JP2007157950A - Multilayer printed wiring board and manufacturing method thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a technique of forming a robust plated film on a smooth surface using a resin excellent in a bonding property to a plated film. <P>SOLUTION: The manufacturing method of a multilayer printed wiring board uses a complex (a) of fibers and resin including a resin layer (b) for forming metal plating. The method comprises the process (A) wherein the complex (a) of fibers and resin are stacked and integrated by heating and pressing on a core wiring board including wiring having connecting pads on the surface, the process (B) wherein the connecting pad is exposed by drilling a via hole in the complex (a) of fibers and resin at a position corresponding to the connecting pad, the process (C) wherein metal plating is formed on the surface of the complex (a) of fibers and resin and on the via hole to electrically connect the surface of the complex (a) of fibers and resin and the connecting pad to each other. As the resin, polyimide is used as a material having an alkylene group or the like. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a method for producing a multilayer printed wiring board having excellent fine wiring formability.

In recent years, with the reduction in size and weight of electronic devices, there has been a demand for thinner multilayer printed wiring boards. A build-up type multilayer printed wiring board is attracting attention as satisfying this demand, and a method of sequentially performing the following steps is known as a manufacturing method thereof.
(1) A first insulating resin layer is formed on the surface of a core wiring board (including a multilayer board) on which wiring has been formed.
(2) A via hole is formed in the first insulating resin layer.
(3) A circuit pattern is formed on the first insulating resin layer by a method such as copper plating. At this time, a conductor is also provided on the surface of the via hole, and the circuit on the core circuit board and the circuit on the first insulating resin layer are electrically connected by this conductor.
(4) Further, a second insulating resin layer is formed on the surface of the substrate obtained above.
Thereafter, the steps (2) to (4) are repeated.

  As described above, a build-up type multilayer printed wiring board in which each circuit layer is connected by via holes is manufactured.

  In this build-up type multilayer printed wiring board, the wiring is not disturbed by the through hole, so the wiring density is improved even if the wiring pitch is the same, compared to the conventional multilayer printed wiring board in which the conductor circuit of each layer is connected by the through hole, In addition, since the insulating resin layer can be formed thin, the multilayer printed wiring board can be made dense and thin.

  Regarding the manufacturing method of the above build-up type multilayer printed wiring board, the insulating resin layer is formed by using a photosensitive resin, the via hole is formed by a photolithographic method, and the insulating resin layer is formed by thermosetting. A method has been proposed in which resin is used and via holes are formed by laser processing. However, in these methods, since the insulating resin layer is formed using a photosensitive resin or a thermosetting resin, there is a problem that the film thickness of the insulating resin layer is not uniform and the flatness of the insulating resin layer is ensured. There was a problem that I could not.

  In order to solve the above problem, a method of using a prepreg of a glass cloth base material as an insulating resin layer is disclosed (Patent Document 1). In general, the core wiring board / prepreg / copper foil is laminated and integrated, the copper foil on the connection pad is removed by etching, a via is formed by a carbon dioxide laser, and a conductor is formed in the via. Taken.

  In this method, since the prepreg of the glass cloth base is used, there is an advantage that the uniformity and flatness of the thickness of the insulating resin layer can be easily secured.

  On the other hand, a method of stacking and integrating with a copper foil, for example, a method using an electrolytic copper foil with a thickness of 18 μm or 35 μm, requires a step of thinning or removing copper by etching to form a via hole. Become up. In addition, prepreg and copper express adhesiveness due to the anchor effect due to the unevenness of the copper, but since copper penetrates into the unevenness, insulation can be secured unless it is etched sufficiently. Therefore, there is a problem that the wiring / wiring width cannot be formed as designed.

  Therefore, in order to deal with the formation of fine wiring, recently, for example, a very thin copper foil (called ultrathin copper foil) such as a few μm thick foil is sometimes used. In addition, there is a problem that reliability is lowered due to the presence of pinholes.

In view of these circumstances, a method of forming a conductor layer by a method such as electroless plating after forming a via on the smooth surface of the cured prepreg and forming a wiring is preferable for forming a fine wiring. The adhesion of the cured prepreg to the smooth surface was low, and such a method could not be used.
JP-A-8-279678

  As described in the background art, since a technique for firmly forming metal plating on a smooth surface has not been established, a method for producing a multilayer printed wiring board capable of forming fine wiring with high accuracy has not yet been found. Accordingly, the present invention has been made to solve the above-described conventional problems, and an object thereof is to provide a method for manufacturing a multilayer printed wiring board capable of forming fine wiring with high accuracy.

As a result of intensive studies in view of the above problems, the present inventors have found that the above problems can be solved by the following laminate. That is,
1) A method for producing a multilayer printed wiring board using a composite of fiber and resin (a), and having the following steps (A) to (C): A method for manufacturing a wiring board.
(A) A core wiring board having wiring including connection pads on its surface has a resin layer (b) for forming metal plating on at least one surface of a composite of fiber and resin (a). A step of stacking and integrating the laminate by heating and pressing.
(B) A step of opening a via hole in the composite (a) of the fiber and resin at a position corresponding to the connection pad and the resin layer (b) for forming metal plating to expose the connection pad.
(C) A step of forming metal plating on the surface of the resin layer (b) for forming metal plating and via holes, and electrically connecting the surface of the resin layer (b) for forming metal plating and the connection pad.
2) A method for producing a multilayer printed wiring board using a composite of fiber and resin (a), and comprising the following steps (A) to (C): A method for manufacturing a wiring board.
(A) A layer (b) for forming a composite of fiber and resin (a) and metal plating on a core wiring board having wiring including connection pads on the surface, and layer (b) A process of stacking and integrating by placing the outermost layer and applying heat and pressure.
(B) A step of opening a via hole in the composite (a) of the fiber and resin at a position corresponding to the connection pad and a layer (b) for forming metal plating to expose the connection pad.
(C) A step of forming metal plating on the surface of the layer (b) for forming metal plating and via holes, and electrically connecting the surface of the resin layer (b) for forming metal plating and the connection pad.
3) The resin layer (b) contains a polyimide resin having one or more structures among the structures represented by any one of the following general formulas (1) to (6) 1) or The manufacturing method of the multilayer printed wiring board as described in 2).

（式中、Ｒ^１およびＲ^３は、Ｃ_ＸＨ_２Ｘで表される２価のアルキレン基、または２価の芳香族基を表す。また、Ｒ^４は、アルキル基、フェニル基、アルコキシ基、またはフェノキシ基を表し、Ｒ^２は、Ｃ_ＸＨ_２Ｘで表される２価のアルキレン基、または２価のフェニレン基を表す。さらに、ｎ＝３〜１００であり、ｍは１以上の整数である。）
４）前記（Ａ）〜（Ｃ）の工程を経た後、サブトラクティブ法により配線形成されることを特徴とする１）〜３）に記載の多層プリント配線板の製造方法。
５）前記（Ａ）〜（Ｃ）の工程を経た後、アディティブ法により配線形成されることを特徴とする１）〜３）に記載の多層プリント配線板の製造方法。
６）前記１）〜５）に記載の製造方法により製造された多層プリント配線板で、配線形成した後に露出した樹脂層の表面粗度が、カットオフ値０．００２ｍｍで測定した算術平均粗さＲａで０．５μｍ未満であることを特徴とする多層プリント配線板。

(Wherein R ¹ and R ³ represent a divalent alkylene group represented by C _X H _2X or a divalent aromatic group. R ⁴ represents an alkyl group, a phenyl group, an alkoxy group, Or a phenoxy group, wherein R ² represents a divalent alkylene group represented by C _X H _2X or a divalent phenylene group, n = 3 to 100, and m is an integer of 1 or more. is there.)
4) The method for producing a multilayer printed wiring board according to 1) to 3), wherein the wiring is formed by a subtractive method after the steps (A) to (C).
5) The method for producing a multilayer printed wiring board according to 1) to 3), wherein after the steps (A) to (C) are performed, wiring is formed by an additive method.
6) In the multilayer printed wiring board manufactured by the manufacturing method described in 1) to 5) above, the surface roughness of the resin layer exposed after the wiring is formed is an arithmetic average roughness measured at a cutoff value of 0.002 mm. A multilayer printed wiring board having a Ra of less than 0.5 μm.

  The manufacturing method of the multilayer printed wiring board of this invention has the advantage that the multilayer printed wiring board excellent in fine wiring formation property can be obtained. Therefore, it can be suitably used for manufacturing a multilayer printed wiring board that requires fine wiring formation.

One embodiment of the present invention will be described in detail below, but the present invention is not limited to the following description.
(Method for producing multilayer printed wiring board of the present invention)
The present invention relates to a method for producing a multilayer printed wiring board using a composite of fiber and resin (a), wherein the composite of fiber and resin (a) is a resin layer for forming metal plating ( b)
And it has the process of the following (A)-(C), It is characterized by the above-mentioned.
(A) A step of laminating and integrating a composite of fiber and resin (a) by heat and pressure on a core wiring board having wiring including connection pads on its surface.
(B) A step of opening a via hole in the composite (a) of the fiber and resin at a position corresponding to the connection pad to expose the connection pad.
(C) A step of forming metal plating on the surface of the composite of fiber and resin (a) and via holes and conducting the surface of the composite of fiber and resin (a) and the connection pad.

  The composite (a) of fiber and resin used in the present invention will be described.

  The composite (a) of the fiber and resin of the present invention has a resin layer (b) for forming metal plating. Here, as the composite (a), for example, a composite (a) of a fiber and a resin composition forming the resin layer (b) may be used, and the resin layer (b) film, fiber, A composite with resin and a core wiring board may be laminated and integrated to obtain a composite / core wiring board of fiber and resin having a resin layer (b) on the surface layer.

  The composite (a) of the fiber and resin of the present invention has a function of satisfactorily embedding the wiring of the core wiring board and firmly bonding the wiring. Therefore, the resin used for the composite (a) is preferably a thermoplastic resin excellent in resin flowability or a resin composition containing a thermosetting component. When a thermosetting component is included, it is essential to be a B stage. Here, the B stage is also referred to as a semi-cured state, and is an intermediate stage of the reaction of the thermosetting component used in the composite of fiber and resin (a), and (a) is softened by heating. However, even if it contacts with a certain kind of liquid, it does not melt or dissolve completely.

  When the composite (a) of the fiber and resin of the present invention contains a thermosetting component, it may be laminated and integrated with the core wiring board and then stopped at the B stage or heated to the C stage. Here, the C stage is a stage in which the thermosetting component used in the composite of fiber and resin (a) is substantially cured and is in an insoluble and infusible state.

  The fiber used in the composite (a) of the present invention is not particularly limited, but considering the use of a printed wiring board, paper, glass woven fabric, glass nonwoven fabric, aramid woven fabric, aramid nonwoven fabric, polytetrafluoroethylene It is preferable that it is at least 1 type chosen from these.

  As the paper, paper made from pulp such as paper pulp, dissolving pulp, synthetic pulp and the like prepared from raw materials such as wood, bark, cotton, hemp and synthetic resin can be used. As the glass woven fabric and the glass nonwoven fabric, a glass woven fabric or glass nonwoven fabric made of E glass or D glass and other glass can be used. As the aramid woven fabric and the aramid nonwoven fabric, a nonwoven fabric made of aromatic polyamide or aromatic polyamideimide can be used. Here, the aromatic polyamide is a conventionally known meta-type aromatic polyamide, para-type aromatic polyamide, or a copolymerized aromatic polyamide thereof. As polytetrafluoroethylene, polytetrafluoroethylene having a fine continuous porous structure that has been stretched can be preferably used.

  Next, the resin of the composite of fiber and resin (a) used in the present invention will be described. There is no restriction | limiting in particular as resin, Resin consisting only of a thermoplastic resin may be sufficient as resin which consists only of a thermosetting component, and resin consisting of a thermoplastic resin and a thermosetting component However, it is essential that the resin flowability is sufficient to sufficiently fill the space between the wirings of the core wiring board. Examples of the thermoplastic resin include polysulfone resin, polyether sulfone resin, thermoplastic polyimide resin, polyphenylene ether resin, polyolefin resin, polycarbonate resin, and polyester resin. Thermosetting components include epoxy resins, thermosetting polyimide resins, cyanate ester resins, hydrosilyl cured resins, bismaleimide resins, bisallyl nadiimide resins, acrylic resins, methacrylic resins, allyl resins, unsaturated polyester resins. , Etc. Moreover, you may use together said thermoplastic resin and a thermosetting component. Furthermore, the resin composition which forms the resin layer (b) described below may be used.

  The composite (a) of the fiber and resin of the present invention has an advantage that low thermal expansion is obtained because of the presence of the fiber. From the viewpoint of obtaining further low thermal expansion, various organic and inorganic fillers are used. It may be added.

  The composite (a) of the present invention has a resin layer (b) for forming metal plating. Since it is essential that the resin layer (b) form a metal plating firmly on its smooth surface, one or more of the structures represented by any of the following general formulas (1) to (6) are used. It is preferable to contain a polyimide resin having a structure.

（式中、Ｒ^１およびＲ^３は、Ｃ_ＸＨ_２Ｘで表される２価のアルキレン基、または２価の芳香族基を表す。また、Ｒ^４は、アルキル基、フェニル基、アルコキシ基、またはフェノキシ基を表し、Ｒ^２は、Ｃ_ＸＨ_２Ｘで表される２価のアルキレン基、または２価のフェニレン基を表す。さらに、ｎ＝３〜１００であり、ｍは１以上の整数である。）
本発明の上記一般式（１）〜（６）のいずれかで表される構造のうち、１つ以上の構造を有するポリイミド樹脂は、上記一般式（１）〜（６）のいずれかで表される構造のうち、１つ以上の構造を有していれば、いかなるポリイミド樹脂を用いても良い。例えば、上記一般式（１）〜（６）のいずれかで表される構造のうち、１つ以上の構造を有する酸二無水物成分あるいは上記一般式（１）〜（６）のいずれかで表される構造のうち、１つ以上の構造を有するジアミン成分を用いて、ポリイミド樹脂の前駆体であるポリアミド酸を製造し、これをイミド化してポリイミド樹脂を製造する方法、官能基を有する酸二無水物成分あるいは官能基を有するジアミン成分を用いて官能基を有するポリアミド酸を製造し、この官能基と反応しうる官能基、及び上記一般式（１）〜（６）のいずれかで表される構造のうち、１つ以上の構造を有する化合物を反応させて、上記一般式（１）〜（６）のいずれかで表される構造が導入されたポリアミド酸を製造し、これをイミド化してポリイミド樹脂を製造する方法、官能基を有する酸二無水物成分あるいは官能基を有するジアミン成分を用いて官能基を有するポリアミド酸を製造し、これをイミド化して官能基を有するポリイミドを製造し、この官能基と反応しうる官能基、及び上記一般式（１）〜（６）のいずれかで表される構造のうち、１つ以上の構造を有する化合物を反応させて、上記一般式（１）〜（６）のいずれかで表される構造が導入されたポリイミド樹脂を製造する方法、などが挙げられる。ここで、上記一般式（１）〜（６）のいずれかで表される構造のうち、１つ以上の構造を有するジアミンは比較的容易に入手することが可能であるため、上記の中でも、酸二無水物成分と、上記一般式（１）〜（６）のいずれかで表される構造のうち、１つ以上の構造を有するジアミン成分とを反応させて目的とするポリイミド樹脂を製造することが好ましい。

(Wherein R ¹ and R ³ represent a divalent alkylene group represented by C _X H _2X or a divalent aromatic group. R ⁴ represents an alkyl group, a phenyl group, an alkoxy group, Or a phenoxy group, wherein R ² represents a divalent alkylene group represented by C _X H _2X or a divalent phenylene group, n = 3 to 100, and m is an integer of 1 or more. is there.)
Of the structures represented by any one of the above general formulas (1) to (6), the polyimide resin having one or more structures is represented by any one of the above general formulas (1) to (6). Any polyimide resin may be used as long as it has one or more structures. For example, in the structure represented by any one of the general formulas (1) to (6), the acid dianhydride component having one or more structures or the general formulas (1) to (6) Among the structures represented, a diamine component having one or more structures is used to produce a polyamic acid that is a precursor of a polyimide resin, and a method of imidizing this to produce a polyimide resin, an acid having a functional group A polyamic acid having a functional group is produced by using a dianhydride component or a diamine component having a functional group, and the functional group capable of reacting with the functional group and any one of the general formulas (1) to (6). A polyamic acid in which the structure represented by any one of the above general formulas (1) to (6) is introduced is produced by reacting a compound having one or more structures among the structures represented by To produce polyimide resin A method, a polyamic acid having a functional group is produced using an acid dianhydride component having a functional group or a diamine component having a functional group, which is imidized to produce a polyimide having a functional group, and reacting with the functional group Among the structures represented by any one of the functional groups and the general formulas (1) to (6) described above, a compound having one or more structures is reacted to give the above general formulas (1) to (6). Or a method for producing a polyimide resin in which a structure represented by any of the above is introduced. Here, among the structures represented by any one of the general formulas (1) to (6), a diamine having one or more structures can be obtained relatively easily. A target polyimide resin is produced by reacting an acid dianhydride component with a diamine component having one or more structures among the structures represented by any of the general formulas (1) to (6). It is preferable.

  Next, as the polyimide resin of the present invention, an acid dianhydride component and a diamine component having one or more structures among the structures represented by any of the general formulas (1) to (6) are used. An example of manufacturing in the case of such a case will be described.

  The acid dianhydride component is not particularly limited, and pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylsulfonetetra Carboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 4,4′-oxydiphthalic anhydride, 3, 3 ′, 4,4′-dimethyldiphenylsilanetetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenyl Propanic acid dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, p-phenylenediphthalic anhydride Such Aromatic tetracarboxylic dianhydride, 4,4′-hexafluoroisopropylidenediphthalic anhydride, 4,4′-oxydiphthalic anhydride, 3,4′-oxydiphthalic anhydride, 3,3′-oxydiphthalate Acid anhydride, 4,4 ′-(4,4′-isopropylidenediphenoxy) bis (phthalic anhydride), 4,4′-hydroquinonebis (phthalic anhydride), 2,2-bis (4-hydroxyphenyl) ) Propanedibenzoate-3,3 ′, 4,4′-tetracarboxylic dianhydride, 1,2-ethylenebis (trimellitic acid monoester anhydride), p-phenylenebis (trimellitic acid monoester anhydride) And the like. These may be used alone or in combination of two or more.

  Subsequently, the diamine component will be described. In this invention, it is preferable that the diamine component represented by the following general formula (1)-(6) is included as a diamine component.

（式中、Ｒ^１およびＲ^３は、Ｃ_ＸＨ_２Ｘで表される２価のアルキレン基、または２価の芳香族基を表す。また、Ｒ^４は、アルキル基、フェニル基、アルコキシ基、またはフェノキシ基を表し、Ｒ^２は、Ｃ_ＸＨ_２Ｘで表される２価のアルキレン基、または２価のフェニレン基を表す。さらに、ｎ＝３〜１００であり、ｍは１以上の整数である。）
一般式（１）〜（６）で表されるジアミン成分を用いることにより、得られるポリイミド樹脂は、金属めっき層と強固に接着するという特徴を有するようになる。

(Wherein R ¹ and R ³ represent a divalent alkylene group represented by C _X H _2X or a divalent aromatic group. R ⁴ represents an alkyl group, a phenyl group, an alkoxy group, Or a phenoxy group, wherein R ² represents a divalent alkylene group represented by C _X H _2X or a divalent phenylene group, n = 3 to 100, and m is an integer of 1 or more. is there.)
By using the diamine component represented by the general formulas (1) to (6), the obtained polyimide resin has a characteristic of being firmly bonded to the metal plating layer.

  Examples of the diamine represented by the general formula (1) include hexamethylene diamine and octamethylene diamine. Examples of the diamine represented by the general formula (2) include 1,3-bis (4-aminophenoxy) propane, 1,4-bis (4-aminophenoxy) butane, and 1,5-bis (4-aminophenoxy). ) Pentane and the like can be mentioned. Examples of the diamine represented by the general formula (3) include Elastomer 1000P, Elastomer 650P, and Elastomer 250P (manufactured by Ihara Chemical Industry Co., Ltd.). In addition, examples of the diamine represented by the general formula (1) include polyether polyamines and polyoxyalkylene polyamines. Jeffamine D-2000 and Jeffamine D-4000 (manufactured by Huntsman Corporation) Etc. can be illustrated. Furthermore, as the diamine represented by the general formula (6), 1,1,3,3-tetramethyl-1,3-bis (4-aminophenyl) disiloxane, 1,1,3,3, -Tetraphenoxy-1,3-bis (4-aminoethyl) disiloxane, 1,1,3,3,5,5-hexamethyl-1,5-bis (4-aminophenyl) trisiloxane, 1,1, 3,3, -tetraphenyl-1,3-bis (2-aminophenyl) disiloxane, 1,1,3,3, -tetraphenyl-1,3-bis (3-aminopropyl) disiloxane, 1,5,5-tetraphenyl-3,3-dimethyl-1,5-bis (3-aminopropyl) trisiloxane, 1,1,5,5, -tetraphenyl-3,3-dimethoxy-1, 5-bis (3-aminobutyl) trisiloxane, 1,1 5,5, -Tetraphenyl-3,3-dimethoxy-1,5-bis (3-aminopentyl) trisiloxane, 1,1,3,3-tetramethyl-1,3-bis (2-aminoethyl) ) Disiloxane, 1,1,3,3-tetramethyl-1,3-bis (3-aminopropyl) disiloxane, 1,1,3,3, -tetramethyl-1,3-bis (4- Aminobutyl) disiloxane, 1,3-dimethyl-1,3-dimethoxy-1,3-bis (4-aminobutyl) disiloxane, 1,1,5,5, -tetramethyl-3,3-dimethoxy- 1,5-bis (2-aminoethyl) trisiloxane, 1,1,5,5, -tetramethyl-3,3-dimethoxy-1,5-bis (4-aminobutyl) trisiloxane, 1,1, 5,5, -tetramethyl-3,3-dimethoxy-1,5 -Bis (5-aminopentyl) trisiloxane, 1,1,3,3,5,5-hexamethyl-1,5-bis (3-aminopropyl) trisiloxane, 1,1,3,3,5,5 -Hexaethyl-1,5-bis (3-aminopropyl) trisiloxane, 1,1,3,3,5,5-hexapropyl-1,5-bis (3-aminopropyl) trisiloxane, etc. . Moreover, Shin-Etsu Chemical Co., Ltd. KF-8010, X-22-161A, X-22-161B, X-22-1660B-3 is represented by the general formula (6) as a relatively easily available diamine. , KF-8008, KF-8012, X-22-9362, and the like. The diamine represented by the general formulas (1) to (6) may be used alone or in combination of two or more.

  For the purpose of improving the heat resistance of the resin layer (b), it is also preferable to use a combination of the diamine represented by the general formulas (1) to (6) and another diamine. As the other diamine component, any diamine can be used, and m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, m-aminobenzylamine, p-aminobenzylamine, bis (3-amino). Phenyl) sulfide, (3-aminophenyl) (4-aminophenyl) sulfide, bis (4-aminophenyl) sulfide, bis (3-aminophenyl) sulfoxide, (3-aminophenyl) (4-aminophenyl) sulfoxide, Bis (3-aminophenyl) sulfone, (3-aminophenyl) (4-aminophenyl) sulfone, bis (4-aminophenyl) sulfone, 3,4'-diaminobenzophenone, 4,4'-diaminobenzophenone, 3, 3'-diaminodiphenylmethane, 3,4'-di Minodiphenylmethane, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ether, 3,3′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, bis [4- (3-aminophenoxy) phenyl] sulfoxide, bis [4- (Aminophenoxy) phenyl] sulfoxide, 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 3,3′-diaminodiphenyl ether, 4,4′-diaminodiphenylthioether, 3,4′-diamino Diphenylthioether, 3,3'-diaminodiphenylthioether, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfur 3,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 4,4'-diaminobenzanilide, 3,4'-diaminobenzanilide, 3,3'-diaminobenzanilide, 4, 4'-diaminobenzophenone, 3,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, bis [4- (3-aminophenoxy) phenyl] methane, bis [4- (4-aminophenoxy) phenyl] methane 1,1-bis [4- (3-aminophenoxy) phenyl] ethane, 1,1-bis [4- (4-aminophenoxy) phenyl] ethane, 1,2-bis [4- (3-aminophenoxy) ) Phenyl] ethane, 1,2-bis [4- (4-aminophenoxy) phenyl] ethane, 2,2-bis [4- (3-aminophenyl) Enoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (3-aminophenoxy) phenyl] butane, 2,2-bis [3- (3-Aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] -1,1,1,3 3,3-hexafluoropropane, 1,3-bis (3-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 1,4′-bis (4-aminophenoxy) benzene, 4, 4′-bis (4-aminophenoxy) biphenyl, bis [4- (3-aminophenoxy) phenyl] ketone, bis [4- (4-aminophenoxy) phenyl] ketone, bis [4- (3- Minophenoxy) phenyl] sulfide, bis [4- (4-aminophenoxy) phenyl] sulfide, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] ether, bis [4- (4-aminophenoxy) phenyl] ether, 1,4-bis [4- (3-aminophenoxy) benzoyl] benzene, 1,3-bis [4- (3-Aminophenoxy) benzoyl] benzene, 4,4′-bis [3- (4-aminophenoxy) benzoyl] diphenyl ether, 4,4′-bis [3- (3-aminophenoxy) benzoyl] diphenyl ether 4,4′-bis [4- (4-amino-α, α-dimethylbenzyl) phenoxy] ben Phenone, 4,4′-bis [4- (4-amino-α, α-dimethylbenzyl) phenoxy] diphenylsulfone, bis [4- {4- (4-aminophenoxy) phenoxy} phenyl] sulfone, 1,4 -Bis [4- (4-aminophenoxy) -α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-aminophenoxy) -α, α-dimethylbenzyl] benzene, 3,3′- Examples thereof include dihydroxy-4,4′-diaminobiphenyl.

  2-100 mol% is preferable with respect to all the diamine components, and, as for the diamine represented by the said General formula (1)-(6), More preferably, it is 5-100 mol%. When the diamine represented by the general formulas (1) to (6) is less than 2 mol% with respect to the total diamine component, the adhesive strength with the metal plating layer may be lowered.

  The polyimide is obtained by dehydrating and ring-closing the corresponding precursor polyamic acid. The polyamic acid is obtained by reacting an acid dianhydride component and a diamine component in substantially equimolar amounts.

  A typical procedure for the reaction is a method in which one or more diamine components are dissolved or dispersed in an organic polar solvent, and then one or more acid dianhydride components are added to obtain a polyamic acid solution. The order of addition of each monomer is not particularly limited, and the acid dianhydride component may be added to the organic polar solvent in advance, and the diamine component may be added to form a polyamic acid polymer solution, or the diamine component may be added to the organic polar solvent. A suitable amount of the acid dianhydride component may be added first, and then an excess amount of the dianhydride component may be added, and a diamine component corresponding to the excess amount may be added to form a polyamic acid polymer solution. There are various other addition methods known to those skilled in the art. Specifically, the following method is mentioned.

As used herein, “dissolution” refers to the case where the solute is uniformly dispersed in the solvent and substantially dissolved in addition to the case where the solvent completely dissolves the solute. Including. The reaction time and reaction temperature are not particularly limited.
1) A method in which a diamine component is dissolved in an organic polar solvent, and this is reacted with a substantially equimolar acid dianhydride component for polymerization.
2) An acid dianhydride component and a small molar amount of the diamine component are reacted with each other in an organic polar solvent to obtain a prepolymer having acid anhydride groups at both ends. Then, the method of superposing | polymerizing using a diamine component so that an acid dianhydride component and a diamine component may become substantially equimolar in all the processes.
3) The acid dianhydride component is reacted with an excess molar amount of the diamine component in an organic polar solvent to obtain a prepolymer having amino groups at both ends. Subsequently, after the diamine component is additionally added, polymerization is performed using the acid dianhydride component so that the acid dianhydride component and the diamine component are substantially equimolar in all steps.
4) A method in which an acid dianhydride component is dissolved in an organic polar solvent and then polymerized using a diamine compound component so as to be substantially equimolar.
5) A method of polymerizing by reacting a substantially equimolar mixture of an acid dianhydride component and a diamine component in an organic polar solvent.

  Examples of the organic polar solvent used in the polyamic acid polymerization reaction include sulfoxide solvents such as dimethyl sulfoxide and diethyl sulfoxide, formamide solvents such as N, N-dimethylformamide and N, N-diethylformamide, N, N- Acetamide solvents such as dimethylacetamide and N, N-diethylacetamide, pyrrolidone solvents such as N-methyl-2-pyrrolidone and N-vinyl-2-pyrrolidone, phenol, o-, m- or p-cresol, xylenol, Examples thereof include phenol solvents such as halogenated phenol and catechol, hexamethylphosphoramide, and γ-butyrolactone. Further, if necessary, these organic polar solvents can be used in combination with an aromatic hydrocarbon such as xylene or toluene.

  The polyamic acid solution obtained by the above method is dehydrated and cyclized by a thermal or chemical method to obtain a polyimide, and a thermal method in which the polyamic acid solution is subjected to heat treatment for dehydration, a chemical method for dehydration using a dehydrating agent. Any of these can be used. Moreover, the method of imidating by heating under reduced pressure can also be used. Each method will be described below.

  As a method of thermally dehydrating and cyclizing, a method of evaporating the solvent at the same time that the polyamic acid solution is subjected to an imidation reaction by heat treatment can be exemplified. By this method, a solid polyimide resin can be obtained. The heating conditions are not particularly limited, but it is preferably performed at a temperature of 200 ° C. or lower for a time range of 1 second to 200 minutes.

  Further, as a method of chemically dehydrating and cyclizing, a method of causing a dehydration reaction by adding a dehydrating agent and a catalyst having a stoichiometric amount or more to the polyamic acid solution and evaporating the organic solvent can be exemplified. Thereby, a solid polyimide resin can be obtained. Examples of the dehydrating agent include aliphatic acid anhydrides such as acetic anhydride and aromatic acid anhydrides such as benzoic anhydride. Examples of the catalyst include aliphatic tertiary amines such as triethylamine, aromatic tertiary amines such as dimethylaniline, and heterocyclic rings such as pyridine, α-picoline, β-picoline, γ-picoline, and isoquinoline. And tertiary amines of the formula. The conditions for chemically dehydrating and cyclizing are preferably 100 ° C. or less, and the organic solvent is preferably evaporated at a temperature of 200 ° C. or less for a period of about 5 minutes to 120 minutes.

  Further, as another method for obtaining a polyimide resin, there is a method in which the solvent is not evaporated in the thermal or chemical dehydration ring closure method. Specifically, a polyimide solution obtained by performing a thermal imidization treatment or a chemical imidization treatment with a dehydrating agent is put into a poor solvent, a polyimide resin is precipitated, and unreacted monomers are removed and purified and dried. And obtaining a solid polyimide resin. As the poor solvent, a solvent that is well mixed with the solvent but is difficult to dissolve polyimide is selected. Illustrative examples include, but are not limited to, acetone, methanol, ethanol, isopropanol, benzene, methyl cellosolve, methyl ethyl ketone, and the like.

  Next, although it is the method of imidating by heating under reduced pressure, according to this imidization method, water generated by imidization can be actively removed out of the system, so that hydrolysis of polyamic acid is suppressed. And a high molecular weight polyimide is obtained. In addition, according to this method, one-sided or both-side ring-opened products existing as impurities in the raw acid dianhydride are closed again, so that a further improvement in molecular weight can be expected.

  The heating condition of the method of heating imidization under reduced pressure is preferably 80 to 400 ° C., more preferably 100 ° C. or more, more preferably 120 ° C. or more, in which imidization is efficiently performed and water is efficiently removed. is there. The maximum temperature is preferably equal to or lower than the thermal decomposition temperature of the target polyimide, and a normal imidization completion temperature, that is, about 150 to 350 ° C. is usually applied.

The conditions for pressure reduction are preferably smaller, but specifically, 9 × 10 ⁴ to 1 × 10 ² Pa, preferably 8 × 10 ⁴ to 1 × 10 ² Pa, more preferably 7 × 10 ⁴ to 1. × 10 ² Pa.

  Although the polyimide resin has been described above, a polyimide resin having one or more structures among the structures represented by any one of the above-described general formulas (1) to (6) may be used. As an example of the polyimide resin containing the general formula (6) that can be used for the resin layer (b) of the present invention and is relatively easily available, X-22-8917 and X-22- manufactured by Shin-Etsu Chemical Co., Ltd. 8904, X-22-8951, X-22-8756, X-22-8984, X-22-8985, and the like. These are polyimide solutions.

  Among the structures represented by any one of the above general formulas (1) to (6) constituting the resin layer (b) of the present invention, the polyimide resin having one or more structures is adhesive to the metal plating layer. Thermoplastic polyimide is preferable from the viewpoint of superiority. Here, the thermoplastic polyimide in the present invention is a temperature range of 10 to 400 ° C. (temperature increase rate: 10 ° C./min) in thermomechanical analysis (TMA) in a compression mode (probe diameter 3 mmφ, load 5 g). This is what causes permanent compression deformation.

  The resin layer (b) can be blended with other components for the purpose of improving the resin flowability and improving the heat resistance. As other components, resins such as thermoplastic resins and thermosetting resins can be used as appropriate. The thermosetting resin contains 3 to 100 parts by weight with respect to 100 parts by weight of the polyimide resin having one or more structures among the structures represented by any one of the general formulas (1) to (6). However, it is preferable because a balanced property of heat resistance and adhesiveness can be obtained.

  Thermoplastic resins include polysulfone resins, polyethersulfone resins, polyphenylene ether resins, phenoxy resins, and thermoplastic polyimides comprising an acid dianhydride component and a diamine component containing a diamine represented by the general formula (1) Examples of the resin include thermoplastic polyimide resins having different structures, and these can be used alone or in appropriate combination.

  Thermosetting resins include bismaleimide resin, bisallyl nadiimide resin, phenol resin, cyanate resin, epoxy resin, acrylic resin, methacrylic resin, triazine resin, hydrosilyl cured resin, allyl cured resin, unsaturated polyester resin, etc. These can be used alone or in appropriate combination. In addition to the thermosetting resin, a side chain reactive group type thermosetting having a reactive group such as an epoxy group, an allyl group, a vinyl group, an alkoxysilyl group or a hydrosilyl group at the side chain or terminal of the polymer chain. It is also possible to use a functional polymer.

  In addition, for the purpose of improving the adhesion to metal plating, various additives may be added to the polymer material and may be present on the surface of the polymer material by a method such as coating. Specific examples include organic thiol compounds, but are not limited thereto.

  Various organic fillers and inorganic fillers can also be added.

  It is important to combine the other components described above within a range that does not increase the surface roughness of the resin layer (b) to the extent that it adversely affects the formation of fine wiring.

  Among the structures represented by any one of the above general formulas (1) to (6) contained in the resin layer (b), the proportion of the polyimide resin having one or more structures is 30% by weight to 100% by weight. It is preferable from the point that the balance between the surface roughness and the adhesion between the metal plating layer is excellent.

  In addition, the resin layer (b) of the present invention refers to a layer having a thickness of 10 mm or more.

  The resin layer (b) of the present invention has an advantage that the adhesive strength with the metal plating layer is high even when the surface roughness is small. Here, the surface roughness referred to in the present invention can be represented by an arithmetic average roughness Ra measured at a cutoff value of 0.002 mm. Arithmetic mean roughness Ra is defined in JIS B 0601 (revised on February 1, 1994). In particular, the numerical value of the arithmetic average roughness Ra of the present invention is a numerical value obtained by observing the surface with an optical interference type surface structure analyzer. The cutoff value of the present invention is described in the above JIS B 0601, and indicates a wavelength set when a roughness curve is obtained from a cross-sectional curve (measured data). That is, the value Ra measured with a cut-off value of 0.002 mm is an arithmetic average roughness calculated from a roughness curve obtained by removing irregularities having a wavelength longer than 0.002 mm from measured data.

The surface roughness of the resin layer (b) of the present invention is preferably less than 0.5 μm in terms of arithmetic average roughness Ra measured at a cutoff value of 0.002 mm. Therefore, it can be said that the resin layer (b) in the present invention has a very smooth surface when the surface roughness in a minute range is observed. Therefore, for example, even when a fine wiring having a line and space of 10 μm / 10 μm or less is formed, there is no adverse effect.
When this condition is satisfied, it has good fine wiring formability. In order to form the resin layer (b) having such a surface, for example,
(1) No surface treatment is performed.
(2) The surface roughness of the surface in contact with the resin layer (b) of a material such as a support or slip paper is appropriately selected.
(3) The composition of the polyimide resin contained in the resin layer (b) and the drying conditions for forming the resin layer (b) are appropriately selected.
These methods may be combined as appropriate.

  The resin layer (b) included in the fiber / resin composite (a) of the present invention has been described above. However, the resin layer (b) is exposed on the surface on which the conductor layer is formed after being integrated with the core wiring board. Any configuration and form may be used as long as they are configured.

  In the present invention, when the composite (a) of the fiber and resin of the present invention is composed of a resin layer (b) / composite of fiber and resin, the composite of fiber and resin and the resin layer (b For the purpose of improving the adhesiveness with the other resin layer, another resin layer can be provided. In order to develop good adhesion to each of the composite of fiber and resin and the resin layer (b), the other resin layer preferably contains a thermosetting component.

  The thickness of the composite (a) of the fiber and resin of the present invention is not particularly limited, but is preferably as thin as possible from the viewpoint of thinning the resulting multilayer printed wiring board, and only enough to embed the inner layer circuit. It preferably has a resin content. At present, the thinnest glass woven fabric is said to be 40 μm. By using such a glass fiber, the composite (a) of the fiber and the resin of the present invention can be thinned. In addition, if a fiber such as a thinner glass woven fabric is obtained as a result of technological advancement, it is possible to further reduce the thickness of the composite (a) of the fiber and resin of the present invention by using such a fiber. Become.

  The manufacturing method of the composite (a) of the fiber and resin of the present invention will be described.

  When the resin of the composite of fiber and resin (a) of the present invention is composed of the resin composition forming the resin layer (b) described above, the resin composition is dissolved in an appropriate solvent to obtain a resin composition solution. It is obtained by impregnating the above-mentioned fibers and further drying by heating. Here, when a thermosetting component is included, it is essential to stop the heat drying at the B stage.

  As another method, it is possible to use a method in which the resin layer (b) molded into a film shape, a fiber, and a core wiring board are used in this order, and the resin layer (b) molded into a film shape, a fiber, a film It is possible to use a method in which the resin layer (b) molded into a shape and the core wiring substrate are stacked in this order. In this case, since the resin layer (b) flows so as to cover the fibers and is embedded between the wirings of the core wiring board at the time of the lamination and integration, as a result, the composite of the fiber and the resin having the resin layer (b) on the surface layer. A body (a) will be obtained.

Moreover, the case where the composite (a) of the fiber and resin of the present invention is composed of a composite of resin layer (b) / fiber and resin will be described. In this case, a commercially available prepreg (composite of B-stage fiber and resin) can be used as the composite of fiber and resin, and the resin composition solution forms the resin layer (b) on the commercially available prepreg. Can be obtained by coating the composite with heat and drying. The heat drying in this case needs to be performed under the condition that the prepreg maintains the B stage. Alternatively, the resin layer (b) molded and processed into a film can be obtained by sticking it to the prepreg. Furthermore, it is possible to use a method in which the resin layer (b) film, the commercially available prepreg, and the core wiring board are used in this order in the lamination step in the production of the multilayer printed wiring board. Also in this case, since the structure which consists of a composite of resin layer (b) / fiber and resin is obtained as a result, it is preferably applicable.
(Metal plating layer)
As the metal plating layer, various types of dry plating such as vapor deposition, sputtering, and CVD, and wet plating such as electroless plating can be applied. However, in consideration of productivity and adhesion with the resin layer (b), there is no need. A layer made of electrolytic plating is preferable. Examples of the electroless plating include electroless copper plating, electroless nickel plating, electroless gold plating, electroless silver plating, electroless tin plating, and the like. From the viewpoint of electrical properties such as migration resistance, electroless copper plating and electroless nickel plating are preferable, and electroless copper plating is particularly preferable. The thickness of the metal plating layer is not particularly limited, but is preferably 5 μm or less and more preferably 3 μm or less in consideration of fine wiring formability.
(Manufacturing method of multilayer printed wiring board)
The manufacturing method of the multilayer printed wiring board of this invention has the process of the following (A)-(C), It is characterized by the above-mentioned.
(A) A step of laminating and integrating a composite of fiber and resin (a) by heat and pressure on a core wiring board having wiring including connection pads on its surface.
(B) A step of opening a via hole in the composite (a) of the fiber and resin at a position corresponding to the connection pad to expose the connection pad.
(C) A step of forming metal plating on the surface of the composite of fiber and resin (a) and via holes and conducting the surface of the composite of fiber and resin (a) and the connection pad.

  Since the manufacturing method of the multilayer printed wiring board of this invention has the resin layer (b) excellent in adhesiveness with metal plating, the multilayer printed wiring board in which fine wiring formation is possible can be provided.

Below, each process is demonstrated concretely.
(Process (A))
There is no particular limitation on the core wiring board having wiring including connection pads on its surface, and any wiring board such as a commercially available glass epoxy resin wiring board or bismaleimide / triazine resin wiring board should be used. Can do. Moreover, when calculating | requiring fine wiring formation property also to a core wiring board, the wiring board produced using the composite (a) of the fiber of this invention and resin can be applied preferably.

  A composite (a) of B-stage fibers and resin is laminated and integrated on the above-described core wiring board by heating and pressing. The composite of fiber and resin (a) may be formed as a composite of fiber and resin (a) when laminated and integrated, and may be laminated and integrated in various forms as shown below. it can.

  One is a method in which the composite (a) / core wiring board of the fiber and the resin composition for forming the resin layer (b) is stacked and integrated in this order.

  One is a method of laminating and integrating the resin layer (b) film / fiber / core wiring board in this order. Similarly, the resin layer (b) film / fiber / resin layer (b) film / core wiring board may be stacked and integrated in this order.

  One is a method of laminating and integrating the B-stage resin layer (b) film / fiber / resin composite / core wiring board in this order. In order to improve the adhesion between the resin layer (b) and the composite of fiber and resin, another resin layer may be provided between them.

  When the resin constituting the composite of fiber and resin contains a thermosetting component, it is essential to be a B stage in order to ensure resin flowability.

  In order to keep the surface roughness of the resin layer (b) at an arithmetic average roughness Ra measured at a cutoff value of 0.002 mm, the slip sheet in contact with the resin layer (b) also has a cutoff value of 0. The arithmetic average roughness Ra measured at 002 mm is preferably less than 0.5 μm. As an example of such a slip sheet, a resin film not subjected to a treatment such as embossing can be given.

  As the laminating method, various thermocompression bonding methods such as hot pressing, vacuum pressing, laminating (thermal laminating), vacuum laminating, hot roll laminating, and vacuum hot roll laminating can be performed. Among these, processing under vacuum, that is, vacuum press processing, vacuum laminating processing, and vacuum hot roll laminating processing can be preferably performed without voids between the circuits, and can be preferably performed. After the lamination, for the purpose of proceeding the curing to the C stage, it is also possible to perform heat drying using a hot air oven or the like.

Since appropriate conditions differ depending on the resin layer (b) to be used and the composite of the fiber and the resin, it is preferable to appropriately optimize the conditions.
(Process (B))
In order to form the via hole, a known drill machine, dry plasma apparatus, carbon dioxide laser, UV laser, excimer laser, or the like can be used. Further, for the purpose of removing smear generated after via hole formation, desmearing is preferably performed by a known technique such as a wet process using permanganate or dry desmear such as plasma.
(Process (C))
As the metal plating layer, various types of dry plating such as vapor deposition, sputtering, and CVD, and wet plating such as electroless plating can be applied. However, in consideration of productivity and adhesion with the resin layer (b), there is no need. A layer made of electrolytic plating is preferable. Examples of the electroless plating include electroless copper plating, electroless nickel plating, electroless gold plating, electroless silver plating, electroless tin plating, and the like. From the viewpoint of electrical properties such as migration resistance, electroless copper plating and electroless nickel plating are preferable, and electroless copper plating is particularly preferable. The thickness of the metal plating layer is not particularly limited, but is preferably 5 μm or less and more preferably 3 μm or less in consideration of fine wiring formability.

The steps (A) to (C) have been described above, but the subsequent steps will be described.
(D) Electrolytic plating is performed.

A metal layer is formed to a desired thickness by electrolytic plating. Many known methods can be applied to the electrolytic plating. Specific examples include electrolytic copper plating, electrolytic solder plating, electrolytic tin plating, electrolytic nickel plating, and electrolytic gold plating. From the viewpoint of electrical characteristics such as industrial viewpoint and migration resistance, electrolytic copper plating and electrolytic nickel plating are preferable, and electrolytic copper plating is particularly preferable.
(E) A plating resist is formed.

As the photosensitive plating resist, known materials widely available on the market can be used. In the method for producing a multilayer printed wiring board of the present invention, it is preferable to use a photosensitive plating resist having a resolution of 50 μm pitch or less in order to cope with fine wiring. Of course, a circuit having a pitch of 50 μm or less and a circuit having a pitch higher than that may be mixed in the wiring pitch of the printed wiring board of the present invention.
(F) A wiring is formed by etching.
A known etchant can be used for the etching. For example, ferric chloride-based etchants, cupric chloride-based etchants, sulfuric acid / hydrogen peroxide-based etchants, ammonium persulfate-based etchants, sodium persulfate-based etchants and the like can be preferably used.
(G) Strip resist.

  For resist stripping, a material suitable for stripping the used plating resist can be used, and there is no particular limitation. For example, an aqueous sodium hydroxide solution or an aqueous potassium hydroxide solution can be used.

  Thus, after forming wiring by what is called a subtractive construction method, the composite (a) of a fiber and resin is laminated | stacked and integrated, and a multilayer printed wiring board is repeatedly performed by repeating the process of (B)-(G). Can be obtained. Moreover, in any process, a heating process can be taken in for the purpose of performing sufficient curing or improving the adhesion with plated copper.

On the other hand, after performing the steps (A) to (C), it is possible to preferably apply wiring formation by a semi-additive method that is more advantageous for forming fine wiring. This will be described below.
(D ′) A plating resist is formed.

As the photosensitive plating resist, known materials widely available on the market can be used. In the method for producing a multilayer printed wiring board of the present invention, it is preferable to use a photosensitive plating resist having a resolution of 50 μm pitch or less in order to cope with fine wiring. Of course, a circuit having a pitch of 50 μm or less and a circuit having a pitch higher than that may be mixed in the wiring pitch of the printed wiring board of the present invention.
(E ′) Electrolytic pattern plating is performed.

A metal layer is formed to a desired thickness by electrolytic plating. Many known methods can be applied to the electrolytic plating. Specific examples include electrolytic copper plating, electrolytic solder plating, electrolytic tin plating, electrolytic nickel plating, and electrolytic gold plating. From the viewpoint of electrical characteristics such as industrial viewpoint and migration resistance, electrolytic copper plating and electrolytic nickel plating are preferable, and electrolytic copper plating is particularly preferable.
(F ') Strip resist.

For resist stripping, a material suitable for stripping the used plating resist can be used, and there is no particular limitation. For example, an aqueous sodium hydroxide solution or an aqueous potassium hydroxide solution can be used.
(G ′) Wiring is formed by quick etching.
A known etchant can be used for the etching. For example, diluted ferric chloride-based etchants, diluted cupric chloride-based etchants, sulfuric acid / hydrogen peroxide-based etchants, ammonium persulfate-based etchants, sodium persulfate-based etchants and the like can be preferably used.

  Thus, after forming the wiring by the so-called semi-additive construction method, the composite (a) of the fiber and the resin is further laminated and integrated, and the steps (B) to (G ′) are repeatedly performed to obtain the multilayer printed wiring. A board can be obtained. Moreover, in any process, a heating process can be taken in for the purpose of performing sufficient curing or improving the adhesion with plated copper.

The present invention will be described more specifically based on examples, but the present invention is not limited to this. Those skilled in the art can make various changes, modifications, and alterations without departing from the scope of the present invention. As the characteristics of the laminate according to the present invention, the surface roughness Ra and the wiring formability were evaluated or calculated as follows.
[Surface roughness Ra measurement]
The surface roughness Ra of the exposed resin surface of the obtained multilayer printed wiring board was measured. In the measurement, the arithmetic average roughness of the surface A was measured under the following conditions using a light wave interference type surface roughness meter (NewView 5030 system manufactured by ZYGO).

(Measurement condition)
Objective lens: 50x Mirau Image zoom: 2
FDA Res: Normal
Analysis conditions:
Remove: Cylinder
Filter: High Pass
Filter Low Wave: 0.002mm
[Wiring formability]
Formation of wiring when the wiring of the obtained multilayer printed wiring board is successfully manufactured as designed without disconnection or shape defect, and × when the disconnection or shape defect has occurred or cannot be manufactured as designed Sex was evaluated.
[Polyimide resin synthesis example 1]
In a glass flask with a volume of 2000 ml, 37 g (0.045 mol) of KF-8010 manufactured by Shin-Etsu Chemical Co., Ltd., 21 g (0.105 mol) of 4,4′-diaminodiphenyl ether, N, N-dimethylformamide (hereinafter, DMF) was added and dissolved while stirring, and 78 g (0.15 mol) of 4,4 ′-(4,4′-isopropylidenediphenoxy) bis (phthalic anhydride) was added and stirred for about 1 hour. A DMF solution of polyamic acid with a solid content concentration of 30% was obtained. The polyamic acid solution was placed in a Teflon (registered trademark) -coated vat and heated in a vacuum oven at 200 ° C. for 120 minutes under reduced pressure at 665 Pa to obtain polyimide resin 1.
[Polyimide resin synthesis example 2]
In a glass flask having a capacity of 2000 ml, 92 g (0.075 mol) of Elastomer 1000P (Ihara Chemical Industry Co., Ltd.), 15 g (0.075 mol) of 4,4′-diaminodiphenyl ether, N, N-dimethylformamide ( (Hereinafter referred to as DMF) and dissolved while stirring, and 78 g (0.15 mol) of 4,4 ′-(4,4′-isopropylidenediphenoxy) bis (phthalic anhydride) was added for about 1 hour. The mixture was stirred to obtain a DMF solution of polyamic acid with a solid content concentration of 30%. The polyamic acid solution was placed in a Teflon (registered trademark) -coated vat and heated in a vacuum oven at 200 ° C. for 120 minutes under reduced pressure at 665 Pa to obtain polyimide resin 2.
[Example 1]
The polyimide resin 1 was dissolved in dioxolane to obtain a solution (A) that forms the resin layer (b). The solid content concentration was adjusted to 5% by weight. The resin solution (A) was cast on a resin film (T-1 (s); 38 μm thickness, manufactured by Panac Co., Ltd.), dried at 60 ° C., and a resin layer (b) film with a resin film having a thickness of 2 μm was obtained. Obtained.

  Resin layer (b) film with resin film, 50 μm thick prepreg (ES-3306S, manufactured by Risho Kogyo Co., Ltd.), core substrate subjected to wiring processing (product number: MCL-E-67, Hitachi Chemical Co., Ltd.) Made by company; copper foil thickness 18 μm), 50 μm thickness prepreg, and resin layer (b) film were laminated in this order and laminated and integrated under the conditions of 170 ° C./4 MPa / 2 hours. The prepreg and the resin layer (b) were overlapped so as to be in contact with each other.

  Thereafter, the resin film attached to the resin layer (b) was peeled off, and a via hole was formed by a carbon dioxide gas laser at a position corresponding to the connection pad of the core substrate.

  Furthermore, desmear and electroless copper plating were performed under the conditions shown in Tables 1 and 2 below.

無電解めっき銅層上にレジストパターンを形成し、パターン銅の厚みが８μｍとなるように電解銅パターンめっきを行った後、レジストパターンを剥離し、さらに露出した無電解めっき銅を硫酸／過酸化水素系エッチャントで除去して、ライン アンド スペース（Ｌ／Ｓ）＝１０μｍ／１０μｍの配線を有する多層プリント配線板を作製した。

After forming a resist pattern on the electroless plated copper layer and performing electrolytic copper pattern plating so that the thickness of the patterned copper is 8 μm, the resist pattern is peeled off, and the exposed electroless plated copper is sulfuric acid / peroxide A multilayer printed wiring board having a line and space (L / S) = 10 μm / 10 μm wiring was prepared by removing with a hydrogen-based etchant.

This wiring board was used for evaluation according to the evaluation procedure for various evaluation items. The evaluation results are shown in Table 3.
[Example 2]
The polyimide resin 1 was dissolved in dioxolane to obtain a solution (B) that forms the resin layer (b). The solid content concentration was set to 30% by weight. The resin solution (B) was cast on a resin film (T-1 (s); 38 μm thickness, manufactured by Panac Co., Ltd.), dried at 60 ° C., and a resin layer (b) film with a resin film (b) having a thickness of 35 μm Obtained.

Resin layer (b) film with resin film, 40 μm thick glass nonwoven fabric, resin layer (b) film with resin film, core substrate subjected to wiring processing (product number: MCL-E-67, Hitachi Chemical Co., Ltd.) ); Manufactured by company; copper foil thickness 18 μm), resin layer with resin film (b) film, 40 μm thick glass nonwoven fabric, resin layer with resin film (b) film are stacked in this order, 170 ° C./4 MPa / 2 After being laminated and integrated under time conditions, a multilayer printed wiring board was produced in the same manner as in Example 1.
This wiring board was used for evaluation according to the evaluation procedure for various evaluation items. The evaluation results are shown in Table 3.
Example 3
The polyimide resin 1 was dissolved in dioxolane to obtain a solution (B) that forms the resin layer (b). The solid content concentration was set to 30% by weight. A 40 μm thick glass nonwoven fabric was impregnated with the solution (B) and then dried at 100 ° C. to obtain a composite of fibers and resin.

  Resin film (T-1 (s); 38 μm thickness, manufactured by Panac Co., Ltd.), composite of fiber and resin, core substrate subjected to wiring processing (product number: MCL-E-67, Hitachi Chemical Co., Ltd.) Made by company; copper foil thickness 18 μm), fiber and resin composite, resin film (T-1 (s); 38 μm thickness, manufactured by Panac Co., Ltd.) in this order, 180 ° C./4 MPa / 1 hour After being laminated and integrated under the conditions, a multilayer printed wiring board was produced in the same manner as in Example 1.

This wiring board was used for evaluation according to the evaluation procedure for various evaluation items. The evaluation results are shown in Table 3.
Example 4
The polyimide resin 2 was dissolved in dioxolane to obtain a solution (C) that forms the resin layer (b). The solid content concentration was adjusted to 5% by weight. A multilayer printed wiring board was produced in the same manner as in Example 1 except that this solution (C) was used.
This wiring board was used for evaluation according to the evaluation procedure for various evaluation items. The evaluation results are shown in Table 3.

[Comparative Example 1]
18 μm thick electrolytic copper foil, 50 μm thick prepreg (ES-3306S, manufactured by Risho Kogyo Co., Ltd.), core substrate subjected to wiring processing (product number: MCL-E-67, manufactured by Hitachi Chemical Co., Ltd .; copper) Foil thickness 18 μm), 50 μm-thick prepreg, and 18 μm-thick electrolytic copper foil were stacked in this order and laminated and integrated under the conditions of 170 ° C./4 MPa / 2 hours.

  Thereafter, the thickness of the copper was reduced to 2 μm by etching, and a via hole was formed by a carbon dioxide laser at a position corresponding to the connection pad of the core substrate.

  Furthermore, desmear and electroless copper plating were performed under the same conditions as in Example 1.

  After forming a resist pattern on the electroless plated copper layer and performing electrolytic copper pattern plating so that the thickness of the patterned copper is 10 μm, the resist pattern is peeled off, and the exposed plated copper is removed with ferric chloride-based etchant The multilayer printed wiring board which has the wiring of line and space (L / S) = 10micrometer / 10micrometer was produced.

  This wiring board was used for evaluation according to the evaluation procedure for various evaluation items. The evaluation results are shown in Table 4. As can be seen from Table 4, the copper layer formed by laminating the electrolytic copper foil has large irregularities on the surface of the resin layer. Therefore, sufficient etching must be performed, and the wiring becomes thin or the wiring collapses. However, fine wiring could not be formed satisfactorily.

なお本発明は、以上説示した各構成に限定されるものではなく、特許請求の範囲に示した範囲で種々の変更が可能であり、異なる実施形態や実施例にそれぞれ開示された技術的手段を適宜組み合わせて得られる実施形態についても本発明の技術的範囲に含まれる。

Note that the present invention is not limited to the configurations described above, and various modifications are possible within the scope of the claims, and technical means disclosed in different embodiments and examples respectively. Embodiments obtained by appropriate combinations are also included in the technical scope of the present invention.

  The method for producing a multilayer printed wiring board according to the present invention is a production of a multilayer printed wiring board that does not require a step of etching a copper foil and that can form good fine wiring, and in particular, a multilayer that requires fine wiring formability. It can use preferably for manufacture of a printed wiring board. Therefore, the present invention can be suitably used in the industrial field of various electronic components.

Claims (6)

A multilayer printed wiring board using a composite of fiber and resin (a), comprising the following steps (A) to (C): Manufacturing method.
(A) A core wiring board having wiring including connection pads on its surface has a resin layer (b) for forming metal plating on at least one surface of a composite of fiber and resin (a). A step of stacking and integrating the laminate by heating and pressing.
(B) A step of opening a via hole in the composite (a) of the fiber and resin at a position corresponding to the connection pad and the resin layer (b) for forming metal plating to expose the connection pad.
(C) A step of forming metal plating on the surface of the resin layer (b) for forming metal plating and via holes, and electrically connecting the surface of the resin layer (b) for forming metal plating and the connection pad. A multilayer printed wiring board using a composite of fiber and resin (a), comprising the following steps (A) to (C): Manufacturing method.
(A) A layer (b) for forming a composite of fiber and resin (a) and metal plating on a core wiring board having wiring including connection pads on the surface, and layer (b) A process of stacking and integrating by placing the outermost layer and applying heat and pressure.
(B) A step of opening a via hole in the composite (a) of the fiber and resin at a position corresponding to the connection pad and a layer (b) for forming metal plating to expose the connection pad.
(C) A step of forming metal plating on the surface of the layer (b) for forming metal plating and via holes, and electrically connecting the surface of the resin layer (b) for forming metal plating and the connection pad. The said resin layer (b) contains the polyimide resin which has one or more structures among the structures represented by either of the following general formula (1)-(6). The manufacturing method of the multilayer printed wiring board as described in 2 ..

(Wherein R ¹ and R ³ represent a divalent alkylene group represented by C _X H _2X or a divalent aromatic group. R ⁴ represents an alkyl group, a phenyl group, an alkoxy group, Or a phenoxy group, wherein R ² represents a divalent alkylene group represented by C _X H _2X or a divalent phenylene group, n = 3 to 100, and m is an integer of 1 or more. is there.) The method for producing a multilayer printed wiring board according to claim 1, wherein after the steps (A) to (C) are performed, wiring is formed by a subtractive method. The method for producing a multilayer printed wiring board according to claim 1, wherein after the steps (A) to (C) are performed, wiring is formed by an additive method. In the multilayer printed wiring board manufactured by the manufacturing method of the said Claims 1-5, the surface roughness of the resin layer exposed after wiring formation is arithmetic mean roughness Ra measured by cut-off value 0.002mm. A multilayer printed wiring board characterized by being less than 0.5 μm.