WO1980000294A1 - Method of fabricating printed circuits - Google Patents

Method of fabricating printed circuits Download PDF

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Publication number
WO1980000294A1
WO1980000294A1 PCT/JP1979/000171 JP7900171W WO8000294A1 WO 1980000294 A1 WO1980000294 A1 WO 1980000294A1 JP 7900171 W JP7900171 W JP 7900171W WO 8000294 A1 WO8000294 A1 WO 8000294A1
Authority
WO
WIPO (PCT)
Prior art keywords
adhesive layer
adhesive
foil
insulating substrate
roughened
Prior art date
Application number
PCT/JP1979/000171
Other languages
French (fr)
Japanese (ja)
Inventor
J Kanoh
K Ikari
H Tomii
T Takamura
Original Assignee
Tokyo Shibaura Electric Co
J Kanoh
K Ikari
H Tomii
T Takamura
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP8459478A external-priority patent/JPS5512716A/en
Priority claimed from JP9317278A external-priority patent/JPS605237B2/en
Priority claimed from JP9317378A external-priority patent/JPS5521105A/en
Application filed by Tokyo Shibaura Electric Co, J Kanoh, K Ikari, H Tomii, T Takamura filed Critical Tokyo Shibaura Electric Co
Publication of WO1980000294A1 publication Critical patent/WO1980000294A1/en

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Classifications

    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00Apparatus or processes for manufacturing printed circuits
    • H05K3/40Forming printed elements for providing electric connections to or between printed circuits
    • H05K3/42Plated through-holes or plated via connections
    • H05K3/425Plated through-holes or plated via connections characterised by the sequence of steps for plating the through-holes or via connections in relation to the conductive pattern
    • H05K3/426Plated through-holes or plated via connections characterised by the sequence of steps for plating the through-holes or via connections in relation to the conductive pattern initial plating of through-holes in substrates without metal
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00Apparatus or processes for manufacturing printed circuits
    • H05K3/38Improvement of the adhesion between the insulating substrate and the metal
    • H05K3/381Improvement of the adhesion between the insulating substrate and the metal by special treatment of the substrate
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00Apparatus or processes for manufacturing printed circuits
    • H05K3/38Improvement of the adhesion between the insulating substrate and the metal
    • H05K3/386Improvement of the adhesion between the insulating substrate and the metal by the use of an organic polymeric bonding layer, e.g. adhesive
    • H05K3/387Improvement of the adhesion between the insulating substrate and the metal by the use of an organic polymeric bonding layer, e.g. adhesive for electroless plating
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/01Dielectrics
    • H05K2201/0104Properties and characteristics in general
    • H05K2201/0133Elastomeric or compliant polymer
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2203/00Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/02Details related to mechanical or acoustic processing, e.g. drilling, punching, cutting, using ultrasound
    • H05K2203/025Abrading, e.g. grinding or sand blasting
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2203/00Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/03Metal processing
    • H05K2203/0315Oxidising metal
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2203/00Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/09Treatments involving charged particles
    • H05K2203/095Plasma, e.g. for treating a substrate to improve adhesion with a conductor or for cleaning holes
    • H05K2203/097Corona discharge
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2203/00Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/11Treatments characterised by their effect, e.g. heating, cooling, roughening
    • H05K2203/1152Replicating the surface structure of a sacrificial layer, e.g. for roughening
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00Apparatus or processes for manufacturing printed circuits
    • H05K3/10Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
    • H05K3/18Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material
    • H05K3/181Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by electroless plating
    • H05K3/182Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by electroless plating characterised by the patterning method
    • H05K3/184Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by electroless plating characterised by the patterning method using masks

Definitions

  • the present invention relates to a method of forming a conductive pattern using chemical plating, which is maintained in a method of forming a blind circuit.
  • the slew-hole 9-circuit reversal is currently in practical use, and the sub-active method is generally used as a manufacturing method.
  • This manufacturing method is based on
  • the adhesion between the circuit layer (metal layer) formed by the plating and the substrate on the insulating substrate is inferior to that of the 1-layer laminate, so that the circuit layer is formed.
  • the disadvantage is that the reliability of the printed circuit is poor.
  • an adhesive layer (base layer) containing -tril rubber as a main component, for example, is provided on the surface to which the non-functional non-glutamine is applied.
  • a method has been proposed in which a hydrous acid solution is used for hydrophilization and chemical plating is applied.However, this method does not provide sufficient adhesion and also uses a chromic acid solution. In order to prevent pollution caused by chrome, waste liquid treatment equipment is required and desirable.
  • an object of the present invention is to provide a method for manufacturing a printed circuit board having excellent adhesion between a circuit layer and a substrate and capable of producing no pollution problem.
  • ⁇ > Further object of the invention process is the ⁇ child a method for producing ⁇ already resistant to nearest given text Lube Ri down bets ⁇ plate with cylinder ⁇ 0
  • an insulating substrate having an adhesive layer mainly composed of a gen-based synthetic rubber whose surface is roughened, and To form a conductive pattern on the surface of the adhesive layer that has been subjected to a discharge process and to the surface of the adhesive layer that was previously treated by corona, and to provide a method for forming a printed circuit. Is done.
  • the refractory having the adhesive layer forms an adhesive layer mainly composed of a gen-based synthetic rubber on the insulating base, and the adhesive layer is It is provided by mechanically polishing the surface.
  • the insulating substrate having the adhesive layer may be made of an aluminum foil or a copper foil having an uneven surface formed by anodizing treatment.
  • An adhesive mainly composed of a gen-based synthetic rubber is applied thereon and dried to form an adhesive layer in a semi-cured state.
  • FIG. 1D show the printer according to the present invention.
  • FIG. 2A is a cross-sectional view showing a specific example of a method for fabricating a printed circuit
  • FIG. 2D is a sectional view showing a specific example of a method for manufacturing a printed circuit according to this method. It is a cross-sectional view showing a dislike!
  • 3Ag and 3Bg are cross-sectional views showing one S of the step of roughening the adhesive layer.
  • Figure 1A shows an insulation base with a through hole 10
  • Examples of the insulating substrate 1 2 include a glass substrate, a glass slope ceramic, an insulating substrate, and an insulating substrate obtained by coating the surface of a metal plate with insulating chyme. It can be.
  • the adhesive used in the present invention is an adhesive containing a gen-based synthetic rubber as a main component.
  • the gen-based synthetic rubber include a butadiene polymer and a butadiene styrene copolymer. Coal, butadiene end-clip-tolyl copolymer, isosobrengomu, or croproprengome. These polymerized copolymers or copolymers may be used as they are. However, in order to improve their electrical properties, heat radiation properties, and shochu properties, thermosetting of epoxy resins, phenolic resins, etc. It is preferable to add a water-soluble resin. Also, silica gel that serves as a reinforcing agent,
  • a "adhesives based di E emissions-based synthetic rubber” we leave for used in the specification incense of 0 may be added to the charge and ⁇ of
  • the invention for providing the structure shown in FIG. 1A by using an adhesive as described above illustrates two methods. This involves directly applying ⁇ to 12 to form an adhesive coating, which is then mechanically polished.
  • the solution of the above (1) is impregnated and coated on a glass base material, and then semi-cured, and this is overlaid on a bridder used for laminating or manufacturing a laminated board. How to generate at the same time.
  • the coated adhesive layer is sufficiently cured in advance of corona release, but it is semi-cured at the time of corona release. As a matter of fact, it may be fully charged after processing or after chemical plating.
  • a method of roughening the adhesive layer by mechanical polishing there are a liquid honing method in which a slurry composed of an abrasive and a liquid is sprayed in a pressurized state, These methods include the dry horning method in which the abrasive is sprayed with powder, the method of brushing the adhesive layer, and the method of rubbing the surface of the adhesive with a brush. Can be used alone or in combination o
  • the particle size of the abrasive is preferably in the range of 400 to 800 mesh (average particle size of 10 to 50 ⁇ ). If the mesh is not in the mesh, it is polished! ? Although it is possible to obtain a rough surface with deep irregularities, the adhesion is not improved, and the adhesion is reduced on the 100 ⁇ mesh because the concave ft of the rough surface is shallow. O
  • / WIP Apply adhesive on 3 l and dry image to color the adhesive layer 11 in a semi-cured state, as shown in Fig. 3B re and the adhesive layer and insulating substrate 12
  • the hay is layered so that it comes into contact with the bribreda, and when ripening and pressing, the ic is integrally molded.
  • V-acid method sulfuric acid method, oxalic acid method, chromic acid method and the like are known.
  • the oxidized foil used for kishiki is obtained by oxidizing the foil in a solution mainly composed of ⁇ 1-acid-acid ⁇ -silk.
  • Ru can be for the flights to those used in ordinary copper-clad laminate ⁇ 0
  • Wire coating, roll coating, force coating, printing, etc. 3 ⁇ 4 Apply any method to the surface of the positive S oxide layer 0 Make this adhesive layer semi-cured
  • the heating conditions required for the method depend on the type of solvent used for the adhesive solution and the ease of curing of the adhesive resin used, and therefore cannot be stated unconditionally. However, the solvent remaining in the adhesive is sufficiently small, and it is necessary to experimentally determine the conditions under which the aluminum foil and the insulated substrate are sufficiently adhered when integrally molded.
  • a temperature of 140 to 190 ° C and a temperature of 50 to : 150 Zci pressure is normal.
  • the electrical, mechanical, and chemical protrusions inherent in the insulating substrate are impaired. Conditions are required.
  • the bridder becomes an insulated board by this integral molding.
  • foil 3 1 integrally molded as on fel 3 ⁇ 4 ⁇
  • the surface roughness of the adhesive agent 11 roughened by the first and second methods on J3 ⁇ 4 is generally 0.5 07 / ⁇ , preferably 1.4 44. .
  • the roughened surface 11a of the adhesive layer 11 provided on the insulating substrate 12 as above is subjected to corona discharge treatment.
  • Figure IB In the case of the corona discharge furnace used in the present invention, the difference between the direct current corona and the alternating corona can be used.
  • the high-frequency corona also has a vacuum system, a spark gap system, a solid state system, and the like, which have different frequencies and high-frequency waveforms from the circuit, but any of these systems can be used. is there.
  • the force increases from about 38 dyne / at to more than 52 dyne.
  • the non-compressing using a chemical copper plating bath or a chemical-nickel plating bath is carried out in the same manner as before.
  • Gist layer 13 was formed by printing or photographic methods and the above plating
  • the desired metal layer ie, the path layer 14 is covered with the resist layer and formed on the adhesive layer and on the inner surface of the through hole (Fig. 1D). ).
  • o-Trill Gum (Nippon Zeon Co., Ltd., trade name; Haika 1 072 2) with a weight of 20% 50% by weight of lutetone solution ... 250 weight metal o phenol tree (Mitsubishi Gas Chemical Co., Ltd., trade name; Nikanol —
  • the adhesive port liquid is applied to a layer of L6 ⁇ single epoxy resin laminated board with a wiper so that the thickness of the dry coating is about 301. After drying for 40 minutes in a 160 ° C oven and hardening completely, the above adhesive surface was immersed in liquid using a 400mesh random. The conditions were as follows.
  • the above-mentioned substrate with an adhesive treated with a corona pack was chemically bred to a thickness of about 400 mm by a usual method.
  • a 328 L process (trade name) manufactured by Shipley was used.
  • electroplating was performed as necessary: the thickness of the Sanju foil was increased to about 30.
  • Appearance after chemical copper plating and adhesion according to J is C-6481 CAS M 1229—response), adhesion strength between breeding foil and sarcasm board was as shown in Table 1.
  • the number in parentheses is the number of congenital cycles when the laminating plate with adhesive was continuously passed through the corona treatment machine.
  • Anodizing treatment was performed using a 50-mm-thick luminous-foil foil (material: ⁇ A30 ⁇ -18) under the following conditions.
  • Pretreatment liquid 1 Rukari, Soak, Cleaner, bath humidity; 90TC, hour
  • Pre-treatment liquid 2 Hydrogen ammonium hydrogen, bath temperature; room temperature, time; 3
  • Electrolytic solution 10 weight H 3 P0 4, the current density; (8 AZdm 2,
  • the upper ⁇ -adhesive-coated aluminum foil is laminated with the upper adhesive surface in contact with the upper surface of the ⁇ 6 3 ⁇ 4 3 ⁇ 4 ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ And molded at a pressure of 20 i3 ⁇ 4 / for 160 min.
  • a Zhen-layer board in which aluminum foil was firmly adhered to the cured paper epoxy resin substrate was obtained.
  • the aluminum alloy was heated for 5 minutes by using an etching solution obtained from an aqueous solution containing 5 weights of a cassette soda and 0.5 weights of a dalcon soda added to the tank.
  • the foil and the lower electrode layer were removed to remove the concave adhesive surface.
  • the substrate with the adhesive subjected to the corona discharge treatment was chemically copper-plated to a thickness of about 400 mm by a usual method.
  • Pretreatment solution Al-Li-Salk-Tarina, bath temperature; OtJ, time;
  • Electrolyte 30 weight ⁇ 3 ⁇ 0 4, the current density; A8AZdrf, bath temperature;
  • the same adhesive solution used in Examples 1 to 5 was sublimated, and the surface was concaved by frequent treatment.
  • the thickness of the foil was 35 mm.
  • the dry coating was applied to a thickness of about 30 ⁇ , and dried in an oven at 120 X) for 20 minutes to obtain a semi-cured state.
  • the above-mentioned substrate with an adhesive that has been subjected to a ⁇ -discharge treatment was chemically attached to the plating metal layer with a thickness of about 400 mm by the usual method.o
  • a plating bath and pretreatment for attachment were made by Shipple Co., Ltd. Three processes (product names) were used.
  • electro copper plating was applied, and the thickness of Kaburaki was increased to about 30.
  • Table 7 shows the appearance of the plating after chemical promotion and the results of the adhesion and the soldering radiation between the plating film and the laminate, which were examined according to JISC-6481. Table 7
  • Example 22 The copper foil treated in the same manner as used in Examples 2 to 26 and the epoxy-based brible blade were integrally formed via a polybutyral-based adhesive.
  • Table 11 shows the adhesion and soldering heat of the Amihari ridge slicing obtained in Example 8 and the comparative example.
  • Table 8 shows the adhesion strength and solder heat when the copper foil and the suboxide expansion of the copper-clad laminate of No. 1 were etched and the copper was directly attached to the uneven surface obtained by chemical etching.
  • the corona discharge treatment was applied to the uneven surface used in Comparative Example 12 and Comparative Example 12
  • Example 22 Examples 2 to 2 except that a spark gap type corona discharge machine was used instead of the solid-state type corona discharger used in Examples 22 to 26 Electroplated in the same way as 6 o
  • the method for forming a printed circuit in accordance with the present invention it is necessary to use a mouthpiece and the like. These characteristics are the performance of the conventional copper-clad laminate.
  • the corona discharge treatment is a relatively simple facility, has no technical requirements, and has a high processing capacity (15 mZmi ii) for printed circuit boards, and is excellent in productivity. & Industrial applicability
  • the method of forming a printed circuit according to the present invention is useful for forming a printed circuit for ICs, LSIs, and the like. It gives a compromised printed circuit board.

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing Of Printed Wiring (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

Printed circuits are fabricated by first providing an insulated substrate (12) having an adhesive layer (11) mainly composed of diene synthetic rubber with a roughened surface. The roughened surface (11a) of the adhesive layer (11) is then subjected to a corona discharge treatment, being followed by forming conductive patterns (14, 23) onto the surface of the adhesive layer (11) by chemical plating, thereby forming a printed circuit.

Description

明 S 書  Akira S
ブ ン ト羈路の形成方法  Method of forming Bunt Freeway
L技裙分野  L skirts
この発明はブ リ ン ト回絡の影成方法に保 、 特に 化学めつき を利用 して導電パ タ ー ンを形成する ブ リ ン  The present invention relates to a method of forming a conductive pattern using chemical plating, which is maintained in a method of forming a blind circuit.
ト 回路の形成方法に関する。  (G) A method for forming a circuit.
2·背景技術  2 Background technology
近年、 I C , L S I の実用化が進むにと も ¾い、 実装される機器の小型化 , 高性能化 , 及び高侰賴性化 が進められて る。 これに対応してブ リ ン ト 回路辍 :  In recent years, as ICs and LSIs have been put to practical use, devices to be mounted have been reduced in size, improved in performance, and enhanced in reliability. Correspondingly, the print circuit:
対 しても、 高密 ¾ ¾鎵化による小型化 , 高镭賴性化お よび低コ ス ト化が強 く要請されている。 On the other hand, there is a strong demand for miniaturization, high rigidity, and low cost due to high density.
これらの要耩に応える ものと して現在ス ル ー ホ ー ルブ 9 ン ト回路叛が実用化されてお j? 、 その製造方法 と してはサブ ト ラ クティ ブ法が一般的である。 この製 造方法は鎘張 積層菽を出発材料と してス ル ーホ ー ル  To meet these requirements, the slew-hole 9-circuit reversal is currently in practical use, and the sub-active method is generally used as a manufacturing method. This manufacturing method is based on
のための穴あけの後、 化学めつき、 S気めつきを鉋 し、 しかる後に回路パタ ー ン部分とス ル ーホ ール部分を レ ジ ス ト で保護 してから不必要部分の銅箔をエ ッ チ ン グ After drilling holes, plan the chemical adhesion and S adhesion, then protect the circuit pattern and through hole with a resist, and then remove the unnecessary copper foil Etching
除去する も ので、 製造工程が複锥で且つ多大の材料費 が必要で、 到底低コス ト化への要請には応えられ Since it is removed, the manufacturing process is complicated and a large amount of material is required, and the demand for cost reduction can be met at all.
とい う欠点を有する。  It has the disadvantage of:
そこで、 最近、 素弒と して積層板を用い、 化学め つきに よ ^ 所望導罨パタ ーン部 ( 回路パタ ー ン部 ) だ O PI  Therefore, recently, a laminated plate was used as the raw material, and the chemical plating was used. ^ The desired compressing pattern part (circuit pattern part) was used.
、 WIPO~ . けを 択的に任意の厚さで形成させるいわゆるアディ ティ ブ法が ¾発され Tt o この方法によれば、 简翠 *製 造工程でス ル ー ホ ール と圉路バタ ー ン が R時に形成で きるぱか D てる く 、 材料 ftが少 ¾ く て済むと う利点 がぁ乡 β済的 JC有利てある o , WIPO ~. A so-called additive method has been developed to selectively form the metal with an arbitrary thickness. According to this method, the through-hole and the knot road pattern are reduced by R in the green manufacturing process. Occasionally, it can be formed, and the advantage that the material ft is small can be obtained.
しかし上 Ε了ディ ティ ブ法では絶縁基板上に、 め つき によって形成された回路層 ( 金属層 ) と基板との 密着力が痢張 1?積層钣に較べて劣るため、 回路層の剝 雄を招きやすく ブ リ ン ト回路と しての信頼性に劣る欠 点がある。 この回路層と絶緣基板との密着力改善策と して、 絶緣基粳の被めつき面に例えば - ト リ ル ゴムを 主成分とする接着剤層 ( 下地層 ) を設けたのち、 ク ロ ム ¾酸溶液で親水化 ^理し、 化学めつきを施す方法が 提案されているが、 この方法にて も十分 ¾密着力が得 られないほか、 ク ロ ム ¾酸溶液を使用するため、 ク ロ ムに よる公害防止上廃液処理設備を必要と し望ま し く ¾い。  However, in the above-mentioned termination method, the adhesion between the circuit layer (metal layer) formed by the plating and the substrate on the insulating substrate is inferior to that of the 1-layer laminate, so that the circuit layer is formed. The disadvantage is that the reliability of the printed circuit is poor. As a measure to improve the adhesion between the circuit layer and the insulating substrate, an adhesive layer (base layer) containing -tril rubber as a main component, for example, is provided on the surface to which the non-functional non-glutamine is applied. A method has been proposed in which a hydrous acid solution is used for hydrophilization and chemical plating is applied.However, this method does not provide sufficient adhesion and also uses a chromic acid solution. In order to prevent pollution caused by chrome, waste liquid treatment equipment is required and desirable.
したがつてこの発明の目的は改良された了ディ テ ィ ブ法によってプ リ ン ト 回路板を製造する方法を提供 するこ とである。  Accordingly, it is an object of the present invention to provide a method for manufacturing a printed circuit board by an improved method.
ま た、 この発明の目的は回路層と基板との密着性 の優れたブ リ ン ト 回路板を製造で き 、 しかも公害問題 のあま 生じ いブ リ ン ト 回路板の製造方法を提供す るし と レ ¾> ο さらにこの発明の目的は工程が筒单で β済性に寄 与てき るブ り ン ト觀路板の製造方法を赛供するこ とで ある 0 Further, an object of the present invention is to provide a method for manufacturing a printed circuit board having excellent adhesion between a circuit layer and a substrate and capable of producing no pollution problem.と> ο Further object of the invention process is the赛供child a method for producing β already resistant to nearest given text Lube Ri down bets觀路plate with cylinder单0
3·発明の鬨示  3) The invention
* この発明によれぱ、 表面が粗面化されたジ ェ ン系 合成ゴ ムを主成分とする接着剤層を有する絶縁基板を 提供し、 前紀接着剤層の粗面化表面を コ ロ ナ放電処理 に供し、 よび前 Εコ ロナ故« ^理した接着剤層表面 に化学めつき によって導 パタ ー ンを形成する と とか ιβ ら: ί:る ブ リ ン ト回路の形成方法が提供される。  * According to the present invention, there is provided an insulating substrate having an adhesive layer mainly composed of a gen-based synthetic rubber whose surface is roughened, and To form a conductive pattern on the surface of the adhesive layer that has been subjected to a discharge process and to the surface of the adhesive layer that was previously treated by corona, and to provide a method for forming a printed circuit. Is done.
この発钥の第 1 の態様において、 前記接着剤層を 有する絶緣基叛は、 絶緣基坂上にジェ ン系合成ゴ ムを 主成分とする接着剤層を影成 し、 こ の接着剤層の表面 を接械的に研磨するこ とによって提供される。  In the first aspect of this invention, the refractory having the adhesive layer forms an adhesive layer mainly composed of a gen-based synthetic rubber on the insulating base, and the adhesive layer is It is provided by mechanically polishing the surface.
15 この癸明の第 2 の態様において、 前記接着剤層を 有する絶緣基板は、 陽極酸化処理によ 1? 凹凸面を彤成 して ¾るア ル ミ ニ ウ ム箔も し く は銅箔上にジェン系合 成ゴ ムを主成分とする接着剤を塗布、 乾燥して半硬化 状態の接着劑層を形成 し、 この接莆剤層と絶緣基钣と 15 In the second aspect of the invention, the insulating substrate having the adhesive layer may be made of an aluminum foil or a copper foil having an uneven surface formed by anodizing treatment. An adhesive mainly composed of a gen-based synthetic rubber is applied thereon and dried to form an adhesive layer in a semi-cured state.
20 を積層 して加熱 , 加圧するこ とに よって一体と し、 し かる後了ル ミ - ゥ ム箔 も し く は鋦箔をエ ツチン ダ狳去 するこ とに よって提供される。20 are laminated and heated and pressurized to be integrated, and then provided by removing the foil or foil.
·図面の簡単 ¾説明  · Easy drawing ¾Description
第 1 Α図ないし第 1 D 図はこの発明に係るプ リ ン ト 回路の J¾造方法の一具体例を工程厭に示す断面図で ぁ 、 第 2 A ® ¾ し第 2 D図はこの癸勇に係るプリ ン ト回路の製造方法の锥の具体例を工程厭に示す断面 図であ!)、 第 3 A gおよび第 3 B gは接着劑層の粗面 化工程の一 Sを示す断面図である。 Figures 1 to 1D show the printer according to the present invention. FIG. 2A is a cross-sectional view showing a specific example of a method for fabricating a printed circuit, and FIG. 2D is a sectional view showing a specific example of a method for manufacturing a printed circuit according to this method. It is a cross-sectional view showing a dislike! ), 3Ag and 3Bg are cross-sectional views showing one S of the step of roughening the adhesive layer.
5·発钥を実 ½するための最良の形態 5 Best form to execute
この発明をよ 詳細に説明するために、 以下添付 図面に従ってこれを説明する。  BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail with reference to the accompanying drawings.
第 1 A図はス ル ー ホ ー ル 1 0 を設けた絶縁基坂  Figure 1A shows an insulation base with a through hole 10
1 2 の両表面上 ^粗面化表面 1 1 a を有する接着剤層 1 1 を設けた状態を示している。  12 shows a state in which an adhesive layer 11 having a roughened surface 11 a on both surfaces of the substrate 12 is provided.
絶緣基板 1 2 と してはブ ラスチッ ク « , ガ ラ ス坂 セ ラ ミ ック钣 , 稷層板 , 金属板表面を絶縁性樹糜で椟 覆して得られる絶鳜基板 ¾ どを挙げるこ とができ る。  Examples of the insulating substrate 1 2 include a glass substrate, a glass slope ceramic, an insulating substrate, and an insulating substrate obtained by coating the surface of a metal plate with insulating chyme. It can be.
また、 この発明に用 られる接着剤はジェン系合 成ゴ ムを主成分とする接着剤であるが、 ジェン系合成 ゴム と しては例えば、 ブタ ジエン重合体 , ブタ ジエン ス チ レ ン共重合体 , ブタ ジエ ン了 ク リ 口 - ト リ ル共重 合体 , ィ ソ ブレ ン ゴ ム , ある はク ロ ロ プ レ ン ゴ ム ¾ どが挙げられる。 とれらの重合倖または共重合体は、 そのまま 用いても よいが、 その電気的特性 , 射熱性 , 酎藥品性を向上させるためにエ ポ キ シ樹脂 , フ エ ノ ー ル樹脂等の熱硬化性樹脂を加えるこ とが好ま しい o ま た、 補強剤と しての役目を杲すと ころのシ リ カ ゲ ル ,  The adhesive used in the present invention is an adhesive containing a gen-based synthetic rubber as a main component. Examples of the gen-based synthetic rubber include a butadiene polymer and a butadiene styrene copolymer. Coal, butadiene end-clip-tolyl copolymer, isosobrengomu, or croproprengome. These polymerized copolymers or copolymers may be used as they are. However, in order to improve their electrical properties, heat radiation properties, and shochu properties, thermosetting of epoxy resins, phenolic resins, etc. It is preferable to add a water-soluble resin. Also, silica gel that serves as a reinforcing agent,
OMPIOMPI
WIPO ケィ 藪ジルコ ニ ウ ム , ケィ康マダネシ ゥ ム等の充滇剡 を加えてもかまわ 0 の明細香で用いて る 「ジ ェン系合成ゴ ムを主成分とする接着剤」 とはそのジェ ン系合成ゴムを少 * く と も 4 0 〜 6 0重量 # 、 好ま し く は約 5 0重量 含む接着剤 ( 残 は熱硬化性樹盥等) のこ とを 昧する o WIPO Kei bush zirconate two U-time, Kei Yasushi Madaneshi ©-time, such as the GETS A "adhesives based di E emissions-based synthetic rubber," we leave for used in the specification incense of 0 may be added to the charge and滇剡of An adhesive containing at least 40 to 60% by weight *, preferably about 50% by weight of synthetic rubber (the remainder is a thermosetting wood tub) o
さて、 上 ¾のよ う ¾接着剤を用いて第 1 A図に示 す構造を鍉供するために の発明は二つの方法を ¾図 して る o 第 1 の方法は上記接着剤を絶緣基板 1 2 に 直接塗 Φ して接着剤展を形成し、 これを接械的 研磨 することを含むものである。  Now, the invention for providing the structure shown in FIG. 1A by using an adhesive as described above illustrates two methods. This involves directly applying Φ to 12 to form an adhesive coating, which is then mechanically polished.
絶緣基板上に、 接着剤層を形成する方法と しては、 例えば次のよ う ¾方法を使用する ことができ る o  As a method for forming an adhesive layer on an insulating substrate, for example, the following method can be used o
(1) ジェン系合成ゴ ムを主成分とする接着剤を有 接溶媒に溶解し、 こ の溶液を絶縁基板上に塗布、 乾燥 せしめる方法 o  (1) A method in which an adhesive mainly composed of gen-based synthetic rubber is dissolved in a solvent, and the solution is applied to an insulating substrate and dried.
(2) 剥離性の良 基轼上に、 上紀(1)の溶液を塗布 • 乾燥せしめ、 半硬化状態で所定の絶緣基板上に転写 せしめる方法。  (2) A method in which the solution of Ebony (1) is applied to a substrate with good releasability. • It is dried and transferred to a specified insulating substrate in a semi-cured state.
(θ) 通常の穰層板を作製する場台と同様、 羝ゃガ  (θ) Similar to the stand for producing ordinary ferro-plates,
ラ ス基材上に上記 (1)の溶液を含.浸被着せしめた後、 半 硬化状態と し、 これを積層衩ま たは積層板作製に用い るブ リ ブレ ダ上に重層せしめて同時に彤成する方法。  The solution of the above (1) is impregnated and coated on a glass base material, and then semi-cured, and this is overlaid on a bridder used for laminating or manufacturing a laminated board. How to generate at the same time.
¾お、 上記接着剤層の形成において、 いずれの場  ¾ In any of the above formations of the adhesive layer,
OMPI一 /·, WIPO一 « OMPI-I / ·, WIPO-I «
0 合も、 被着彩成 した接着剤層を、 コ eナ放《¾理に先 立ってあらかじめ充分 ¾化せしめてお ぐととが好ま し が、 コ ロ ナ放馕 ½理時点では半硬化状趣に しておき、 コ πナ故 « ½理後も しく は化学めつき後に て、 充 分 «化せしめても よい。 0 In this case, it is preferable that the coated adhesive layer is sufficiently cured in advance of corona release, but it is semi-cured at the time of corona release. As a matter of fact, it may be fully charged after processing or after chemical plating.
この発明にお て、 接械的研磨に よ る接着剤層を 粗面化する方法と しては、 研磨剤と液体から成るス ラ リ ーを、 加圧状態で吹付ける液体ホ ーニング法 , 研磨 剤を粉体で吹付ける ドライ ホ ー -ング法 , 接荣剤層を ブ ラ シ研磨する方法 , ェメ リ 一羝で接薰剤屠表面を摩 擦する方法 ¾ どで、 これらの方法を 独または耝合せ て、 使用する事ができ る o  In the present invention, as a method of roughening the adhesive layer by mechanical polishing, there are a liquid honing method in which a slurry composed of an abrasive and a liquid is sprayed in a pressurized state, These methods include the dry horning method in which the abrasive is sprayed with powder, the method of brushing the adhesive layer, and the method of rubbing the surface of the adhesive with a brush. Can be used alone or in combination o
研磨剤と しては、 了 ラ ン ダム , コ ラ ンダム , カー ボ ラ ン ダム , ガ ラ ス ビ ーズ , ガ ラ ス粉 , ヤシ 3¾ ¾ どを 使用でき るが、 研磨作用が大で、 かつ接着翔層への喰 い込みが少¾い点で、 了 ラ ン ダム , コ ラ ン ダ ムが特に 優れて る。 靳磨材の粒度は、 4 0 0〜 8 0 0 メ ッ シ ュ (平均粒径 1 0〜 5 0 μ ) の範囲が好ま しい。 4 0 0 メ ッ シュ未潢では研磨によ !?深 凹凸の粗面を得るこ と がで き るが、 密着力が向上せず、 1 Ό 0 0 メ ッ シ ュ^ 上では粗面の凹 ftが浅いために密着力は低下するから であ る o  As abrasives, Randam, Corandam, Carborandum, glass beads, glass powder, coconut palm, etc. can be used, but the polishing action is large. In addition, Randam and Crandum are particularly excellent in that they have little bite into the adhesive layer.粒度 The particle size of the abrasive is preferably in the range of 400 to 800 mesh (average particle size of 10 to 50 µ). If the mesh is not in the mesh, it is polished! ? Although it is possible to obtain a rough surface with deep irregularities, the adhesion is not improved, and the adhesion is reduced on the 100Ό mesh because the concave ft of the rough surface is shallow. O
第 2 の方法は、 第 3 A図に示すよ う に、 陽極酸化 して表面に ΰ凹を設けた了ル ミ - ゥ ム も しく は銅の箔  In the second method, as shown in Fig. 3A, aluminum foil or copper foil with anodized and concaved surface is used as shown in Fig. 3A.
ΟΜΡ ΟΜΡ
、/ WIP 3 l に上 te接着蒴を塗布 し乾像して半硬化状態の接着 剤層 1 1 を彩成し、 第 3 B図 re示すよ う にとの接萦剤 層と絶縁基板 1 2 も しく はブ リ ブレダとが接するよ う にとれら两者を秣層 し、 加熟加圧時 ic一体成形し、 し , / WIP Apply adhesive on 3 l and dry image to color the adhesive layer 11 in a semi-cured state, as shown in Fig. 3B re and the adhesive layer and insulating substrate 12 The hay is layered so that it comes into contact with the bribreda, and when ripening and pressing, the ic is integrally molded.
« かる後箔 3 1 をエ ッチン グ、によ 除去する とを含む  «Etching the foil 31 after removal, including removing
ものである。  Things.
一般に、 ア ル ミ ニ ウ ム表面の陽極酸化法と しては  In general, the anodic oxidation of aluminum
V ン酸法 , 蓰豫法 , シユウ酸法 , ク ロ ム酸法る どが知 られているが、 この発明では特に リ ン酸法に よ る陽極  V-acid method, sulfuric acid method, oxalic acid method, chromic acid method and the like are known.
ιβ 酸化処理が好ま しく、 密着力を! ¾上させる 0 ま た、 こ ιβ Oxidation treatment is preferred and adhesion is good! 0
の癸钥に用いる陽萑醭化 ( 亜酸化鏑化 ) 処理した鎘箔 は一殻に ¾1酸酸性の檁酸絹を主成分とする溶液中て銪 箔を陽 S酸化して得られるも ので、 普通銅張積層钣に 用いる ものを便用でき る 0 The oxidized foil used for kishiki is obtained by oxidizing the foil in a solution mainly composed of 酸 1-acid-acid 絹 -silk. , Ru can be for the flights to those used in ordinary copper-clad laminate钣0
15 上記接着剤を陽極酸化処理しぇ箔面に設けるには、  15 To anodize the adhesive and provide it on the foil surface,
接着剤を溶剤に溶解させその接着剤镲液を調整したの  Dissolve the adhesive in the solvent and adjust the adhesive solution
も ワ イ ヤ 一パー コ ー ト , ロ ー ルコ ー ト , 力 一テン コ ー ト 潦 , 印刷 ¾ どの方法に よ 陽 S酸化層表面に塗 布する 0 この接着剤層を半硬化状態にするに必要な加 熱条件は接着剤溶液に使用する溶剤の種類、 使周する 接着剤樹脂の'硬化の し易さに依存するので一概に述べ るこ と ができ い。 しかし、 接着剤中に残存する溶剤 が十分に少 く 、 一体成形した際にア ル ミ - ゥ ム箔と 絶綠基板とが十分に密着する条件を実驗的に求める必 Wire coating, roll coating, force coating, printing, etc. ¾ Apply any method to the surface of the positive S oxide layer 0 Make this adhesive layer semi-cured The heating conditions required for the method depend on the type of solvent used for the adhesive solution and the ease of curing of the adhesive resin used, and therefore cannot be stated unconditionally. However, the solvent remaining in the adhesive is sufficiently small, and it is necessary to experimentally determine the conditions under which the aluminum foil and the insulated substrate are sufficiently adhered when integrally molded.
O PI _ Λ. WIPO - 要がある o —体成形時における加 , 加圧条件は上 接着剤雇を設けた箔と ブ 9ブレ ダを一体成影する麇に は、 接着剤の硬化条件と プ リ ブレ グの硬化条件を一 ¾ させることが望ま し o プ リ ブレダと して «基材にフO PI _ Λ. WIPO- It is necessary to apply o—The pressing and pressurizing conditions during body molding are above. To integrally form the foil with the adhesive and the bladder, the curing condition of the adhesive and the curing condition of the pre-leg O It is desirable to make the
, エノ ール樹糜を含 させたも の、 ガ ラ ス基材にェボキ シ樹脂を含 Sさせたも のを使用する場合には、 1 4 0 〜 1 9 0 ¾の温度、 5 0 〜 : 1 5 0 Zciの圧力が普通で ある。 また、 接着剤層を設けた箔と絶鱖基辍を一体成 形する際には、 絶緣基板が本来有する電気的 , 接械的 w および化学的性突を損わ ¾: 如鹬 , 加圧条件が要求さ れる。 、 ブリ ブ レ ダはこの一体成形 よって絶緣 基板と る o In the case of using a glass base material containing phenolic styrene or a glass base material containing S-box resin, a temperature of 140 to 190 ° C and a temperature of 50 to : 150 Zci pressure is normal. In addition, when integrally forming the foil provided with the adhesive layer and the insulating substrate, the electrical, mechanical, and chemical protrusions inherent in the insulating substrate are impaired. Conditions are required. The bridder becomes an insulated board by this integral molding.
fel上のよ う に一体成形された箔 3 1 付き ¾緣基坂 から箔を除去して H凸のある接着剤層を露出させるに is は、 箔がアル ミ ニ ウ ムの場合、 水漀化ナ ト リ ウ ム水溶 液または塩酸をエ ッ チン グ剤と し、 箔が飼の場合塩化 第二鉄も しく は塩化第二痢の水溶液をエ ッ チン グ剤と し箔をエ ッ チン グ除去する。 こ う して第 1 A図に示す 構造が得られる。  With foil 3 1 integrally molded as on fel ¾ 緣 To remove the foil from the base slope and expose the adhesive layer with H convex, is if the foil is aluminum, water An aqueous solution of sodium chloride or hydrochloric acid is used as an etching agent, and when a foil is used, an aqueous solution of ferric chloride or diarrhea chloride is used as an etching agent, and the foil is etched. Removed. Thus, the structure shown in FIG. 1A is obtained.
s J¾上の第 1 および第 2の方法で粗面化された接薰 剤展 1 1 の表面粗さは一般に 0· 5 〜 7 /< πι、 好ま し く は 1. 4 〜 4. である。 s The surface roughness of the adhesive agent 11 roughened by the first and second methods on J¾ is generally 0.5 07 / <πι, preferably 1.4 44. .
^上の よ う に絶縁基板 1 2上に設けられた接着剤 層 1 1 の粗面化表面 1 1 a を コ ロナ放電処理に供する ( 第 I B図 ) 。 この発明に便用する コ ロナ放竃 ½理に いては直流 コ ロナ , 交 ¾コ ロナの ずれも便用でき るが、 処理面に対して均一も コ ロ ナが得られる高周波 コ ロナが望ま し 。 ま 、 高周波コ ロナについて も回 s 路上から真空方式 , ス パークギャ ッ プ方式 , ソ リ ッ ド ス テー ト方式 どがあ 、 周波数、 高周波波形に差異 があるが、 これらいずれの方式も使用可能である。 ^ The roughened surface 11a of the adhesive layer 11 provided on the insulating substrate 12 as above is subjected to corona discharge treatment. (Figure IB). In the case of the corona discharge furnace used in the present invention, the difference between the direct current corona and the alternating corona can be used. And The high-frequency corona also has a vacuum system, a spark gap system, a solid state system, and the like, which have different frequencies and high-frequency waveforms from the circuit, but any of these systems can be used. is there.
このコ ロ ナ放電処理に よって絶綠基钣と ^後形成 するめつき金属層との密着力が向上する理由は、 機械 The reason why this corona discharge treatment improves the adhesion between the insulating substrate and the subsequently formed metal layer is that mechanical
0 的 ¾研磨処理に よ ]?接着剤表面に形成される大き *凹 凸の一つ一つに、 コ ロ ナ放電処理に よ !? さ らに小さ " 凹 ώが、 形成される と同時にコ ロ ナ放置処理に ょ 表 面が親水化されるため、 化学めつ き の金属層が接着剤 層の十分深 部分から形成されるためと考えられる。0 ¾ ¾ Polishing process ?? The size formed on the surface of the adhesive. ? Since the surface is made hydrophilic when the corona is left at the same time as the smaller "concavities" are formed, the metal layer for chemical bonding is formed from a sufficiently deep part of the adhesive layer. it is conceivable that.
5 実際、 上記接着剤 Sに コ 口 ナ放電処理を旌すと表面張 5 In fact, if the above adhesive S is subjected to
力は約 3 8 dyne/at から 5 2 dyne 以上に増加する。  The force increases from about 38 dyne / at to more than 52 dyne.
この発明にお て、 上記コ ロ ナ放罨処理後は従来 と同様に して化学銅めつき浴や化学- ッ ケ ルめつき浴 を用いた無罨解めつき にょ 乡 、 または のよ 5 ¾無電0 解めつき と電気めつき を併用 して所要のブ リ ン ト 回路 ' を形成する。 す ¾わち、 無電解めつきだけに よってブ リ ン ト 回路を形成するには、 第 1. c 図に示すよ う に、 接着剤層 1 1 の表面に選^的にめっ き レ ジ ス ト 層 1 3 を印刷ま たは写真的手方法によ り形成し、 上記めつき  According to the present invention, after the above-mentioned corona-compressing treatment, the non-compressing using a chemical copper plating bath or a chemical-nickel plating bath is carried out in the same manner as before. ¾Make the required blind circuit 'by using both the zero and the electric plating. That is, in order to form a printed circuit only by electroless plating, as shown in Fig. 1.c, the surface of the adhesive layer 11 is selectively plated. Gist layer 13 was formed by printing or photographic methods and the above plating
OMPI OMPI
醫 o 浴を用 て、 所望の金属層す ¾わち圔路層 1 4 をレ ジ ス ト屠 i よって覆われて ¾ 接着剤層上およびス ル ホ ー ル内表面に形成する ( 第 1 D図 ) 。 Doctor o Using a bath, the desired metal layer, ie, the path layer 14 is covered with the resist layer and formed on the adhesive layer and on the inner surface of the through hole (Fig. 1D). ).
無《解めつき と《気めっき とを併用してブ リ ン ト i @ ¾を彩成する場合は、 第 2 A に示すよ う に、 まず、 接着剤 1 1 層表面全体およびス ル ーホ ー ル 1 0 内表面 に接って上 1£の よ う 4無罨解めつきによ 金属層 2 1 を ¾着し、 ついで所定镩分にめっき レ ジス ト 2 2 を ¾ 着する ( 第 2 Β図 ) ο しかる後、 通常の ¾気めっき  No << When coloring b @ i @@ using a combination of brazing and air plating, first, as shown in 2A, first, the entire surface of the adhesive 11 layer and the thread 1 Attach the inner surface of the hole 10. Attach the metal layer 2 1 with the upper pack of 1 £ 4 without packing, and then attach the plating register 2 2 in a predetermined amount ( Fig. 2) ο After a while, normal hot plating
10 よ 金属屠 2 3 をさ らに被着し ( 第 2 C図 ) 、 レ ジス ト 2 2を除去し、 しかる後レ ジス ト眉直下にある金属 餍 2 1 をエ ッチング除去して所望ブ リ ン ト園路が得ら れる ( 第 2 D図 ) 0 10 Further apply a metal slaughter 23 (Fig. 2C), remove the resist 22 and then remove the metal 餍 21 directly under the resist eyebrows by etching. You can get the Rin Garden Road (Fig. 2D) 0
上 ¾のごと く この洚明によれば、 ク ロ ム ¾酸溶液 15 による処理 ¾ どを ¾せすに しかも強固に密着し、 はん だ射鵲性: S: どの点ですぐれた回路拔が容易に得られる o  As described above, according to this description, even if the treatment with the chromic acid solution 15 is repeated, it is firmly adhered and soldered. Is easily obtained o
下この発明の実 JS Sを Eす。  Below, the actual JSS of the present invention is described.
実 ½例 1 〜 5  Example 1 to 5
下 ¾の材料をホモジナイ ザーで混合した後に、 三 « 本ロ ー ル 、 * よ!?十分均一に混練した o しかる後に、 プチル セ 口 ソ ルブ溶液で 2 5重量 の接着剤溶液に希 釈調整した。  After mixing the following ingredients with a homogenizer, three rolls, * yo! ? After the mixture was kneaded sufficiently uniformly, the mixture was diluted with a solvent solution of butyl cellulose to 25 wt.
o - ト リ ル ゴ ム ( 日本ゼ オ ン鵜製 , 商品名 ; ハ イ カ一 1 0 7 2 ) の 2 0重量 のメ チルェチ ルケ ト ン溶液一… 2 5 0重量瑯 o フ エノ ール樹擻 (三菱ガス化学《軀 , 商品名 ; ニ カ ノ ール — の 5 0重量o-Trill Gum (Nippon Zeon Co., Ltd., trade name; Haika 1 072 2) with a weight of 20% 50% by weight of lutetone solution ... 250 weight metal o phenol tree (Mitsubishi Gas Chemical Co., Ltd., trade name; Nikanol —
51 のメ タ ノ ール港液 ·"··· 5 0重量餺 5 o エポキシ樹癍 ( シェル石油化学《製 , 商品名 51 metal port liquids ····· 50 weight 餺 5 o epoxy resin (Shell Petrochemical Co., Ltd., trade name
: ェ ビ コ ー ト 1 0 0 1 ) の 8 0重量 の メ チ ルェ チルケ ン ト溶液…… 3 1 重量部 o 酸無水物系樹脂硬化剤 ( 日本化案糠製 , 商品 名 ; カ ャハ ー ド C L A ) の 2 0重量 の ブチ 10 ルセ ロ ン ルブ溶液 …… 1 3重量郁 80% by weight of methyl alcohol solution of 1001) ... 31 parts by weight o Acid anhydride resin hardener (Nippon Kadenka Brand, trade name; Kahaha) 20 weight of Butyl 10 Luceron Lube solution …… 13 weight
この接薰剤港液を厚さ : L 6 βの ¾一エポキ シ系積 層板上に、 乾搡塗嫫の厚さが約 3 0 1 に ¾る よ う ヮ ィ ヤ ーパーにて塗布 し、 1 6 0 のオ ー ブン中で 4 0 分間乾燥 してほ 完全に硬化させた o is しかる後、 4 0 0 メ ッ シュのア ラ ン ダムを使用 し て、 上記接着剤表面を液体ホ ー - ン グ処理した β 処理 - 条件は次のとお であった。  The adhesive port liquid is applied to a layer of L6β single epoxy resin laminated board with a wiper so that the thickness of the dry coating is about 301. After drying for 40 minutes in a 160 ° C oven and hardening completely, the above adhesive surface was immersed in liquid using a 400mesh random. The conditions were as follows.
ο 装 置 不二耪機珠製 F — 5型 ο 噴射圧力 & 0 "οί  ο Equipment FUJI MOUSE F-type 5 ο Injection pressure & 0 "οί
ο 咦射钜離 1 5 0 » ο 噴射角度 (接着剤表面に対して ) 9 0° 。 接着剤付.き基板送 速度 0.4 8 01 /^^  ο Ejection 150 ° »ο Spray angle (90 ° with respect to adhesive surface). Substrate feed rate with adhesive 0.4 8 01 / ^^
上記処理に よ 接着剤表面に、 表面粗さ釣 3 の 凹凸を設けた。  By the above treatment, irregularities of surface roughness 3 were formed on the surface of the adhesive.
O PI 鶴 o 装 置 ビラ一社製 モデル ZIKVJ o 印加 i圧 8 5 0 0 V O PI Crane o Apparatus Villa Model ZIKVJ o Applied i pressure 8.50 V
周 波 数 a€ H X 接着剤付き基裉送 速度 5 m/ min o 入力 «力 1 4 5 V 2 A  Frequency a € H X Base speed with adhesive 5 m / min o Input force 1 4 5 V 2 A
o 間ギヤッブ 2· 4 β  o Gearbox 2.4 β
上記の コ ロ ナ放罨処理した接着剤付き基板を、 通 常の方法で厚さ約 4 0 0 0 Αに化学飼めつき した。 め つき浴、 およびめつき前処理にはシ ッ プレ ー社製 328 L プ ロ セス ( 商品名 ) を使用 した。 更に化学めつき後 必要に応じて電気鐦めっきを: し粲箔の厚さを約 3 0 に肉盛 した。 化学銅めつき後の外観及び J i s C - 6481 C AS M 1 229— 対応 ) に準 ¾して 検封 した、 飼箔と稷層板の密着強度篋、 はんた '》熱僚 の結果は、 第 1 表に示すとお i?であった。  The above-mentioned substrate with an adhesive treated with a corona pack was chemically bred to a thickness of about 400 mm by a usual method. For the plating bath and plating pretreatment, a 328 L process (trade name) manufactured by Shipley was used. Further, after the chemical plating, electroplating was performed as necessary: the thickness of the Sanju foil was increased to about 30. Appearance after chemical copper plating and adhesion according to J is C-6481 CAS M 1229—response), adhesion strength between breeding foil and sarcasm board Was as shown in Table 1.
O WIO WI
W1 繽 表 W1 Table
Figure imgf000015_0001
来測定不能…密着力又ははんだ尉熬値を測定するに 足る十分均一るめつきが得られ ¾かつ た。
Figure imgf000015_0001
Unmeasurable from now on ... Sufficient uniform lug was obtained enough to measure the adhesion or soldering value.
m ( ) 中の数字は、 コ ロ ナ処理機に接着剤付き稹 層板を連続的に通 ¾させた時の通遏回数  m The number in parentheses is the number of congenital cycles when the laminating plate with adhesive was continuously passed through the corona treatment machine.
第 1 表の結果から以下が判る o The results in Table 1 show the following: o
① 本発明に従った接着剤層の塗布 , 機械的研磨処理 コ ロ ナ処理の組合わせが著しく 優れたも ので、 密 着力 , はんだ耐熱を向上させるこ と。  (1) The combination of the application of the adhesive layer according to the present invention, the mechanical polishing treatment, and the corona treatment is remarkably excellent, so that the adhesive strength and solder heat resistance are improved.
WIPO T (D コ ロ ナ放電 ½理回数はー闼で十分で、 1 5 mZ»in の送 速度を考臘すると、 本発明の方法は量童に 邃し、 且つ β済性に優れて る。 WIPO T (The number of D corona discharge treatments is sufficient, and considering the feed rate of 15 mZ »in, the method of the present invention is suitable for mass production and is excellent in β quality.
実 ¾例 6および 7 Examples 6 and 7
り 5* ドステー ト型コ ロナ放髦 ½理機の代乡 に、 ス パークギャ ップ型のコ 0ナ放電^理機を用 飽の条 件は実旄例 1 〜 5 と同様に して化学めつき後髦気めつ きを施した。 めっき外観は良好で密着力、 はんだ »熱 値は第 2表に示すとお!?であった。 To 5 * Dosute of preparative corona Ho髦½ physical machine Dai乡, conditions of use saturated the scan Pakugya-up type of co-0 na discharge ^ physical machine in the same manner as the actual旄例1 to 5 chemical Ri After the mess, I gave a fame reminder. Plating appearance is good and adhesion is good. Solder »The heat value is shown in Table 2! ? Met.
2 表 2 Table
Figure imgf000016_0001
Figure imgf000016_0001
この場合も、 コ ロナ^理回数に拘らず、 良好 ¾密着力 はんだ耐熟髖であった。 In this case as well, regardless of the number of times of the corona treatment, good “adhesion strength and soldering resistance” were obtained.
実 ½例 8および 9 Examples 8 and 9
機械的研磨 ½理と して液体ホ ー -ン グ処理の代乡 に、 研磨剤と ブ ラ シ研磨を併して周い、 飽の条件は実 施例 1〜 5 と同様の条件で処理して化学めつき後電気 めっきま でを施 した。. めっき外観は良好で密着力、 は んだ射熱性は第 3表に示すと !? であった。  As a mechanical polishing process, instead of the liquid honing process, a polishing agent and brush polishing are used together, and the conditions of saturation are the same as in Examples 1 to 5. After chemical plating, electroplating was performed. Plating appearance is good and adhesion is good. Solder heat radiation is shown in Table 3! ? Met.
ο 硏 磨 剤 4 0 0メッシュ ァランダム  ο 磨 Abrasive 4 0 0 mesh
OMPI WIPO o ブラシ研磨橡 ¾¾两面スクラバー(センチユ 一社製) 第 3 表 OMPI WIPO o Brush polishing rubber surface scrubber (Centiyu Ichisha) Table 3
Figure imgf000017_0001
以上の実施例の特性試験の結果は J I s
Figure imgf000017_0001
The results of the characteristic tests of the above examples are based on JI s
( 紙エポキシ系鏑張 i>狭層钣の場合 ) 密着力 ; 1· 4  (Paper-epoxy-based Kabari i> Narrow layer 钣) Adhesion;
Ζ»はんだ耐熱僮 ; 1 0秒を @えてお 、 実用的に 十分 ¾篚である。  Ζ »Solder heat resistance: 10 seconds is enough for practical use.
実施例 1 0〜 1 4 Examples 10 to 14
厚さ 5 0 の了ル ミ - ゥ ム箔 ( 材熨 : ΑΙ A30Η- 1 8 ) を用いて下記の条件で陽極酸化処理した。  Anodizing treatment was performed using a 50-mm-thick luminous-foil foil (material: ΑΙA30Η-18) under the following conditions.
前処理液 1 : 了ルカリ · ソーク ·クリーナ,浴湿; 90TC,時  Pretreatment liquid 1: Rukari, Soak, Cleaner, bath humidity; 90TC, hour
; 5分  ; 5 minutes
前処理液 2 : フッ if匕水素アンモ-ゥム,浴温;室温,時間; 3  Pre-treatment liquid 2: Hydrogen ammonium hydrogen, bath temperature; room temperature, time; 3
 Minute
電 解 液 : 10重量 の H3P04,電流密度;( 8 AZdm2, Electrolytic solution: 10 weight H 3 P0 4, the current density; (8 AZdm 2,
浴温: 50 *C ,時間: 15分  Bath temperature: 50 * C, time: 15 minutes
実施例 1〜 5 で用いたと 同 じ接着剤溶液を、 陽極 酸化処理して表面を凹凸に した上記了 ル ミ - ゥ ム箔上  The same adhesive solution used in Examples 1 to 5 was anodized to form an uneven surface on the aluminum foil.
に ワ イ ヤ ーパーにて塗布 し、 1 2 0 TDのオ ーブ ン中で With a wire wiper, and in a 120 TD oven.
O PI WIPO一 - mo 2 0分 ia乾煉して半硬化状態と した o O PI WIPO one-mo 20 minutes ia Dry and semi-hardened o
次に上 ε接着剤村き アル ミ -ゥ ム箔を厚さ ι· 6 « の ¾ェボキシ系稜層板の表襄两面に上 接着剤面を接 して重ね合せ、 多 ¾ヒ ー ト ブレスに入れ 2 0 i¾/ の圧 力で 1 6 0 tJ . 6 0分間の条件で一体成形した。 その 結果硬化 した紙エポキ シ樹脂基材にアル ミ -ゥ ム箔が 強固に密着 した臻層板が得られた。  Next, the upper ε-adhesive-coated aluminum foil is laminated with the upper adhesive surface in contact with the upper surface of the ι 6 ¾ ¾ 稜 キ シ 系 稜 稜 層 層And molded at a pressure of 20 i¾ / for 160 min. As a result, a Zhen-layer board in which aluminum foil was firmly adhered to the cured paper epoxy resin substrate was obtained.
さ らに 5 0 Ϊ5に加滠された 5重量 のカ セィ ソ ー ダ と 0· 5重量 のダル コ ン漦 ソ ー ダを含む水溶液から ¾るエッチング液を用いて 5 分 滾しアル ミ ニゥ ム 箔および降極敷化層を除去して凹 ώのある接着剤面を 鬆出させた。  Further, the aluminum alloy was heated for 5 minutes by using an etching solution obtained from an aqueous solution containing 5 weights of a cassette soda and 0.5 weights of a dalcon soda added to the tank. The foil and the lower electrode layer were removed to remove the concave adhesive surface.
次に ソ リ ッ ドステ ー ト型コ ロ ナ放 S接によ !) 、 上 κ凹凸面のある接着剤層をコ ロ ナ故髦処理した。 処理 条件は下記の通 である。  Next, a solid state type corona discharge S-contact! The adhesive layer having the upper κ uneven surface was treated with a corona filter. The processing conditions are as follows.
o 装 置 ビラ一 モデル 2»1KVA o 印如電圧 8500 V  o Equipment Villa model 2 »1KVA o Inscription voltage 8500 V
o 周 波 数 eKHz  o Frequency eKHz
o 鶴剤付き基板送 躯 15 m/ min  o Substrate transport with crane 15 m / min
ο 入力 力 143.5 V , 12A  ο Input force 143.5 V, 12A
ο 電梃間ギャ ップ 2.4»  ο Electric lever gap 2.4 »
上記コ ロ ナ放電処理した接着剤付き基板を通常の 方法でめっき金属層の厚さが約 4 0 0 0 Αに化学銅め つき した。 めっき浴およびめつき前処理にはシ ッ プレ  The substrate with the adhesive subjected to the corona discharge treatment was chemically copper-plated to a thickness of about 400 mm by a usual method. Ship for plating bath and plating pretreatment
OMP WIP 一社觑 3 2 8 L プ ロ セス ( 商品名 ) を使^ した o さ ら に《気銅めつきを饑し、 銅箔の厚さを約 3 0 /| に肉盛 ϊ> した。 化学飼めつき後の外観および J I S C一 6481 に準拯して検射し: feめっき鎮腠と稜層板の密荣力、 は んだ耐熱镇の結果は第 4表の通 であった。 OMP WIP Using the company's 3288L process (brand name) o The company also starved the copper bronze and increased the thickness of the copper foil to about 30 / |. The appearance after chemical breeding and inspection in accordance with JISC-6481 were performed as shown in Table 4 below.
Figure imgf000019_0001
米かっこ内の数字は上記コ Π ナ放電機に接着剤付 き稜層板を違続的に通過させたと きの ¾遏回数 第 4表で実施例 1 0〜 1 4 はこの究明の接着剤層 があ 、 ア ル ミ -ゥ ム箔に陽極酸化処理を し、 かつコ ロナ放 理を施したもので、 この結果は J I s C 一 6 4 β 2 に基づ く規格僚 ( 紙エポキシ系銅張積層梗の 場合 ) 、 赛漦力 ; 14J¾?Z», はんだ耐 餐 (260: t) 秒 ) : 1 0秒を越えてぉ 、 実用的に十分 值である こ とが分る o これに反し比較例 6〜 : I 0 はこの発明の 接着剤層と コ πナ放電処理の ずれか一方が欠ける場 合、 ま たは両者と も ¾い場合であ ]? 、 いずれも密着力 よびはんだ耐熟镶で著しく 劣る。 4お藪化ア ル ミ - ゥ ム屠は密着力とはんだ耐熬馥向上のための檷完的役 割を杲すものと考えられる o
Figure imgf000019_0001
The numbers in parentheses indicate the number of conditions in which the corneal plate with adhesive was passed intermittently through the above-mentioned corner discharge machine. Layer, anodized aluminum foil, and core Rona release, the result is a standard based on JIS C164β2 (in the case of paper-epoxy-based copper-clad laminate), strength: 14J¾? Z », solder resist (260: t) seconds): It was found that を was more than 10 seconds, which was practically sufficient. 比較 On the other hand, Comparative Example 6 ~: I 0 was the same as the adhesive layer of the present invention. When either one of the discharge treatments is missing or when both are too strong], both of them are remarkably inferior in adhesion strength and solder maturity. 4 Yabu Ka Aluminium-Bamboo is considered to play a complete role in improving adhesion and soldering resistance o
実施 ¾ 1 5〜 1 9 Implementation ¾ 15-1 9
実旛例 1 0〜 1 4 で用いた工程の ¾かで歸極酸化 ½理と して下記を用いる ^外、 実飽例 1 0〜 1 4 と同 一の条件で化学めつき、 ¾気めつきま でを ¾し、 粲箔 の厚さを約 3 0 に肉盛 ]? した。 化学飼めつき後の外 観および J I S C一 6 4 8 1に準拠して検討しためつ き銅腠と稜屠梗の密着力, はんだ耐熱锒の結果は第 5 表の通 であった 0 In the steps used in Examples 10 to 14, the following is used as the final oxidation treatment. ^ In addition, chemical plating is performed under the same conditions as in Examples 10 to 14. The thickness of the corkscrew was increased to about 30]. Chemical shepherd plated appearance and JISC one 6 4 8 1 dark-out was studied in compliance with Do腠and adhesion crest Hofu梗after, results in solder heat锒was passing of Table 5 0
前処理液;アル力リ ·ソーク ·タリーナ,浴温; OtJ,時閬;  Pretreatment solution; Al-Li-Salk-Tarina, bath temperature; OtJ, time;
10分  10 minutes
電解液; 30重量 の Η3Ρ04 ,電流密度; a8AZdrf,浴温; Electrolyte; 30 weight Η 3 Ρ0 4, the current density; A8AZdrf, bath temperature;
301D,時間;約 1分  301D, time; about 1 minute
OMP OMP
/ WIP 第 5 表 / WIP Table 5
Figure imgf000021_0001
Figure imgf000021_0001
来かっこ内の数字はコ ロ ナ放電機に接着剤付き積 層粳を連鎵的に通遏させたと きの通過回教 第 5表のごと く異¾る陽極醭化処理を旎して も、 この発明の接着剤届がぁ 、 かつコ ロ ナ放電を行えば、 J I S C — 6 4 8 2 に基づ く規袼镇を越えて ϋ 、 突 施例 1 〜 5 同棕に、 実用的に十分: S:值であるこ とが分 o  The figures in parentheses indicate the number of passages when laminar non-adhesives with an adhesive were continuously degraded in a corona discharge machine. If the adhesive of the present invention is used and the corona discharge is carried out, it can be practically enough to exceed the standards based on JISC-6482, and to the first to fifth embodiments. : S: 值 is a minute o
実旌例 2 0 よび 2 1 Jeongjeong 2 0 and 2 1
実施例 1 0〜 1 4 で用いた ソ リ ッ ドステー ト型コ ロ ナ放電機の代 D にス パークギャッ プ型コ ロ ナ放罨機 を用いる以外は実鑰例 1 0〜 1 4 と同様^ して電気め つき を施 した。 めっき外観は良好で密着力とはんだ酎 熱値は第 6表の通 で実施例 1 0〜 1 4 の結果と同等 で J I S C 一 6 4 8 2 に基づ く規格値を越えてお ]? 、 実用的に十分 ¾镇であるこ とが分る。 6 表 了ルマイ ト コロナ処理 密着力 はん ¾fc值 層レブリカ 通し回数 Same as Examples 10 to 14 except that a spark gap type corona discharger was used instead of the solid state type corona discharger D used in Examples 10 to 14 ^ Then, electric plating was performed. The plating appearance is good, and the adhesion and solder heat value are the same as the results of Examples 10 to 14 as shown in Table 6 and exceed the standard values based on JISC 16482. It turns out that ¾ 镇 is practically sufficient. 6 Luminite Corona treatment Adhesion force ¾fc 值 layer
の有無  Presence
実 ifi o あ i? 1 18 45  Real ifi o oh i? 1 18 45
* 21 あ 1? 2 1.8 45 上記のごと く この発明に従った接着剤屠、 了ル ミ ユウム箔層除去によ るレ ブリ 力 , コ ロナ放電処理によ るブ リ ン ト回路形成方法によればク ロ ム どを使用 するこ とる く 密着力, はんだ ¾ "熱性にすぐれたブ リ ン ト回路基坂 得られる。 又コ ロナ放《 ^理は比較的籣 単 ¾設镭で、 無公害であ ]) ブ リ ン ト基板の処理能力  * 21 a 1 to 2 1.8 45 As described above, the adhesive slicing and the lithography according to the present invention are performed. According to this method, it is possible to obtain a printed circuit board with excellent adhesion and soldering properties without using a chromium or the like. Due to pollution]) Processing capacity of printed circuit boards
( 15mZmin)が高 く 、 本発明の方法は量産的てかつ β 済性にもすぐれて る 0 (15mZmin) is rather high, the method of the present invention is Ru superior to the mass production Heck one β already of 0
実 例 2 2〜 2 6 Example 2 2 to 2 6
実施例 1 〜 5 で用 たと同 じ接着剤溶液を亜教化 頻処理して表面を凹 ώに した厚さ 3 5 ίの銪箔 ( 飼張 穰層板に使用する も ので表面租さ約 4 ) 上に乾燥塗 嫫の厚さが約 3 0 < にるる よ う に塗布 し、 1 2 0 X)の オ ー ブ ン中で 2 0 分間乾燥して半硬化状態と した。  The same adhesive solution used in Examples 1 to 5 was sublimated, and the surface was concaved by frequent treatment. The thickness of the foil was 35 mm. ) The dry coating was applied to a thickness of about 30 <, and dried in an oven at 120 X) for 20 minutes to obtain a semi-cured state.
次に厚さ 1. 6 «の紙エ ポ キ シ系積層板の表裏両面に 上記接着剤面を接 して機械ブ レ ス中に置き、 20 Ζα の圧力て 1 6 0 TC , 4 0分閬の条件で一体成形した。  Next, put the above adhesive surface on both sides of the 1.6mm-thick paper-epoxy laminate, place it in the machine press, and apply a pressure of 20 ° α for 160TC, 40 min. It was integrally molded under the conditions of 閬.
さ らに塩化第二鉄溶液から ¾るエ ッ チ ン グ液を用  In addition, use an etching solution from ferric chloride solution.
_ΟΜ WIP いて通常の条件で銅箔 よび夏 SSHヒ縈層を除去して凹 凸のある接着剤面を露出させ 。 _ΟΜ WIP Then, the copper foil and the summer SSH layer were removed under normal conditions to expose the uneven adhesive surface.
次 ソ リ ッ ドステー ト型コ ロナ放 «橡に よ ]?上記 凹凸面のある接着剤層をコ ロ ナ放電 理した。 ¾理条 件は下おの通 である o  Next, a solid-state corona discharger was used. The corrugated discharge was applied to the adhesive layer with the uneven surface. ¾The processing conditions are as follows o
Ο 装 置 ビラ 一社製 モデル 2«1Κ ΓΑ ο 印加鷺圧 8 5 0 0 V  ビ Equipment Villa One-company model 2 «1Κ ο ο Applied pressure 8500 V
ο 周 波 数 6 KHz  ο Frequency 6 KHz
ο 接着剤付き基梗送!?速度 15m/min  ο Basic infarction with adhesive !? Speed 15m / min
ο 入力電力 14 &5 V , 12A  ο Input power 14 & 5 V, 12A
ο 電極間ギャップ 2· 4騮 .  ο Gap between electrodes 2.4 騮.
上記コ π ナ放電処理した接着剤付き基板を通常の 方法でめっき金属層の厚さが約 4 0 0 0 Αに化学鎖め つき した o めっき浴 よびめつき前処理にはシ ップレ 一社製 3 プ ロ セ ス ( 商品名 ) を使 した。 さ ら に電気銅めつきを施 し、 鏑箔の厚さを約 3 0 に肉盛 ϊ> した。 化学銷めっき後の外観および J I S C— 6481 に準 ¾して検討 しためっき鎘膜と積層 ¾の密着力, は んだ射 値の結果は第 7表の通 であった。 第 7 表 The above-mentioned substrate with an adhesive that has been subjected to a π-discharge treatment was chemically attached to the plating metal layer with a thickness of about 400 mm by the usual method.o A plating bath and pretreatment for attachment were made by Shipple Co., Ltd. Three processes (product names) were used. In addition, electro copper plating was applied, and the thickness of Kaburaki was increased to about 30. Table 7 shows the appearance of the plating after chemical promotion and the results of the adhesion and the soldering radiation between the plating film and the laminate, which were examined according to JISC-6481. Table 7
Figure imgf000024_0001
Figure imgf000024_0001
来上記コ π ナ放鷺接に接着剤付き積屠板を連耪的 に通遏させたと きの ¾¾回数  The number of times when the slaughter board with adhesive was continuously constipated in the above
この結果は J I S C— 6482に基づ く規格値 ( 羝ェ ボ キ シ系粲張狭層板の場合 ) 、 密漦力 ; Ζ», は んだ耐熱饞 ( 260 Ϊ 秒 ) ; 1 0狰を越えてお 、 実用的に十分 ¾値であるこ とが分る。  The results are based on JISC-6482 standard values (in the case of a narrow board made of glue-based box), tightness; heat resistance, solder heat resistance (260 seconds); 10%. It can be seen that the value is practically sufficiently low.
比較例 1 1 〜 1 4 Comparative Examples 11 to 14
実施例 2 2〜 2 6 で使周 した亜豫化飼処理した銅 箔と弒エ ポ キ シ系ブ リ ブ レ ダを ボ リ ビ - ル ブチ ラ ー ル 系接着剤を介して一体成形して得た網張稜屠拔の密着 力とはんだ射熱值を第 8表の比軟钙 1 1 に、 又比較例 Example 22 The copper foil treated in the same manner as used in Examples 2 to 26 and the epoxy-based brible blade were integrally formed via a polybutyral-based adhesive. Table 11 shows the adhesion and soldering heat of the Amihari ridge slicing obtained in Example 8 and the comparative example.
1 1 の銅張積層板の銅箔および亜酸化鲴展をエ ツ チ ン グ除去して得られる凹凸面に直接化学銅めつき した場 合の密着力とはんだ «·熱値を第 8表の比較例 1 2 に、 さ らに比較例 1 2で用 た凹凸面にコ ロ ナ放電処理し Table 8 shows the adhesion strength and solder heat when the copper foil and the suboxide expansion of the copper-clad laminate of No. 1 were etched and the copper was directly attached to the uneven surface obtained by chemical etching. The corona discharge treatment was applied to the uneven surface used in Comparative Example 12 and Comparative Example 12
OMPI てから化学銅めつき し^場合の街着力とはん 耐熟饞 を第 8表の比較例 1 3 に、 又実麄例 2 2で得た S3凸面 にコ π ナ放鼋 ½理せず直接化学飼めつき した場合の密 着力とはんだ耐熱值を第 8表の比敕例 1 それぞれ 示した。 ずれの場合も本発明の実施例 22に比軟し密 着力およびはんだ耐熱値について劣るこ とが明らかで あ 。 第 8 表 OMPI The results are shown in Table 8 for Comparative Example 13 and Comparative Example 13 in the case of chemical copper plating, and the S3 convexity obtained in Example 22 was not subjected to π-na emission treatment. Table 8 shows the adhesion and soldering heat resistance when direct chemical breeding was carried out. It is clear that even in the case of deviation, the adhesiveness and solder heat resistance are inferior to Example 22 of the present invention. Table 8
Figure imgf000025_0001
実施例 2 7 および 2 8
Figure imgf000025_0001
Examples 27 and 28
実施例 2 2 〜 2 6 で用いたソ リ ッ ド ステ ー ト型コ 口 ナ放電機の代 ]? にス パークギャ ップ型コ ロ ナ放鶯機 を用いる以外は実旌例 2 2 〜 2 6 と同様に して電気め つきを施 した o  Example 22 Examples 2 to 2 except that a spark gap type corona discharge machine was used instead of the solid-state type corona discharger used in Examples 22 to 26 Electroplated in the same way as 6 o
めっき外観は良好で密着力とはんだ酎熱値は第 9 表の通 で実施例 2 2 〜 2 6 の結果と同等で J I S C 一 6 4 8 2 に基づ く規格値を越えてお 1) 、 実用的に十分 値である こ と が分る。  The plating appearance is good, and the adhesion and solder heat value are the same as the results of Examples 22 to 26 as shown in Table 9 and exceed the standard values based on JISC 16482 1), It turns out that the value is practically sufficient.
REA REA
OMPI 整 Q コロナ 理 密着力 はん t B "熱值 OMPI Correction Q Corona treatment Adhesion force t B "
実肺 j  Real lung j
通し回数  Number of passes
27 1 2.5 75 27 1 2.5 75
28 2 2.5 70 上記のごと く この発明に従ったブ リ ン ト 回路形成 方法によればク 口 ム蒙 ¾ どを使用するこ と ¾ く 密着力 はんだ耐熱性にすぐれたプ リ ン ト回路基 «が得られ、 これらの特性は锭来の銅張積層板の性能を して る。 又コ ロナ放 «処理は比敉的撺単 設備で、 無公窖 であ ブ リ ン ト基板の処理能力 ( 15mZmi ii)が高 く惫 産性にもすぐれて る。 &産業上の利用可能性  28 2 2.5 70 As described above, according to the method for forming a printed circuit in accordance with the present invention, it is necessary to use a mouthpiece and the like. These characteristics are the performance of the conventional copper-clad laminate. In addition, the corona discharge treatment is a relatively simple facility, has no technical requirements, and has a high processing capacity (15 mZmi ii) for printed circuit boards, and is excellent in productivity. & Industrial applicability
以上のよ う に、 この発明に保るブ リ ン ト 回路の形 成方法は I C , L S I 等用のブ リ ン ト 回路の形成に有 用でぁ 、 回路屠と基裉との密着力の侵れたプ リ ン ト 回路基板を与える も のである。  As described above, the method of forming a printed circuit according to the present invention is useful for forming a printed circuit for ICs, LSIs, and the like. It gives a compromised printed circuit board.
OM WIP OM WIP

Claims

請 求 の 範 囲  The scope of the claims
L ジェン系合成ゴムを主成分とする接着剤層を有す る絶锾基板を提供し、 前 £接着剤層表面に化学めつき によって導鼋パタ ーンを形成してもる、 ブ リ ン ト 回路 s の形成方法にお て、 翁 e接着剤層の表面を粗面化し、 しかる後この粗面化表面をコ ロ ナ放置処理に供するこ とを特截とするブ リ ン ト回路の形成方法。  It provides an insulating substrate having an adhesive layer containing L-gen-based synthetic rubber as a main component, and a conductive pattern formed on the surface of the adhesive layer by chemical plating. In the method of forming the circuit s, the surface of the adhesive layer is roughened, and then the roughened surface is subjected to a corona treatment. Forming method.
2. 絶像基板上にジェン系合成ゴムを主成分とする接 着剤層を形成 し、 こ の接着剤層の表面を接械的に研磨 2. An adhesive layer mainly composed of gen-based synthetic rubber is formed on the image-stabilized substrate, and the surface of this adhesive layer is mechanically polished.
10 して粗面化するこ とによって前 ¾表面が粗面化された . 接荣剤層を有する絶縁基钣を提供するこ とを特徼とす る請求の範囲第 1項記載の方法。 The method according to claim 1, characterized in that the surface is roughened by roughening. The method according to claim 1, characterized in that an insulating substrate having an adhesive layer is provided.
3. 平均粒径 1 0 し 5 0 /*の研磨剤を用いて前記 接着剤層の表面を砑磨するこ とを特 とする請求の範 is 囲第 2項記載の方法。  3. The method according to claim 2, wherein the surface of the adhesive layer is polished with an abrasive having an average particle diameter of 10 to 50 / *.
陽 酸化処理に よ 凹凸面を形成 したアル ミ - ゥ ム も し く は銷の箔上にジェ ン系合成ゴムを主成分とす る接着剤を塗布、 乾燥 して半硬化状態の接着剤層を形 成 し、 こ の接着剤層と絶緣基板またはプ リ ブ レダを稷 ίο 眉 して加熱、 加 EE時に一体成形し、 しかる後上記箔を エ ツチ ング除去する こ と に よつて前記表面が粗面化さ れた接着剤層を有する絶緣基板を提供するこ とを特徵 とする請求の範囲第 1項記載の方法。  An adhesive whose main component is gen-based synthetic rubber is applied to aluminum or promotion foil with irregularities formed by anodization, dried and semi-cured. Then, the adhesive layer and the insulating substrate or pre-blender are integrally formed at the time of heating and heating by heating, and then the above-mentioned surface is removed by etching and removing the foil. 2. The method according to claim 1, wherein an insulating substrate having an adhesive layer having a roughened surface is provided.
5. 箔がア ル ミ ニ ウ ム よ ]) るこ とを特徵とする請求 の範囲第 4項 £截の方法 o 5. The foil is aluminum.]) Section 4 of the method
6. »柩戮化を リ ン蒙法に よっておこ う こ とを特微 とする請求の範囲第 5項 £載の方法。  6. »The method described in claim 5, characterized in that the hearseing is performed by the Lin Meng method.
Z 箱が飼よ U ¾るこ とを特微とする請求の範囲第 4 * 項紀載の方法。  The method described in the claim 4 *, which claims that the box Z is owned by the owner.
a 陽極酸化を ¾漦漦性の ¾酸鋦を主成分とする溶液 を用いておこな う こ とを特徴とする請求の範囲第 7項 記載の方法。  a. The method according to claim 7, wherein the anodization is performed using a solution containing a non-acidic acid as a main component.
接着剤がブタ ジ エ ン 了 ク リ 口 - ト リ ル共重合体を The glue is used to cure the butadiene end-to-trile copolymer.
0 含んで ¾る こ とを特微とする請求の範囲第 1項¾ し : 第 8項のいずれかに JE載の方法。 0 Claim including claim 1 Claim: A method listed in any one of claims 8 and JE.
ια 接着剤が熱硬化性樹脂をさ らに含んで ¾るこ とを 特徴とする請求の範囲第 9項記載の方法。  10. The method according to claim 9, wherein the iα adhesive further comprises a thermosetting resin.
1L 接着剤層の粗面化表面の粗さが 0L 5 ¾い し 1L Adhesive layer roughened Surface roughness 0L 5
s であるこ とを特锒とする請求の範囲第 1 項 し第 10 項のいずれかに記載の方法 0 The method according to any one of paragraph 10 to claim 1, wherein the the s Dearuko and Toku锒0
12. 接着剤層の粗面化表面の粗さが 3L 4 ¾い し 4.0 xm であるこ とを特徴とする請求の範囲第 1 1項 E載の方  12. The method according to claim 11, wherein the roughened surface of the adhesive layer has a roughness of 3L 4 to 4.0 xm.
OMPI WIPO OMPI WIPO
PCT/JP1979/000171 1978-07-13 1979-06-30 Method of fabricating printed circuits WO1980000294A1 (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP8459478A JPS5512716A (en) 1978-07-13 1978-07-13 Method of forming printed circuit
JP9317278A JPS605237B2 (en) 1978-08-01 1978-08-01 How to form printed circuits
JP9317378A JPS5521105A (en) 1978-08-01 1978-08-01 Method of forming printed circuit
JP78/93172 1978-08-01

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WO1980000294A1 true WO1980000294A1 (en) 1980-02-21

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