JP4647386B2 - Method for producing plating material and method for forming electroless plating film - Google Patents

Description

  The present invention relates to a method for producing a plating material that can be suitably used when performing electroless plating, and a method for forming an electroless plating film on the surface of the material.

  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 technology is widely applied to functionalize the surface of conductive materials, such as decorative plating for parts such as automobile grills, marks, and household appliance knobs by applying electroless plating to ABS and polypropylene resins. Examples of application to functional plating such as through-hole plating of printed wiring boards can be given.

  However, electroless plating often has low adhesion to the surfaces of the various materials. In particular, when applied to the production of the above-described printed wiring board, the problem is that the adhesion between the electroless plating film and the insulating material is low.

  In order to solve the above problems, insulating resin materials used for printed wiring boards have roughened the surface by various methods, and have obtained adhesion to the electroless plating film by a so-called anchor effect (for example, Patent Documents) 1). However, this method cannot meet the recent demand for fine wiring formability. This is because, when fine wiring is formed using this technique, problems such as tilting or falling of the wiring occur due to the large surface roughness of the roughened surface. As can be seen from this, in order to meet the demand for fine wiring formation, a technique for strongly forming metal plating on a smooth resin surface is required.

On the other hand, a metal foil with resin in which a polyimide siloxane precursor is applied on at least one side of a heat resistant resin film and a metal plating layer is laminated, or a polyimide siloxane precursor is applied on at least one side of a heat resistant resin film and imidized. A metal foil with a resin having a metal plating layer formed thereon is disclosed (see Patent Document 2). However, in the future, in applications such as printed wiring boards, it is considered that the circuit will become increasingly thin, and further, a material excellent in adhesiveness with the metal layer will be required. In particular, a technique for improving the adhesiveness with the electroless plating film as described above is still under development, and a technique capable of forming the electroless plating film more firmly on a material having a smooth surface is required.
JP2000-198907 JP 2002-264255 A

  As described in the background art, in the present invention, a method for manufacturing a plating material capable of forming metal plating more firmly on a smooth resin surface and a method for forming an electroless plating film on the material surface are provided. The purpose is to provide.

  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. The purpose is to provide a method for producing a plating material having improved adhesion and excellent heat resistance. Functional plating on various plastics, glass, ceramics, wood, etc., automotive grills and marks, home appliances It can be used suitably for decorative plating on parts such as knobs, especially for the production of various printed wiring boards, and also for flexible printed wiring boards, rigid printed wiring boards, and multilayer flexible printing that require fine wiring formation. A method for producing a plating material that can be suitably used for production of printed wiring boards such as wiring boards and build-up wiring boards, and To provide a method for forming an electroless plating film on the charge surface.

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 method for producing a plating material. That is,
1) A method for producing an electroless plating material having a layer A for forming an electroless plating layer, comprising a step of applying a solution containing a polyimide resin a having a siloxane structure on a support. A method for producing an electroless plating material.
2) The method for producing an electroless plating material according to 1), further comprising a step of drying the solvent and a step of removing the support after applying a solution containing the polyimide resin a having a siloxane structure.
3) The method for producing a plating material according to 1) or 2), wherein the support is a polymer.
4) A method for producing an electroless plating material having a layer A for forming an electroless plating layer, comprising a step of applying a solution containing a polyimide resin a having a siloxane structure on a polymer film. A method for producing a material for electroless plating characterized by the following.
5) A step of forming a layer A for forming an electroless plating layer by applying a solution containing a polyimide resin a having a siloxane structure on the surface of the material, and a step of performing electroless plating on the layer A A method for forming an electroless plating film, comprising:
6) A step of forming a layer A for forming an electroless plating layer by applying a solution containing a polyimide resin a having a siloxane structure on the support, a step of removing the support, and on the layer A A method for forming an electroless plating film, comprising the step of applying electroless plating to the substrate.
7) A step of forming a layer A for forming an electroless plating layer by applying a solution containing a polyimide resin a having a siloxane structure on the polymer film, and performing electroless plating on the layer A A method for forming an electroless plating film, comprising a step.

  In the present invention, it is possible to provide a plating material having excellent adhesion to electroless plating despite having a smooth surface by applying a solution containing a polyimide resin to the surface of the material. It becomes. Therefore, the plating material produced by the production method of the present invention includes 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, printed wiring such as flexible printed wiring boards, rigid printed wiring boards, multilayer flexible printed wiring boards and build-up wiring boards that require fine wiring formation. There is also an effect that it can be suitably used for manufacturing a plate.

One embodiment of the present invention will be described in detail below, but the present invention is not limited to the following description.
[Production Method of Plating Material of the Present Invention]
In the method for producing a plating material of the present invention, a layer containing a polyimide resin having a siloxane structure is formed on a support by applying a solution containing the polyimide resin a having a siloxane structure. A layer containing a polyimide resin having a function as a layer (layer A) for performing electroless plating thereon. In this case, after the support is removed, electroless plating is formed on the exposed surface of the layer A, and the support serves as a base material for forming the layer A.

  Or it is a manufacturing method of the material for electroless-plating characterized by having the process of apply | coating the solution containing the polyimide resin a which has a siloxane structure on a polymer film. This polymer film plays a role such as imparting flexibility and heat resistance, low thermal expansion and high insulation, and maintaining uniformity of the insulating layer thickness.

  Then, about the manufacturing method of the material for plating of this invention, hereafter, the manufacturing of the solution containing the polyimide resin a which has a siloxane structure, a support body, a polymer film, the formation method of the layer A, the plating obtained by the manufacturing method of this invention The structure of the materials will be described in the order.

(Production of solution containing polyimide resin a)
In the present invention, a solution containing a polyimide resin a that is stable in a solution state is used. Therefore, it is essential that the polyimide resin a is soluble. Here, the term “soluble” as used in the present invention refers to at least one solvent selected from dioxolane, dioxane, tetrahydrofuran, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, and the like. It means that 1% by weight or more dissolves in a temperature range of room temperature to 100 ° C.

  The polyimide resin a of the present invention may be any polyimide resin as long as it has a siloxane structure and is soluble. 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. As the diamine having a siloxane structure, it is preferable to use a diamine represented by the following general formula (1).

（式中、ｇは１以上の整数を表す。また、Ｒ１１及びＲ２２は、それぞれ同一、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は、それぞれ同一、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。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。）
前記ポリイミドは、対応する前駆体のポリアミド酸を脱水閉環して得られる。ポリアミド酸は、酸二無水物成分とジアミン成分とを実質的に等モル反応させて得られ、例えば以下のような方法で得ることができる。
１）芳香族ジアミンを有機極性溶媒中に溶解し、これと実質的に等モルの芳香族テトラカルボン酸二無水物を反応させて重合する方法。
２）芳香族テトラカルボン酸二無水物とこれに対し過小モル量の芳香族ジアミン化合物とを有機極性溶媒中で反応させ、両末端に酸無水物基を有するプレポリマーを得る。続いて、全工程において芳香族テトラカルボン酸二無水物と芳香族ジアミン化合物が実質的に等モルとなるように芳香族ジアミン化合物を用いて重合させる方法。
３）芳香族テトラカルボン酸二無水物とこれに対し過剰モル量の芳香族ジアミン化合物とを有機極性溶媒中で反応させ、両末端にアミノ基を有するプレポリマーを得る。続いてここに芳香族ジアミン化合物を追加添加後、全工程において芳香族テトラカルボン酸二無水物と芳香族ジアミン化合物が実質的に等モルとなるように芳香族テトラカルボン酸二無水物を用いて重合する方法。
４）芳香族テトラカルボン酸二無水物を有機極性溶媒中に溶解及び／または分散させた後、実質的に等モルとなるように芳香族ジアミン化合物を用いて重合させる方法。
５）実質的に等モルの芳香族テトラカルボン酸二無水物と芳香族ジアミンの混合物を有機極性溶媒中で反応させて重合する方法。

(In the formula, g represents an integer of 1 or more. R11 and R22 may be the same or different, and each represents an alkylene group or a phenylene group. R33 may be the same or different, and alkyl. Represents a group, a phenyl group, a phenoxy group, or an alkoxy group, preferably g is 1 or more and 100 or less, and R11 and R22 are each an alkylene group or a phenylene group having 1 to 20 carbon atoms. R33 is preferably an alkyl group having 1 to 20 carbon atoms, a phenyl group, a phenoxy group, or an alkoxy group.
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 substantially in an equimolar amount, and can be obtained by, for example, the following method.
1) A method in which an aromatic diamine is dissolved in an organic polar solvent and this is reacted with a substantially equimolar amount of an aromatic tetracarboxylic dianhydride for polymerization.
2) An aromatic tetracarboxylic dianhydride is reacted with a small molar amount of an aromatic diamine compound in an organic polar solvent to obtain a prepolymer having acid anhydride groups at both ends. Then, the method of superposing | polymerizing using an aromatic diamine compound so that an aromatic tetracarboxylic dianhydride and an aromatic diamine compound may become substantially equimolar in all the processes.
3) An aromatic tetracarboxylic dianhydride and an excess molar amount of the aromatic diamine compound are reacted in an organic polar solvent to obtain a prepolymer having amino groups at both ends. Subsequently, after adding an aromatic diamine compound here, using the aromatic tetracarboxylic dianhydride so that the aromatic tetracarboxylic dianhydride and the aromatic diamine compound are substantially equimolar in all steps. How to polymerize.
4) A method in which an aromatic tetracarboxylic dianhydride is dissolved and / or dispersed in an organic polar solvent and then polymerized using an aromatic diamine compound so as to be substantially equimolar.
5) A method of polymerizing by reacting a substantially equimolar mixture of aromatic tetracarboxylic dianhydride and aromatic diamine in an organic polar solvent.

  The reaction time and reaction temperature are not particularly limited.

  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, N, N-diethylacetamide, pyrrolidone solvents such as N-methyl-2-pyrrolidone, 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.

Next, the acid dianhydride component used for the polymerization of polyamic acid 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 Aromatic tetraca Boronic acid dianhydride, 4,4′-hexafluoroisopropylidenediphthalic anhydride, 4,4′-oxydiphthalic anhydride, 3,4′-oxydiphthalic anhydride, 3,3′-oxydiphthalic anhydride 4,4 ′-(4,4′-isopropylidenediphenoxy) bis (phthalic anhydride), 4,4′-hydroquinonebis (phthalic anhydride), 2,2-bis (4-hydroxyphenyl) propanedi Benzoate-3,3 ′, 4,4′-tetracarboxylic dianhydride, 1,2-ethylenebis (trimellitic acid monoester anhydride), p-phenylenebis (trimellitic acid monoester anhydride), etc. Can be mentioned. These may be used alone or in combination of two or more. Here, from the viewpoint of obtaining a soluble polyimide resin a, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride 4,4′-hexafluoroisopropylidenediphthalic anhydride, 4,4′-oxydiphthalic anhydride, 3,4′-oxydiphthalic anhydride, 3,3′-oxydiphthalic anhydride, 4,4 ′ -(4,4'-isopropylidenediphenoxy) bis (phthalic anhydride), 4,4'-hydroquinone bis (phthalic anhydride), 2,2-bis (4-hydroxyphenyl) propanedibenzoate-3,3 Choose from ', 4,4'-tetracarboxylic dianhydride, 1,2-ethylenebis (trimellitic acid monoester anhydride), p-phenylenebis (trimellitic acid monoester anhydride) It is preferable that the acid anhydride component to be included is contained in the total acid dianhydride component in an amount of 50 mol% to 100 mol%.

  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、それぞれ同一、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は、それぞれ同一、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。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。）
一般式（１）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、無電解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。

(In the formula, g represents an integer of 1 or more. R11 and R22 may be the same or different, and each represents an alkylene group or a phenylene group. R33 may be the same or different, and alkyl. Represents a group, a phenyl group, a phenoxy group, or an alkoxy group, preferably g is 1 or more and 100 or less, and R11 and R22 are each an alkylene group or a phenylene group having 1 to 20 carbon atoms. R33 is 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. In addition, as relatively easily available diamines represented by the general formula (1), KF-8010, X-22-161A, X-22-161B, X-22-1660B-3 manufactured by Shin-Etsu Chemical Co., Ltd. , 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 obtained polyimide resin a, obtaining a soluble polyimide resin a, and the like, 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 layer A and the electroless plating film is lowered, or the solubility of the resulting polyimide resin is lowered. There is a case.

  The polyamic acid solution thus obtained is subjected to dehydration and ring closure by a thermal or chemical method to obtain a polyimide. The polyamic acid solution is dehydrated by heat treatment, and the dehydrating agent is chemically dehydrated. Any of the methods 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 imidation completion temperature, that is, about 250 to 350 ° C. is usually applied. The condition for the pressure to be reduced is 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 a constituting the layer A 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 layer A include X-22-8915, X-22-8904, X-22-8951, and X-manufactured by Shin-Etsu Chemical Co., Ltd. 22-8156, X-22-8984, X-22-8985, and the like. In addition, since these are polyimide solutions, they can be used as they are as a solution containing the polyimide resin a.

  The polyimide resin a having a siloxane structure thus obtained is dissolved in a solvent to obtain a solution containing the polyimide resin a. Any solvent that dissolves the resin component can be used as the solvent. Here, dissolving means that the resin component is dissolved by 1% by weight or more with respect to the solvent.

  The solvent used in the solution containing the polyimide resin a of the present invention preferably has a boiling point of 230 ° C. or less from the viewpoint of suppressing foaming during drying and reducing the residual solvent. Examples include tetrahydrofuran (hereinafter abbreviated as THF, boiling point 66 ° C.), 1,4-dioxane (hereinafter abbreviated as dioxane, boiling point 103 ° C.), monoglyme (boiling point 84 ° C.), dioxolane (boiling point 76 ° C.), toluene. (Boiling point 110 ° C), tetrahydropyran (boiling point 88 ° C), dimethoxyethane (boiling point 85 ° C), N, N-dimethylformamide (boiling point 153 ° C), N-methyl-2-pyrrolidone (boiling point 205 ° C), etc. Can do. In addition to those exemplified above, any solvent having a boiling point of 230 ° C. or lower can be preferably used. These may be used alone or in combination of two or more.

  Further, for example, the polyamic acid solution may be imidized thermally or chemically, and the solution may be a solution containing the polyimide resin a.

  The solution containing the polyimide resin a having a siloxane structure may contain other components for the purpose of improving the heat resistance of the obtained material. As other components, resins such as thermoplastic resins and thermosetting resins can be used as appropriate. Examples of the thermoplastic resin include a polysulfone resin, a polyethersulfone resin, a polyphenylene ether resin, a phenoxy resin, and a thermoplastic polyimide resin, 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 layer 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, when the layer A is formed, 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 and enhancing 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 layer A to such an extent that the fine wiring formation is adversely affected, and does not reduce the adhesion between the layer A and the electroless plating film. This point needs attention.

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

(Support)
As the support used for the plating material of the present invention, various polymer films, metal foils such as copper foil and aluminum foil, and the like can be used. In the present invention, a metal layer may be formed on the surface from which the support has been removed, but in the case of this production method, since the surface state of the support is transferred to layer A, the surface roughness of the support is sufficiently small. Is preferred. Here, in order to keep the surface roughness of the layer A of the present invention sufficiently small, the surface roughness of the support is an arithmetic average roughness Ra measured at a cutoff value of 0.002 mm and less than 0.5 μm. Is preferred. For this reason, a polymer film is preferred as the support used in the present invention. Examples of the polymer film include a polyethylene terephthalate film, a polyethylene naphthalate film, a polycarbonate film, a polyethylene film, a polypropylene film, and a fluororesin film. It is also preferable to subject these polymer films to various surface treatments for the purpose of improving releasability.

(Polymer film)
As a plating material to which this production method can be preferably applied, a material composed of layer A / polymer film, a material composed of layer A / polymer film / layer A, and layer A / polymer film A material for plating in which the layer A is formed directly on the polymer film, such as a material composed of / layer B, can be mentioned.

  Unlike the above-described support, the polymer film used here is not removed, but is used as a part of the plating material. In flexible printed wiring board applications, It plays a role such as role, flexibility and heat resistance, etc., and in multilayer printed wiring board applications such as build-up wiring boards, it maintains low thermal expansion, high insulation, uniformity of insulation layer thickness, etc. To play a role. The polymer film is not particularly limited, but a non-thermoplastic polyimide film is preferable from the viewpoint of heat resistance and low thermal expansion.

(Formation method of layer A)
A layer A can be formed by applying a solution containing the polyimide resin a by a known method such as dipping, spray coating, or spin coating on a material for which electroless plating is to be formed.

  Or the layer A can be formed by apply | coating the solution containing the polyimide resin a on the above-mentioned support body. By this method, a support-equipped plating material having a support / layer A configuration can be obtained. Further, by further forming layer B on the layer A side, a plating material with a support having a structure of support / layer A / layer B can be obtained. Examples of the method for forming the layer B include a method in which the solution for forming the layer B is applied to the layer A side of the plating material with support and dried as necessary. Further, the layer B formed in advance in a film shape and the plating material with a support are overlapped so that the layer A and the layer B face each other, and are subjected to pressure bonding by a method such as pressing or laminating. It is also possible to form the layer B on the plating material with a support.

  Another method for producing the plating material according to the present invention is a method for producing a plating material characterized in that a layer A is formed by applying a solution containing a polyimide resin a onto a polymer film. be able to. Plating materials to which this production method can be preferably applied include materials composed of layer A / polymer film, materials composed of layer A / polymer film / layer A, and layer A / polymer. Examples thereof include a plating material in which the layer A is formed immediately above the polymer film, such as a material composed of the film / layer B.

  Here, the polymer film is not particularly limited, but a non-thermoplastic polyimide film is preferable from the viewpoint of heat resistance and low thermal expansion.

  On the polymer film, a solution containing the polyimide resin a is applied by a known method such as dipping, spray coating, spin coating, etc., and dried as necessary to obtain a layer A / polymer film configuration plating material. Obtainable. Further, by further forming layer A or layer B on the polymer film side, a plating material having a layer A / polymer film / layer A configuration or a layer A / polymer film / layer B configuration can be obtained. it can.

  In the present invention, in order to make the adhesion with the electroless plating film stronger when the electroless plating film is formed on the layer A, it is not a polyamic acid lacking stability in a solution state but a solution state. It is important to apply a polyimide resin solution containing a stable and stable polyimide resin. An electroless plating film is formed on a layer having a polyimide resin a formed by applying a solution of polyamic acid corresponding to the polyimide resin a on a material on which an electroless plating is to be formed or a support and then drying and imidizing. Compared with the case of forming, the further excellent adhesion.

  The “layer” of the layer A for applying electroless plating thus formed refers to a layer having a thickness of 1 nm or more.

    The layer A thus formed 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 layer A of the present invention is preferably less than 0.5 μm in arithmetic average roughness Ra measured at a cutoff value of 0.002 mm. 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 have such a surface, it is necessary 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. is there.

(Configuration of plating material obtained by the production method of the present invention)
The structure of the plating material obtained by the production method of the present invention will be described in detail. As long as the layer A is provided, any material may be used. For example, when the plating material of the present invention is applied to, for example, a build-up wiring board or the like, it may be a film material made only of the material constituting the layer A, or may be opposed to the layer A and the formed circuit. The material comprised from the layer B for making it may be sufficient, and the material comprised from layer A / polymer film / layer B may be sufficient. Further, when the plating material of the present invention is applied to, for example, a flexible printed wiring board, it may be a material composed of layer A / polymer film, or from layer A / polymer film / layer A. It may be a composed material.

  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. Among these, it is preferable that an epoxy resin is included from the viewpoint of obtaining a layer B having excellent processability.

  A thermoplastic resin may be further added to these thermosetting resin compositions. Examples of the thermoplastic resin include a polysulfone resin, a polyethersulfone resin, a polyphenylene ether resin, a phenoxy resin, and a thermoplastic polyimide resin, and these can be used alone or in appropriate combination. In addition, various fillers can be combined for low thermal expansion.

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

(Utilization of plating material obtained by the method for manufacturing a plating material of the present invention)
As a method of using the plating material obtained by the method for producing a plating material of the present invention, a printed wiring board which is a typical use of the electroless plating material obtained by the production method of the present invention and the electroless plating method This will be explained in the order.

(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 applied to the plating material of the present invention, the electroplating material of the present invention may be directly applied, or after various surface treatments such as desmear treatment, the electroless plating is performed. Also good.

<Printed wiring board>
Below, the manufacturing method of the printed wiring board using the material for plating obtained by the manufacturing method of this invention is illustrated.

  First, the case where the plating material obtained by the method for producing a plating material of the present invention is composed of a plating material / support including the layer A will be described. When this material is used for applications such as flexible printed wiring boards, the support is removed, electroless plating is applied on layer A, a metal layer for a wiring pattern is obtained, wiring is formed, and single-sided or double-sided printed wiring A board can be obtained. Since the surface of the layer A that is in contact with the support is prevented from adhering dust and the like, it is preferable to apply electroless plating to this surface. Moreover, as a wiring formation method, any of a semi-additive method and a subtractive method may be applied.

  Further, when the above material is used for a multilayer wiring board such as a build-up wiring board, the plating material of the present invention and the inner layer substrate on which the circuit pattern is formed are sequentially laminated, and then the support is removed and the exposed layer A Electroless plating is performed on the surface to obtain a metal layer for a wiring pattern, and then wiring is formed to obtain a multilayer printed wiring board. 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. At the time of lamination, in order not to contaminate the surface of the layer A, it is preferable to use various resin films as interleaving paper immediately above the layer A side. However, in the case of the plating material / support structure having the layer A, from the support It does not peel off and can be used as a slip sheet as it is. 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. After that, it is possible to conduct by electroless plating, which is preferably performed.

  Next, the case where the plating material obtained by the method for producing a plating material of the present invention is composed of a plating material / layer containing the layer A will be described. When this material is used for applications such as a flexible printed wiring board, electroless plating is performed on the layer A to obtain a metal layer for a wiring pattern, and then wiring is formed to obtain a single-sided or double-sided printed wiring board. As a wiring formation method, any of a semi-additive method and a subtractive method may be applied.

  In addition, when using the above material for a multilayer wiring board such as a build-up wiring board, the plating material of the present invention and the inner layer substrate on which the circuit pattern is formed are laminated in order, and electroless plating is performed on the exposed layer A surface. Then, after obtaining a metal layer for a wiring pattern, wiring is formed, and a multilayer printed wiring board can be obtained. 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. At the time of lamination, in order not to contaminate the surface of the layer A, it is preferable to use various resin films as interleaving paper immediately above the layer A side. 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. After that, it is possible to conduct by electroless plating, which is preferably performed.

  In the process of manufacturing the printed wiring board, it is possible to perform a treatment such as a desmear treatment before the electroless plating. Moreover, it is also possible to heat-process after forming an electroless-plating layer in order to improve the adhesiveness of the layer A and an 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, surface roughness, and fine wiring formation property were evaluated as follows.
〔Adhesiveness〕
[Adhesion evaluation]
Plating material having layer A / Plating material with support consisting of support and glass epoxy substrate FR-4 (product number: MCL-E-67, manufactured by Hitachi Chemical Co., Ltd .; copper foil thickness 50 μm And the whole thickness 1.2 mm), and after heating and pressurizing for 6 minutes under the conditions of a temperature of 170 ° C., a pressure of 1 MPa, and a vacuum, the support is peeled off, and then at 130 ° C. for 10 minutes. Heating was carried out at 150 ° C. for 10 minutes and at 180 ° C. for 30 minutes to obtain a laminate made of plating material / 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、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 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
[Fine wiring formability]
Plating material having layer A / Plating material with support consisting of support and glass epoxy substrate FR-4 (product number: MCL-E-67, manufactured by Hitachi Chemical Co., Ltd .; copper foil thickness 50 μm And the whole thickness 1.2 mm), and after heating and pressurizing for 6 minutes under the conditions of a temperature of 170 ° C., a pressure of 1 MPa, and a vacuum, the support is peeled off, and then at 130 ° C. for 10 minutes. Heating was carried out at 150 ° C. for 10 minutes and at 180 ° C. for 30 minutes to obtain a laminate made of plating material / FR-4 having surface A. Thereafter, the exposed surface A was subjected to desmearing and electroless copper plating under the conditions described in Tables 1 and 2 above. Thereafter, a resist pattern is formed on the formed copper plating layer, and after applying electrolytic copper plating with a thickness of 10 μm, the resist pattern is peeled off, and the exposed plated copper is removed with a sulfuric acid / hydrogen peroxide-based etchant, A printed wiring board having a wiring of L / S = 10 μm / 10 μm was produced. The case where the wiring of this printed wiring board was able to produce satisfactorily without a disconnection and a shape defect was evaluated as a pass ((circle)), and the case where the disconnection and the shape defect were produced was evaluated as a rejection (x).

[Synthesis example of polyimide resin]
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 X of polyamic acid having a solid content concentration of 30% by weight 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.

[Formulation Example 1 of solution for forming surface A]
The polyimide resin 1 was dissolved in dioxolane to obtain a solution (a) for forming the layer A. The solid content concentration was set to 20% by weight.
[Formulation Example 2 of solution for forming surface A]
Polyimide resin 1 was dissolved in dioxolane to obtain a solution (b) for forming layer A. The solid content concentration was adjusted to 5% by weight.
[Example 3 of preparation of solution for forming surface A]
In the above polyimide resin synthesis example, the DMF solution X having a solid content concentration of 30% by weight polyamic acid was adjusted to 5% by weight with DMF to obtain a solution (c) for forming the layer A.

[Example of formulation of solution for forming layer B]
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. 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 180 minutes at 665 Pa to obtain polyimide resin 2.

  Polyimide resin 2 was dissolved in dioxolane to obtain a solution (d) having a solid concentration of 25% by weight. On the other hand, YE4000H 32.1 g of biphenyl type epoxy resin manufactured by Japan Epoxy Resins Co., Ltd., 17.9 g of bis [4- (3-aminophenoxy) phenyl] sulfone diamine manufactured by Wakayama Seika Kogyo Co., Ltd., Shikoku Chemicals Epoxy curing agent, 2,4-diamino-6- [2'-undecylimidazolyl- (1 ')]-ethyl-s-triazine, 0.2 g, dissolved in dioxolane and having a solid content of 50% Solution (e) was obtained. 50 g of the solution (d) and 25 g of the solution (e) were mixed to obtain a solution (f) that forms the layer B.

[Example 1]
The solution (a) for forming the layer A was cast-coated on the surface of a polyethylene terephthalate film (trade name Therapy HP, manufactured by Toyo Metallizing Co., Ltd.) serving as a support. Then, it dried at 60 degreeC, 100 degreeC, and 150 degreeC with hot-air oven, and obtained the plating material with a support which consists of layer A / support whose thickness is 25 micrometers. Using the support-equipped plating material, the evaluation was performed according to the evaluation procedures for the various evaluation items described above. The evaluation results are shown in Table 3.

[Example 2]
The solution (b) for forming the layer A was cast-coated on the surface of a polyethylene terephthalate film (trade name Therapy HP, manufactured by Toyo Metallizing Co., Ltd.) serving as a support. Then, it dried at 60 degreeC with the hot-air oven, and obtained the material which consists of a 2 micrometer-thick layer A / support body. Further, the solution (f) for forming the layer B is cast on the surface of the layer A / the material comprising the layer A / support, and dried at 60 ° C., 100 ° C., 150 ° C. in a hot air oven, A plating material with a support composed of a layer B of 38 μm / layer A of 2 μm thickness / support was obtained. Using the support-equipped plating material, the evaluation was performed according to the evaluation procedures for the various evaluation items described above. The evaluation results are shown in Table 3.

Example 3
The solution (b) forming the layer A was cast-coated on the surface of a non-thermoplastic polyimide film (trade name Apical NPI, manufactured by Kaneka Corporation). Then, it dried at the temperature of 60 degreeC with a hot air oven, and obtained the material which consists of a 2 micrometer-thick layer A / polyimide film. Further, the solution (f) for forming the layer B is cast on the surface of the polyimide film made of the layer A / polymer film and dried at a temperature of 60 ° C., 100 ° C., 120 ° C., and 150 ° C. Thus, a plating material comprising a layer B having a thickness of 38 μm / a polyimide film / a layer A having a thickness of 2 μm was obtained. The plating material and a glass epoxy substrate FR-4 (product number: MCL-E-67, manufactured by Hitachi Chemical Co., Ltd .; copper foil thickness 50 μm, overall thickness 1.2 mm) are opposed to each other, For plating with surface A after heating and pressurizing for 6 minutes under conditions of temperature 170 ° C, pressure 1 MPa, and vacuum, then heating at 130 ° C for 10 minutes, 150 ° C for 10 minutes, and 180 ° C for 30 minutes A laminate comprising material / FR-4 was obtained. In addition, at the time of heating and pressing, a polyethylene terephthalate film (trade name Therapy HP, manufactured by Toyo Metallizing Co., Ltd.) is sandwiched immediately above the layer A side, and after heating and pressing, the polyethylene terephthalate film is peeled off, and then the heating is performed. went. Thus, after obtaining the laminated body, it evaluated according to the evaluation procedure of the above-mentioned various evaluation items. The evaluation results are shown in Table 3.

[Comparative Example 1]
The solution (c) for forming the layer A was cast-coated on the surface of a polyethylene naphthalate film (trade name: Teonex Q51, manufactured by Teijin DuPont Films Ltd.) serving as a support. Then, drying and imidation were performed by heating at 60 ° C. and 250 ° C. for 5 minutes in a hot air oven to obtain a material composed of layer A / support having a thickness of 2 μm. Further, the solution (f) for forming the layer B is cast-coated on the surface of the layer A / the material comprising the layer A / support, and dried at 60 ° C., 100 ° C. and 150 ° C. in a hot air oven to obtain a thickness. A plating material with a support composed of a layer B of 38 μm / layer A of 2 μm thickness / support was obtained. Using the support-equipped plating material, the evaluation was performed according to the evaluation procedures for the various evaluation items described above. The evaluation results are shown in Table 4.

  As can be seen from Table 4, in Comparative Example 1, the adhesive strength between the electroless plating film and layer A was low, and fine wiring could not be formed well.

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 plating material according to the present invention is capable of constantly producing a plating material having high adhesion to an electroless plating film without causing a decrease in physical properties in spite of a smooth surface. is there. Therefore, the plating material produced by the method of the present invention can be suitably used for a printed wiring board that requires fine wiring formation. 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 (1)

A step of forming a layer A for forming an electroless plating layer by applying a solution containing a polyimide resin a having a siloxane structure on the support, a step of removing the support, and no application on the layer A A method of forming an electroless plating film, comprising a step of performing electrolytic plating.