating only the layer of the resin composition which is exposed without being permeated and curing it, the portion of the metal foil where the via hole is formed is removed and then exposed. Dissolving an uncured resin composition to provide via holes in the resin composition layer, roughening the surface of the resin composition layer, and plating a metal on the surface of the resin composition layer by plating A method for producing a multilayer printed wiring board is described, which comprises a step of depositing and a step of forming an outer layer conductor circuit pattern by removing unnecessary metal. This manufacturing method uses a metal foil as an electron beam resist to form a via hole, thereby forming a cured product of a resin composition having a high resolution, and thereby a large amount of via holes having small diameter holes. It is possible to form.

Patent Document 2 describes a varnish excellent not only in heat resistance and adhesiveness but also in standing stability. Patent Document 3 discloses a resin composition that is excellent not only in heat resistance and adhesiveness but also in storage stability, can be easily applied to fields such as coating and impregnation, and has excellent flexibility in cured products. And varnishes are described. Patent Document 4 describes a varnish useful for a heat-resistant laminate using a heat-resistant prepreg. In addition, in each of Patent Documents 2 to 4, a copper foil with resin is described, and a laminate using the copper foil with resin is described.
Yasuhiro Uranishi, “All-Layer IVH Structure“ ALIVH ””, Electronics Packaging Technology, Technical Research Committee, March 2005, Vol. 21 No. 3 JP 2002-94243 A Japanese Patent Laid-Open No. 10-195377 Japanese Patent Laid-Open No. 11-80595 JP-A-8-302273

  A high-density multilayer wiring board on which an integrated circuit (IC) is mounted is required to have good interlayer adhesion reliability such as moisture absorption heat resistance in order to be used stably for a long period of time. Further, it is required to reduce the via diameter and shorten the distance between vias (via pitch), and it is necessary to ensure interlayer connectivity reliability that is in a trade-off relationship with these. In component mounting, it is required in the future to mount components with a pitch of 0.5 mm, and further with a pitch of 0.4 mm, 0.3 mm, and 0.15 mm on a printed circuit board.

  However, in the case of a heat-fusible insulating sheet composed of a prepreg filled with a conductive paste described in Non-Patent Document 1, an epoxy prepreg is used. There is a problem that the epoxy resin flows around the pattern portion and is hardened to impair the interlayer connection reliability, or the shortening of the via pitch distance is restricted. In addition, the epoxy resin itself has a high relative dielectric constant and dielectric loss tangent, and there are problems such as insufficient transmission characteristics for high frequency applications.

  Moreover, although the manufacturing method of the multilayer wiring board of patent document 1 describes the copper foil with a resin in which the layer of the active energy ray-curable resin composition was formed on the metal foil, a plurality of copper foils with a resin are described. It is not described that a multilayer wiring board is manufactured by stacking layers. Further, even if a multilayer wiring board is produced by laminating a plurality of resin-coated copper foils described in Patent Document 1, it is not possible to cause metal diffusion bonding in a via hole, and the multilayer wiring has excellent interlayer connection reliability. A substrate could not be produced.

  Moreover, although the copper foil with a resin and laminated board of patent documents 2-4 have the heat resistance, adhesiveness, etc. which are the characteristics of a varnish, interlayer connection reliability is not considered. Therefore, even if via holes are formed in this resin-coated copper foil and a paste filled with conductive paste is laminated, metal diffusion bonding cannot be produced, and a multilayer wiring board having interlayer connection reliability is produced. I can't do it.

  Therefore, the present invention provides a resin-coated copper foil that has extremely high interlayer adhesion reliability and interlayer connection reliability, and can be used to successively and successively produce a high-density, high-multilayer multilayer wiring board. Is an issue.

  The present invention will be described below. In order to facilitate understanding of the present invention, reference numerals in the accompanying drawings are added in parentheses, but the present invention is not limited to the illustrated embodiment.

  The first aspect of the present invention is an insulating base material (10) made of a resin composition, a copper foil (20a) laminated on one surface of the insulating base material (10), and the other of the insulating base material (10). A resin-coated copper foil (100a) comprising an adhesive layer (30a) laminated on the surface of the resin, wherein the adhesive layer (30a) is formed of a mixture of an alkenylphenol compound and maleimides. is there.

  In the first aspect of the present invention, the mixing ratio of the alkenylphenol compound and maleimides in the adhesive layer (30a) is preferably 30/70 or more and less than 70/30 in molar ratio. Thereby, it can prevent that the contact bonding layer (30b) formed when an alkenyl phenol compound and maleimide bridge | crosslink become weak, and can exhibit high interlayer adhesive reliability.

  In the first aspect of the present invention, the thickness of the adhesive layer (30a) is preferably less than 1/5 of the thickness of the insulating substrate (10). As a result, when the wiring board is laminated, the mixture of the alkenylphenol compound and the maleimide flows into the via hole, or the conductive paste (40) in the via hole is discharged out of the via, and sufficient pressure is applied to the via portion. In addition, it is possible to prevent a situation in which the inter-layer connection reliability of the multilayer wiring board is hindered such that the metal diffusion bonding is not formed in the via or the conductive pattern portion of the upper and lower substrates.

  In the first aspect of the present invention, the adhesive layer (30a) is solidified at room temperature and preferably has a melting point of 40 ° C. or higher and lower than 100 ° C. Thereby, an adhesive layer (30a) can be fixed on an insulating base material (10) at room temperature. Moreover, it is preferable that an alkenyl phenol compound and maleimides become a linear polymer by an ene addition reaction at 120 ° C. or higher and a cross-linked product by a Diels-Alder reaction at 200 ° C. or higher. This makes it easy for secondary bonds to occur between the insulating base material (10) and the general-purpose wiring board (200) from the melting point of the alkenylphenol compound and maleimide to the completion of curing, thereby improving interlayer adhesion reliability. Can be expressed. Moreover, it is preferable that the contact bonding layer (30b) obtained by this addition reaction and this crosslinking reaction has a glass transition temperature of 300 degreeC or more. Thereby, the formed contact bonding layer (30b) can express non-lead solder heat resistance.

  In the first aspect of the present invention, the alkenylphenol compound is preferably dimethallylbisphenol A, and the maleimide is preferably bis (4-maleimidophenyl) methane. By setting it as the contact bonding layer (30a) which consists of these mixtures, interlayer adhesion reliability can be made more favorable.

  In the first aspect of the present invention, the resin composition constituting the insulating substrate (10) includes a crystalline thermoplastic resin having a crystal melting peak temperature of 260 ° C. or higher, and an amorphous thermoplastic resin having a glass transition temperature of 260 ° C. or higher. Liquid crystal polymer having a liquid crystal transition temperature of 260 ° C. or higher, Non-thermoplastic polyimide resin having a glass transition temperature of 300 ° C. or higher, epoxy resin, addition-type polyimide resin, bismaleimide triazine resin, or thermosetting polyphenylene ether resin It is preferable that

  By forming the insulating base material (10) with these resin compositions, the resin-coated copper foil (100a) of the present invention is filled with the conductive paste composition (40) by forming via holes (100b, 100c), when the conductive paste composition (40) and the conductor pattern portion (20b) are sequentially laminated on the general-purpose wiring board (200) or the already laminated copper foil with resin (100b, 100c). Metal diffusion bonding occurs between the metal forming the metal. This also makes it possible to produce a multilayer wiring board having extremely high connection reliability and excellent moisture absorption heat resistance, connection reliability, and conductor adhesive strength.

  The resin-coated copper foil (100) of the first aspect of the present invention has a via hole penetrating the insulating substrate (10) and the adhesive layer (30a), and the via hole is filled with the conductive paste composition (40) ( 100b, 100c), and by extremely thermocompression bonding in a predetermined manner on a general-purpose wiring board (200) or already laminated copper foil with resin (100b, 100c) under predetermined conditions, extremely high interlayer adhesion reliability In addition, it is possible to manufacture a multilayer wiring board having a high density and a high multi-layer structure with interlayer connection reliability.

  In the above forms (100b, 100c), the conductive paste composition (40) includes a conductive powder and a binder component, and the mass ratio of the conductive powder and the binder component is 90/10 or more and less than 98/2. Preferably, the conductive powder is composed of first alloy particles and second metal particles, and the first alloy particles are non-lead solder particles having a melting point of 180 ° C. or higher and lower than 260 ° C., 2 metal particles are at least one selected from the group consisting of Au, Ag, and Cu, and the mass ratio of the first alloy particles to the second metal particles is 76/24 or more and less than 90/10. Preferably, the binder component is a mixture of polymerizable monomers that are cured by heating, and the melting point of the lead-free solder particles is preferably included in the curing temperature range of the binder component.

  By using such a conductive paste composition (40), metal diffusion bonding occurs between the conductive paste composition (40) and the metal forming the conductor pattern portion (20b), and in the multilayer wiring board. The resistance value of the via hole can be made very small, and a multilayer wiring board excellent in moisture absorption heat resistance, connection reliability, and conductor adhesive strength can be obtained.

  By using the resin-coated copper foil (100) of the present invention, a multilayer wiring board having extremely high interlayer adhesion reliability and interlayer connection reliability, and having a high density and a high multi-layer structure can be sequentially laminated. it can. Also, by combining with a specific conductive paste composition (40), metal diffusion bonding can be produced, and the resistance value of the via hole in the multilayer wiring board can be made extremely small, moisture absorption heat resistance, connection reliability, and A multilayer wiring board having excellent conductor adhesive strength can be produced. Further, when combined with an insulating base material (10) made of a specific resin composition, this metal diffusion bonding can be further promoted.

  As shown to Fig.1 (a), as for the copper foil 100a with a resin of this invention, copper foil (20a) is laminated | stacked on one surface of the insulating base material (10) which consists of a resin composition, and it adhere | attaches on the other surface. The layer (30a) is laminated.

<Use of resin-coated copper foil 100a>
The use of the resin-coated copper foil 100a of the present invention will be described below. The copper foil with resin 100a of the present invention includes, for example, the steps shown in FIGS. 1 (a), (b), (c) and (d), and FIGS. 1 (a), (e), (f), ( g), (h), and (i) are sequentially laminated by any one of the steps shown in (i) to form a multilayer wiring board.

  First, the steps shown in FIGS. 1A, 1B, 1C, and 1D will be described. First, as shown in FIG. 1B, a resist pattern is applied on the copper foil 20a to form a resist pattern, and the conductor pattern 20b is formed by a normal method of etching the copper foil 20a using the resist pattern as a mask. The Then, a via hole penetrating the adhesive layer 30a and the insulating substrate 10 is formed by a laser or the like. Then, this via hole is filled with a conductive paste composition 40, which will be described later, to form (100b) as shown in FIG.

  And as shown in FIG.1 (c), the copper foil 100a with resin is piled up on the various general purpose wiring board 200 in which the conductor pattern was formed via the contact bonding layer 30a, and it heat-seal | fuses by predetermined conditions. The Note that via holes are formed in the bonding sheet 100b in accordance with the positions of the conductor patterns provided on the general-purpose wiring board 200 to be laminated, and the conductive paste composition 40 is filled. As conditions for heat sealing, it is preferable that temperature: 200 degreeC or more and 250 degrees C or less, and pressure: 3 MPa or more and 8 MPa or less. By this thermal fusion, the adhesive layer 30a is cured to become the adhesive layer 30b.

  And as shown in FIG.1 (d), the copper foil 100b with resin is further piled up on the already laminated copper foil 100b with resin through the contact bonding layer 30a, and it heat-seal | fuses on the same conditions. By repeating these steps of FIGS. 1C and 1D, the resin-coated copper foil 100b of the present invention can be sequentially laminated to produce a multilayer wiring board having a desired number of laminations.

  The process shown in FIGS. 1A, 1E, 1F, 1G, 1H, and 1I, which is another process, will be described. In the copper foil with resin 100a, a via hole penetrating the adhesive layer 30a and the insulating substrate 10 is formed by a laser or the like, and this via hole is filled with a conductive paste composition 40 to be described later, and FIG. The form (100c) is as shown.

  And as shown in FIG.1 (f), it overlaps on the various general purpose wiring board 200 in which the conductor pattern was formed via the contact bonding layer 30a, and is heat-seal | fused on predetermined conditions. The conditions for heat sealing and the formation positions of the via holes are the same as described above with reference to FIG.

  Then, after forming a multilayer wiring board, a conductor pattern 20b is formed as shown in FIG. 1 (g) by an ordinary method of applying a resist on the copper foil 20a on the surface and etching.

  The copper foil with resin 100c is further laminated via the adhesive layer 30a on the surface of the copper foil with resin 100c already laminated, on which the conductor pattern 20b is formed, and heat-sealed under the same conditions (FIG. 1 (h)). Then, the process of forming the conductor pattern 20b is repeated (FIG. 1 (i)). Thus, the process of heat-sealing the copper foil with resin 100c and the process of forming the conductor pattern 20b can be repeated to produce a multilayer wiring board having a desired number of layers.

  Thus, as in the steps shown in FIGS. 1A, 1B, 1C, and 1D, a desired number of resin-coated copper foils 100b in which various conductor patterns are formed in advance are combined and sequentially applied. It is possible to adopt a process suitable for mass production, which is laminated on a multilayer wiring board, as shown in FIGS. 1 (a), (e), (f), (g), (h) and (i). As in the process, it is possible to adopt a process suitable for small-scale production in which a conductor pattern is individually formed after forming a multilayer wiring board without forming a conductor pattern at the stage of the copper foil with resin 100c.

<Insulating base material 10 made of resin composition>
The insulating base material 10 made of the resin composition includes a crystalline thermoplastic resin having a crystal melting peak temperature of 260 ° C. or higher, an amorphous thermoplastic resin having a glass transition temperature of 260 ° C. or higher, and a liquid crystal having a liquid crystal transition temperature of 260 ° C. or higher. It is preferable that it is comprised by the composition which consists of thermoplastic resins, such as a polymer.

  As the crystalline thermoplastic resin having a crystal melting peak temperature of 260 ° C. or higher, it is preferable to use a mixed composition of a polyaryl ketone resin and an amorphous polyetherimide resin. As the amorphous thermoplastic resin having a glass transition temperature of 260 ° C. or higher, it is preferable to use thermoplastic polyimide. As the liquid crystal polymer having a liquid crystal transition temperature of 260 ° C. or higher, it is preferable to use a wholly aromatic polyester resin (LCPI type, II type).

  Moreover, it is preferable that the insulating base material 10 which consists of a resin composition is comprised with the non-thermoplastic polyimide resin whose glass transition temperature is 300 degreeC or more. Here, the non-thermoplastic polyimide resin is formed by a condensation reaction of polymellitic anhydride and aromatic diamine. This combined aromatic diamine molecular structure creates a distinctive product. Examples of the polyimide having a glass transition temperature of 300 ° C. or higher include Kapton H film (DuPont), Upilex S (Ube Industries), and the like.

  The insulating substrate 10 made of a resin composition is preferably composed of a composition made of a thermosetting resin such as an epoxy resin, an addition-type polyimide resin, a bismaleimide triazine resin, or a thermosetting polyphenylene ether resin. . As the epoxy resin, it is preferable to use brominated bisphenol A type epoxy resin or the like. The bismaleimide triazine resin is a copolymer of bismaleimide and triazine. It is preferable that the insulation base material 10 comprised with the composition which consists of these thermosetting resins is hardened | cured completely in the state of the copper foil 100a with resin. This is because if the resin is completely cured after the via hole is formed or laminated with another wiring substrate 200, the resin flows at the time of curing, so that it is difficult to ensure the interlayer connection reliability.

  By using the above-described insulating base material 10 made of the resin composition, metal diffusion bonding of the conductive paste composition 40 in the via hole described below can be more effectively generated.

  Among the materials described above, the insulating base material 10 made of the resin composition is a crystal having a crystal melting peak temperature of 260 ° C. or higher from the viewpoint of more effectively causing metal diffusion bonding of the conductive paste composition 40. It is preferable to use an insulating substrate composed of a composition made of a thermoplastic resin.

  Hereinafter, an insulating base material constituted by a composition made of a crystalline thermoplastic resin having a crystal melting peak temperature of 260 ° C. or higher, which is one of the preferred forms of the insulating base material 10 made of the above resin composition, will be described. To do. As a composition comprising a crystalline thermoplastic resin having a crystal melting peak temperature of 260 ° C. or higher, a mixed composition of a polyaryl ketone resin and an amorphous polyetherimide resin is preferably used. These resins are compatible systems. The mixed composition has one crystal melting peak temperature, and the crystal melting peak temperature is 260 ° C. or higher. When a mixed composition of a polyaryl ketone resin and an amorphous polyetherimide resin is used as a material constituting the insulating substrate 10, in addition to the pressure applied from above and below the conductive paste composition in the via hole described above The tightening pressure is applied from the left and right due to the change in the elastic modulus of the insulating substrate 10. Therefore, it is considered that the effect of causing metal diffusion bonding is greater. The manner in which the elastic modulus of the insulating base material 10 changes with temperature will be described later.

  This polyaryl ketone resin is a thermoplastic resin having an aromatic nucleus bond, an ether bond and a ketone bond in its structural unit, and representative examples include polyether ketone, polyether ether ketone, polyether ketone ketone, etc. Of these, polyetheretherketone is preferred. Polyether ether ketone is commercially available as “PEEK151G”, “PEEK381G”, “PEEK450G” (all are trade names of VICTREX), and the like.

  The amorphous polyetherimide resin is an amorphous thermoplastic resin containing an aromatic nucleus bond, an ether bond and an imide bond in the structural unit, and is not particularly limited. Polyetherimide is commercially available as “Ultem CRS 5001”, “Ultem 1000” (both are trade names of General Electric).

  As a mixing ratio of the polyaryl ketone resin and the amorphous polyetherimide resin, when considering the adhesion with the adhesive layer 30 to be laminated, the polyaryl ketone resin is contained in an amount of 30% by mass to 70% by mass, and the balance It is preferable to use a mixed composition containing amorphous polyetherimide resin and inevitable impurities. Here, the reason why the content of the polyaryl ketone resin is limited to 30% by mass or more and 70% by mass or less is that when the content of the polyaryl ketone resin is too high, the crystallinity of the thermoplastic resin composition is high. This is because familiarity with the adhesive layer 30 cannot be obtained at the time of lamination, and the lamination reliability is lowered. If the content of the polyaryl ketone resin is too low, the heat resistance of the entire thermoplastic resin composition is lowered, and the like. This is because the reflow heat resistance as a multilayer wiring board after being laminated with the general-purpose substrate 200 is reduced.

  This thermoplastic resin composition may contain an inorganic filler. There is no restriction | limiting in particular as an inorganic filler, Any well-known thing can be used. Examples thereof include talc, mica, mica, glass flake, boron nitride (BN), plate-like carbon cal, plate-like aluminum hydroxide, plate-like silica, and plate-like potassium titanate. These may be added singly or in combination of two or more. In particular, a scale-like inorganic filler having an average particle size of 15 μm or less and an aspect ratio (particle size / thickness) of 30 or more can keep the linear expansion coefficient ratio in the plane direction and the thickness direction low, and the thermal shock cycle test. This is preferable because generation of cracks in the substrate at the time can be suppressed.

  The added amount of the inorganic filler is preferably 20 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the thermoplastic resin. This is because if the amount of the inorganic filler added is too large, a problem of poor dispersion of the inorganic filler occurs, and the linear expansion coefficient tends to vary or the strength tends to decrease. Also, if the amount of the inorganic filler added is too small, the effect of reducing the linear expansion coefficient and improving the dimensional stability is small, resulting from the difference in the linear expansion coefficient from the other wiring substrate 200 and the conductive pattern 20b in the reflow process. This is because internal stress is generated, and the substrate is warped and twisted.

  In addition, the thermoplastic resin composition has various additives other than other resins and inorganic fillers, such as a stabilizer, an ultraviolet absorber, a light stabilizer, a nucleating agent, a colorant, and a lubricant, to the extent that the properties are not impaired. In addition, flame retardants and the like may be appropriately contained. As a method of adding various additives including these inorganic fillers, a known method, for example, the following methods (a) and (b) can be used.

  (A) Various additives were mixed with a polyaryl ketone resin and / or an amorphous polyetherimide resin base material (base resin) at a high concentration (typically about 10 to 60% by mass). A method of preparing a master batch separately, adjusting the concentration of the master batch and mixing the resin, and mechanically blending it using a kneader or an extruder. (B) A method in which various additives are mechanically blended directly with a resin to be used using a kneader or an extruder. Among these methods, the method (a) is preferable from the viewpoint of dispersibility and workability. Furthermore, the surface of the insulating base material 10 made of the resin composition may be appropriately subjected to corona treatment or the like for the purpose of improving the lamination property.

<Copper foil 20a>
As the copper foil 20a, an electric field copper foil or a rolled copper foil can be used. The thickness is not particularly limited, but is preferably 9 to 18 μm from the viewpoint of forming a high-density wiring.

<Adhesive layer 30a>
The adhesive layer 30a in the present invention is a layer made of a mixture of an alkenylphenol compound and maleimides.

  Examples of the alkenylphenol compound include alkenylphenol compounds having at least two alkenyl groups in the molecule, that is, phenolic compounds in which a part of the hydrogen atoms of the aromatic ring are substituted with alkenyl groups. Specifically, examples of such alkenylphenol compounds include compounds in which an alkenyl group is bonded to bisphenol A or a phenolic hydroxyl group-containing biphenyl skeleton. More specifically, 3,3′-bis (2-propenyl) -4,4′-biphenyldiol, 3,3′-bis (2-propenyl) -2,2′-biphenyldiol, 3,3 ′ Dialkenyl biphenyldiol compounds such as -bis (2-methyl-2-propenyl) -4,4'-biphenyldiol and 3,3'-bis (2-methyl-2-propenyl) -2,2'-biphenyldiol 2,2-bis [4-hydroxy-3- (2-propenyl) phenyl] propane, 2,2-bis [4-hydroxy-3- (2-methyl-2-propenyl) phenyl] propane (hereinafter “ And dialkenyl bisphenol compounds such as “dimethallyl bisphenol A”). Among these, it is preferable to use dimethallyl bisphenol A as the alkenylphenol compound from the viewpoint that the raw material cost is low and stable supply is possible. The structural formula of dimethallylbisphenol A is shown in Formula 1.

  Examples of maleimides include maleimide compounds having at least two maleimide groups in the molecule. Specific examples thereof include bismaleimides such as bis (4-maleimidophenyl) methane and tris (4-maleimidophenyl) methane. And trismaleimide such as bis (3,4-dimaleimidophenyl) methane, and polymaleimide such as poly (4-maleimidostyrene). Among these, as maleimides, it is preferable to use bis (4-maleimidophenyl) methane because raw material costs are low and stable supply is possible. The structural formula of bis (4-maleimidophenyl) methane is shown in Formula 2.

  The adhesive layer 30a is solidified at room temperature, and preferably has a melting point of 40 ° C. or higher and lower than 100 ° C. Thereby, the adhesive layer 30 a can be solidified and fixed on the insulating base material 10. Further, from the viewpoint of improving the film forming property when a solution is applied on the insulating substrate 10, it is preferable to use high molecular weight alkenylphenol compounds and maleimides.

  The mixing ratio of the alkenylphenol compound and maleimides in the adhesive layer 30a is preferably not less than “30/70” and less than “70/30” in terms of molar ratio (“alkenylphenol compound” / “maleimides”). If either component is too much beyond this range, the resulting adhesive layer 30b becomes brittle and the interlayer adhesion reliability is poor.

  The curing reaction in the adhesive layer 30a will be described below. The alkenyl group in the alkenylphenol compound undergoes alternating copolymerization and / or addition reaction with the ethylenically unsaturated group of the maleimide compound, and the phenolic hydroxyl group also undergoes addition reaction with the ethylenically unsaturated group of the maleimide group. Hereinafter, the curing mechanism of dimethallylbisphenol A and bis (4-maleimidophenyl) methane exemplified as the binder component will be specifically described. First, in the stage heated to 120-180 degreeC, the linear polymer shown by the following formula | equation 3 is obtained.

  Furthermore, when heated to 200 ° C. or higher, for example, a three-dimensionally crosslinked polymer represented by the following formula 4 is obtained. The adhesive layer 30b obtained by these addition reaction and crosslinking reaction has a glass transition temperature of 300 ° C. or higher. Thereby, the effect of non-lead solder heat resistance is exhibited.

  In the resin-coated copper foil of the present invention, when the insulating base material 10 is made of a mixed composition of a polyaryl ketone resin and an amorphous polyetherimide resin, the insulating base material 10 is softened by heating. Then, after the adhesive layer 30a is softened, the insulating substrate 10 is cured. Therefore, there exists a temperature range in which both the insulating base material 10 and the adhesive layer 30a are softened. Thereby, both are familiar (intermolecular force works), and adhesiveness is developed between the insulating substrate 10 and the adhesive layer 30.

  Further, the adhesiveness between the insulating base material 10 and the general-purpose wiring board 200 that has a high glass transition temperature and does not soften during lamination is such that the adhesive layer 30a is softened so that the insulating base material 10 and the general-purpose wiring board 200 can be bonded. Adhesiveness is manifested by the anchor effect produced by the adhesive layer 30a entering the minute irregularities on the surface, hydrogen bonding, and the like.

  The adhesive layer 30a is considered to promote the metal diffusion bonding of the conductive paste composition 40 in the via hole. The adhesive layer 30a is in a softened state until completely cured and becomes the adhesive layer 30b, and the elastic modulus of the adhesive layer 30a is reduced. While the elastic modulus of the adhesive layer 30a is decreasing, the pressure during lamination is concentrated on the conductive paste composition 40 in the via hole in the resin-coated copper foils 100b and 100c through the softened adhesive layer 30a. In such a state that the pressure is applied to the conductive paste composition 40, it is considered that when the temperature exceeds the melting point of the lead-free solder particles in the conductive paste composition 40, the metal diffusion bonding proceeds rapidly. Yes.

  In the copper foil with resin 100 of the present invention, the thickness of the adhesive layer 30a is preferably less than 1/5 of the thickness of the insulating base material 10. By doing so, it is possible to prevent the mixture of the alkenylphenol compound and the maleimide from flowing into the via hole when laminating with the general-purpose wiring board 200, thereby hindering the interlayer connection reliability of the multilayer wiring board. Moreover, when the adhesive layer 30a is too thick and laminated with the general-purpose wiring board 200, the mixture of the alkenylphenol compound and maleimide flows out, and sufficient pressure is not applied to the conductive paste composition in the via hole. In addition, it is possible to prevent a situation in which metal diffusion bonding cannot be generated.

  Moreover, the thickness of the insulating base material 10 is preferably 25 to 400 μm, more preferably 50 to 300 μm, and is appropriately determined depending on the use of the resin-coated copper foil. The thickness of the adhesive layer 30a is preferably less than 1/5 of the thickness of the insulating substrate 10 and is preferably as thick as possible from the viewpoint of interlayer adhesion reliability.

<Conductive paste composition 40>
In the copper foil with resin 100a of the present invention, as shown in FIGS. 1B and 1E, via holes are formed through the adhesive layer 30a and the insulating substrate 10, and the conductive paste composition 40 is formed in the via holes. Is used in the state 100b, 100c filled. The conductive paste composition 40 used in the present invention contains conductive powder and a binder component.

(Conductive powder)
The conductive powder is composed of first alloy particles and second metal particles.

  The first alloy particles are non-lead solder particles having a melting point of 180 ° C. or higher and lower than 260 ° C. Examples of such lead-free solder particles include Sn—Cu, Sn—Sb, Sn—Ag—Cu, Sn—Ag—Cu—Bi, Sn—Ag—In, Sn—Ag—In—Bi, and Sn—. Zn, Sn-Zn-Bi, and Sn-Ag-Bi can be mentioned. These lead-free solder particles are reliable in the effect of metal diffusion of tin. As the first alloy particles, a mixture of two or more of these non-lead solder particles can also be used.

  The second metal particles are at least one or more metal particles selected from the group consisting of Au, Ag, and Cu. The second metal particle is a particle formed of a metal having a low electric resistance value, and bears the electric conductivity of the via hole. The second metal particles have a higher melting point than the first alloy particles, and have a role of maintaining the viscosity of the conductive paste composition 40 during heating.

  The mixing ratio of the first alloy particles and the second metal particles in the conductive powder is “76/24” or more and less than “90/10” by mass ratio (“first alloy particles” / “second” Metal particles "). If the amount of the first alloy particles is too large beyond this range, the viscosity of the conductive paste composition 40 is greatly reduced when the substrate is heated and laminated, and the conductive paste composition 40 flows out of the via hole. There is a risk that.

  The average particle diameter of the first alloy particles and the second metal particles is preferably 10 μm or less. By setting the first alloy particles to such a particle size, the conductive paste composition 40 can be easily filled in the via holes, and metal diffusion can easily occur. Moreover, the effect which adjusts the viscosity of the electrically conductive paste composition 40 at the time of carrying out heating lamination | stacking of a board | substrate by using a 2nd metal particle as such a particle size becomes favorable.

  The average particle size difference between the first alloy particles and the second metal particles is preferably 2 μm or less. By aligning the particle diameters as much as possible, metal diffusion bonding can be easily generated.

(Binder component)
The binder component used in the present invention is a mixture of polymerizable monomers that are cured by heating. Examples of such a binder component include a mixture of an alkenylphenol compound and maleimides. In addition, even if the alkenylphenol compound and / or maleimide is a polymer compound, it can be included in the polymerizable monomer of the present invention as long as it is cured by crosslinking reaction by heating. And

  As the alkenylphenol compound and maleimide, those described in the adhesive layer 30a can be used.

  In this binder component, the molar ratio of the alkenylphenol compound and maleimide is preferably “30/70” or more and less than “70/30” (“alkenylphenol compound” / “maleimides”). If either of the components in the binder component is too much beyond this range, the resulting resin becomes brittle and the adhesive force between the conductive paste composition 40 and the conductor pattern portion 20b is reduced.

  The curing reaction of the binder component is the same as that in the adhesive layer 30a described above. In the present invention, the hardening by such three-dimensional crosslinking of the binder component promotes the metal diffusion of the solder component to the metal forming the second metal particles and / or the conductor pattern portion 20b, thereby achieving a high degree of It is believed that a metal diffusion bond is formed. That is, when the binder component is cured, pressure is applied to the first alloy particles and the second metal particles in the via hole, whereby the solder component is diffused into the metal forming the metal particles and the conductor pattern portion 20b. Is believed to be promoted. FIG. 2 shows how the elastic modulus of the binder component changes with temperature. The elastic modulus of the monomer mixture decreases with increasing temperature. However, the elastic modulus suddenly increases due to the formation of the linear polymer represented by Formula 3 at 120 to 180 ° C. (From the graph of “monomer mixture” in FIG. 2, “after crosslinking”). It becomes a graph of.) Thereafter, the linear polymer is considered to change into a three-dimensionally crosslinked polymer represented by Formula 4 at 200 ° C. or higher. The graph after crosslinking tends to decrease with increasing temperature. However, a constant elastic modulus is maintained without melting even in a high temperature region.

  Thus, when the lead-free solder particles are melted at 180 to 260 ° C., the binder component undergoes a curing reaction to maintain a certain elastic modulus. As described above, it is considered that the molten lead-free solder particles are subjected to pressure due to the binder being cured, and thereby, metal diffusion bonding occurs in the conductive paste composition 40. And the multilayer wiring board using such a conductive paste composition 40 has a very low resistance value of the via hole, and has excellent moisture absorption heat resistance, connection reliability, and conductor adhesive strength. Conceivable.

  From such a viewpoint, the binder component needs to be cured at the stage where the solder particles are dissolved, and the melting point of the lead-free solder particles needs to be included in the curing temperature range of the binder component. On the other hand, when the melting point of the lead-free solder particles is too high compared to the curing temperature range of the binder component, the lead-free solder particles are not yet melted at the stage where the binder component is cured. The effect of being promoted cannot be enjoyed. In addition, when the melting point of the non-lead solder particles is too low as compared with the curing temperature range of the binder component, the dissolved solder component may protrude from the via hole.

  As described above, the conductive paste composition 40 contains a conductive powder and a binder component. The mixing ratio of the conductive powder and the binder component is “90/10” or more and “98 / 2 "(" conductive powder "/" binder component "). If the amount of the conductive powder is too small beyond this range, the electrical resistance value of the conductive paste filled in the via hole will increase. Further, if the amount of the conductive powder is too much beyond this range, the workability of printing and filling the conductive paste composition 40 in the via hole is deteriorated, and the conductive paste composition 40 and the conductor pattern portion 20b Adhesive strength will decrease.

<Method for Producing Copper Foil 100a, 100b, 100c with Resin>
A method for producing the resin-coated copper foil 100a of the present invention whose configuration is shown in FIG. First, the insulating base material 10 made of a resin composition is formed on the copper foil 20a. The formation method is not particularly limited. For example, the method of forming the insulating base material 10 by extrusion laminating the resin composition constituting the insulating base material 10 on the copper foil 20a using a T-die is stable productivity. From the point of view, it is preferable.

  The molding temperature in the extrusion laminating is appropriately adjusted depending on the flow characteristics and film-forming properties of the resin used. Generally, the polyaryl ketone resin and the amorphous polyetherimide resin having a crystal melting peak temperature of 260 ° C. or higher are used. In the case of a mixed composition, it is 360-400 degreeC. In addition, it is necessary to form an amorphous film by rapidly forming a film during extrusion casting. Thereby, since the area | region where an elasticity modulus falls in 170-230 degreeC vicinity is expressed, thermoforming and heat fusion in this temperature range are attained. Specifically, the elastic modulus starts to decrease at around 170 ° C., and thermoforming and heat fusion are possible at around 200 ° C. The graph shown in FIG. 4 shows the elastic modulus measured at a rate of temperature increase of 3 ° C./min. When the rate of temperature increase is 10 ° C./min, the transition from amorphous to crystalline is delayed. In the vicinity of 230 ° C., the elastic modulus is the lowest.

  Next, an adhesive layer 30 a is formed on the insulating substrate 10. Although the formation method of the contact bonding layer 30a is not specifically limited, It is preferable that it is the method shown to Fig.3 (a) or FIG.3 (b). The method shown in FIG. 3 (a) is a method of forming an adhesive layer 30a by directly applying a solution containing a mixture of an alkenylphenol compound and maleimides on an insulating substrate 10 and drying and solidifying the solution. is there. The method for applying the solution is not particularly limited, and a bar coater or the like can be employed. The solvent in the solution is not particularly limited as long as it can dissolve alkenylphenol compounds and maleimides, but it is preferable to use γ-butyrolactone, methyl ethyl ketone, or the like.

  In the method shown in FIG. 3B, first, a peelable film 60 such as a PET film is coated with a solution containing a mixture of an alkenylphenol compound and a maleimide, dried and solidified, and then the peelable film. The adhesive layer 30a is formed on the insulating substrate 10, and the adhesive layer 30a is stacked on the insulating substrate 10, heated and thermally transferred, finally the film 60 is peeled off, and the adhesive layer 30a is formed on the insulating substrate 10. It is a method of forming. Thus, the resin-coated copper foil 100a of the present invention is produced.

  Next, a resist is applied on the copper foil 20a to form a resist pattern, and the conductor pattern 20b is formed by a normal method of etching the copper foil 20a using the resist pattern as a mask. Then, a via hole penetrating the adhesive layer 30a and the insulating base material 10 is formed at a predetermined position using a laser or a mechanical drill, and the conductive paste composition 40 is applied to the via hole by a normal printing method such as screen printing. By filling, a resin-coated copper foil 100b as shown in FIG. 1B is formed. The conductor pattern 20b may be formed after forming a via hole and filling the conductive paste 40, and the order of these steps is not particularly limited.

  Further, the resin-coated copper foil 100c shown in FIG. 1 (e) is formed by forming a via hole and filling a conductive paste in the same manner as the resin-coated copper foil 100b except that a resist pattern is not formed. Can do.

<Behavior of elastic modulus of insulating substrate 10 made of resin composition with respect to temperature>
Here, the behavior of the elastic modulus with respect to the temperature of the insulating base material 10 made of the resin composition will be described. In the case where a composition comprising a crystalline thermoplastic resin having a crystal melting peak temperature of 260 ° C. or higher is used as the resin composition, polyether ether ketone and amorphous polyetherimide are used as the crystalline thermoplastic resin. FIG. 4 shows the behavior of the elastic modulus of the insulating base material 10 with respect to temperature in the case of using a resin composition.

  “Before lamination” is a graph showing the behavior of the elastic modulus of the insulating base material 10 with respect to temperature before lamination as a multilayer wiring board. Also, “after lamination” is a graph showing the behavior of the elastic modulus of the insulating base material 10 with respect to temperature after forming a multilayer wiring board by heating and pressing under predetermined conditions. In the state before lamination, as described above, the insulating base material 10 is formed into an amorphous film by rapid cooling. Therefore, the elastic modulus is sufficiently lowered in a relatively low temperature region of around 200 ° C. Thereby, the insulating base material 10 before lamination can be thermoformed and heat-sealed at a relatively low temperature.

  The insulating base material 10 formed into an amorphous film changes to crystallinity by heating and pressure molding under predetermined conditions when manufacturing a multilayer wiring board. Along with this, the elastic modulus of the insulating base material 10 is greatly changed to behave as shown in the graph after lamination in FIG. As a result, the effect of promoting metal diffusion bonding as described below is demonstrated, and the multilayer wiring board can have a very small resistance value of its via hole, and also has moisture absorption heat resistance, connection reliability, In addition, it is considered that the conductor adhesion can be excellent.

  Next, how metal diffusion bonding is promoted will be described. Here, the relationship between the lead-free solder particles in the conductive paste composition 40 and the insulating substrate 10 made of the resin composition is important, and the storage elastic modulus of the resin composition at the melting point of the lead-free solder particles is: It is preferably 10 MPa or more and less than 5 GPa. In addition, when the mixed composition of polyether ether ketone and amorphous polyether imide, which is the above-described preferred form, is used as the thermoplastic resin composition for forming the insulating base material 10 made of the resin composition, 4, the storage elastic modulus of the thermoplastic resin composition at the melting point of the lead-free solder particles of 180 ° C. or higher and lower than 260 ° C. is 10 MPa or higher and lower than 5 GPa. The storage elastic modulus of the thermoplastic resin composition is a value measured using a viscoelasticity evaluation apparatus at a measurement frequency of 1 Hz and a temperature increase rate of 3 ° C./min.

  As described above, the thermoplastic resin composition has a storage elastic modulus of 10 MPa or more and less than 5 GPa at the melting point of the lead-free solder particles. It means that a certain degree of elastic modulus is maintained without being melted while having flexibility.

  Thus, by giving the thermoplastic resin composition a certain degree of flexibility at the melting point of the lead-free solder particles, the conductive paste composition 40 and the thermoplastic resin composition can be compatible with each other, and the conductive Adhesiveness between the insulating paste composition 40 and the insulating substrate 10 made of the thermoplastic resin composition is improved. In addition, the thermoplastic resin composition does not melt at the melting point of the lead-free solder particles and maintains a certain degree of elastic modulus, so that the conductive copper foils 100b and 100c are electrically conductive when laminated by thermal fusion. The paste composition 40 can be clamped by the thermoplastic resin composition that is the side surface of the via hole, and pressure can be applied to the conductive paste composition 40. Thereby, it is considered that the tin component in the lead-free solder particles can diffuse into the metal forming the second metal particles and / or the conductor pattern portion 20b, thereby forming a metal diffusion bonding.

<General-purpose wiring board 200>
The general-purpose wiring board 200 used when the resin-coated copper foils 100b and 100c of the present invention are sequentially laminated to form a multilayer wiring board includes a glass epoxy board (FR4 board), a two-layer polyimide board, and three layers. Examples include a polyimide substrate, an LCP substrate, and an LTCC substrate. These general-purpose wiring boards 200 may be laminated together to form a multilayer board.

  A method for manufacturing a glass epoxy substrate (FR4 substrate) will be described. First, an insulating base material (prepreg) in which a glass cloth is impregnated with a thermosetting resin to form a semi-cured state (B stage) is prepared. Next, a through-hole penetrating the insulating base material is formed at a predetermined position of the insulating base material using a laser or a mechanical drill, and this is used as a via hole. Next, a conductive paste is filled into the via hole by screen printing or the like. Then, if necessary, the conductive paste is solidified by heating to volatilize the solvent. The conductive paste used for the general-purpose wiring board 200 is not particularly limited, and a general conductive paste used for filling via holes can be used. Moreover, the electrically conductive paste composition 40 used in the copper foils 100b and 100c with resin of this invention can also be used. Next, if necessary, the dried and solidified product of the conductive paste protruding on the surface of the insulating base material is removed by mechanical polishing or the like, and copper foil is applied to one or both surfaces of the insulating base material. The insulating substrate is completely cured simultaneously with thermocompression bonding (C-stage). Next, the copper foil is patterned to form a conductor pattern. From the above, a general-purpose wiring board 200 using a glass epoxy board can be manufactured.

  A method for manufacturing a liquid crystal polymer (LCP) substrate will be described. First, an insulating substrate made of LCP is prepared. As the LCP, LCPI type (liquid crystal transition temperature: 350 ° C.), LCP II type (liquid crystal transition temperature: 300 ° C.), or the like can be used. As the insulating substrate made of LCP, a film shape, a thin plate shape, or a sheet shape is preferable. The molding method is preferably a known method, for example, an extrusion casting method using a T die, a calendar method, an inflation molding method, or the like, and is not particularly limited. Considering, an extrusion casting method using a T die is preferable. The molding temperature in the extrusion casting method using a T-die is appropriately adjusted depending on the fluidity and film-forming property of the resin used, but is generally 400 to 420 ° C. for the LCPI type resin and 350 for the LCP II type resin. ~ 370 ° C. In the manufacturing method of the glass epoxy substrate described above, a copper foil is attached at the time of film formation, then a via hole is formed in the insulating base material, a conductive paste composition is filled, and a conductive pattern is formed by patterning. Same as the case.

  A two-layer polyimide substrate in which a polyimide layer is formed on a copper foil by a casting method or a casting method, a pseudo two-layer polyimide substrate in which a thermoplastic polyimide layer is bonded as an adhesive layer between a polyimide film and a copper foil, and a polyimide film A three-layer polyimide substrate using a thermosetting adhesive between copper foils can also be manufactured by the same manufacturing method as the above-described FR4 substrate and LCP substrate.

  The LTCC (low temperature fired ceramic) substrate was produced by forming via holes in an LTCC (low temperature fired ceramic) substrate before firing, filling the via holes with Ag paste, and applying Ag paste wiring to the surface layer and firing.

<Manufacturing method of multilayer wiring board>
As described in the application of the resin-coated copper foil 100a, the multilayer wiring board can be produced by sequentially laminating the resin-coated copper foil 100a of the present invention on the general-purpose wiring board 200. In addition, in FIG. 5, the form which heat-seal | fuses the general purpose wiring board 200 and the copper foil 100c with resin of this invention was shown typically. As shown in the figure, a cushion film 51 having elasticity and releasability from the lower side, a general-purpose wiring board 200, a copper foil with resin 100c, and a cushion film 51 are stacked on the laminated jig 50 with a built-in heater. Thereafter, the pressing jig 52 is pressed down in the direction of the arrow shown in the drawing to perform thermocompression bonding, and these can be laminated and integrated. By repeating such a laminating operation and sequentially laminating the resin-coated copper foils 100b and 100c on the general-purpose wiring board 200, a multilayer wiring board having a desired number of laminations is manufactured. Can do.

<Example 1>
(Formation of resin-coated copper foil 100a)
For 100 parts by mass of a resin mixture composed of 40% by mass of a polyether ether ketone resin (PEEK450G, Tm = 335 ° C.) and 60% by mass of an amorphous polyetherimide resin (Ultem 1000), an average particle diameter of 5 μm and an average A thermoplastic resin composition obtained by mixing 39 parts by mass of synthetic mica having an aspect ratio of 50 was melt-kneaded, and this mixture was placed on a copper foil (thickness: 12 μm) using a T die at a set temperature of 380 ° C. And an insulating base material having a thickness of 50 μm was formed on the copper foil.
Next, a solution in which 80 parts by mass of a mixture of polymerizable monomers mixed at a ratio of 50% by mass of dimethallylbisphenol A and 50% by mass of bis (4-maleimidophenyl) methane and 20 parts by mass of γ-butyrolactone was prepared as described above. The surface of the insulating substrate was applied using a bar coater and dried at 100 ° C. for 45 minutes to form an adhesive layer having a thickness of 5 μm on the surface of the insulating substrate to produce a copper foil with resin.

(Preparation of conductive paste composition)
Sn-Ag-Cu alloy particles (average particle size 5.55 μm, melting point 220 ° C., Sn: Ag: Cu (mass ratio) = 96.5 : 3: 0.5) 76% by mass and Cu particles (average particle size 5 μm) ) 3 mass of a mixture of polymerizable monomers mixed at a ratio of 50 mass% of dimethallylbisphenol A and 50 mass% of bis (4-maleimidophenyl) methane with respect to 97 mass parts of the conductive powder mixed at a ratio of 24 mass%. And 7.2 parts by mass of γ-butyrolactone as a solvent were added and kneaded with three rolls to prepare a conductive paste composition.

(Formation of resin-coated copper foil 100c)
A via hole having a diameter of 100 μm that penetrates the adhesive layer and the insulating base material was formed using a laser at a desired position of the copper foil with resin 100a produced above. Then, the conductive paste composition prepared above was filled in this via hole by screen printing. After filling, it was heated at 125 ° C. for 45 minutes to evaporate the solvent, and the conductive paste was dried and solidified to produce a resin-coated copper foil 100c. Next, a conductor pattern was formed on the copper foil by photolithography. The formed vias and wiring patterns are 100 μm vias and high density patterns with a pitch of 150 μm.

(Production of general-purpose wiring board 200)
As the general-purpose wiring board 200, a glass epoxy board (FR4 board) was used. First, a glass cloth was impregnated with an epoxy resin composition to prepare a semi-cured (B stage) prepreg having a thickness of 100 μm. Via holes were formed by laser at predetermined positions of the prepreg, and the conductive paste composition prepared above was filled into the via holes by screen printing. After filling, the conductive paste was dried and solidified by heating at 125 ° C. for 45 minutes to evaporate the solvent. Then, a 12 μm thick copper foil was attached to both surfaces of the prepreg by thermocompression bonding at 180 ° C. and 5 MPa for 30 minutes, and at the same time, the epoxy resin was completely cured (C stage). Next, a conductor pattern was formed on the copper foil by a photolithography method, and the FR4 substrate 200 was produced.

(Production of multilayer wiring board)
Prepare one copper foil 100c with resin and one FR4 substrate obtained above, and overlay the adhesive layer of the copper foil 100c with resin on the conductor pattern of the FR4 substrate. And stacked by vacuum pressing at a temperature of 230 ° C. and 5 MPa for 20 minutes to form a two-layer multilayer wiring board.

<Comparative Example 1>
The epoxy resin composition was applied on a copper foil having a thickness of 12 μm to form a 50 μm B-stage epoxy prepreg layer. On the other hand, via holes were formed, conductive paste compositions were filled, and conductor patterns were formed by photolithography, as in Example 1. And it laminated with the general purpose wiring board 200, and produced the multilayer wiring board.

<Reference Example 1>
Resin-coated copper foil 100c and a multilayer wiring board were produced in the same manner as in Example 1, except that the thickness of the adhesive layer was 15 μm.

<Reference Example 2>
Resin-coated copper was prepared in the same manner as in Example 1 except that the composition of the mixture of polymerizable monomers forming the adhesive layer was 75% by mass of dimethallylbisphenol A and 25% by mass of bis (4-maleimidophenyl) methane. A foil 100c and a multilayer wiring board were produced.

<Reference Example 3>
Resin-coated copper in the same manner as in Example 1 except that the composition of the mixture of polymerizable monomers forming the adhesive layer was 25% by mass of dimethallylbisphenol A and 75% by mass of bis (4-maleimidophenyl) methane. A foil 100c and a multilayer wiring board were produced.

<Reference Example 4>
A conductive paste composition was prepared in the same manner as in Example 1 except that the conductive powder in the conductive paste composition was 98 parts by mass and the mixture of polymerizable monomers was 2 parts by mass. A foil 100c and a multilayer wiring board were produced.

<Reference Example 5>
A conductive paste composition was prepared in the same manner as in Example 1 except that 89 parts by weight of the conductive powder in the conductive paste composition and 11 parts by weight of the mixture of polymerizable monomers were prepared, and resin-coated copper. A foil 100c and a multilayer wiring board were produced.

<Evaluation method>
The following evaluation was performed on the produced multilayer wiring board. The evaluations obtained are summarized in Table 1.

(Interlayer connection reliability (thermal shock test))
A cycle of 9 minutes at −25 ° C. and 9 minutes at 125 ° C. was repeated 1000 times as a thermal shock test in a constant temperature and humidity chamber. The resistance of the multilayer wiring board before and after the thermal shock test was measured to determine the resistance change rate. The resistance change rate is a value represented by “| resistance value before test−resistance value after test | / resistance value before test” × 100 (%). Interlayer connection reliability was evaluated according to the following criteria.
○: The rate of change in resistance is less than 20% at both normal temperature and constant temperature (25 ° C.).
X: The rate of change in resistance is 20% or more at either room temperature or constant temperature (25 ° C.).

(Hygroscopic heat resistance)
The obtained multilayer wiring board is dried at 125 ° C. for 4 hours. Then, the treatment in a constant temperature and humidity chamber of 30 ° C. and a humidity of 85% for 96 hours was repeated twice, followed by heating in a reflow furnace having a peak temperature of 250 ° C. The obtained multilayer wiring board was evaluated according to the following criteria.
◯: There is no peeling at the laminated interface between the substrates, and no swelling occurs in the via hole.
X: Peeling occurred at the laminated interface between the substrates and / or swelling occurred in the via hole.

(Conductor bond strength (pat pull strength))
A wire was soldered to the conductor pattern portion exposed on the multilayer wiring board, the wire was pulled up, and the strength when the conductor pattern portion was peeled was measured.
A: The strength was 1 N / mm or more.
X: The strength was less than 1 N / mm.

(Initial resistance value)
In the test pattern portion where wiring was applied from the uppermost layer to the lowermost layer of the obtained multilayer wiring board, the following criteria were evaluated.
○: Resistance value is less than 1 × 10 ⁻⁴ Ωcm ×: Resistance value is 1 × 10 ⁻⁴ Ωcm or more

  <Evaluation results>

It is the figure which showed the outline | summary of the manufacturing method of the multilayer wiring board using the copper foil with resin 100a of this invention. It is the figure which showed a mode that the elasticity modulus of contact bonding layer 30a, 30b changed with temperature. It is the figure which showed the outline of the formation method of the contact bonding layer 30a. It is the figure which showed a mode that the elasticity modulus of the specific thermoplastic resin composition which comprises the insulating base material 10 changes with temperature. It is a conceptual diagram of the lamination | stacking jig | tool 50 for carrying out the thermocompression bonding of the general purpose wiring board 200 and the resin-coated copper foil 100c of this invention sequentially in a laminated manner.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 Insulation base material which consists of resin composition 20a Copper foil 20b Conductive pattern part 30a Adhesive layer (before hardening)
30b Adhesive layer (after curing)
40 conductive paste composition 100a, 100b, 100c copper foil with resin 200 general-purpose wiring board 50 laminating jig 51 cushion film 52 pressing jig

Claims (6)

An insulating base material made of a resin composition, a copper foil laminated on one surface of the insulating base material, and a resin-coated copper foil consisting of an adhesive layer laminated on the other surface of the insulating base material,
The adhesive layer is formed of a mixture of an alkenylphenol compound and maleimides;
The thickness of the adhesive layer is state, and are less than 1/5 of the thickness of the insulating substrate,
The mixing ratio of the alkenylphenol compound and the maleimides in the adhesive layer is 30/70 or more and less than 70/30 in molar ratio,
Furthermore, the copper foil with resin which has a via hole which penetrates the said insulation base material and the said contact bonding layer, and is filled with a conductive paste composition in this via hole . The adhesive layer is solidified at room temperature and has a melting point of 40 ° C. or higher and lower than 100 ° C .;
The layer obtained by the alkenylphenol compound and the maleimide being a linear polymer by an ene addition reaction at 120 ° C. or higher, and a crosslinked product by a Diels-Alder reaction at 200 ° C. or higher. There has a glass transition temperature above 300 ° C., the resin-coated copper foil according to claim 1. The copper foil with resin according to claim 1 or 2 , wherein the alkenylphenol compound is dimethallylbisphenol A and the maleimides are bis (4-maleimidophenyl) methane. The resin composition constituting the insulating base material is a crystalline thermoplastic resin having a crystal melting peak temperature of 260 ° C. or higher, an amorphous thermoplastic resin having a glass transition temperature of 260 ° C. or higher, and a liquid crystal transition temperature of 260 ° C. or higher. liquid crystal polymer, the glass transition temperature is above 300 ° C. non-thermoplastic polyimide resin, epoxy resin, addition type polyimide resin, bismaleimide triazine resin, or either thermosetting polyphenylene ether resin of claim 1-3 The copper foil with resin in any one. The conductive paste composition includes a conductive powder and a binder component, and a mass ratio of the conductive powder and the binder component is 90/10 or more and less than 98/2,
The conductive powder comprises first alloy particles and second metal particles,
The first alloy particles are non-lead solder particles having a melting point of 180 ° C. or higher and less than 260 ° C., and the second metal particles are at least one selected from the group consisting of Au, Ag, and Cu; The mass ratio between the first alloy particles and the second metal particles is 76/24 or more and less than 90/10,
The binder component is a mixture of polymerizable monomers that is cured by heating, the melting point of the non-lead solder particles are contained in the curing temperature range of the binder component, in any one of claims 1 to 4 The copper foil with resin of description. The resin-coated copper foil according to claim 5, wherein the binder component is a mixture of an alkenylphenol compound and maleimides.

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