KR900001798B1 - Manufacture of printed wiring board - Google Patents

Manufacture of printed wiring board Download PDF

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Publication number
KR900001798B1
KR900001798B1 KR1019860007119A KR860007119A KR900001798B1 KR 900001798 B1 KR900001798 B1 KR 900001798B1 KR 1019860007119 A KR1019860007119 A KR 1019860007119A KR 860007119 A KR860007119 A KR 860007119A KR 900001798 B1 KR900001798 B1 KR 900001798B1
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KR
South Korea
Prior art keywords
resin
hole
printed wiring
copper
wiring board
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KR1019860007119A
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Korean (ko)
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KR880002413A (en
Inventor
기요시 이도
히도시 아라이
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미쓰비시전기 주식회사
시끼모리야
간사이페인트 가부시끼가이샤
야마다 모또조
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    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
    • H05K3/06—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed chemically or electrolytically, e.g. by photo-etch process
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/16—Coating processes; Apparatus therefor
    • G03F7/164—Coating processes; Apparatus therefor using electric, electrostatic or magnetic means; powder coating
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/0073—Masks not provided for in groups H05K3/02 - H05K3/46, e.g. for photomechanical production of patterned surfaces
    • H05K3/0079—Masks not provided for in groups H05K3/02 - H05K3/46, e.g. for photomechanical production of patterned surfaces characterised by the method of application or removal of the mask
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/13—Moulding and encapsulation; Deposition techniques; Protective layers
    • H05K2203/1333—Deposition techniques, e.g. coating
    • H05K2203/135—Electrophoretic deposition of insulating material
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
    • H05K3/06—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed chemically or electrolytically, e.g. by photo-etch process
    • H05K3/061—Etching masks
    • H05K3/064—Photoresists

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing Of Printed Circuit Boards (AREA)

Abstract

In the prodn. of printed circuits on Cu-plated insulating laminated boards, a photoresist film is electro-deposited by immersing the board in a bath based on a water-soluble or dispersible photocurable plastics and applying a d.c. current. The process is claimed for use with a board having through-holes and as one stage of an automatic process. It avoids loss of material and allows an overall resist film to be applied without using costly equipment and additional personnel.

Description

프린트배선판의 제조방법Manufacturing method of printed wiring board

제1도는 이 발명의 일실시예의 실시사항을 표시하는 단면도.1 is a cross-sectional view showing an embodiment of this embodiment of the present invention.

제2도는 상기 실시예에 있어서의 전해조를 자동처리라인에 조성한 응용예를 표시하는 개념적 측면도.FIG. 2 is a conceptual side view showing an application example in which an electrolytic cell is formed in an automatic processing line in the embodiment. FIG.

제3도는 종래 사용되고 있는 로울코터(Roll coater)방법에 의한 동박(箔)적층판의 관통공(Through hole)을 메꾸는 상황을 표시하는 원리 단면도.3 is a cross-sectional view showing a state of filling a through hole of a copper clad laminate by a roll coater method conventionally used.

제4도는 종래 사용되고 있는 일반적인 드라이 필름레지스터(Dry film resist)의 구성을 표시하는 측면도.4 is a side view showing the configuration of a general dry film resist used in the related art.

제5도는 이 드라이필름의 첨부상황을 표시하는 원리적 측면도.5 is a principle side view showing the attachment status of this dry film.

* 도면의 주요부분에 대한 부호의 설명* Explanation of symbols for main parts of the drawings

1 : 동박적층절연판 2 : 관통공1: Copper Clad Laminated Plate 2: Through Hole

11 : 전착도장용 전해조 12 : 전착도료화 수용성 감광수지11: Electrolytic cell for electrodeposition coating 12: Electrodeposition paint water soluble photosensitive resin

15 : 자동처리용 탱크군 16 : 자동반송장치15: tank group for automatic processing 16: automatic transfer device

이 발명은 관통공등의 구멍이 있는 프린트배선판의 제조공정에 있어서, 관통공등의 내부 및 동박적층절연판(이하 동박적층판으로 약칭한다)의 표면동박상에 동시에 감광성 레지스트막을 형성하는 방법에 관한 것이다.This invention relates to a method of simultaneously forming a photosensitive resist film on the surface copper foil of the inside of a through hole and the copper foil laminated insulation board (henceforth a copper foil laminated board) in the manufacturing process of a printed wiring board with a hole, such as a through hole. .

관통공등의 구멍이 있는 프린트판의 제조방법에는 통상동박적층판(銅箔積層板)에 관통공을 뚫어 이 구멍에 도금(통상 동도금)을 실시하고 열등으로 경화하는 구멍메우기용 수지로 채워 그후 동박적층판의 표면동박상에 감광성 레지스트막을 형성하며, 이에 소정패턴의 노출을 시킨 다음 현상처리하여 레지스트막패턴을 얻으며 다시 이것을 마스크(Mask)로 하여 상기 표면동박에 에징(edging)시공후 구멍을 메꾼 수지를 제거하여 소망의 배선패턴을 얻는 방법은 옛부터 사용되고 있다.In the manufacturing method of a printed plate with holes such as through holes, a hole is usually drilled through a copper-clad laminate and plated with this resin (usually copper plating), and filled with a resin for filling holes, which is then hardened by inferior copper foil. A photosensitive resist film is formed on the surface copper foil of the laminated plate, and a predetermined pattern is exposed, followed by development to obtain a resist film pattern, which is then masked to fill the hole after edging the surface copper foil. The method of obtaining the desired wiring pattern by removing the has been used since ancient times.

혹은 동박적층판에 뚫은 관통공을 감광성 레지스트막으로 덮고 다음에 동박적층판의 표면동박상에 감광성 레지스트막을 형성하고 이것에 소망의 패턴을 노출시킨 다음에 형상처리하여 레지스트막패턴을 얻고 이어서 이것을 마스크로하여 상기 표면은박에 에징시공하여서 소망의 배선패턴을 얻는 방법이 사용되고 있다.Alternatively, the through-holes drilled through the copper-clad laminates are covered with a photosensitive resist film, and then a photosensitive resist film is formed on the surface copper foil of the copper-clad laminate, a desired pattern is exposed to it, and then subjected to a shape treatment to obtain a resist film pattern, which is then used as a mask. The surface is etched in foil and the method of obtaining a desired wiring pattern is used.

이 관통공등으로 사용되는 구멍을 수지로 메꾸는 방법으로서는 중첩인쇄(Surprint) 또는 로울코터에 의한 구멍메우기방법등이 사용되며 다음에 동박적층판의 표면동박상에 감광성 레지스트막을 형성하려면 액상레지스트재를 침지(浸漬), 로울러코팅, 원심도포등의 방법으로 도포하는 방법이나, 드라이필름레지스트(예를 들면 듀퐁사제 리스톤필름)로 불리는 필름상 감광막을 전용첩부기를 사용하여 적층(laminate)하는 방법을 채택하고 있었다.As a method of filling the holes used as the through holes with resin, a method of filling a hole by a surface printing or roll coater is used. Next, in order to form a photosensitive resist film on the surface copper foil of the copper clad laminate, a liquid resist material is used. The method of coating by immersion, roller coating, centrifugal coating, etc., or the method of laminating a film-shaped photosensitive film called dry film resist (for example, DuPont's Listone film) using a dedicated pasting machine. Adopted.

제3도는 이 종래의 로울코터법에 의한 관통공을 메꾸는 상황을 표시하는 원리단면도이며, 1은 동박적층판, 2는 이 동박적층판(1)에 설치된 관통공, 3은 이 관통공(2) 메꾸기용 수지로서 동박적층판(1)에 로울코터에 도포로울러(4a) 및 보조로울러(4b)를 사용하여 코팅하며 동시에 동박적층판(1)의 관통공(2)에 압입된다.3 is a sectional view showing the principle of filling the through hole by the conventional roll coater method, 1 is a copper clad laminate, 2 is a through hole provided in this copper clad laminate 1, and 3 is a through hole 2 As a resin for filling, the copper foil laminated plate 1 is coated with a roller coater using an application roller 4a and an auxiliary roller 4b, and is pressed into the through hole 2 of the copper foil laminated plate 1 at the same time.

이 수지(3)의 경화건조후에 동박적층판(1)의 표면의 수지만 제거하며 그후 표면동박상에 감광레지스트막을 형성하여 소망의 배선패턴을 얻는 것이다.After hardening and drying of this resin 3, only the resin of the surface of the copper clad laminated board 1 is removed, a photoresist film is formed on a surface copper foil, and a desired wiring pattern is obtained.

제4도는 이 소망배선패턴이 이룩된 동박적층판(1)의 표면에 첩부한 일반적인 드라이필름레지스트의 구성을 표시하는 측면도이며, 드라이필름(5)의 표면에는 보호필름(6)이 첩부되어 있다.4 is a side view showing the structure of a general dry film resist affixed to the surface of the copper-clad laminate 1 on which the desired wiring pattern is formed, and a protective film 6 is attached to the surface of the dry film 5.

제5도는 이 드라이필름(5)의 첩부상황을 표시하는 원리적 측면도이며, 관통공(2)에 수지(3)을 메꾼 동박적층판(1)의 양측에 각각 제1 및 제2의 드라이필름(5a) 및 (5b)를 첩부하는 경우를 표시한다.FIG. 5 is a principle side view showing the sticking state of the dry film 5, and the first and second dry films (2) on both sides of the copper-clad laminate 1 having the resin 3 filled in the through holes 2, respectively. The case where 5a) and (5b) are affixed is shown.

제1 및 제2의 드라이필름공급로울러(7a) 및 (7b)에서 각각 공급되는 제1 및 제2의 드라이필름(5a) 및 (5b)는 각각 제1 및 제2의 보호필름(6a) 및 (6b)가 벗겨져 이들의 보호필름(6a) 및 (6b)는 각각 제1 및 제2의 보호필름권회로울러(8a) 및 (8b)에 감겨진다.The first and second dry films 5a and 5b supplied from the first and second dry film supply rollers 7a and 7b are respectively the first and second protective films 6a and 6b is peeled off, and these protective films 6a and 6b are wound on the first and second protective film windings 8a and 8b, respectively.

각 보호필름(6a) 및 (6b)이 벗겨진 제1및 제2의 드라이필름(5a) 및 (5b)은 각각 제1 및 제2의 가열로울러(9a) 및 (9b)에 의하여 그들 사이를 통하는 동박적층판(1)의 각면에 첩부하고 있었다.Each of the first and second dry films 5a and 5b with the respective protective films 6a and 6b peeled off passes through them by the first and second heating rollers 9a and 9b, respectively. It stuck to each surface of the copper clad laminated board 1.

그리고 10a는 제2의 드라이필름(5a)의 안내로울러, 10b는 제2의 드라이필름(5b)을 안내하는 동시에 제2의 보호필름(6b)을 벗기는 안내로울러이다.10a guides the second dry film 5a and 10b guides the second dry film 5b and at the same time removes the second protective film 6b.

종래는 이상과 같이 동박적층판(1)에 설치된 관통공(2)은 구멍메꾸기용의 수지로 미리 메꾼후 동박적층판에 이것과는 전혀 별개로 제조된 드라이필름을 상술과 같이 첩부하기 때문에 관통공(2)의 구멍메꾸기용 수지(3)의 건조공정이 별도 필요하였다.Conventionally, the through-hole 2 provided in the copper-clad laminate 1 is filled with a resin for filling holes in advance, and then the dry film manufactured completely separate from this is attached to the copper-laminated laminate as described above. The drying process of the resin 3 for hole filling of 2) was needed separately.

또 다음의 드라이필름을 사용하는 공정에서는 드라이필름의 폭을 동박적층판(1)의 규격에 맞추는 과정에서 폭방향, 길이방향에 상당한 드라이필름의 손실이 발생하고 있었다.Moreover, in the process of using the following dry film, the loss of the dry film in the width direction and the longitudinal direction generate | occur | produced in the process of adjusting the width of the dry film to the specification of the copper clad laminated board (1).

또한 관통공(2)이 메꾸어진 동박적층판의 투입측과 드라이필름 첩부후의 받는 측이 대향하고 있으므로 2인의 작업원을 필요로 한다든가 최근에는 자동라미네이터등이 출현하고 있지만 고가이다.In addition, since the input side of the copper-clad laminate in which the through-holes 2 are filled and the receiving side after the dry film pasting are opposed to each other, two workers are required, and automatic laminators and the like have recently appeared, but are expensive.

더우기 은박표면에 흠집이 있으면 그 흠집에는 충분히 충전되지 않으며 패턴에징시에 단선 또는 단락이 생기는 등의 문제점이 있었다.Moreover, if there were scratches on the surface of the silver foil, the scratches were not sufficiently filled and there was a problem such as disconnection or short circuit at the time of pattern edging.

이 발명은 이상과 같은 문제점을 해소하기 위한 것으로서 관통공이 있는 동박적층판의 표면전체에 감광성 수지재료의 손실이 없고 균일하게 또한 은박표면의 흠집 및 관통공도 완전히 충전도포 가능하므로 품질향상을 기할 수 있는 동시에 고가의 설비나 여분의 인력이 불필요한 자동라인에 조정 가능한 방법을 얻는 것을 목적으로 한다.The present invention is to solve the above problems, there is no loss of the photosensitive resin material on the entire surface of the copper foil laminated plate having a through hole, and evenly scratches and through holes on the surface of the foil foil can be completely filled and improved quality. The objective is to obtain a method that can be adjusted to automatic lines that do not require expensive equipment or extra manpower.

이 발명에 관한 프린트배선판의 제조방법에서는 전착도장용 전해조에 수용한 수용성 감광수지에 관통공을 가지는 동박적층판을 침지하여 직류전해로서 감광막을 석출시킨다.In the manufacturing method of the printed wiring board which concerns on this invention, the copper foil laminated plate which has a through-hole is immersed in the water-soluble photosensitive resin accommodated in the electrolytic cell for electrodeposition coating, and a photosensitive film is deposited as direct current electrolysis.

이 발명에서는 전해조에 수용한 전착도료화 수용성 감광수지에 관통공을 설치한 동박적층판을 침지하여 직류전해에 의하여 관통공표면 및 동박상에 감광수지를 석출시켜 그후에 가열조건시킴으로써 감광막을 얻게 되는 것으로, 재료의 손실없이 균일하게 하며 동박표면에 흠집이 있어도 완전히 충전도포할 수 있는 것이다.In the present invention, the photoresist film is obtained by immersing the copper foil laminated plate provided with the through hole in the electrodeposition paint soluble photosensitive resin accommodated in the electrolytic cell, depositing the photoresist on the surface of the through hole and the copper foil by direct current electrolysis, and then heating the film. It can be uniformly filled without loss of material and can be completely filled even if there is a scratch on the surface of the copper foil.

제1도는 이 발명의 일실시예의 실시상황을 표시하는 단면도이며, 11은 전해조, 12는 그안에 수용된 관통공(2)이 설치된 동박적층판(1)을 침지하는 전착도표화된 수용성 감광수지, 13은 관통공이 설치된 동박적층판(1)과 대향하여 침지된 스테인레스등으로 된 음극, 14는 액 교반용 공기송출파이프이다.1 is a cross-sectional view showing an embodiment of an embodiment of the present invention, 11 is an electrolytic cell, 12 is an electrodeposited tabulated water-soluble photosensitive resin immersed in a copper clad laminate 1 having a through hole 2 accommodated therein, 13 is A negative electrode made of stainless steel or the like immersed in opposition to the copper foil laminated plate 1 provided with a through hole, 14 is an air delivery pipe for liquid stirring.

관통공부 동박적층판(1)과 음극(13)과의 사이에 200V 정도의 직류전압을 인가하므로서 액(12)중에 용해 또는 분산하여 마이너스로 대전하고 있던 감광수지가 동박적층판(1)의 관통공내 및 표면상에 전착하며 막 두께의 증대에 따라서 전류는 저하하고 일정의 막 두께를 얻는 동시에 탈수도 행해진다.The photosensitive resin that was dissolved or dispersed in the liquid 12 and was charged negatively by applying a DC voltage of about 200 V between the copper-clad laminate 1 and the cathode 13 of the through-hole was formed in the through-hole of the copper-clad laminate 1 and As the electrode is deposited on the surface and the film thickness increases, the current decreases and a constant film thickness is obtained, and dehydration is also performed.

그후 동박적층판(1)을 인양하여 가열건조시킴으로써 감광막을 얻게 된다.Thereafter, the copper foil laminated plate 1 is lifted and dried to obtain a photosensitive film.

제2도는 상기 실시예에서의 전해조를 자동처리라인에 조성한 응용예를 표시하는 개념적 측면도이며, 일련의 자동처리용 탱크군(15)중 제1도와 같은 전착도장용 전해조(11)가 조성되어 있으며 동박적층판(1)은 자동반송장치(16)에 의하여 소정시간에 소정위치로 반송되어 처리된다.FIG. 2 is a conceptual side view showing an application example in which the electrolytic cell is formed in an automatic processing line in the above embodiment, and an electrodeposition coating electrolytic cell 11 as in FIG. 1 is formed among a series of automatic processing tank groups 15. The copper foil laminated sheet 1 is conveyed to a predetermined position by the automatic conveyance apparatus 16, and is processed.

또 상기예에서는 음극(13)에 스테인레스동판을 사용하였지만 탄소나 기타의 도전재를 사용하여도 된다.In the above example, a stainless copper plate is used for the negative electrode 13, but carbon or other conductive material may be used.

또 상기 실시예에서는 동박적층판(1)을 양극으로 하였지만 인가전압의 극성을 역으로 하여 동박적층판(1)을 음극으로 하고 그것에 적합한 전착감광성수지를 사용하여도 된다.In the above embodiment, the copper-clad laminate 1 is used as the anode, but the copper-laminated laminate 1 may be used as the cathode by reversing the polarity of the applied voltage, and an electrodeposition photosensitive resin suitable for it may be used.

또한 상기예에서는 전착도료로서 수용성 감광수지를 사용하는 것을 표시하였지만 수용성 또는 수분산성의 광경화성수지 예를 들면 미국 특허 3,954,587에 기재된 음극전착도료나 그외의 양극전착도료를 사용하여도 동일한 효과를 얻을 수 있다.In the above example, the use of a water-soluble photosensitive resin as the electrodeposition paint is indicated, but the same effect can be obtained by using a water-soluble or water-dispersible photocurable resin, for example, a cathode electrodeposition paint described in US Pat. No. 3,954,587 or other anode electrodeposition paints. have.

상기 음극전착도료는 산가 20-300, 불포화당량 약 150-약 3000 및 수평균분자량 약 300 이상인 수용성 또는 수분산성의 중합성 불포화수지를 포함하는 하기 (1)-(5)군에서 선택된 성분 및 비수용성 중합개시제 예를 들면 벤조인등을 주성분으로 하여 된 수용성 또는 수분산성의 광경화성 조성물로 된 것이다.The negative electrodeposition coating is a component and ratio selected from the following groups (1)-(5) comprising an acid value of 20-300, an unsaturated equivalent of about 150- about 3000, and a water-soluble or water-dispersible polymerizable unsaturated resin having a number average molecular weight of about 300 or more. A water-soluble polymerization initiator, for example, is a water-soluble or water-dispersible photocurable composition composed mainly of benzoin and the like.

(1) 1분자중에 중합성 불포화결합 및 수산기를 가진 화합물과 디이소시아네이트계 화합물과의 반응물을 골격중에 수산기를 갖게 한 고산가 아크릴수지에 부가시켜서 된 중합성 불포화수지, 이들과 1분자중에 중합성 불포화결합을 1개 이상 가지는 에틸렌성 불포화 화합물과를 병용한 것을 주성분으로 한 성분.(1) A polymerizable unsaturated resin obtained by adding a reactant between a compound having a polymerizable unsaturated bond and a hydroxyl group in one molecule and a diisocyanate compound to a high acid acrylic resin having a hydroxyl group in the skeleton, and polymerizable unsaturated in one molecule. A component whose main component is a combination of an ethylenically unsaturated compound having at least one bond.

(2) 에폭시기를 가진 에폭시수지와 불포화지방산과의 에스테르화물에서의 지방산체인중의 불포화결합에 α,β에틸렌성 불포화 2염기산 또는 그의 무수물을 부가시켜서 된 중합성 불포화수지와 1분자중에 중합성 불포화 결합을 1개 이상 가지는 에틸렌성 불포화 화합물과의 혼합물을 중주성분으로 한 성분.(2) Polymerizable unsaturated resin and polymerizable in 1 molecule by adding α, β ethylenically unsaturated dibasic acid or its anhydride to unsaturated bond in fatty acid chain in esterified product of epoxy resin with epoxy group and unsaturated fatty acid A component containing, as a main component, a mixture with an ethylenically unsaturated compound having at least one unsaturated bond.

(3) 불포화지방산변성고산가 알키드수지로 된 중합성 불포화수지와 1분자중에 중합성 불포화결합을 1개 이상 가지는 에틸렌성 불포화 화합물과의 혼합물을 주성분으로 하는 성분.(3) A component comprising, as a main component, a mixture of an unsaturated fatty acid-modified high acid polymerizable unsaturated resin of an alkyd resin and an ethylenically unsaturated compound having at least one polymerizable unsaturated bond in one molecule.

(4) 말레인화유로 된 중합성 불포화수지와 1분자중에 중합성 불포화결합을 1개 이상 가지는 에틸렌성 불포화 화합물의 혼합물을 주성분으로 하는 성분.(4) A component comprising, as a main component, a mixture of a polymerizable unsaturated resin of maleated oil and an ethylenically unsaturated compound having at least one polymerizable unsaturated bond in one molecule.

(5) 1분자중에 중합성 불포화결합 및 글리시릴기를 가지는 화합물을 고산가아크릴수지에 부가하여서 된 중합성 불포화수지, 또는 이들과 1분자중에 중합성 불포화결합을 1개 이상 가지는 에틸렌성 불포화 화합물과를 병용한 것을 주성분으로 하는 성분.(5) A polymerizable unsaturated resin obtained by adding a compound having a polymerizable unsaturated bond and a glycyryl group in one molecule to a high acid acrylic resin, or an ethylenically unsaturated compound having at least one polymerizable unsaturated bond in one molecule thereof. The ingredient which has used together as a main component.

상기 양극전착도료는 수지골격중에 에틸렌성 불포화기와 아미노기를 함유하는 하기 (6)-(8)의 군에서 선택된 수용성 또는 수분산성의 중합성 불포화수지 및 비수용성광중합개시제를 주성분으로 하여 된 수용성 또는 수분산성의 광경화성 조성물로 된 것이다.The positive electrodeposition paint is a water-soluble or water-based water-based or water-based photopolymerization initiator containing water-soluble or water-dispersible polymerizable unsaturated resins selected from the group (6)-(8) containing ethylenically unsaturated groups and amino groups in the resin skeleton. It is made of an acidic photocurable composition.

(6) 에폭시 화합물에 1급 또는 2급아민을 부가후 수산기에 에틸렌성 불포화기함유 이소시아네이트 화합물을 부가하여 된 수지; 에폭시 화합물로서는 비스페놀 A형 에폭시수지, 비스페놀 F형 에폭시수지, 비스페놀 S형 에폭시수지, 지방족 에폭시수지, 노볼락형 에폭시수지, 스틸렌, 메틸(메타), 아크릴레이트, 2-히드록시에틸(메타) 아크릴레이트등의 비닐단량체와 글리시딜(메타) 아크릴레이트등의 글리시딜기함유 불포화단량체를 함께 중합한 수지등이 사용된다.(6) A resin obtained by adding an ethylenically unsaturated group-containing isocyanate compound to a hydroxyl group after addition of a primary or secondary amine to an epoxy compound; Examples of the epoxy compound include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, aliphatic epoxy resins, novolac type epoxy resins, styrene, methyl (meth), acrylates, and 2-hydroxyethyl (meth) acrylics. Resin etc. which superposed | polymerized together with vinyl monomers, such as a rate, and glycidyl group containing unsaturated monomers, such as glycidyl (meth) acrylate, are used.

아민으로서는 모노에틸아민, 모노부틸아민, 디에틸아민, 디부틸아민, 모노에틸모노에타놀아민, 디에타놀아민등이 사용된다.As the amine, monoethylamine, monobutylamine, diethylamine, dibutylamine, monoethyl monoethanolamine, diethanolamine and the like are used.

또 에틸렌성 불포화기함유 이소시아네이트 화합물로서는 톨릴렌 디이소시아네이트, 이소포론 이소시아네이트, 키실렌 디이소시아네이트, 1,6-헥산 디이소시아네이트등의 디이소시아네이트 화합물의 한쪽 이소시아네이트기에 2-히드록시 에틸아크릴레이트, 2-히드록시 에틸메타크릴레이트, 2-히드록시 프로필아크릴레이트와 2-히드록시 프로필메타크릴레이트등의 히드록시기함유 불포화단량체를 부가한 화합물 이소시안산 에틸메타크릴레이트등을 들을 수 있다.Moreover, as an ethylenically unsaturated group containing isocyanate compound, 2-hydroxyethyl acrylate and 2-hydride of one isocyanate group of diisocyanate compounds, such as tolylene diisocyanate, isophorone isocyanate, xylene diisocyanate, and 1, 6- hexane diisocyanate, etc. Compound isocyanate ethyl methacrylate etc. which added the hydroxyl group containing unsaturated monomer, such as hydroxy ethyl methacrylate, 2-hydroxy propyl acrylate, and 2-hydroxy propyl methacrylate, are mentioned.

(7) 에폭시기와 3급아미노기를 함유하는 수지의 에폭시기에 에틸렌성 불포화기와 카르복실기를 함유하는 화합물을 부가하여서 된 수지; 에폭시기와 3급 아미노기를 함유하는 수지는 에폭시기수지의 에폭수지의 일부를 2급아민과 반응시키므로서 얻게 된다.(7) A resin obtained by adding a compound containing an ethylenically unsaturated group and a carboxyl group to an epoxy group of a resin containing an epoxy group and a tertiary amino group; Resin containing an epoxy group and a tertiary amino group is obtained by making a part of the epoxy resin of an epoxy base resin react with a secondary amine.

이 수지중의 나머지의 에폭시기에 (메타)아크릴산등의 불포화기와 카르복실기를 함유하는 화합물을 부가하므로서 합성된다.It is synthesize | combined by adding the compound containing unsaturated groups, such as (meth) acrylic acid, and a carboxyl group to the remaining epoxy groups in this resin.

(8) 모노에폭시 화합물에 1급아민을 부가하여 2급아미노화 한 후 에폭시 화합물, 또는 디-에폭시 화합물을 2급아민 에폭시기의 단량수가 1 : 2 이상이 되도록 부가한 후 나머지의 에폭시기에 전기한 에틸렌성 불포화기와 카르복실기를 함유하는 화합물을 부가하든가 수산기에 전기한 에틸렌성 불포화기함유 이소시아네이트 화합물을 부가한 수지; 모노에폭시 화합물로서는 아릴글리시딜에테르, 페닐글리시딜에테르, 에틸렌옥사이드, 프로필렌옥사이드, 부틸렌옥사이드등이 사용된다. 디에폭시 화합물 또는 디에폭시 화합물로서는 비스페놀형에폭시수지, 지방족에폭시수지, 노볼라크형에폭시수지등이 사용된다.(8) After adding a primary amine to the monoepoxy compound for secondary aminoation, an epoxy compound or a di-epoxy compound is added so that the number of units of the secondary amine epoxy group is at least 1: 2, and the remaining epoxy group is then added. Resin which added the compound containing an ethylenically unsaturated group and a carboxyl group, or added the ethylenically unsaturated group containing isocyanate compound described above in the hydroxyl group; As the monoepoxy compound, arylglycidyl ether, phenylglycidyl ether, ethylene oxide, propylene oxide, butylene oxide and the like are used. As the diepoxy compound or diepoxy compound, bisphenol-type epoxy resins, aliphatic epoxy resins, novolak-type epoxy resins and the like are used.

다음은 전착도료의 실시예에 관하여 설명한다.Next, an embodiment of electrodeposition paint will be described.

메틸메타클릴레이트 40중량부, 부틸아크릴레이트 40중량부, 아크릴산 20중량부 및 아조비스 이소부티로니트릴 2중량부로 된 혼합액을 질소가스분위기하에서 110℃로 유지한 프로필렌글리콜모노메틸에테르(친수성용제) 90중량부중에 3시간에 걸쳐 적하한다. 적하후 1시간 숙성시켜 아조비스디메틸발레토니트릴 1중량부 및 프로필렌글리클모노메틸에테르 10중량부로 된 혼합액을 1시간에 걸쳐 적하하고 이어서 5시간 숙성시켜서 고산가아크릴수지(산가 155)용액을 얻는다.Propylene glycol monomethyl ether (hydrophilic solvent) in which a mixed solution of 40 parts by weight of methyl methacrylate, 40 parts by weight of butyl acrylate, 20 parts by weight of acrylic acid and 2 parts by weight of azobis isobutyronitrile was maintained at 110 ° C. under a nitrogen gas atmosphere. ) It is dripped over 3 hours in 90 weight part. After dripping for 1 hour, a mixed solution of 1 part by weight of azobisdimethylvaletonitrile and 10 parts by weight of propylene glycol monomethyl ether is added dropwise over 1 hour, and then aged for 5 hours to obtain a high acid acrylic resin (acid value 155) solution.

다음에 이 용액에 글리시딜메타클릴레이트 242중량부, 히드로키논 0.12중량부 및 테트라메틸암모늄브로마이드 0.6중량부를 첨가하여 공기를 송풍하면서 110℃에서 5시간 반응시켜서 중합성 불포화수지(산가 약 50, 불포화당량 약 740, 수평균분자량 20,000)용액을 얻는다.Next, 242 parts by weight of glycidyl methacrylate, 0.12 part by weight of hydrokinone and 0.6 part by weight of tetramethylammonium bromide were added to the solution, and reacted at 110 ° C. for 5 hours while blowing air to produce a polymerizable unsaturated resin (acid value of about 50 , An unsaturated equivalent weight of about 740, and a number average molecular weight of 20,000) are obtained.

이 중합성 불포화수지를 트리에틸아민으로 0.6당량 중화한후 아세틸아세톤 6중량부, 광개시제로서 α-히드록시이소부틸페논 6중량부를 첨가한후 고형분함유율이 10중량%가 되도록 물을 첨가하여 전착도장제(PH 7.0)로 한다.This polymerizable unsaturated resin was neutralized by 0.6 equivalents with triethylamine, and then 6 parts by weight of acetylacetone and 6 parts by weight of α-hydroxyisobutylphenone were added as photoinitiators, followed by the addition of water so that the solid content was 10% by weight. It is set as (PH 7.0).

이상 설명한 바와 같이 이 발명에서는 관통공부 동박적층판의 관통공내 및 표면의 감광막을 전착도장에 의하여 형성하도록 하였으므로 재료의 손실이 없어지고 자동화도 극히 용이하며 또한 품질의 안정에도 기여하고 공장공간의 효율적 이용도 가능하게 하는 것이다.As described above, in the present invention, the photoresist film of the through hole of the through-hole copper clad laminate is formed by electrodeposition coating, so that loss of material is eliminated, automation is extremely easy, contributing to stability of quality, and efficient use of factory space. To make it possible.

Claims (3)

관통공등의 구멍이 있는 프린트배선판에 있어서, 이 관통공내 및 프린트배선용 동박적층절연판의 표면에 감광성 레지스트막을 형성하는 경우에 상기 동박적층절연판을 전착도장용 전해조에 수용한 전착도료화 수용성 감광수지에 침지하고 직류전해에 의하여 감광성 레지스트막을 석출시키는 공정이 있는 것을 특징으로 하는 프린트배선판의 제조방법.In a printed wiring board having a hole such as a through hole, in the case where a photosensitive resist film is formed in the through hole and on the surface of the copper foil laminated insulating plate for printed wiring, the electrodeposited paint-soluble water-soluble photosensitive resin containing the copper foil laminated insulating plate in an electrolytic cell for electrodeposition coating. A method of manufacturing a printed wiring board, comprising a step of immersing and depositing a photosensitive resist film by direct current electrolysis. 제1항에 있어서, 동박적층절연판을 수용성이나 수분산성의 광경화성수지를 주성분으로 하는 전착도료의 도장용 전해조에 침지하는 것을 특징으로 하는 프린트배선판의 제조방법.The method of manufacturing a printed wiring board according to claim 1, wherein the copper-clad insulating board is immersed in an electrolytic cell for coating an electrodeposition paint containing water-soluble or water-dispersible photocurable resin as a main component. 제1항 또는 제2항에 있어서, 자동처리용 탱크군중에 조정된 전착도장용 전해조에 있어서 자동처리의 1단계로서 감광성 레지스트막을 형성하는 것을 특징으로 하는 프린트배선판의 제조방법.The method of manufacturing a printed wiring board according to claim 1 or 2, wherein a photosensitive resist film is formed as one step of automatic processing in the electrodeposition coating electrolytic cell adjusted in the group of automatic processing tanks.
KR1019860007119A 1986-07-09 1986-08-27 Manufacture of printed wiring board KR900001798B1 (en)

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JP86-161422 1986-07-09
JP161422 1986-07-09
JP61161422A JPS6317592A (en) 1986-07-09 1986-07-09 Manufacture of printed wiring board

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KR880002413A KR880002413A (en) 1988-04-30
KR900001798B1 true KR900001798B1 (en) 1990-03-24

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US4943346A (en) * 1988-09-29 1990-07-24 Siemens Aktiengesellschaft Method for manufacturing printed circuit boards
EP0370133A1 (en) * 1988-11-24 1990-05-30 Siemens Aktiengesellschaft Process for producing printed-circuit boards
US5268256A (en) * 1990-08-02 1993-12-07 Ppg Industries, Inc. Photoimageable electrodepositable photoresist composition for producing non-tacky films
EP0469537B1 (en) * 1990-08-02 1998-12-30 Ppg Industries, Inc. Photoimageable electrodepositable photoresist composition
JPH04146687A (en) * 1990-10-08 1992-05-20 Nippon Paint Co Ltd Manufacture of solder masked circuit board
US5223116A (en) * 1992-05-11 1993-06-29 Siemens Aktiengesellschaft Apparatus for electrophoretic application of a lacquer onto plate-shaped work pieces
KR100465613B1 (en) * 2002-11-01 2005-01-13 태창엔지니어링 주식회사 Electrodeposition resist coating apparatus
CN101144967B (en) * 2007-06-28 2011-04-06 武汉立胜超滤科技发展有限公司 Electrophoresis coating method and whole set apparatus for pattern transfer of positive electrophoresis coating on printing board
CN108811359B (en) * 2018-07-03 2019-11-08 刘平 A kind of two-sided and multilayer printed circuit board production method

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DE3586263D1 (en) * 1984-03-07 1992-08-06 Ciba Geigy Ag METHOD FOR PRODUCING IMAGES.
US4592816A (en) * 1984-09-26 1986-06-03 Rohm And Haas Company Electrophoretic deposition process

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