JPH06155461A - Manufacture of laminate - Google Patents
Manufacture of laminateInfo
- Publication number
- JPH06155461A JPH06155461A JP4312135A JP31213592A JPH06155461A JP H06155461 A JPH06155461 A JP H06155461A JP 4312135 A JP4312135 A JP 4312135A JP 31213592 A JP31213592 A JP 31213592A JP H06155461 A JPH06155461 A JP H06155461A
- Authority
- JP
- Japan
- Prior art keywords
- laminate
- thermosetting resin
- paper
- water
- silver
- Prior art date
- Legal status (The legal status 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 status listed.)
- Pending
Links
- 238000004519 manufacturing process Methods 0.000 title description 2
- 229920005989 resin Polymers 0.000 claims abstract description 27
- 239000011347 resin Substances 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229920001187 thermosetting polymer Polymers 0.000 claims abstract description 14
- 229910052709 silver Inorganic materials 0.000 abstract description 24
- 239000004332 silver Substances 0.000 abstract description 24
- 239000012535 impurity Substances 0.000 abstract description 22
- 238000013508 migration Methods 0.000 abstract description 15
- 230000005012 migration Effects 0.000 abstract description 15
- 238000010828 elution Methods 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 6
- 239000000835 fiber Substances 0.000 abstract description 4
- 238000004061 bleaching Methods 0.000 abstract description 2
- 238000000034 method Methods 0.000 abstract description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 23
- 239000000123 paper Substances 0.000 description 15
- 239000003921 oil Substances 0.000 description 6
- 235000019198 oils Nutrition 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 5
- 238000012360 testing method Methods 0.000 description 4
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 229920003987 resole Polymers 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 244000055346 Paulownia Species 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 230000009545 invasion Effects 0.000 description 2
- 239000002383 tung oil Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 235000019492 Cashew oil Nutrition 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000010467 cashew oil Substances 0.000 description 1
- 229940059459 cashew oil Drugs 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 125000005456 glyceride group Chemical group 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- 239000002655 kraft paper Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 235000021388 linseed oil Nutrition 0.000 description 1
- 239000000944 linseed oil Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
Landscapes
- Reinforced Plastic Materials (AREA)
- Laminated Bodies (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は銀の移行現象の発生しに
くい（以下、耐銀移行性に優れたと称する）印刷回路板
用紙基材熱硬化性樹脂積層板（以下、積層板と称する）
に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is a printed circuit board paper base material thermosetting resin laminated plate (hereinafter referred to as laminated plate) in which silver migration phenomenon is unlikely to occur (hereinafter referred to as excellent in silver migration resistance).
Regarding
【０００２】[0002]
【従来の技術】従来、このような積層板は熱硬化性樹脂
配合物ワニスをクラフト紙またはリンター紙等に含浸さ
せ、該含浸紙を複数枚積層し用途に応じてこの片面又は
両面に接着剤付き銅箔を重ねた後、加熱加圧成形して製
造されている。このようにして得られた積層板は、温湿
度条件下において、積層板に形成された２つの銀電極
（銀ジャンパ、銀スルーホール等）間に電圧を加えると
時間経過に伴い銀の移行現象が発生することはよく知ら
れている。近年の電気製品の軽薄短小化の傾向は印刷回
路配線板の高密度化を要求し、銀スルーホール間ピッチ
も、２.５mm〜２.０mmへ狭小化し、現在では１.５mm ピ
ッチのものさえ実用化されようとしている。このため、
銀の移行現象による短絡が起こりやすくなり、印刷回路
板の信頼性を確保するため、より耐銀移行性の優れた積
層板の要求が高まっている。積層板における銀移行現象
は、以下の反応により銀がイオン化することが主要因で
あると考えられている。2. Description of the Related Art Conventionally, such a laminated board is obtained by impregnating kraft paper or linter paper with a varnish containing a thermosetting resin, laminating a plurality of the impregnated papers, and applying an adhesive on one or both sides depending on the application. It is manufactured by stacking coated copper foils and then heat-pressing. The laminated plate thus obtained exhibits a migration phenomenon of silver over time when a voltage is applied between two silver electrodes (silver jumper, silver through hole, etc.) formed on the laminated plate under temperature and humidity conditions. It is well known that In recent years, the trend toward lighter, thinner, shorter, and smaller electrical products requires higher density of printed circuit wiring boards, and the pitch between silver through-holes has been narrowed to 2.5 mm to 2.0 mm. It is about to be put to practical use. For this reason,
Short circuits due to the migration phenomenon of silver are likely to occur, and in order to secure the reliability of the printed circuit board, there is an increasing demand for a laminated board having more excellent silver migration resistance. It is considered that the silver migration phenomenon in the laminated plate is mainly due to the ionization of silver by the following reaction.
【０００３】[0003]
【化１】 [Chemical 1]
【０００４】この反応式に示されるように、銀のイオン
化が主要因であるため、銀移行現象の発生には積層板中
への水分の侵入が不可欠である。更に、侵入した水分中
にイオン性不純物が溶出することにより、積層板の電気
特性を劣化させ、特に銀のイオン化が促進され耐銀移行
性が著しく低下する。従って、積層板中への水分の侵入
を抑えるために、紙基材への樹脂の含浸性を高めたり、
樹脂を疎水性にするなどの方法がとられてきたが、紙基
材に樹脂を含浸させるという積層板の本質的特徴のため
大幅な改良には限界があった。As shown in this reaction formula, since the ionization of silver is the main factor, the penetration of water into the laminate is indispensable for the occurrence of the silver migration phenomenon. Further, the elution of ionic impurities into the invaded water deteriorates the electrical characteristics of the laminate, and particularly the ionization of silver is promoted, resulting in a marked decrease in silver migration resistance. Therefore, in order to suppress the invasion of water into the laminated board, it is possible to improve the impregnation property of the resin into the paper base material,
Although the method of making the resin hydrophobic has been taken, there has been a limit to the significant improvement due to the essential feature of the laminate in which the paper base material is impregnated with the resin.
【０００５】[0005]
【発明の解決しようとする課題】本発明は、高温高圧条
件下で積層板中より抽出されるイオン性不純物量を低減
することにより、耐銀移行性に優れた積層板を得ること
ができるとの知見を得、これに基づいて種々検討した結
果完成されたものである。According to the present invention, it is possible to obtain a laminate excellent in silver migration resistance by reducing the amount of ionic impurities extracted from the laminate under high temperature and high pressure conditions. It was completed as a result of various findings based on this knowledge.
【０００６】[0006]
【問題を解決するための手段】本発明は、加圧下で１２
０℃の熱水中で４８時間処理したときに、抽出されるＮ
ａ+ 及びＣｌ- の量が積層板の ０.１重量％以下である
ことを特徴とする積層板に関する。本発明者は、積層板
にイオン性不純物が含まれていても、水分中に溶出しな
ければ電気特性、特に銀移行現象に影響を与えないとい
う知見を得た。また銀移行現象の原因となる積層板中へ
の水分の侵入は、紙基材に樹脂を含浸させるという積層
板の本質的特徴からみて、完全には抑制できないと考
え、種々検討した結果、侵入した水分へ積層板中のイオ
ン性不純物が溶出するのを抑えることにより耐銀移行性
を向上させることに成功したものである。侵入した水分
中へのイオン性不純物の溶出を抑える手段としては、 水洗処理などを施したイオン性不純物含量の少ない
樹脂を用いる、 紙の漂白工程の変更によるイオン性不純物含量の少
ない紙を用いる、 熱硬化性樹脂を含浸させる前に、紙の繊維表面を水
溶性熱硬化性樹脂でコーティングすることにより紙に含
まれるイオン性不純物の溶出を抑える、 という３つの手段がある。SUMMARY OF THE INVENTION The present invention provides 12
N extracted when treated in hot water at 0 ° C for 48 hours
It relates to a laminate characterized in that the amount of a + and Cl − is not more than 0.1% by weight of the laminate. The present inventor has found that even if the laminated plate contains an ionic impurity, it does not affect the electrical characteristics, particularly the silver migration phenomenon, unless it is eluted into water. In addition, it is thought that the invasion of water into the laminate, which causes the phenomenon of silver migration, cannot be completely suppressed in view of the essential feature of the laminate in which the paper base material is impregnated with resin. By suppressing the elution of ionic impurities in the laminated plate into the water content, the silver migration resistance was successfully improved. As a means to suppress the elution of ionic impurities into the invading water, use a resin with a low ionic impurity content that has been washed with water, use a paper with a low ionic impurity content by changing the bleaching process of the paper, There are three means of suppressing the elution of ionic impurities contained in the paper by coating the fiber surface of the paper with the water-soluble thermosetting resin before impregnating the thermosetting resin.
【０００７】また、積層板中へ侵入した水分へのイオン
性不純物の溶出量は、下記のように高温高圧条件下で抽
出されるイオン性不純物量により測定することができ
る。 （測定方法）板厚１.６mm の積層板を２５mm×２５mmの
正方形に裁断しよく洗浄する。この積層板４枚を純水４
０ｍｌと共に耐圧容器中に入れ、１２０℃で４８時間熱
水中で抽出し、抽出液中のイオン濃度をイオンクロマト
グラフィーにて測定する。このイオン濃度の値を積層板
の重量に対する割合に換算する。本発明においては、抽
出されるイオンとしてＮａ+ 及びＣｌ- を代表に選ん
だ。その他のイオンはＮａ+ 及びＣｌ- に比較すれば少
なく、抽出される種々のイオン濃度の割合も積層板によ
って大差はない。本発明で用いられる熱硬化性樹脂とし
ては、フェノール樹脂、エポキシ樹脂、不飽和ポリエス
テル樹脂、メラミン樹脂など、またこれらを桐油、トー
ル脂肪酸、カシュー油、アマニ油、ヒマシ油、リノレン
油、リノール油、エポキシ化植物油などの乾性油、半乾
性油、あるいはこれらのグリセリド、エポキシ化ポリブ
タジエン、ポリエチレングリコール、ポリエステル、ポ
リエーテルなどの可撓性付与剤で変性したものがあげら
れ、これらは単独又は併用して用いられる。Further, the elution amount of ionic impurities into the water that has penetrated into the laminated plate can be measured by the amount of ionic impurities extracted under high temperature and high pressure conditions as described below. (Measurement method) A 1.6 mm thick laminated plate is cut into 25 mm x 25 mm squares and thoroughly washed. Pure water 4
It is put in a pressure resistant container together with 0 ml and extracted in hot water at 120 ° C. for 48 hours, and the ion concentration in the extract is measured by ion chromatography. The value of this ion concentration is converted into a ratio with respect to the weight of the laminated plate. In the present invention, Na + and Cl − are selected as representative ions to be extracted. The amount of other ions is smaller than that of Na + and Cl − , and the ratios of various ion concentrations to be extracted do not differ much depending on the laminated plate. As the thermosetting resin used in the present invention, phenol resin, epoxy resin, unsaturated polyester resin, melamine resin and the like, and tung oil, tall fatty acid, cashew oil, linseed oil, castor oil, linolenic oil, linole oil, Drying oils such as epoxidized vegetable oils, semi-drying oils, or glycerides thereof, those modified with a flexibility-imparting agent such as epoxidized polybutadiene, polyethylene glycol, polyester, polyether, and the like, and these may be used alone or in combination. Used.
【０００８】[0008]
【実施例】以下、本発明を実施例に基づいて詳細に説明
するが、本発明はこれに限定されるものではない。 《実施例１》イオン性不純物含量の少ない紙（Ｎａ+：
０.４８％，Ｃｌ-：０.９５％）に、予め水溶性熱硬化
樹脂にて紙繊維表面をコーティングした。次いで、水洗
などでイオン性不純物含量を減少させた桐油変性率３５
％のレゾール樹脂を含浸させてプリプレグａ（樹脂付着
量４５〜５０％）を得た。 《実施例２》イオン性不純物含量の多い紙（Ｎａ+：０.
９２％，Ｃｌ-：１.９５％）に、予め水溶性熱硬化樹脂
にて紙繊維表面をコーティングした。次いで、水洗など
でイオン性不純物含量を減少させた桐油変性率３５％の
レゾール樹脂を含浸させてプリプレグｂ（樹脂付着量４
５〜５０％）を得た。EXAMPLES The present invention will now be described in detail based on examples, but the present invention is not limited thereto. Example 1 Paper with a low content of ionic impurities (Na + :
0.48%, Cl − : 0.95%), the surface of the paper fiber was previously coated with a water-soluble thermosetting resin. Then, the paulownia oil modification rate of 35 was obtained by reducing the content of ionic impurities by washing with water.
% Resol resin was impregnated to obtain a prepreg a (resin adhesion amount 45 to 50%). Example 2 Paper with a high ionic impurity content (Na + : 0.03).
92%, Cl − : 1.95%) was previously coated on the surface of the paper fiber with a water-soluble thermosetting resin. Next, a prepreg b (resin adhesion amount 4
5 to 50%) was obtained.
【０００９】《比較例１》イオン性不純物含量の多い紙
に（Ｎａ+：０.９２％，Ｃｌ-：１.９５％）、桐油変性
率３５％のレゾール樹脂を含浸させてプリプレグｃ（樹
脂付着量４５〜５０％）を得た。 《比較例２》イオン性不純物含量の少ない紙（Ｎａ+：
０.４８％，Ｃｌ-：０.９５％）に、水洗などでイオン
性不純物含有量を減少させた桐油変性率３５％のレゾー
ル樹脂を含浸させてプリプレグｄ（樹脂付着量４５〜５
０％）を得た。Comparative Example 1 Paper containing a large amount of ionic impurities (Na + : 0.92%, Cl − : 1.95%) was impregnated with a resole resin having a tung oil modification rate of 35% to prepare a prepreg c (resin). An adhesion amount of 45-50%) was obtained. << Comparative Example 2 >> Paper containing a small amount of ionic impurities (Na + :
(0.48%, Cl − : 0.95%) is impregnated with a resole resin having a paulownia oil modification rate of 35%, which has a reduced ionic impurity content by washing with water, and the like, and is impregnated with prepreg d (resin adhesion amount 45 to 5).
0%).
【００１０】前記のようにして得られたそれぞれのプリ
プレグ８枚と接着剤付き銅箔とを１組として加熱加圧
し、板厚１.６mmの４種類の積層板Ａ，Ｂ，Ｃ及びＤを
得た。以上得られた積層板の特性を表１に示す。Eight pieces of each prepreg obtained as described above and a copper foil with an adhesive as one set are heated and pressed to obtain four kinds of laminated plates A, B, C and D having a thickness of 1.6 mm. Obtained. Table 1 shows the properties of the laminated board obtained above.
【表１】 [Table 1]
【００１１】（試験方法） １．抽出イオン性不純物量 よく洗浄し、２５mm×２５mmに切断した板厚１.６mm の
積層板４枚を４０mlの純水とともに耐圧容器に入れ、１
２０℃で４８時間抽出した後、耐圧容器内の水中に含ま
れるイオン性不純物量を測定した。更に、この値から積
層板に含まれるイオン性不純物の含有量を求めた。 ２．耐銀移行性 ランド径１.５mm、スルーホール径０.７mmの銀スル
ーホールが１００穴連続してつながっている回路２本
を、スルーホール間ピッチが ２.０mmになるように隣接
して配置したテストパターンを作成した。このテストパ
ターンを使用して、印加電圧５０ＶＤＣ、温度４０℃、
湿度９３％ＲＨの条件下にて２０００時間処理後の回路
間絶縁抵抗を測定した。 ランド径１.２mm、スルーホール径０.４mmの銀スル
ーホールが１００穴連続してつながっている回路２本
を、スルーホール間ピッチが １.５mmになるように隣接
して配置したテストパターンを作成した。このテストパ
ターンを使用して、印加電圧５０ＶＤＣ、温度４０℃、
湿度９３％ＲＨの条件下にて２０００時間処理後の回路
間絶縁抵抗を測定した。(Test method) 1. Amount of extracted ionic impurities Washed well and put four 1.6 mm thick laminated plates cut into 25 mm x 25 mm into a pressure vessel with 40 ml of pure water.
After extraction at 20 ° C. for 48 hours, the amount of ionic impurities contained in water in the pressure vessel was measured. Furthermore, the content of the ionic impurities contained in the laminate was determined from this value. 2. Resistance to silver migration Two circuits with 100 continuous silver through-holes with a land diameter of 1.5 mm and a through-hole diameter of 0.7 mm are arranged adjacent to each other with a pitch between the through-holes of 2.0 mm. The test pattern was created. Using this test pattern, applied voltage 50VDC, temperature 40 ℃,
The insulation resistance between circuits was measured after 2000 hours of treatment under the condition of a humidity of 93% RH. A test pattern in which two circuits in which 100 silver through-holes with a land diameter of 1.2 mm and a through-hole diameter of 0.4 mm are continuously connected are arranged adjacent to each other with a pitch between through holes of 1.5 mm. Created. Using this test pattern, applied voltage 50VDC, temperature 40 ℃,
The insulation resistance between circuits was measured after 2000 hours of treatment under the condition of a humidity of 93% RH.
【００１２】[0012]
【発明の効果】以上の結果から明らかなように、本発明
の積層板は極めて優れた耐銀移行性を有する。As is clear from the above results, the laminate of the present invention has extremely excellent resistance to silver migration.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｈ０５Ｋ 1/03 Ｊ 7011−4Ｅ // Ｂ２９Ｄ 9/00 8823−4Ｆ Ｂ２９Ｋ 105:06 ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 5 Identification number Office reference number FI technical display location H05K 1/03 J 7011-4E // B29D 9/00 8823-4F B29K 105: 06
Claims (1)
の熱水中で４８時間処理したときに、抽出されるＮａ+
及びＣｌ- の量が前記熱硬化性樹脂積層板の０.１重量
％以下であることを特徴とする紙基材熱硬化性樹脂積層
板。1. A thermosetting resin laminate is heated to 120 ° C. under pressure.
Na + extracted when treated in hot water for 48 hours
And the amount of Cl − is 0.1% by weight or less of the thermosetting resin laminate, a paper-based thermosetting resin laminate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4312135A JPH06155461A (en) | 1992-11-20 | 1992-11-20 | Manufacture of laminate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4312135A JPH06155461A (en) | 1992-11-20 | 1992-11-20 | Manufacture of laminate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH06155461A true JPH06155461A (en) | 1994-06-03 |
Family
ID=18025680
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4312135A Pending JPH06155461A (en) | 1992-11-20 | 1992-11-20 | Manufacture of laminate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH06155461A (en) |
-
1992
- 1992-11-20 JP JP4312135A patent/JPH06155461A/en active Pending
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