JP2006108314A - Metal plated board, manufacturing method thereof, flexible printed wiring board, and multilayer printed wiring board - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a metal plated board along with a flexible printed wiring board and multilayer printed wiring board using the same, which is bendable and excellent in dimension stability, circuit forming property, and conductor peeling resistance. <P>SOLUTION: The fabric substrate of a thermo-setting adhesive sheet is impregnated with an adhesive composition of which elasticity of curing material is 500-7,000 MPa (measured according to ASTM D-882). A plating coat is formed at least one surface of the sheet, which is thermally cured to provide a metal plated board. The flexible printed wiring board uses the metal plated board. The multilayer printed wiring board is obtained by integrally jointing layers on which a circuit is formed to an inner layer circuit board through the adhesive sheet using the metal plated board. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a metal plating substrate, a manufacturing method thereof, a flexible printed wiring board, and a multilayer printed wiring board. More specifically, the present invention is a bendable, dimensional stability, circuit formability, conductor obtained by using a thermosetting adhesive sheet obtained by impregnating a fiber base material with a specific adhesive composition. The present invention relates to a metal-plated substrate such as a copper-clad laminate having excellent peel strength, a method for efficiently producing the same, and a flexible printed wiring board and a multilayer printed wiring board using the metal-plated substrate.

In recent years, with the diversification of electronic devices such as miniaturization and sophistication, the demand for flexible wiring boards is increasing. In this flexible wiring board, a circuit is generally produced on a flexible printed wiring board in which an electrically insulating film and a metal foil are laminated and integrated via an adhesive if necessary, and this flexible circuit board is used for protecting the circuit. The coverlay is bonded and cured through a semi-cured adhesive layer and integrated.
Such flexible wiring boards have flexibility, and are used for wiring of electrical equipment and electronic equipment. The required characteristics include adhesiveness, heat resistance, solvent resistance, electrical characteristics, and dimensional stability. And excellent long-term heat resistance.
Furthermore, in recent years, this flexible wiring board has come to be frequently used for wiring of repeated bending and sliding parts. In addition, the flexible wiring board itself is used for high-density arrangement in a housing space by utilizing its characteristics. There is an increasing demand for thinness, reliability such as bending during use, and incorporation into an extremely narrow gap. Therefore, the flexible wiring board is required to have excellent bending characteristics and bending characteristics as well as its own thinness, in addition to the above required characteristics.

Flexible copper-clad laminates used for such flexible wiring boards generally have an insulating layer made of polyimide film and are very flexible, but do not contain reinforcing materials such as glass cloth. There were drawbacks such as poor handling, low strength, and poor dimensional stability.
A polyimide two-layer copper-clad laminate is also known in which sputtering is performed on the surface of a polyimide film and electroplating is performed thereon. However, although this polyimide two-layer copper-clad laminate is excellent in bendability, circuit formability, and dimensional stability, it has the disadvantages of being expensive and having low conductor peeling strength.

On the other hand, with higher performance and higher speed of electronic devices, high-density mounting and high-density wiring are required for printed wiring boards, and build-up type multilayer printed wiring boards are attracting attention as satisfying the requirements. I'm bathing. Build-up type multilayer printed wiring boards are formed by stacking insulating layers, conductor layers and interlayer connection vias one by one, and various manufacturing methods are known depending on the insulating layer forming method and via forming method. Yes.
Furthermore, in recent years, with the miniaturization of electrical and electronic equipment, multilayer printed wiring boards are increasingly required to be thinner and denser, and build-up type multilayers using adhesive sheets (thermosetting resin sheets). Printed wiring boards have come to be used.

  The present invention, under such circumstances, bendable, excellent in dimensional stability, circuit formability, conductor peel strength, etc., a metal plating substrate such as a copper clad laminate, a method for efficiently producing this, And it aims at providing the flexible printed wiring board and multilayer printed wiring board which use the said metal plating board | substrate.

  As a result of intensive studies to achieve the above object, the inventors of the present invention have made it possible to impregnate a fiber base material with an adhesive composition having an elastic modulus of a cured product in a specific range. A metal plating substrate formed by forming a plating film on at least one surface of the substrate and heat-curing the adhesive sheet can be adapted to the purpose, and the metal plating substrate is, for example, an adhesive specific to a fiber base material. It has been found that at least one surface of a thermosetting adhesive sheet impregnated with the composition is obtained by subjecting the adhesive sheet to heat curing after subjecting it to electroless plating treatment and then electrolytic plating treatment. The present invention has been completed based on such findings.

That is, the present invention
(1) A plating film is formed on at least one surface of a thermosetting adhesive sheet obtained by impregnating a fiber base material with an adhesive composition having a cured product having an elastic modulus of 500 to 7000 MPa (measured according to ASTM D-882). A metal-plated substrate formed and heat-cured on the adhesive sheet,
(2) The adhesive composition is a composition containing (A) an epoxy resin, (B) a curing agent for epoxy resin, (C) a curing accelerator for epoxy resin, (D) an elastomer and (E) an inorganic filler. In the above item (1), the content of the component (D) is 5 to 80% by mass and the content of the component (E) is 3 to 50% by mass based on the solid content of the composition. Metal-plated substrate as described in
(3) The metal-plated substrate according to (1) or (2) above, wherein the elastomer of component (D) is at least one selected from synthetic rubber, rubber-modified polymer compound and polymer epoxy resin,
(4) The metal plating substrate according to (1), (2) or (3) above, wherein the fiber substrate is a glass cloth,
(5) The plating film according to any one of (1) to (4) above, wherein the plating film has a structure in which the electroplating film is formed on the electroless plating film provided on the surface of the thermosetting adhesive sheet. Metal plating substrate,
(6) The metal-plated substrate according to any one of (1) to (5) above, which is a copper-clad laminate,

(7) At least one surface of a thermosetting adhesive sheet obtained by impregnating a fiber base material with an adhesive composition whose cured product has an elastic modulus of 500 to 7000 MPa (measured according to ASTM D-882) is electroless. A method for producing a metal-plated substrate, characterized by subjecting the adhesive sheet to heat-curing after the plating treatment and then the electrolytic plating treatment;
(8) The adhesive composition is a composition containing (A) an epoxy resin, (B) a curing agent for epoxy resin, (C) a curing accelerator for epoxy resin, (D) an elastomer, and (E) an inorganic filler. Item (7) above, wherein the content of the component (D) is 5 to 80% by mass and the content of the component (E) is 3 to 50% by mass based on the solid content of the composition. A method for producing a metal-plated substrate according to claim 1,
(9) A flexible printed wiring board using the metal plating substrate according to any one of (1) to (6) above,
(10) The inner layer circuit board obtained by using the metal plating substrate according to any one of (1) to (6) above is integrally joined to each layer on which a circuit is formed via an adhesive sheet. A multilayer printed wiring board, and (11) the multilayer printed wiring board according to (10) above, wherein the adhesive sheet is made of a resin composition containing an epoxy resin as an essential component;
Is to provide.

  According to the present invention, it is possible to bend using a thermosetting adhesive sheet obtained by impregnating a fiber base material with a specific adhesive composition, and has dimensional stability, circuit formability, and conductor peeling. It is possible to provide a metal plated substrate such as a copper clad laminate having excellent strength, a method for efficiently producing the same, and a flexible printed wiring board and a multilayer printed wiring board using the metal plated substrate.

First, the metal plating substrate of the present invention will be described.
The metal plating substrate of the present invention is obtained by forming a plating film on at least one surface of a thermosetting adhesive sheet obtained by impregnating a fiber base material with an adhesive composition, and heat-curing the adhesive sheet.
There is no restriction | limiting in particular in the fiber base material used for the said metal plating board | substrate, From the well-known base materials conventionally used as a fiber base material, such as a copper clad laminated board, it can use arbitrarily selecting and using. it can. Examples of the fiber base material include inorganic fiber base materials such as glass cloth and glass paper, and organic fiber base materials such as aromatic polyamide fibers, cellulose fibers, and polyester fibers. These may be used individually by 1 type, and may be used in combination of 2 or more types.
The fiber base material is preferably a glass cloth, and the glass cloth can be used without any particular limitation, but a plain weave E glass cloth defined in IPC-EG-140, etc. It is preferable to use it, and in order to give flexibility, a material having a thickness of 50 μm or less such as 1080 type or 1037 type is particularly preferable.

In the metal plating substrate of the present invention, as the adhesive composition impregnated in the fiber base material, a cured product having an elastic modulus in the range of 500 to 7000 MPa is used. If the elastic modulus is 500 MPa or more, handling properties, strength, dimensional accuracy and the like are good, while if it is 7000 MPa or less, it has an appropriate rigidity and hardly breaks or falls off the resin. The elastic modulus of the cured product is preferably in the range of 500 to 7000 MPa, more preferably 800 to 5000 MPa.
In the present invention, the elastic modulus of the cured product of the adhesive composition is measured according to ASTM D-882, and a film-shaped cured product having a thickness of 50 μm is used as a test piece, “DMS6100” manufactured by Seiko Instruments Inc. Is the tensile modulus measured at a frequency of 1 Hz.

Examples of the adhesive composition that gives such a cured product include (A) epoxy resin, (B) epoxy resin curing agent, (C) epoxy resin curing accelerator, (D) elastomer, and (E) inorganic filler. A composition in which the content of the component (D) is 5 to 80% by mass and the content of the component (E) is 3 to 50% by mass can be preferably used.
The epoxy resin of component (A) in the adhesive composition is an epoxy resin having two or more epoxy groups in one molecule, such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, novolak type epoxy resin, glycidyl. Examples thereof include an epoxy resin such as an ether type epoxy resin, an alicyclic epoxy resin, and a heterocyclic type epoxy resin, and a polyfunctional epoxy resin containing a biphenyl skeleton. These may be used individually by 1 type, and may be used in combination of 2 or more types. When imparting flame retardancy, an epoxy resin having a general flame retardant mechanism such as a brominated epoxy resin or a phosphorus-modified epoxy resin can be used.

  These epoxy resins can usually be used by dissolving in a solvent. The solvent only needs to dissolve the epoxy resin, the epoxy resin curing agent, the epoxy resin curing accelerator, the elastomer, and the flame retardant used as required, but the solvent remains in the coating and drying process of the adhesive composition. It is desirable that the solvent has a boiling point of 160 ° C. or lower. Specific examples of the solvent include methyl ethyl ketone, toluene, acetone, ethyl cellosolve, methyl cellosolve, and cyclohexanone. These can be used alone or in combination of two or more.

As the curing agent for the epoxy resin of the component (A), there is no particular limitation as long as it is a compound that is usually used for curing an epoxy resin. Examples of the amine curing system include dicyandiamide and aromatic diamine. Examples of the phenol curing system include phenol novolak resins, quesol novolak resins, bisphenol A type novolak resins, triazine-modified phenol novolak resins, and the like, which can be used alone or in combination of two or more.
The content of the curing agent for epoxy resin is usually about 1 to 50 parts by weight, preferably 5 to 100 parts by weight of the epoxy resin of the component (A), from the viewpoint of balance between curability and physical properties of the cured product. It is selected in the range of 30 parts by mass.

The (C) component epoxy resin curing accelerator is usually used as an epoxy resin curing accelerator, such as 2-ethyl-4-methylimidazole, 1-benzyl-2-methylimidazole, etc. Imidazole compound, boron trifluoride amine complex, triphenylphosphine and the like. These curing accelerators can be used alone or in combination of two or more.
The content of the curing accelerator for epoxy resin is usually about 0.1 to 10 parts by mass with respect to 100 parts by mass of the epoxy resin of the component (A), from the viewpoint of balance between curing acceleration and physical properties of the cured resin. Preferably it is selected in the range of 0.3 to 5 parts by mass.

The elastomer of the component (D) may be any elastomer having a rubber elastic modulus around room temperature. For example, various synthetic rubbers such as acrylic rubber, acrylonitrile butadiene rubber, carboxyl group-containing acrylonitrile butadiene rubber, and rubber-modified polymers. Examples thereof include a compound, a polymer epoxy resin, a phenoxy resin, a modified polyimide, a modified polyamideimide, and the like. These can be used alone or in combination of two or more. Among these, synthetic rubbers, rubber-modified polymer compounds, and polymer epoxy resins are preferable, and carboxyl group-containing acrylonitrile butadiene rubber can be particularly preferably used.
The content of the elastomer is usually selected in the range of 5 to 80% by mass, preferably 10 to 60% by mass, based on the solid content of the composition. If the content is 5% by mass or more, the elastic modulus is moderately reduced, and the resin does not easily fall off. On the other hand, if the content is 80% by mass or less, the impregnation property to the fiber base material is good.

  There is no restriction | limiting in particular as an inorganic filler of the said (E) component, A talc, an alumina, aluminum hydroxide, magnesium hydroxide, a fused silica, a synthetic silica etc. are mentioned, These are used individually or in combination of 2 or more types. be able to. Although there is no restriction | limiting in particular about the particle size of this inorganic filler, It is an average particle diameter and is about 0.5-5 micrometers normally, Preferably it is 0.5-2 micrometers. Further, the content is preferably 3 to 50% by mass, more preferably 10 to 30% by mass, based on the solid content of the composition. If the content is 3% by mass or more, Deterioration of workability due to tackiness of the resulting thermosetting adhesive sheet and dimensional change are less likely to be adversely affected. On the other hand, if it is 50% by mass or less, it has an appropriate elastic modulus and suppresses the resin from falling off. Can do.

In the adhesive composition, in addition to the components (A) to (E), in order to impart flame retardancy, for example, a bromine compound, a phosphorus compound, a metal hydrate, and the like can be blended. Furthermore, if necessary, fine powder inorganic or organic fillers, pigments, deterioration inhibitors and the like can be appropriately contained within a range not impairing the effects of the present invention.
The adhesive composition can be prepared by, for example, uniformly dissolving or dispersing each of the above components in a medium composed of methyl ethyl ketone, toluene, acetone, ethyl cellosolve, methyl cellosolve, cyclohexanone, or a mixture thereof. it can.
In the present invention, the adhesive composition thus obtained is adjusted to a concentration suitable for impregnating the fiber base material using the medium, and fibers such as glass cloth are used according to a conventionally known method. The substrate is impregnated and dried to produce a thermosetting adhesive sheet. When glass cloth is used as the fiber base material, it is preferable to coat the glass cloth with a coupling agent such as a silane compound in order to improve adhesiveness with the resin.

The metal plating substrate of the present invention is obtained by forming a plating film on at least one surface of the thermosetting adhesive sheet and heat-curing the adhesive sheet.
The plating film is not particularly limited, and may be an electroless plating film or a structure in which an electroplating film is formed on the electroless plating film. Those having a structure in which an electrolytic plating film is formed on an electroless plating film provided on the surface of the substrate are preferable. Moreover, as a kind of plating metal, if it is a normal use for printed wiring boards, electroless copper plating and electrolytic copper plating are common. In this case, the obtained metal plating substrate is a copper clad laminate.
The thickness of the plating film in the metal plating substrate of the present invention is usually about 1 to 35 μm, preferably 2 to 8 μm.

Next, the manufacturing method of the metal plating board | substrate of this invention is demonstrated.
In the method of the present invention, at least one surface of a thermosetting adhesive sheet obtained by impregnating a fibrous base material with the adhesive composition having a cured product having an elastic modulus of 500 to 7000 MPa is first subjected to electroless plating. Then, after performing an electroplating treatment, the desired metal plating substrate can be manufactured by heating and curing the adhesive sheet.
In the method of the present invention, the electroless plating treatment and the electrolytic plating treatment are generally performed as follows: (1) desmear treatment step (conditioning, desmear), (2) electroless plating step (conditioning, microetching, (Pre-catalyzing, catalyzing, acceleration, electroless plating) and (3) electrolytic plating steps are performed in sequence.

[Desmear treatment process]
When electroless plating is applied to the thermosetting adhesive sheet, the state of the resin surface serving as a base greatly affects the adhesion and uniformity of plating. Therefore, in this step, first, conditioning (resin swelling treatment) is performed, and after washing with water, desmear treatment is performed. The desmear treatment is usually performed at a temperature of about 60 to 80 ° C. using an alkaline potassium permanganate solution. After the desmear treatment, it is washed with water, subjected to a reduction treatment as necessary, and then washed with water and dried before being sent to the next step.

[Electroless plating process]
In this step, the desmear completed product obtained in the previous step is first conditioned using a surfactant to facilitate catalyst adsorption on the resin surface. Next, after performing micro-etching treatment with a solution containing persulfate or sulfuric acid-hydrogen peroxide, acid washing with sulfuric acid and water washing are performed.
Next, the treated product is immersed in a catalyzing solution (including a catalyst) to adsorb a catalyst for starting electroless plating. At this time, in order to stabilize the catalyzing solution, the catalyst is immersed (pre-dip) in the pre-catalyzing solution immediately before being immersed in the catalyzing solution as it is without being washed with water, and the catalyzing process is performed. The catalyzing solution is a solution containing a complex compound or colloid of tin-palladium.
Next, after rinsing with water, the substrate is immersed in a strongly acidic accelerator solution that removes unnecessary portions of the complex compound, subjected to acceleration, washed with water, and subjected to electroless plating. When this electroless plating is electroless copper plating, the bath composition is generally copper salt (CuSO ₄ etc.)
Reducing agent (HCHO etc.)
pH adjuster (NaOH, KOH, etc.)
Chelating agent (EDTA, Rochelle salt)
Additives (polyethylene glycol, piperidyl, etc.)
It is. The electroless copper plating treatment is usually carried out by using a plating bath having the above composition and immersing it in a solution at about 50 ° C., performing gentle stirring and filtration.
After the electroless plating treatment, it is sent to the next process after washing and drying.

[Electrolytic plating process]
The electroless plating product obtained in the above step is subjected to an electrolytic plating treatment after acid cleaning and water washing. When this electrolytic plating treatment is an electrolytic copper plating treatment, an acidic copper sulfate bath is usually used as a plating bath, and copper sulfate plating is performed by a conventionally known method.
After the electrolytic plating process is performed to a predetermined thickness, in order to collect the attached plating solution, it is dipped in a drag-out tank, washed with water, and then subjected to a rust prevention process as necessary. A benzotriazole-based rust inhibitor is usually used for the rust prevention treatment. After rust prevention, wash and dry.

Thus, after forming a plating film on at least one surface of the thermosetting adhesive sheet, the adhesive sheet is preferably heat-cured at a temperature of 100 to 200 ° C., more preferably 120 to 195 ° C. The metal plating substrate of the invention is obtained.
This metal plating substrate is bendable and has excellent dimensional stability, circuit formability, conductor peeling strength, and the like. As the metal plating substrate, a flexible copper clad laminate is particularly suitable.

The present invention also provides a flexible printed wiring board and a multilayer printed wiring board using the metal plating substrate described above.
The flexible printed wiring board of the present invention comprises a coverlay having a circuit formed on the metal plating substrate, preferably a flexible copper-clad laminate, drilled with holes if necessary, and then with holes formed at predetermined locations. It can be produced by a general method such as repeated heating and pressure forming.
In addition, the multilayer printed wiring board of the present invention has a structure in which each layer on which a circuit is formed is integrally bonded to an inner circuit board obtained using the above-described metal plating substrate via an adhesive sheet. For example, it can be manufactured by a build-up process or the like. As said adhesive sheet, what consists of a resin composition which has an epoxy resin composition as an essential component is used preferably.

EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.
In addition, the various characteristics in each example were calculated | required according to the method shown below.
(1) Conductor peeling strength in copper-clad laminate It conformed to IPC TM-650 2.4.8.
(2) Dimensional change rate after pressing and after reflowing in a flexible printed wiring board substrate with a reinforcing plate (a) After pressing It conformed to IPC TM-650 2.4.39.
(B) After reflow It conformed to IPC TM-650 2.4.39.
(3) Flexibility of flexible printed wiring board substrate with reinforcing plate compliant with JIS C 6471.

Example 1
(1) Production of glass cloth-containing adhesive sheet 36 parts by mass of carboxyl group-containing acrylonitrile butadiene rubber [manufactured by Zeon Corporation, trade name “Nipol 1072”], brominated bisphenol A type epoxy resin [manufactured by Toto Kasei Co., Ltd., trade name “YDB -400 ", epoxy equivalent 400] 18.5 parts by mass, brominated novolac epoxy resin [manufactured by Nippon Kayaku Co., Ltd., trade name" BREN S ", epoxy equivalent 284] 18.5 parts by mass, 4,4'-diamino 6.9 parts by mass of diphenylsulfone (amine equivalent 62), 0.2 part by mass of 2-ethyl-4-methylimidazole, 20 parts by mass of aluminum hydroxide, and N, N′-di-2-naphthyl-antioxidant 1 part by mass of p-phenylenediamine is dissolved or dispersed in a mixed medium of methyl ethyl ketone / toluene mass ratio = 6/4, and an adhesive solution is obtained. This was impregnated into glass cloth “AS1501 / AS891AW” (1545 type manufactured by Asahi Sebel) and dried at 180 ° C. for 3 minutes to produce a glass cloth-containing adhesive sheet having a resin content of 40 mass%.
(2) Production of copper-clad laminate An adhesive sheet containing glass cloth obtained in (1) above is subjected to a desmear treatment step under the conditions shown in Table 1, and an electroless copper plating treatment step under the conditions shown in Table 2. After sequentially performing the electrolytic copper plating treatment step under the conditions shown in No. 3, a copper clad laminate having a thickness of 0.045 mm was produced by heat curing at 170 ° C. for 60 minutes. The peel strength of the conductor in this copper clad laminate was measured, and the results are shown in Table 4.
(3) Fabrication of substrate for flexible printed wiring board with reinforcing plate After bonding a 125 μm thick polyimide reinforcing plate with a 25 μm thick bonding sheet [“TFA-880” manufactured by Kyocera Chemical Co., Ltd.] using a 120 ° C. laminating roll. Then, the board release paper is peeled off, and the copper-clad laminate obtained in (2) above is overlapped with this, and heat-pressed and bonded for 20 minutes under the conditions of 160 ° C. and 0.5 MPa, for flexible printed wiring boards with reinforcing plates A substrate was produced.
With respect to this flexible printed wiring board substrate with a reinforcing plate, the dimensional change rate and the flexibility after pressing the reinforcing plate and after reflowing were determined, and the results are shown in Table 4.

Example 2
(1) Preparation of glass cloth-containing adhesive sheet Carboxyl group-containing acrylonitrile butadiene rubber “Nipol 1072” (supra) 9.5 parts by mass, brominated bisphenol A type epoxy resin “YDB-400” (supra) 35.9 mass Parts, brominated novolac epoxy resin “BREN S” (supra) 35.9 parts by mass, 4,4′-diaminodiphenylsulfone (amine equivalent 62) 13.4 parts by mass, 2-ethyl-4-methylimidazole 0 .3 parts by mass, 5 parts by mass of aluminum hydroxide, and 0.5 parts by mass of N, N′-di-2-naphthyl-p-phenylenediamine as an anti-aging agent were mixed in a methyl ethyl ketone / toluene mass ratio = 6/4. An adhesive solution was prepared by dissolving or dispersing in a medium, and this was prepared as a glass cloth “AS1501 / AS891AW” (15 by Asahi Sebel Corporation). 45 type) was impregnated and dried at 180 ° C. for 3 minutes to produce an adhesive sheet containing glass cloth having a resin content of 40% by mass.
Hereafter, it implemented similarly to (2) and (3) of Example 1. The results are shown in Table 4.

Comparative Example 1
The adhesive liquid of Example 1 was apply | coated to the release film so that the thickness after drying might be set to 35 micrometers, and the adhesive sheet was manufactured by drying at 180 degreeC for 3 minute (s).
It implemented similarly to (2) and (3) of Example 1 except having used the said adhesive sheet instead of the adhesive sheet containing glass cloth. The results are shown in Table 4.

Comparative Example 2
The adhesive liquid of Example 2 was apply | coated to the release film so that the thickness after drying might be set to 35 micrometers, and the adhesive sheet was manufactured by drying at 180 degreeC for 3 minute (s).
It implemented similarly to (2) and (3) of Example 1 except having used the said adhesive sheet instead of the adhesive sheet containing glass cloth. The results are shown in Table 4.

Comparative Example 3
It implemented similarly to (2) and (3) of Example 1 except having used the polyimide film [Ube Industries, Ltd. make, brand name "UPILEX XT"] of thickness 25micrometer instead of the adhesive sheet containing glass cloth. . The results are shown in Table 4.

（注）
マキュダイザ−９２０４：日本マクダーミッド社製、商品名
マキュダイザー９２７５：日本マクダーミッド社製、商品名
マキュダイザー９２７６：日本マクダーミッド社製、商品名
マキュダイザー９２７９：日本マクダーミッド社製、商品名

(note)
Macudizer-9204: manufactured by Nihon McDermid Co., Ltd., trade name Macudizer 9275: manufactured by Nihon McDermid Co., Ltd., trade name Macudizer 9276: manufactured by Nihon McDermid Co., Ltd.

（注）
ＰＲ−３１２ ：日本マクダーミッド社製、商品名
メテックスＧ−５Ｓ ：日本マクダーミッド社製、商品名
メテックス９００８Ｌ：日本マクダーミッド社製、商品名
マクチベート１０ ：日本マクダーミッド社製、商品名
メテックス９０７４ ：日本マクダーミッド社製、商品名
メテックス９０７５ ：日本マクダーミッド社製、商品名
ＣＵ−１５０ＡＣ ：日本マクダーミッド社製、商品名
ＣＵ−１５０Ｂ ：日本マクダーミッド社製、商品名

(note)
PR-312: Made by Nihon McDermid Co., Ltd., trade name Metex G-5S: Made by Nihon McDermid Co., Ltd., trade name Metex 9008L: Made by Nihon Mcder Mid Co., Ltd., trade name Mactivate 10: Made by Nihon McDermid, Inc. , Trade name Metex 9075: made by Nihon McDermid Co., Ltd., trade name CU-150AC: made by Nihon McDermid Co., Ltd.

（注）
ＥＣ−１０３Ａ ：日本マクダーミッド社製、商品名
ＥＣ−１０３Ｄ ：日本マクダーミッド社製、商品名
メテックスＭ−６６７：日本マクダーミッド社製、商品名

(note)
EC-103A: Made by Nihon McDermid Co., Ltd., trade name EC-103D: Made by Nihon McDermid, Inc.

  As is apparent from Table 4, by using a plastic polymer component in the adhesive composition, plating can be performed before curing, and bending using an adhesive sheet in which the above composition is impregnated into a glass cloth. It is possible to manufacture a plated substrate that is excellent in dimensional stability, circuit formability, peel strength, and dimensional stability.

The metal plating substrate of the present invention is a bendable, dimensional stability, circuit formability, conductor obtained by using a thermosetting adhesive sheet obtained by impregnating a fiber base material with a specific adhesive composition. It has excellent peel strength and is suitably used for flexible printed wiring boards and multilayer printed wiring boards.

Claims (11)

  Forming a plating film on at least one surface of a thermosetting adhesive sheet obtained by impregnating a fiber base material with an adhesive composition having an elastic modulus of 500 to 7000 MPa (measured according to ASTM D-882); A metal plating substrate, wherein the adhesive sheet is heat-cured. The adhesive composition comprises (A) an epoxy resin, (B) a curing agent for epoxy resin, (C) a curing accelerator for epoxy resin, (D) an elastomer, and (E) an inorganic filler, The metal plating according to claim 1, wherein the content of the component (D) is 5 to 80% by mass and the content of the component (E) is 3 to 50% by mass based on the solid content of the composition. substrate.   The metal-plated substrate according to claim 1 or 2, wherein the elastomer of component (D) is at least one selected from synthetic rubber, rubber-modified polymer compound and polymer epoxy resin.   The metal-plated substrate according to claim 1, 2 or 3, wherein the fiber base material is a glass cloth.   The metal plating substrate according to any one of claims 1 to 4, wherein the plating film has a structure in which an electrolytic plating film is formed on an electroless plating film provided on a surface of a thermosetting adhesive sheet.   It is a copper clad laminated board, The metal plating board | substrate in any one of Claims 1-5.   Electroless plating treatment is applied to at least one surface of a thermosetting adhesive sheet obtained by impregnating a fiber base material with an adhesive composition having a cured product having an elastic modulus of 500 to 7000 MPa (measured according to ASTM D-882). And then subjecting the adhesive sheet to heat-curing after the electrolytic plating treatment.   The adhesive composition comprises (A) an epoxy resin, (B) a curing agent for epoxy resin, (C) a curing accelerator for epoxy resin, (D) an elastomer, and (E) an inorganic filler, The metal-plated substrate according to claim 7, wherein the content of the component (D) is 5 to 80% by mass and the content of the component (E) is 3 to 50% by mass based on the solid content of the composition. Manufacturing method.   The flexible printed wiring board formed using the metal plating board | substrate in any one of Claims 1-6.   The multilayer printed wiring board formed by integrally bonding each layer which formed the circuit to the inner-layer circuit board obtained using the metal plating board in any one of Claims 1-6 via an adhesive sheet. The multilayer printed wiring board according to claim 10, wherein the adhesive sheet is made of a resin composition containing an epoxy resin as an essential component.