JP2006183132A - Solution, material for plating, and printed wiring board - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a material for plating which can be suitably used in printed wiring board manufacture and the like, the material for plating and a solution having excellent adhesion to an electroless plating film formed on the material surface even when the surface roughness of the material surface is small, and a printed wiring board manufactured by using such material for plating and solution. <P>SOLUTION: The material for electroless plating has at least a surface (a) whereupon electroless plating is to be performed, and the surface roughness of the surface (a) is 0.5 μm or less in an arithmetic average roughness measured with a cut off value of 0.002 mm and the surface (a) contains a polyimide resin having siloxane structure. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention is a solution and a plating material that can be suitably used when performing electroless plating, and in particular, a solution and a plating material that can be suitably used for production of a printed wiring board and the like. The present invention relates to a printed wiring board to be used.

  Electroless plating, in which a reducing agent is placed in an aqueous solution of a metal salt without using electrical energy, and the metal is deposited on the substrate by the reducing action of its decomposition, is the insulation of various plastics, glass, ceramics, wood, etc. This technique is widely applied to functionalize the surface of the conductive material. For example, apply electroless plating to ABS resin or polypropylene resin, and use functional plating such as decorative plating for parts such as grills and marks for automobiles, knobs for household appliances, and through-hole plating for printed wiring boards. Can do.

  However, electroless plating often has low adhesion to the surfaces of the various materials. In particular, when applied to the production of the printed wiring board described above, the problem is that the adhesion between the electroless plating film and the insulating material is low. In particular, when a method of forming an electroless plating film is used as a method for directly forming a metal layer on an insulating material, the electroless plating is firmly adhered to an insulating material having a smooth surface with a small surface roughness. It was very difficult to do.

  This is because it is considered that the electroless plating is formed so as to be deposited mainly via a catalyst such as palladium.

  On the other hand, when manufacturing an electroless plating film on an insulating material, for example, when manufacturing a printed wiring board having a wiring formed on the surface, the electroless plating film may be firmly formed on a smooth surface as much as possible. Highly desirable.

  The insulating sheet used for the printed wiring board known so far has roughened the surface by various methods, and has obtained adhesion with the electroless plating film by a so-called anchor effect (see, for example, Patent Document 1). However, when the surface roughness is small, the adhesion between the electroless plating film and the resin material is low, and there is a limit to the formation of fine wiring.

  In order to improve the adhesion of the circuit wiring formed on the resin surface with a small surface roughness, a certain underlying metal layer is formed on the surface of the polyimide film by a physical method such as vapor deposition or sputtering, and a good conductive material is formed on it. Some copper had to be formed (see Patent Document 2). When this method is used, the base metal layer and the polyimide film have excellent adhesive strength. However, this is not due to the chemical bonding force between the polyimide film and the metal, but a micro underlayer is microscopically placed on the surface of the substrate, while copper is metal / metal bonded through the underlayer. The adhesive force is expressed. However, this method uses a metal other than copper for the underlayer, and the underlayer may not be completely removed with a copper etchant. As a result, there is a concern that the migration resistance between wirings may be reduced. Further, since a vacuum process is used, there are disadvantages that the cost is high and the productivity is inferior.

  On the other hand, an interlayer insulating adhesion technique using an adhesive containing polyimide siloxane has been disclosed (for example, see Patent Document 3). However, the technique described in Patent Document 2 uses polyimide having a siloxane structure as an interlayer adhesive and is used for bonding to a circuit board. Therefore, use as a layer for forming an electroless plating film is not disclosed.

Further, a metal foil with resin in which a metal precursor layer is laminated after applying a polyimide precursor having a siloxane structure is disclosed (Patent Document 4). However, in Patent Document 4, a chromium sputtering method and an electroless plating method are described in parallel as a method for forming a metal layer, and adhesion of an electroless plating film which is considered to have low adhesion to an insulating material. The relationship between the strength and the surface roughness of the surface on which electroless plating is to be formed has not been confirmed.
JP2000-198907 JP 08-330728 A JP 2000-290606 A JP 2002-264255 A

  As described in the background art, a material having high adhesion between a resin material and an electroless plating film has not yet been found even when the surface roughness is small.

  Therefore, the present invention has been made to solve the above-mentioned conventional problems, and the object thereof is to form the surface of various materials subjected to electroless plating so that between the electroless plating and various materials. In order to provide plating materials to improve adhesion, functional plating on various plastics, glass, ceramics, wood, etc., decorative plating on parts such as automobile grills and marks, and household appliance knobs In particular, it can be suitably used for the production of various printed wiring boards, and further, flexible printed wiring boards, rigid printed wiring boards, multilayer flexible printed wiring boards, multilayer rigid wiring boards and build-ups that require fine wiring formation. Solutions and plating materials that can be suitably used in the production of printed wiring boards such as wiring boards, and printed distributions using the same. It is to provide a plate.

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 plating materials. That is,
1) A material for electroless plating having at least a surface a for performing electroless plating, and the surface roughness of the surface a is 0.5 μm or less as an arithmetic average roughness measured at a cutoff value of 0.002 mm. And the surface a contains a polyimide resin having a siloxane structure.
2) The polyimide resin having a siloxane structure is a polyimide resin using as a raw material an acid dianhydride component and a diamine component containing a diamine represented by the following general formula (1). Material for plating.

（式中、ｇは１以上の整数を表す。また、Ｒ¹¹及びＲ²²は、同一、または異なっていてよく、アルキレン基またはフェニレン基を表す。Ｒ³³〜Ｒ⁶⁶は、同一、または異なっていてよく、アルキル基、またはフェニル基、またはフェノキシ基、またはアルコキシ基を表す。）３）無電解めっきが、無電解銅めっきであることを特徴とする１）または２）に記載のめっき用材料。
４）無電解めっきを施すための表面ａを有し、かつ、シロキサン構造を有するポリイミド樹脂を含有する単層シートであって、表面ａの表面粗度はカットオフ値０．００２ｍｍで測定した算術平均粗さで０．５μｍ以下となっていることを特徴とする単層シート。
５）無電解めっきが、無電解銅めっきであることを特徴とする４）記載の単層シート。
６）少なくとも無電解めっきを施すための表面ａを有する層Ａを含む２層以上の層から構成された絶縁シートであって、表面ａの表面粗度はカットオフ値０．００２ｍｍで測定した算術平均粗さで０．５μｍ以下となっており、かつ層Ａは、シロキサン構造を有するポリイミド樹脂を含有することを特徴とする絶縁シート。
７）無電解めっきが、無電解銅めっきであることを特徴とする請求項６記載の絶縁シート。
８）４）記載の単層シートまたは、６）記載の絶縁シートの、層Ａ上に無電解めっき皮膜が形成されていることを特徴とする積層体。
９）４）記載の単層シートまたは、６）記載の絶縁シートを用いてなるプリント配線板。
１０）シロキサン構造を有するポリイミド樹脂を含有する溶液であって、１）に記載の表面ａを形成するために用いられることを特徴とするポリイミド樹脂を含有する溶液。
１１）シロキサン構造を有するポリイミド樹脂の前駆体を含有する溶液であって、１）に記載の表面ａを形成するために用いられることを特徴とするポリアミド酸を含有する溶液。

(In the formula, g represents an integer of 1 or more. R ¹¹ and R ²² may be the same or different and each represents an alkylene group or a phenylene group. R ^{33 to} R ⁶⁶ are the same or different. And represents an alkyl group, a phenyl group, a phenoxy group, or an alkoxy group.) 3) The plating material according to 1) or 2), wherein the electroless plating is electroless copper plating .
4) A single-layer sheet having a surface a for electroless plating and containing a polyimide resin having a siloxane structure, and the surface roughness of the surface a is an arithmetic value measured at a cutoff value of 0.002 mm. A single-layer sheet having an average roughness of 0.5 μm or less.
5) The monolayer sheet according to 4), wherein the electroless plating is electroless copper plating.
6) An insulating sheet composed of two or more layers including a layer A having a surface a for performing electroless plating, and the surface roughness of the surface a is an arithmetic value measured at a cutoff value of 0.002 mm. An insulating sheet having an average roughness of 0.5 μm or less, and the layer A contains a polyimide resin having a siloxane structure.
7) The insulating sheet according to claim 6, wherein the electroless plating is electroless copper plating.
8) A laminate in which an electroless plating film is formed on the layer A of the single-layer sheet according to 4) or the insulating sheet according to 6).
9) A printed wiring board using the single-layer sheet described in 4) or the insulating sheet described in 6).
10) A solution containing a polyimide resin having a siloxane structure, which is used to form the surface a according to 1).
11) A solution containing a precursor of a polyimide resin having a siloxane structure, the solution containing a polyamic acid, which is used to form the surface a according to 1).

    In the present invention, by using a polyimide resin having a surface a for performing electroless plating and having a specific structure on the surface a, electroless plating is performed even though the surface roughness of the surface to be plated is small. High adhesive strength with the layer. Further, the plating material of the present invention is excellent in adhesiveness with other various materials. Therefore, if the plating material of the present invention is first formed on the surface of the material to be electrolessly plated, and then electroless plating is performed, the plating material of the present invention and the electroless plating are firmly bonded. Have.

  In addition, since the plating material of the present invention has excellent heat resistance by containing a polyimide resin, it can be suitably used for the production of various printed wiring boards, and in particular, surface roughening should be performed. Flexible printed wiring boards, rigid printed wiring boards, multilayer flexible printed wiring boards, multilayer rigid wiring boards, and build-up wiring boards that require fine wiring formation, taking advantage of the high adhesive strength with the electroless plating layer The effect that it can use suitably for manufacture for printed wiring boards, etc. is also produced.

  One embodiment of the present invention will be described in detail below, but the present invention is not limited to the following description.

[Configuration of plating material of the present invention]
The plating material of the present invention is an electroless plating material having at least a surface a for performing electroless plating, and the surface roughness of the surface a is an arithmetic average roughness measured at a cutoff value of 0.002 mm. The surface a is a plating material characterized by containing a polyimide resin having a siloxane structure.

  By using a polyimide resin having a siloxane structure on the surface a, an electroless plating layer is firmly formed even when the surface roughness is as small as 0.5 μm or less in arithmetic average roughness measured at a cutoff value of 0.002 mm. can do.

  Interlayer adhesives using polyimides with a siloxane structure have been known so far, but pay attention to the surface roughness and the adhesive strength between electroless plating films when used as a layer for electroless plating. This is the first time the inventors have made it. The present inventors examined the adhesion between the surface roughness and the electroless plating film, which is not usually considered when used for an interlayer adhesive, and sufficient adhesion was obtained even when the surface roughness was small. It has been found that.

  The plating material of the present invention may be any material or form as long as it has the surface a. For example, when the plating material of the present invention is used for a printed wiring board, the surface a may be a film-like material composed only of a material containing a polyimide resin having a siloxane structure. It may be a material composed of the layer A having the layer A and the layer B facing the formed circuit, or a material composed of the layer A having the surface a / the polymer film C / the layer B. There may be. Moreover, the material comprised from the layer A which has the surface a, and the polymer C may be sufficient, and the material comprised from the layer A which has the surface a / polymer film C / layer A which has the surface a. There may be.

  In order to obtain the plating material of the present invention, a solution containing a polyimide resin is preferably used. In order to obtain the plating material of the present invention, a solution containing polyamic acid is preferably used.

  The plating material of the present invention only needs to have at least the surface A for performing electroless plating. However, first, the plating material of the present invention is formed on the surface of the material to be electrolessly plated, and then A method of applying electrolytic plating is preferably used. As a result, the plating material of the present invention plays the role of an interlayer adhesive, making use of the advantage that the electroless plating and the material are firmly bonded, and can be applied to various decorative plating applications and functional plating applications. Is possible. Among them, it has heat resistance and can be suitably used as a plating material for a printed wiring board by taking advantage of the ability to firmly form an electroless plating layer even when the surface roughness is small.

  The case of applying the plating material of the present invention to a printed wiring board will be described below.

[Polyimide resin contained in surface a]
The polyimide resin having a siloxane structure of the present invention may be any polyimide resin as long as it has a siloxane structure. For example, (1) using a dianhydride component having a siloxane structure or a diamine component having a siloxane structure, a polyamic acid that is a precursor of a polyimide resin is produced, and this is imidized to produce a polyimide resin; (2) 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, and the functional group capable of reacting with the functional group and a compound having a siloxane structure are reacted. A polyamic acid having a siloxane structure introduced, and imidizing it to produce a polyimide resin; (3) functionalization using an acid dianhydride component having a functional group or a diamine component having a functional group; A polyamic acid having a functional group, imidized to produce a polyimide having a functional group, and reacting with the functional group. That functional group, and by reacting a compound having a siloxane structure, a method of producing a polyimide resin siloxane structure is introduced, and the like. Here, since the diamine having a siloxane structure can be obtained relatively easily, among them, the acid dianhydride component and the diamine having a siloxane structure are reacted to produce a target polyimide resin. It is preferable to use a diamine represented by the following general formula (1) as the diamine having a siloxane structure.

（式中、ｇは１以上の整数を表す。また、Ｒ¹¹及びＲ²²は、同一、または異なっていてよく、アルキレン基またはフェニレン基を表す。Ｒ³³〜Ｒ⁶⁶は、同一、または異なっていてよく、アルキル基、またはフェニル基、またはフェノキシ基、またはアルコキシ基を表す。）
上記一般式（１）において、好ましくは、ｇは１以上１００以下である。またＲ１１及びＲ２２は、炭素数が１〜２０のアルキレン基またはフェニレン基であることが好ましい。さらにＲ３３〜Ｒ６６は、炭素数１〜２０のアルキル基、またはフェニル基、またはフェノキシ基、またはアルコキシ基であることが好ましい。

(In the formula, g represents an integer of 1 or more. R ¹¹ and R ²² may be the same or different and each represents an alkylene group or a phenylene group. R ^{33 to} R ⁶⁶ are the same or different. And represents an alkyl group, a phenyl group, a phenoxy group, or an alkoxy group.)
In the above general formula (1), preferably, g is 1 or more and 100 or less. R11 and R22 are preferably an alkylene group having 1 to 20 carbon atoms or a phenylene group. Further, R33 to R66 are preferably an alkyl group having 1 to 20 carbon atoms, a phenyl group, a phenoxy group, or an alkoxy group.

  A polyimide resin is obtained by reacting an acid dianhydride component and a diamine component. Hereinafter, the acid dianhydride component 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 following General formula (1) is included as a diamine component.

（式中、ｇは１以上の整数を表す。また、Ｒ¹¹及びＲ²²は、同一、または異なっていてよく、アルキレン基またはフェニレン基を表す。Ｒ³³〜Ｒ⁶⁶は、同一、または異なっていてよく、アルキル基、またはフェニル基、またはフェノキシ基、またはアルコキシ基を表す。）
上記一般式（１）において、好ましくは、ｇは１以上１００以下である。またＲ１１及びＲ２２は、炭素数が１〜２０のアルキレン基またはフェニレン基であることが好ましい。さらにＲ３３〜Ｒ６６は、炭素数１〜２０のアルキル基、またはフェニル基、またはフェノキシ基、またはアルコキシ基であることが好ましい。

(In the formula, g represents an integer of 1 or more. R ¹¹ and R ²² may be the same or different and each represents an alkylene group or a phenylene group. R ^{33 to} R ⁶⁶ are the same or different. And represents an alkyl group, a phenyl group, a phenoxy group, or an alkoxy group.)
In the above general formula (1), preferably, g is 1 or more and 100 or less. R11 and R22 are preferably an alkylene group having 1 to 20 carbon atoms or a phenylene group. Further, R33 to R66 are preferably an alkyl group having 1 to 20 carbon atoms, a phenyl group, a phenoxy group, or an alkoxy group.

  By using the diamine component represented by the general formula (1), the obtained polyimide resin has a characteristic of being firmly bonded to the electroless plating layer.

  The diamine represented by the general formula (1) is 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, 1,1,5 , 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,- Traphenyl-3,3-dimethoxy-1,5-bis (3-aminopentyl) trisiloxane, 1,1,3,3, -tetramethyl-1,3-bis (2-aminoethyl) disiloxane, , 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, Examples include 5-bis (3-aminopropyl) trisiloxane, 1,1,3,3,5,5-hexapropyl-1,5-bis (3-aminopropyl) trisiloxane, and the like. Moreover, Shin-Etsu Chemical Co., Ltd. KF-8010, X-22-161A, X-22-161B, X-22-1660B-3 as a diamine represented by General formula (1), which is relatively easily available. , KF-8008, KF-8012, X-22-9362, and the like. The said diamine may be used independently and may mix 2 or more types.

  For the purpose of improving the heat resistance of the surface a, it is also preferable to use a combination of the above diamine 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 General formula (1), More preferably, it is 5-100 mol%. When the diamine represented by the general formula (1) is less than 2 mol% with respect to the total diamine component, the adhesive strength between the surface a and the electroless plating film may be lowered.

  The polyimide is obtained by dehydrating and ring-closing the corresponding precursor polyamic acid polymer. The polyamic acid polymer 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 for 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 phenols and catechols, 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 commercially available polyimide resin having a siloxane structure may also be used. Examples of polyimide resins containing a relatively easily available siloxane structure that can be used for the surface A of the laminate of the present invention include X-22-8917, X-22-8904, and X-manufactured by Shin-Etsu Chemical Co., Ltd. 22-8951, X-22-8756, X-22-8984, X-22-8985, and the like. These are polyimide solutions.

  The polyimide resin having a siloxane structure constituting the layer A of the present invention is preferably a thermoplastic polyimide from the viewpoint of excellent adhesion to electroless plating. 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.

[Layer A having surface a]
The layer having the surface a always contains the polyimide resin having the above-described siloxane structure, but the layer having the surface a may contain other components. As other components, resins such as thermoplastic resins and thermosetting resins can be used as appropriate. This makes it possible to improve the heat resistance without impairing the adhesion with the electroless plating film. In particular, it is preferable to use a thermosetting resin because the heat resistance of the layer A is improved and the adhesiveness to the layer B and the polymer film C is improved. The thermosetting resin is preferably contained in an amount of 3 to 100 parts by weight with respect to 100 parts by weight of the polyimide resin having a siloxane structure, since a balanced characteristic 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 further improving the adhesion between the surface a and the electroless plating film, 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.

  In addition, various organic fillers and inorganic fillers can be added for the purpose of forming a surface roughness that does not hinder the formation of fine wiring on the surface A and enhancing the adhesion to the electroless plating film.

  It is important to combine the above-mentioned other components within a range that does not increase the surface roughness of the surface A to such an extent that the fine wiring formation is adversely affected, and does not reduce the adhesion between the surface a and the electroless plating film. This point needs attention.

  The ratio of the polyimide resin having a siloxane structure contained in the surface a is preferably 30% by weight to 100% by weight because the balance between the surface roughness and the adhesion with the electroless plating film is excellent.

  The surface “a” in the present invention refers to a surface having a thickness of 10 mm or more.

  The surface a of the present invention has an advantage that the adhesive strength with the electroless 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 surface a 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 surface a in the present invention has a very smooth surface when the roughness of the surface 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, particularly when the plating material of the present invention is used for printed wiring board applications, it has good fine wiring formability. In order to form the layer A having such a surface, for example,
(1) No surface treatment is performed.

  (2) Appropriately selecting the surface roughness of the surface of the support or the material such as the slip sheet in contact with the layer a for electroless plating.

  (3) In the case of a sheet composed of at least two layers including the layer A having the surface a for performing electroless plating, the surface roughness of the layer in contact with the layer A is appropriately selected.

  (4) The composition of the polyimide resin contained in the layer A and the drying conditions when forming the layer A are appropriately selected.

  These methods may be combined as appropriate.

  Specifically, it is preferable not to perform physical surface roughening such as sandblasting or chemical surface roughening such as blending an alkali-soluble component and treating with an alkali solution.

  Further, when the plating material of the present invention is a sheet formed on a support, it is preferable that the surface roughness of the support is sufficiently small. Further, when the sheet is laminated with the inner wiring board, it is preferable that the surface roughness of the interleaving paper opposed to the sheet at the time of lamination is sufficiently reduced. Accordingly, the surface roughness of the support or the slip sheet is preferably 0.5 μm or less in terms of arithmetic average roughness measured at a cutoff value of 0.002 mm.

  In the case of a sheet composed of two or more layers including the layer A having the surface a for performing electroless plating, the surface roughness of the layer in contact with the layer A affects the surface of the layer A. In some cases, the surface roughness of the layer in contact with the layer A is preferably sufficiently small. Therefore, the surface roughness of the layer in contact with the layer A is preferably 0.5 μm or less in terms of arithmetic average roughness measured at a cutoff value of 0.002 mm.

  Moreover, the surface roughness of the surface a for performing electroless plating varies depending on the type and blending ratio of the acid dianhydride component and the diamine component used in the polyimide resin having a siloxane structure. For example, when a large amount of diamine having a siloxane bond is used, Ra may increase due to phase separation depending on the type of acid dianhydride component or other diamine component to be combined. Further, when a polyimide resin having a siloxane bond and a thermoplastic polyimide resin are blended, phase separation tends to occur and Ra tends to increase. Also consider the drying conditions. Since the surface roughness of the surface a for applying the electroless plating of the present invention is such that the surface roughness in a very small range is small, the composition of the polyimide resin having a siloxane structure contained in the layer A and the layer A Depending on the combination of drying conditions, the surface roughness varies. Therefore, what is necessary is just to confirm that the target surface roughness is obtained by variously changing the composition of the polyimide resin and the drying conditions of the layer A.

  In addition, when other components are contained, depending on the blending amount and the resin combination, phase separation may occur and Ra may increase. Therefore, various blending amounts and resins of other components may be changed. It is sufficient to confirm that the desired surface roughness is obtained.

  The plating material or insulating sheet of the present invention may be subjected to an alkali treatment such as desmear before forming an electroless plating film. The surface of a conventionally known material, such as an epoxy resin material, is roughened by an alkali treatment such as desmear, whereas the surface a for performing electroless plating of the present invention has a siloxane structure. Since the polyimide resin is present, the surface can be kept smooth without being roughened even with an alkali treatment such as desmear, and a strong electroless plating film can be formed.

[Single-layer sheet having surface a]
A single layer sheet having a surface a for applying electroless plating and containing a polyimide resin having a siloxane structure will be described. For example, the sheet | seat which has the surface a is manufactured by carrying out casting application | coating of the solution which forms the surface a which performs electroless plating on a support body, and making it dry after that. The surface a can be formed by laminating this sheet on a desired material such as an inner wiring board or a polymer film. When a solution containing a polyimide resin is used as the solution for forming the surface a, the solution is cast on a support and then dried using a hot air oven or the like. There is no particular limitation on the drying conditions, but it is preferable to dry under such conditions that the solvent dissolving the resin is sufficiently volatilized. Further, in order to suppress foaming of the sheet, the temperature may be changed stepwise to be dried.

When a solution containing polyamic acid is used as a solution for forming the surface a, the solution is cast on a support and then dried using a hot air oven or the like. In this case, it is preferable to carry out until imidization at the time of drying because the production efficiency is good and it is preferable to finally perform drying and imidization at a temperature of 150 to 400 ° C.
The thickness of the single layer sheet is preferably 2 to 100 μm from the viewpoints of adhesion with electroless plating and circuit embedding properties.

(Other layers)
The plating material of the present invention may be any material as long as it has the surface a. For example, when the plating material of the present invention is applied to a printed wiring board, particularly a rigid printed wiring board such as a build-up wiring board, it may be a single layer sheet containing a polyimide resin having a siloxane structure, or a surface a May be a material composed of a layer A having a surface and a layer B for facing a formed circuit, or a material composed of a layer A having a surface a / a polymer film C / a layer B It may be. Further, when the plating material of the present invention is applied to a printed wiring board, particularly a flexible printed wiring board, it may be a material composed of a layer having surface A / polymer C, or a layer having surface a. A material composed of A / polymer film C / layer A having surface a may be used.

  When the layer B is laminated on the surface having the formed circuit, the layer B needs to have excellent workability so that the layer B flows between the circuits and the circuit can be embedded. In general, the thermosetting resin is excellent in the processability, and the layer B preferably contains a thermosetting resin. This thermosetting resin composition includes epoxy resin, phenol resin, thermosetting polyimide resin, cyanate ester resin, hydrosilyl cured resin, bismaleimide resin, bisallyl nadiimide resin, acrylic resin, methacrylic resin, allyl resin, Thermosetting resin such as saturated polyester resin; side chain reactive group type thermosetting polymer having reactive groups such as allyl group, vinyl group, alkoxysilyl group, hydrosilyl group at the side chain or terminal of polymer chain It can be applied as a thermosetting resin composition in combination with an appropriate thermosetting agent and a curing catalyst. It is also possible to preferably add a thermoplastic polymer to these thermosetting resin compositions. For example, a thermosetting resin composition containing an epoxy resin and a phenoxy resin, or a heat containing an epoxy resin and a thermoplastic polyimide resin. A curable resin composition, a thermosetting resin composition containing a cyanate resin and a thermoplastic polyimide resin, and the like can be preferably implemented. Among these, a thermosetting resin composition including an epoxy resin and a thermoplastic polyimide resin that are excellent in a balance of various properties required as a plating material is most preferable. In addition, various fillers can be combined for low thermal expansion.

  The polymer film C is not particularly limited, and any polymer film can be used, but a non-thermoplastic polyimide film is preferable from the viewpoint of heat resistance and low thermal expansion.

(Electroless plating)
Examples of the electroless plating according to the present invention include electroless copper plating, electroless nickel plating, electroless gold plating, electroless silver plating, electroless tin plating, and the like. From the viewpoint of electrical characteristics such as industrial viewpoint and migration resistance, electroless copper plating and electroless nickel plating are preferable, and electroless copper plating is particularly preferable. When electroless plating is performed on the laminate of the present invention, electroless plating may be applied directly to the laminate, or electroless plating may be applied after desmear treatment.
(Solution of the present invention)
The solution of the present invention is a solution containing a polyimide resin, which is used for forming the surface a. As described above, the solution may contain other components in addition to the polyimide solution, and any solvent that dissolves these resin components can be used. Here, dissolving means that the resin component is dissolved by 1% by weight or more with respect to the solvent.

  The surface a can be formed by applying and drying the solution on a desired material by a known method such as dipping, spray coating or spin coating.

  The solution of the present invention is a solution containing polyamic acid, which is used to form the surface a. As described above, the solution may contain other components in addition to the polyamic acid solution, and any solvent that dissolves these resin components can be used. Here, dissolving means that the resin component is dissolved by 1% by weight or more with respect to the solvent.

  The surface A can be formed by applying and imidizing the solution on a desired material by a known method such as dipping, spray coating, spin coating or the like by a known method. As described above, imidation can be carried out using either a thermal method in which a polyamic acid solution is heat-treated for dehydration or a chemical method for dehydration using a dehydrating agent. Moreover, the method of imidating by heating under reduced pressure can also be used. Among these, from the viewpoint of simple treatment and good production efficiency, a method of imidization by a thermal method of heat treatment and dehydration can be preferably used.

(Form and manufacturing method of plating material of the present invention)
Next, one of the forms of the plating material of the present invention for explaining the method for producing the plating material of the present invention is a solution containing a polyimide resin. For example, the above solution for forming the surface A for electroless plating is manufactured, and the desired material such as an inner wiring board or a polymer film is produced by a known method such as immersion, spray coating, spin coating, etc. The surface a can be formed by applying and drying on.

  One of the forms of the plating material of the present invention is a polyamic acid solution. For example, the above solution for forming the surface A for electroless plating is manufactured, and the desired material such as an inner wiring board or a polymer film is produced by a known method such as immersion, spray coating, spin coating, etc. The surface a can be formed by coating and imidizing on the surface.

  Another form of the plating material of the present invention is a sheet. For example, the sheet | seat which has the surface a is manufactured by carrying out casting application | coating of the solution which forms the surface A which performs electroless plating on a support body, and making it dry after that. The surface a can be formed by laminating this sheet on a desired material such as an inner wiring board or a polymer film.

  As described above, the surface A of the present invention refers to a surface having a thickness of 10 mm or more. For example, when the plating material of the present invention having the surface a is in the form of a sheet, it may be a sheet made of a material containing a polyimide resin having a siloxane structure that constitutes the surface a, and at least one surface a is It may be a sheet that is a polyimide resin having a siloxane structure.

  As mentioned above, although it illustrated about the form and usage method of the material for plating of this invention, it is not limited to this.

<Printed wiring board>
The plating material of the present invention can be preferably used for printed wiring board applications. Here, as a method of manufacturing a printed wiring board using the sheet-like plating material of the present invention, a sheet-like plating material with a resin film base material and an inner layer substrate on which a circuit pattern is formed are sequentially laminated. Then, it is possible to obtain a metal layer for a circuit pattern by performing electroless plating on the surface A exposed by peeling the resin film substrate.

  In the above, when a flexible printed wiring board is used for the inner layer board, a multilayer flexible wiring board is manufactured, and when a printed wiring board using a glass-epoxy base material is used, a multilayer rigid wiring board or build An up-wiring board will be manufactured. In addition, vias must be formed on the multilayer printed wiring board for vertical electrical connection. In the printed wiring board of the present invention, vias are formed by a known method such as laser, mechanical drilling or punching. However, it can be made conductive by a known method such as electroless plating and is preferably carried out.

  At the time of lamination, thermocompression treatment such as heat press treatment, vacuum press treatment, laminating treatment (heat laminating treatment), vacuum laminating treatment, hot roll laminating treatment, vacuum hot roll laminating treatment 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.

  In addition, for the purpose of improving the adhesion between the surface A and the electroless plating layer, it is possible to perform a heat treatment after forming the electroless plating layer.

  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. In addition, as a characteristic of the material for plating concerning this invention, adhesiveness with electroless-plated copper and surface roughness Ra were evaluated or calculated as follows.

[Adhesion evaluation]
An insulating sheet composed of layer A / support (polyethylene terephthalate film) having surface a is prepared, and layer A and glass epoxy substrate FR-4 (product number: MCL-E-67, manufactured by Hitachi Chemical Co., Ltd.); (The thickness of the copper foil is 50 μm, the total thickness is 1.2 mm), and after heating and pressurizing for 6 minutes under the conditions of temperature 170 ° C., pressure 1 MPa, and vacuum, the polyethylene terephthalate film is peeled off. And heating at 130 ° C. for 10 minutes, 150 ° C. for 10 minutes, and 180 ° C. for 30 minutes to obtain a laminate composed of layer A / FR-4 having surface a. Thereafter, a copper layer was formed on the exposed surface a. The copper layer was formed by performing desmearing and electroless copper plating, and then forming an electroplated copper layer having a thickness of 18 μm on the electroless plated copper. Thereafter, after drying at 180 ° C. for 30 minutes, the adhesive strength after normal and pressure cooker tests (PCT) was measured according to JPCA-BU01-1998 (published by Japan Printed Circuit Industry Association). In addition, desmear and electroless copper plating were implemented by the process of the following Tables 1-2.
Normal adhesive strength: Adhesive strength measured after standing for 24 hours in an atmosphere at a temperature of 25 ° C. and a humidity of 50%.
Adhesive strength after PCT: Adhesive strength measured after standing for 96 hours in an atmosphere of a temperature of 121 ° C. and a humidity of 100%.

〔表面粗度Ｒａ測定〕
上記接着性測定項目のサンプル作製手順において、無電解めっきをする前の状態（デスミアまで行った状態）のサンプルを用い、表面ａの表面粗度Ｒａの測定を行った。測定は、光波干渉式表面粗さ計（ＺＹＧＯ社製ＮｅｗＶｉｅｗ５０３０システム）を用いて下記の条件で表面Ａの算術平均粗さを測定した。

[Surface roughness Ra measurement]
In the sample preparation procedure of the adhesiveness measurement item, the surface roughness Ra of the surface a was measured using a sample in a state before electroless plating (a state where desmearing was performed). 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
[Polyimide resin synthesis example 1]
In a glass flask having a volume of 2000 ml, 62 g (0.075 mol) of KF-8010 manufactured by Shin-Etsu Chemical Co., Ltd., 15 g (0.075 mol) of 4,4′-diaminodiphenyl ether, N, N-dimethylformamide (hereinafter referred to as “Frequency”) DMF) was added and dissolved while stirring, and 78 g (0.15 mol) of 4,4 ′-(4,4′-isopropylidenediphenoxy) bis (phthalic anhydride) was added. The mixture was stirred for a time to obtain a DMF solution of polyamic acid having a solid content concentration of 30%. The polyamic acid solution was placed in a vat coated with Teflon (registered trademark) and heated in a vacuum oven at 200 ° C. for 120 minutes at 665 Pa to obtain polyimide resin 1.

[Polyimide resin synthesis example 2]
In a glass flask with a capacity of 2000 ml, 37 g (0.05 mol) of KF-8010 manufactured by Shin-Etsu Chemical Co., Ltd., 21 g (0.10 mol) of 4,4′-diaminodiphenyl ether and DMF are added and dissolved while stirring. 78 g (0.15 mol) of 4,4 ′-(4,4′-isopropylidenediphenoxy) bis (phthalic anhydride) was added and stirred at 20 ° C. for about 1 hour. A DMF solution 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 2.

[Polyimide resin synthesis example 3]
123 g (0.15 mol) of KF-8010 manufactured by Shin-Etsu Chemical Co., Ltd. and DMF are introduced into a glass flask having a volume of 2000 ml, dissolved with stirring, and 4,4 ′-(4,4′-isopropyl propylene. 78 g (0.15 mol) of lidenediphenoxy) bis (phthalic anhydride) was added, and the mixture was stirred at 20 ° C. for about 1 hour to obtain a DMF solution of polyamic acid with a solid content concentration of 30%. The polyamic acid solution was placed in a vat coated with Teflon (registered trademark) and heated under reduced pressure at 200 ° C. for 120 minutes at 665 Pa in a vacuum oven to obtain a thermoplastic polyimide resin 3.

[Polyimide resin synthesis example 4]
In a glass flask having a capacity of 2000 ml, 41 g (0.143 mol) of 1,3-bis (3-aminophenoxy) benzene and 1.6 g (0.007 mol) of 3,3′-dihydroxy-4,4′-diaminobiphenyl were added. Then, 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 at 20 ° C. 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 under reduced pressure at 200 ° C. for 180 minutes at 665 Pa in a vacuum oven to obtain polyimide resin 4.

[Formulation Example 1 of solution for forming layer A]
The polyimide resin 1 was dissolved in dioxolane to obtain a solution (1) for forming the layer A. The solid content concentration was 15% by weight.

[Formulation Example 2 for Forming Layer A]
The polyimide resin 2 was dissolved in dioxolane to obtain a solution (2) for forming the layer A. The solid content concentration was 15% by weight.

[Formulation Example 3 for Forming Layer A]
The polyimide resin 3 was dissolved in dioxolane to obtain a solution (3) for forming the layer A. The solid content concentration was 15% by weight.

[Formulation example 4 of solution for forming layer A]
The polyimide resin 4 was dissolved in dioxolane to obtain a solution (4) for forming the layer A. The solid content concentration was 15% by weight. 90 g of the solution (3) and 10 g of the solution (4) were mixed to obtain a solution (5) that forms layer A.
[Formulation example 5 of solution for forming layer A]
A polyimide silicone solution, X-22-8917 (solid content concentration 20% by weight, cyclohexanone solution) manufactured by Shin-Etsu Chemical Co., Ltd. was used as a solution (6) for forming layer A.

[Formulation Example 6 for forming the layer A]
Japan Epoxy Resin Co., Ltd. YX4000H 32.1g of biphenyl type epoxy resin, Wakayama Seika Kogyo Co., Ltd. bis [4- (3-aminophenoxy) phenyl] sulfone 17.9g, Shikoku Kasei Kogyo Co., Ltd. ) Epoxy curing agent, 2,4-diamino-6- [2'-undecylimidazolyl- (1 ')]-ethyl-s-triazine (0.2 g) was dissolved in dioxolane to obtain a solution (7). . The solid content concentration of the solution was 50% by weight. 90 g of the solution (1) and 3 g of the solution (7) were mixed to obtain a solution (8) for forming the layer A.

[Preparation Example 7 of Solution Forming Layer A]
As shown in Table 4, 27 g of the solution (7) and 10 g of epoxy modified polybutadiene rubber (E1000-8) manufactured by Nippon Petrochemical Co., Ltd. were mixed to obtain a solution (9) for forming the layer A.

[Formulation example 1 of layer B solution]
As shown in Table 3, 83 g of the solution (4), 50 g of the solution (7), and 7.5 g of silica (Admafine S0-C5, average particle size = 1.5 μm) manufactured by Tatsumori Co., Ltd. were mixed. A layer B solution (10) was obtained.

[Production Example 1 of non-thermoplastic polyimide film]
A 25 μm non-thermoplastic polyimide film was prepared and used as the polymer film. In a separable flask, 1 equivalent each of paraphenylenediamine (hereinafter referred to as PDA) and 4,4′-diaminodiphenyl ether (hereinafter referred to as ODA) was dissolved in DMF, and then p-phenylenebis (trimellitic acid monoester anhydride) (hereinafter referred to as TMHQ). ) 1 equivalent was added and stirred for 30 minutes. Thereafter, 0.9 equivalent of pyromellitic dianhydride (hereinafter PMDA) was added and stirred for 30 minutes. Next, a DMF solution of PMDA (concentration 7%) was added while paying attention to an increase in viscosity, and the viscosity at 23 ° C. was adjusted to 2000 to 3000 poises to obtain a DMF solution of a polyamic acid polymer. The amount of DMF used was such that the monomer charge concentration of the diamine component and tetracarboxylic dianhydride component was 18% by weight. Moreover, superposition | polymerization was performed at 40 degreeC. To 100 g of the above polyamic acid solution, 10 g of acetic anhydride and 10 g of isoquinoline are added and stirred uniformly, then defoamed, cast on a glass plate, dried at about 110 ° C. for about 5 minutes, and then polyamic acid. The coating film was peeled off from the glass plate to obtain a gel film having self-supporting properties. The gel film is fixed to a frame, then heated at about 200 ° C. for about 1 minute, about 300 ° C. for about 1 minute, about 400 ° C. for about 1 minute, about 500 ° C. for about 1 minute, dehydrated and ring-closed and dried, A non-thermoplastic polyimide film (a) having a thickness of about 25 μm was obtained. The thermal expansion coefficient of this film was 12 ppm. Further, in thermomechanical analysis measurement (TMA) in the compression mode (probe diameter 3 mmφ, load 5 g), permanent compression deformation was not caused in the temperature range of 10 to 400 ° C. (temperature increase rate: 10 ° C./min), so that non-heat The plastic polyimide was determined. The obtained non-thermoplastic polyimide film had a surface roughness Ra of 0.01 μm.

[Example 1]
The solution for forming the layer A shown in Table 3 was cast-coated on the surface of a resin film (trade name Therapy HP, manufactured by Toyo Metallizing Co., Ltd., surface roughness Ra = 0.02 μm) serving as a support. Then, it was heat-dried at a temperature of 60 ° C., 100 ° C. and 150 ° C. for 1 minute each in a hot air oven to obtain an insulating sheet with a support having a layer A having a thickness of 25 μm. Using the obtained sheet, the evaluation was performed according to the evaluation procedure for various evaluation items. The evaluation results are shown in Table 3.

[Examples 2 to 6]
According to the solution which forms the layer A shown in Table 3, the insulating sheet with a support body which has the layer A in the same procedure as Example 1 was obtained. The obtained sheet | seat was evaluated in accordance with the evaluation procedure of various evaluation items. The evaluation results are shown in Table 3.

Example 7
The solution for forming the layer A shown in Table 3 was cast-coated on the surface of a resin film (trade name Therapy HP, manufactured by Toyo Metallizing Co., Ltd., surface roughness Ra = 0.02 μm) serving as a support. Then, it was heat-dried at a temperature of 60 ° C. for 1 minute in a hot air oven to obtain an insulating sheet with a support having a layer A having a thickness of 5 μm.

  Subsequently, the outermost layer B solution shown in Table 3 was cast and applied to layer A, and heated and dried at 80 ° C., 100 ° C., 120 ° C., 140 ° C., and 150 ° C. for 1 minute each in a hot air oven. An insulating sheet with a support having a thickness of 40 μm was obtained by combining both A and layer B. The obtained sheet | seat was evaluated in accordance with the evaluation procedure of various evaluation items. The evaluation results are shown in Table 3.

Example 8
The solution for forming the layer A shown in Table 3 was cast on a 25 μm polyimide film (a). Then, it was heat-dried at a temperature of 60 ° C. for 1 minute in a hot air oven to obtain a polyimide film having a surface A having a thickness of 5 μm.
Subsequently, the outermost layer B solution shown in Table 3 was cast and applied to the surface of the polyimide film opposite to the formed layer A, and heated at 80 ° C., 100 ° C., 120 ° C., 150 ° C. and 170 ° C. in a hot air oven. It was heated and dried for 1 minute at a time to obtain an insulating sheet composed of 5 μm surface A / 25 μm polyimide film / 35 μm layer B. The obtained insulating sheet was evaluated according to the evaluation procedure of various evaluation items. The evaluation results are shown in Table 3.

[Comparative Example 1]
Evaluation was made according to the evaluation procedure for various evaluation items in the same procedure as in Example 1 except that the desmear treatment was not performed using the solution (9). The evaluation results are shown in Table 4. As can be seen from Table 4, the surface roughness is sufficiently small, but the adhesive strength is low.

[Comparative Example 2]
Evaluation was made according to the evaluation procedure for various evaluation items in the same procedure as in Comparative Example 1 except that the desmear treatment was performed using the solution (9). The evaluation results are shown in Table 4. As can be seen from Table 4, the adhesive strength is high, but the surface roughness is large.

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 plating material according to the present invention has high adhesion not only with various materials but also with an electroless plating film. Furthermore, even when the surface roughness of the present invention is small, the adhesiveness with the electroless plating film is high, so that it can be suitably used particularly for the production of printed wiring boards. Therefore, the present invention can be suitably used not only in the material processing industry such as resin compositions and adhesives and various chemical industries, but also in the industrial field of various electronic components.

Claims (11)

A material for electroless plating having at least a surface a for applying electroless plating, and the surface roughness of the surface a is 0.5 μm or less as an arithmetic average roughness measured at a cutoff value of 0.002 mm. And the surface a contains a polyimide resin having a siloxane structure. 2. The plating resin according to claim 1, wherein the polyimide resin having a siloxane structure is a polyimide resin using a diamine component containing an acid dianhydride component and a diamine represented by the following general formula (1) as a raw material. material.

(In the formula, g represents an integer of 1 or more. R ¹¹ and R ²² may be the same or different and each represents an alkylene group or a phenylene group. R ^{33 to} R ⁶⁶ are the same or different. And represents an alkyl group, a phenyl group, a phenoxy group, or an alkoxy group.) The plating material according to claim 1 or 2, wherein the electroless plating is electroless copper plating. A single-layer sheet having a surface a for applying electroless plating and containing a polyimide resin having a siloxane structure, the surface roughness of the surface a being an arithmetic average roughness measured at a cutoff value of 0.002 mm A single-layer sheet characterized by being 0.5 μm or less. The single layer sheet according to claim 4, wherein the electroless plating is electroless copper plating. An insulating sheet comprising at least two layers including a layer A having a surface a for electroless plating, the surface roughness of the surface a being an arithmetic average roughness measured at a cutoff value of 0.002 mm The insulating sheet is 0.5 μm or less, and the layer A contains a polyimide resin having a siloxane structure. The insulating sheet according to claim 6, wherein the electroless plating is electroless copper plating. A laminate comprising an electroless plating film formed on the layer A of the single-layer sheet according to claim 4 or the insulating sheet according to claim 6. A printed wiring board using the single-layer sheet according to claim 4 or the insulating sheet according to claim 6. A solution containing a polyimide resin having a siloxane structure, which is used for forming the surface a according to claim 1. A solution containing a precursor of a polyimide resin having a siloxane structure, which is used for forming the surface a according to claim 1.