JP2001181417A - Prepreg and copper-clad laminate - Google Patents
Prepreg and copper-clad laminateInfo
- Publication number
- JP2001181417A JP2001181417A JP37338199A JP37338199A JP2001181417A JP 2001181417 A JP2001181417 A JP 2001181417A JP 37338199 A JP37338199 A JP 37338199A JP 37338199 A JP37338199 A JP 37338199A JP 2001181417 A JP2001181417 A JP 2001181417A
- Authority
- JP
- Japan
- Prior art keywords
- phenol
- resin
- modified
- copper
- prepreg
- 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.)
- Withdrawn
Links
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- Reinforced Plastic Materials (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、耐熱性、耐湿性及
び打抜加工性に優れるフェノール樹脂を用いたプリプレ
グ及び銅張積層板に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a prepreg and a copper-clad laminate using a phenolic resin having excellent heat resistance, moisture resistance and punching workability.
【０００２】[0002]
【従来の技術】紙基材フェノール樹脂積層板は、加工性
が良いため、打抜加工が多用されている。フェノール類
とホルムアルデヒドだけで合成されたフェノール樹脂
は、硬く、可塑性が無く、現在の積層板に要求されてい
る打抜加工性が得られない。そのために、低弾性率の紙
基材を使用する。このほか、フェノール樹脂自体に可塑
性を付与するようにしている。フェノール樹脂に可塑性
を付与する手段としては、乾性油でフェノール樹脂を変
性する手法が広く採用されている。2. Description of the Related Art A punching process is frequently used for a paper-based phenolic resin laminate because of its good workability. A phenolic resin synthesized only with phenols and formaldehyde is hard, lacks plasticity, and cannot provide the punching workability required for a current laminate. For this purpose, a low elastic modulus paper substrate is used. In addition, plasticity is imparted to the phenol resin itself. As a means for imparting plasticity to a phenol resin, a technique of modifying the phenol resin with a drying oil is widely used.
【０００３】また、基材としては、クラフト紙、リンタ
ー紙等の紙を用いる。紙基材に水溶性メラミン樹脂、ま
たは水溶性フェノール樹脂を含浸した後、乾性油変性フ
ェノール樹脂を含浸して難燃性、耐湿性などを向上させ
る方法も知られている。[0003] Paper such as kraft paper and linter paper is used as a base material. A method is also known in which a paper base material is impregnated with a water-soluble melamine resin or a water-soluble phenol resin, and then impregnated with a dry oil-modified phenol resin to improve flame retardancy, moisture resistance, and the like.
【０００４】[0004]
【発明が解決しようとする課題】しかしながら、乾性油
変性フェノール樹脂を用いた場合、耐熱性、耐湿性、打
抜加工性が劣ることがあるという問題があった。また、
紙基材を水溶性メラミン樹脂で処理すると、難燃性が向
上するが、耐湿性が劣る。また、紙基材を水溶性フェノ
ール樹脂で処理すると、耐熱性、耐湿性は向上するが、
難燃性、打抜加工性が劣り、諸特性をバランスよくとる
のが困難であった。そこで、本発明は、耐熱性、耐湿性
及び打抜加工性に優れるフェノール樹脂を用いたプリプ
レグ及び銅張り積層板を提供するものである。However, when a dry oil-modified phenol resin is used, there has been a problem that heat resistance, moisture resistance and punching workability may be inferior. Also,
When a paper substrate is treated with a water-soluble melamine resin, flame retardancy is improved, but moisture resistance is poor. When the paper base is treated with a water-soluble phenol resin, heat resistance and moisture resistance are improved,
Flame retardancy and punching workability were poor, and it was difficult to balance various properties. Therefore, the present invention provides a prepreg and a copper-clad laminate using a phenol resin having excellent heat resistance, moisture resistance and punching workability.
【０００５】[0005]
【課題を解決するための手段】本発明は、次のものに関
する。 （１） 基材に乾性油変性フェノール樹脂ワニスを含浸
し、加熱乾燥させてなるプリプレグにおいて、乾性油変
性フェノール樹脂が、フェノール若しくはフェノールと
改質樹脂の反応物と乾性油との反応物であって、重量平
均分子量が５０００〜２２０００であるものにアルデヒ
ドを反応させて得られるものであるプリプレグ。 （２） 項（１）記載のプリプレグを複数枚重ね、その
片面若しくは両面に銅はくを重ね併せ、加熱加圧成形し
てなる銅張積層板。The present invention relates to the following. (1) In a prepreg obtained by impregnating a substrate with a drying oil-modified phenol resin varnish and drying by heating, the drying oil-modified phenol resin is a reaction product of phenol or a reaction product of phenol and a modified resin with a drying oil. A prepreg obtained by reacting an aldehyde with a compound having a weight average molecular weight of 5,000 to 22,000. (2) A copper-clad laminate obtained by laminating a plurality of the prepregs according to item (1), laminating copper foil on one or both sides thereof, and forming the laminate under heat and pressure.
【０００６】[0006]
【発明の実施の形態】基材としては、打ち抜き加工性の
点から、紙系基材を用いるのが好ましい。紙系基材とし
ては、クラフトパルプを抄造して得られるクラフト紙が
主に用いられるが、コットンリンター紙、リンターとク
ラフトパルプの混抄紙、ガラスペーパー、ガラス不織
布、ガラス繊維と紙繊維との混抄紙なども使用できる。
これらの基材には、乾性油変性フェノール樹脂との親和
性を良好にするためにあらかじめ水溶性フェノール樹
脂、メラミン樹脂等の下塗り剤を付着させておくのが好
ましい。BEST MODE FOR CARRYING OUT THE INVENTION As a substrate, it is preferable to use a paper-based substrate from the viewpoint of punching workability. Kraft paper obtained by making kraft pulp is mainly used as a paper base material.Cotton linter paper, mixed paper of linter and kraft pulp, glass paper, glass nonwoven fabric, and mixture of glass fiber and paper fiber are used. Papermaking can also be used.
It is preferable that an undercoat agent such as a water-soluble phenol resin or a melamine resin is previously adhered to these base materials in order to improve the affinity with the drying oil-modified phenol resin.
【０００７】本発明において、乾性油変性フェノール樹
脂は、フェノール類と乾性油とを酸触媒の存在下に反応
させることにより乾性油をフェノール類に付加させ，乾
性油を付加したフェノール類とアルデヒド類とをアルカ
リ触媒の存在下に反応させることにより製造されるも
の、また、フェノール類と改質樹脂とを予め反応させて
おき、得られたフェノール類と改質樹脂との反応物に乾
性油を酸触媒の存在下に反応た後、反応生成物とアルデ
ヒド類とをアルカリ触媒の存在下に反応させることによ
り製造されるものである。In the present invention, the drying oil-modified phenol resin is obtained by reacting a phenol with a drying oil in the presence of an acid catalyst to add the drying oil to the phenol, and the phenol and aldehyde to which the drying oil has been added. And phenols and a modified resin are reacted in advance, and a drying oil is added to the reaction product between the obtained phenols and the modified resin. It is produced by reacting the reaction product with an aldehyde in the presence of an alkali catalyst in the presence of an acid catalyst.
【０００８】上記の乾性油変性フェノール樹脂におい
て、フェノール若しくはフェノールと改質樹脂の反応物
と乾性油との反応物の重量平均分子量は、５０００〜２
２０００、好ましくは６，０００〜２０，０００、より
好ましくは１０，０００〜１８，０００である。上記反
応物の重量平均分子量が５，０００未満では、架橋密度
が低く、耐熱性、耐湿性、打抜加工性がり、上記反応物
の重量平均分子量が２２，０００を超えるものを得るこ
とは通常の反応では難しく、増粘したり、ワニスの保存
安定性等の管理が困難になる。また、紙への含浸性も低
下し、積層板用フェノール樹脂として適さなくなる。な
お、本発明おいて、重量平均分子量は、ゲルパーミエー
ションクロマトグラフィーにより、標準ポリスチレンの
検量線を用いて測定したものである。In the above-mentioned drying oil-modified phenol resin, the weight average molecular weight of the reaction product of phenol or phenol and the modified resin and the drying oil is 5,000 to 2
2000, preferably 6,000-20,000, more preferably 10,000-18,000. When the weight average molecular weight of the reactant is less than 5,000, the crosslinking density is low, heat resistance, moisture resistance, punching workability are increased, and it is usual to obtain the reactant having a weight average molecular weight exceeding 22,000. The reaction is difficult, and it becomes difficult to control the varnish, such as thickening and storage stability. In addition, the impregnating property of the paper is reduced, and the paper is not suitable as a phenol resin for a laminate. In the present invention, the weight average molecular weight is measured by gel permeation chromatography using a standard polystyrene calibration curve.
【０００９】前記フェノール類としては、フェノール、
メタクレゾール、パラクレゾール、オルソクレゾール、
イソプロピルフェノール、パラターシャリブチルフェノ
ール、パライソプロペニルフェノールオリゴマー、ノニ
ルフェノール、ビスフェノールＡ、キシレノール、カテ
コール、レゾルシン、ヒドロキノン等を用いることがで
きる。The phenols include phenol,
Meta-cresol, para-cresol, ortho-cresol,
Isopropyl phenol, para-tert-butyl phenol, para-isopropenyl phenol oligomer, nonyl phenol, bisphenol A, xylenol, catechol, resorcin, hydroquinone and the like can be used.
【００１０】発明で用いられる改質樹脂としては、キシ
レン樹脂などが挙げられる。改質樹脂は、フェノール類
１００重量部に対して１０〜５０重量部の範囲で配合さ
れるのが好ましく、２０〜４０重量部の範囲で配合され
ることがより好ましい。改質樹脂の配合量が、１０重量
部未満であるとフェノール類と乾性油との反応の際にゲ
ル化を生ずる可能性があり、５０重量部を超えると、レ
ゾール反応を経て得られるワニスの相溶性が不充分とな
る可能性がある。The modified resin used in the present invention includes a xylene resin and the like. The modified resin is preferably blended in a range of 10 to 50 parts by weight, more preferably 20 to 40 parts by weight, based on 100 parts by weight of the phenol. If the amount of the modified resin is less than 10 parts by weight, gelation may occur during the reaction between the phenol and the drying oil. If the amount exceeds 50 parts by weight, the varnish obtained via the resole reaction may be used. The compatibility may be insufficient.
【００１１】フェノール類と改質樹脂とは、酸触媒の存
在下に、フェノール類の還流温度で加熱することにより
反応させることができる。この反応に使用される酸触媒
としては、パラトルエンスルホン酸、ベンゼンスルホン
酸などが挙げられる。酸触媒は、フェノール類１００重
量部に対して、０．０８〜０．３重量部の範囲で配合さ
れるのが好ましく、０．１０〜０．２０重量部の範囲で
配合されるのがより好ましい。０．０８重量部未満では
反応が遅くて工業的生産性が低下する傾向にあり、０．
３重量部を超えると積層板としたときの電気的特性が低
下する傾向にある。The phenol and the modified resin can be reacted by heating at the reflux temperature of the phenol in the presence of an acid catalyst. Examples of the acid catalyst used in this reaction include p-toluenesulfonic acid, benzenesulfonic acid and the like. The acid catalyst is preferably blended in a range of 0.08 to 0.3 parts by weight, more preferably in a range of 0.10 to 0.20 parts by weight, based on 100 parts by weight of the phenol. preferable. If it is less than 0.08 parts by weight, the reaction tends to be slow and the industrial productivity tends to decrease.
If the amount exceeds 3 parts by weight, the electrical properties of the laminate tend to decrease.
【００１２】前記の乾性油としては、桐油、アマニ油、
脱水ヒマシ油、オイチシカ油、サフラワー油、大豆油、
ゴマ油、綿実油等が使用される。乾性油は、フェノール
類又はフェノール類と改質樹脂との反応物１００重量部
に対して、３０〜７０重量部の範囲で配合されるのが好
ましく、４０〜６０重量部の範囲で配合されるのがより
好ましい。３０重量部より少ないと打ち抜き加工性が低
下する傾向にあり、７０重量部を超えるとフェノール積
層板の硬化性が低下する傾向にあるThe drying oil includes tung oil, linseed oil,
Dehydrated castor oil, deer oil, safflower oil, soybean oil,
Sesame oil, cottonseed oil and the like are used. The drying oil is preferably blended in an amount of 30 to 70 parts by weight, and more preferably in an amount of 40 to 60 parts by weight, based on 100 parts by weight of the phenol or the reaction product of the phenol and the modified resin. Is more preferred. If the amount is less than 30 parts by weight, the punchability tends to decrease, and if it exceeds 70 parts by weight, the curability of the phenol laminate tends to decrease.
【００１３】フェノール類又はフェノール類と改質樹脂
との反応物に乾性油を付加させる反応はフェノール類と
改質樹脂との反応と同様にして酸触媒の存在下に行われ
る。酸触媒としては、前記したものが使用できるが、フ
ェノール類と改質樹脂との反応物を使用した場合は、別
途配合する必要はなく、フェノール類と改質樹脂との反
応に際して用いられた酸触媒をそのまま作用させること
ができる。The reaction of adding a drying oil to the phenol or a reaction product of the phenol and the modified resin is carried out in the presence of an acid catalyst in the same manner as the reaction between the phenol and the modified resin. As the acid catalyst, those described above can be used, but when a reactant of a phenol and a modified resin is used, it is not necessary to separately mix the acid and the acid used in the reaction between the phenol and the modified resin. The catalyst can be used as it is.
【００１４】乾性油を反応させた後、アルデヒド類をア
ルカリ触媒の存在下に反応させ、その後脱水濃縮するこ
とにより乾性油変性フェノール樹脂（レゾール樹脂）が
得られる。アルデヒド類としては、ホルムアルデヒド、
パラホルムアルデヒド、アセトアルデヒド、パラアセト
アルデヒド、ブチルアルデヒド、オクチルアルデヒド、
べンズアルデヒドなどが挙げられる。一般にはホルムア
ルデヒド又はパラホルムアルデヒドが使用される。After the reaction of the drying oil, the aldehyde is reacted in the presence of an alkali catalyst, followed by dehydration and concentration to obtain a drying oil-modified phenol resin (resole resin). Aldehydes include formaldehyde,
Paraformaldehyde, acetaldehyde, paraacetaldehyde, butyraldehyde, octylaldehyde,
Benzaldehyde and the like. Generally, formaldehyde or paraformaldehyde is used.
【００１５】アルデヒド類は、乾性油を付加させたフェ
ノール類又はフェノール類と改質樹脂との反応物のフェ
ノール性水酸基１モルに対して１．１〜１．５モルの範
囲で配合されるのが好ましく、１．１５〜１．４モルの
範囲で配合されるのがより好ましい。アルデヒド類が少
なすぎると、樹脂の架橋密度が小さくなり、電気的な諸
特性が不充分となる傾向があり、アルデヒド類が多すぎ
ると、未反応のアルデヒド類が残留する傾向がある。ア
ルカリ触媒は、金属イオンを含まないアンモニア、１級
アミン、２級アミン、３級アミン（例えば、トリメチル
アミン、トリエチルアミン、トリ−ｎ−プロピルアミ
ン、ベンジルアミンなど）が好ましく用いられる。これ
らのアルカリ触媒は電気的な諸特性を低下させるような
金属イオンを含まないからである。アルカリ触媒は、乾
性油を付加させたフェノール類と改質樹脂との反応物の
フェノール性水酸基１モルに対して０．８〜１．５モル
の範囲とするのが好ましく、１．０〜１．３モルの範囲
とするのがより好ましい。０．８モル未満であると未反
応物が残り、積層板としたときの耐熱性が低下する傾向
にあり、１．５モルを超えると反応が進み過ぎて高分子
量化して含浸などの作業性を低下させる傾向がある。The aldehyde is added in an amount of 1.1 to 1.5 moles per 1 mole of the phenolic hydroxyl group of the phenol to which the drying oil has been added or the reaction product of the phenol and the modified resin. , And more preferably in the range of 1.15 to 1.4 mol. If the amount of aldehydes is too small, the crosslink density of the resin tends to be low, and electrical properties tend to be insufficient. If the amount of aldehydes is too large, unreacted aldehydes tend to remain. Ammonia, primary amine, secondary amine, tertiary amine (for example, trimethylamine, triethylamine, tri-n-propylamine, benzylamine, etc.) containing no metal ion are preferably used as the alkali catalyst. This is because these alkali catalysts do not contain metal ions that degrade electrical properties. The amount of the alkali catalyst is preferably in the range of 0.8 to 1.5 mol, and more preferably in the range of 1.0 to 1 mol, per mol of the phenolic hydroxyl group of the reaction product of the phenol to which the drying oil has been added and the modified resin. More preferably, it is in the range of 0.3 mol. If the amount is less than 0.8 mol, unreacted substances remain, and the heat resistance of the laminated board tends to decrease. If the amount exceeds 1.5 mol, the reaction proceeds too much to increase the molecular weight and workability such as impregnation. Tends to decrease.
【００１６】本発明の方法により製造された乾性油変性
フェノール樹脂は溶剤に溶解してワニスとして基材に含
浸され１る。ワニスとするときの溶剤としては、トルエ
ン、メタノール、メチルエチルケトン、２−メトキシエ
タノール、アセトン、スチレンなどが用いられ、特に制
限ない。ワニスには、臭素系難燃剤、りん系難燃剤など
の各種難燃剤その他の添加剤を配合してもよく、配合す
る添加剤については特に制限はない。The dry oil-modified phenolic resin produced by the method of the present invention is dissolved in a solvent and impregnated into a substrate as a varnish. As a solvent for forming a varnish, toluene, methanol, methyl ethyl ketone, 2-methoxyethanol, acetone, styrene and the like are used without any particular limitation. The varnish may be blended with various flame retardants such as a brominated flame retardant and a phosphorus flame retardant, and other additives, and the additives to be blended are not particularly limited.
【００１７】また、リン酸エステルのようなリン系化合
物、ブロム化フェノールやブロム化エポキシ化合物のよ
うなブロム系化合物、メラミン化合物やトリアジン化合
物のような窒素系化合物又は三酸化アンチモンのような
無機化合物を単独または混合して乾性油変性フェノール
樹脂に添加して難燃化することができる。具体的には、
前記ワニスに添加、配合すればよい。Further, phosphorus compounds such as phosphate esters, bromo compounds such as brominated phenols and brominated epoxy compounds, nitrogen compounds such as melamine compounds and triazine compounds, and inorganic compounds such as antimony trioxide. Can be added to the drying oil-modified phenolic resin alone or as a mixture to make it flame-retardant. In particular,
What is necessary is just to add and mix with the said varnish.
【００１８】前記のワニスを基材に含浸乾燥してプリプ
レグとし、得られたプリプレグを所定枚数重ね、加熱加
圧することによりフェノール樹脂積層板が得られる。こ
のとき、プリプレグの最外層に銅はくを重ねることによ
り銅張積層板とすることができる。加熱加圧条件につい
ては特に制限はなく、公知の条件、例えば、温度は１５
０〜１８０℃、圧力は９〜２０ＭＰａ、成形時間は８０
〜１００分間がそれぞれ好ましい。なお、銅はくとして
は、接着剤付き銅はくを用いることが好ましい。上記の
銅張積層板は、常法に従い回路加工することによりプリ
ント配線板とすることができる。The varnish is impregnated into a substrate and dried to form a prepreg. A predetermined number of the obtained prepregs are stacked, and heated and pressed to obtain a phenol resin laminate. At this time, a copper clad laminate can be obtained by laminating a copper foil on the outermost layer of the prepreg. The heating and pressing conditions are not particularly limited, and known conditions, for example, a temperature of 15
0-180 ° C, pressure 9-20MPa, molding time 80
-100 minutes are preferred. In addition, it is preferable to use a copper foil with an adhesive as the copper foil. The above-mentioned copper-clad laminate can be made into a printed wiring board by processing a circuit according to a conventional method.
【００１９】[0019]
【実施例】次に、本発明の実施例を示す。以下、「部」
は「重量部」を意味する。 実施例１ （１）桐油変性フェーノール樹脂ワニスの調製 フェノール３７１部、キシレン樹脂（三菱瓦新化学株式
会社製、ニカノールＨ（商品名）を使用）３０部及ぴパ
ラ卜ルエンスルホンホン酸０．２部を反応釜に仕込み、
９０℃で１時間反応させた後、桐油２００部を投入し、
９０℃で１時間反応させて、重量平均分子量６，０００
とした桐油変性率３５％の桐油−フエノール付加反応物
を得た。得られた桐油−フェノール付加反応物１００
部、パラホルムアルデヒド２７部（桐油−フェノール付
加反応物のフェノール性水酸基１モルに対し、ホルムア
ルデヒド１．２モル相当量）及び２５重量％アンモニア
水２．５部を反応釜に仕込み、７５℃で２時間反応させ
た後、減圧下で脱水濃縮して桐油変性フェノール樹脂を
得た。得られた桐油変性フェノール樹脂にメタノールを
５０部加えて桐油変性フェーノール樹脂ワニスを調製し
た。 （２）水溶性フェノール樹脂ワニスの調製 フェノール１モルを反応釜に仕込み、これに３７重量％
ホルマリンをホルムアルデヒド換算で１．２モル相当量
加え、次に３０重量％トリメチルアミン水溶液をトリメ
チルアミン０．４モル相当量加え、７０℃で６時間反応
させ、これに、メタノールと水の等重量混合溶剤を加え
て固形分２０重量％の水溶性フェノール樹脂ワニスを調
製した。 （３）プリプレグの調製 上記で得た水溶性フェノール樹脂を付着樹脂分が１６〜
２４％になるように、紙基材（クラフト紙、坪量１２０
ｇ／ｍ2）に含浸乾燥し，更に桐油変性率が３５％であ
るフェノール樹脂を樹脂付着量４８〜６０％になるよう
に含浸乾燥し，プリプレグを得た。 （４）両面銅張積層板の調製 このプリプレグ８枚と接着剤付き銅はく２枚を重ね合わ
せ，１７０℃，１０ＭＰａで加熱加圧して１．６ｍｍの
両面銅張積層板を得た。Next, examples of the present invention will be described. Below,
Means "parts by weight". Example 1 (1) Preparation of Tung Oil Modified Phenol Resin Varnish 371 parts of phenol, 30 parts of xylene resin (using Nikanol H (trade name) manufactured by Mitsubishi Kawashin Chemical Co., Ltd.) and 0.2 parts of paratoluenesulfonic acid 0.2 Parts into a reaction kettle,
After reacting at 90 ° C. for 1 hour, 200 parts of tung oil is added,
The mixture was reacted at 90 ° C. for 1 hour, and had a weight average molecular weight of 6,000.
Tung oil-phenol addition reaction product having a modified tung oil ratio of 35% was obtained. The obtained tung oil-phenol addition reaction product 100
Parts, 27 parts of paraformaldehyde (equivalent to 1.2 mol of formaldehyde with respect to 1 mol of phenolic hydroxyl groups of the tung oil-phenol addition reaction product) and 2.5 parts of 25% by weight ammonia water were charged into a reaction vessel, and the mixture was charged at 75 ° C with 2 parts. After reacting for an hour, the mixture was dehydrated and concentrated under reduced pressure to obtain a tung oil-modified phenol resin. 50 parts of methanol was added to the obtained tung oil-modified phenol resin to prepare a tung oil-modified phenol resin varnish. (2) Preparation of water-soluble phenolic resin varnish 1 mol of phenol was charged into a reaction vessel, and 37% by weight was added thereto.
Formalin was added in an amount equivalent to 1.2 moles in terms of formaldehyde, then a 30% by weight aqueous solution of trimethylamine was added in an amount equivalent to 0.4 moles of trimethylamine, and reacted at 70 ° C. for 6 hours. In addition, a water-soluble phenol resin varnish having a solid content of 20% by weight was prepared. (3) Preparation of prepreg The water-soluble phenolic resin obtained above had a resin content of 16 to
Paper base material (kraft paper, basis weight 120
g / m 2 ), and further impregnated and dried with a phenol resin having a tung oil modification rate of 35% to a resin adhesion amount of 48 to 60% to obtain a prepreg. (4) Preparation of double-sided copper-clad laminate The eight prepregs and two copper foils with an adhesive were overlapped, and heated and pressed at 170 ° C. and 10 MPa to obtain a 1.6-mm double-sided copper-clad laminate.
【００２０】実施例２ 実施例１において，桐油投入後，９０℃で２時間反応さ
せた反応物の重量平均分子量を１４，０００としたこと
以外は実施例１と全く同様にして桐油変性フェノール樹
脂を得た。以下実施例１と同様にして片面銅張積層板を
作製した。Example 2 Tung oil-modified phenolic resin was prepared in exactly the same manner as in Example 1 except that the weight-average molecular weight of the reaction product obtained after charging tung oil at 90 ° C. for 2 hours was 14,000. I got Thereafter, a single-sided copper-clad laminate was produced in the same manner as in Example 1.
【００２１】実施例３ 実施例１において，桐油投入後，９ぴＣで３時間反応さ
せた反応物の重量平均分子量を２０，０００としたこと
以外は実施例１と全く同様にして桐油変性フェノール樹
脂を得た。以下実施例１と同様にして片面銅張フェノー
ル樹脂積層板を作製した。Example 3 Tung oil-modified phenol was prepared in exactly the same manner as in Example 1 except that the weight average molecular weight of the reaction product, which was reacted at 9 ° C. for 3 hours after the addition of tung oil, was 20,000. A resin was obtained. Thereafter, a single-sided copper-clad phenolic resin laminate was produced in the same manner as in Example 1.
【００２２】比較例１ 実施例１において，桐油投入後，９０℃で３０分反応さ
せた反応物の重量平均分子量を３，０００としたこと以
外は実施例１と全く同様にして桐油変性フェノール樹脂
を得た。以下実施例１と同様にして片面銅張フェノール
樹脂積層板を作製した。Comparative Example 1 Tung oil-modified phenolic resin was prepared in exactly the same manner as in Example 1 except that the weight average molecular weight of the reaction product obtained after charging the tung oil at 90 ° C. for 30 minutes was 3,000. I got Thereafter, a single-sided copper-clad phenolic resin laminate was produced in the same manner as in Example 1.
【００２３】得られた積層板の打抜加工性、耐熱性、耐
湿性試験を行った。その結果を表１に示す。また、前記
実施例で得られた銅張り積層板に対して通常のエッチン
グ加工を施してプリント配線板を作製した。The obtained laminate was subjected to punching workability, heat resistance and moisture resistance tests. Table 1 shows the results. Further, ordinary etching was performed on the copper-clad laminate obtained in the above example.
Then, a printed wiring board was manufactured by performing a grinding process .
【００２４】[0024]
【表１】 [Table 1]
【００２５】打抜加工性：８０トンプレスにより、穴間
ピッチ１．７８ｍｍ、穴径０．７ｍｍで穴あけした時
の、表面温度４０℃でのはくり、目白、クラックの有無
を評価する。尚、表１において打抜加工性の評価は、
〇：良好、△：やや悪い、×：不良として行った。 はんだ耐熱性（ＪＩＳ Ｃ ６４８１）：２６０℃に加
熱されたはんだ槽に試験片を浮かべ、ふくれを生ずるま
での時間を測定した。 絶縁抵抗（ＪＩＳ Ｃ ６４８１）：６０℃、９０％Ｒ
Ｈの雰囲気に９６時間さらした後の２極間の絶縁抵抗値
を測定した。Punching workability: Evaluate peeling, surface whiteness and cracks at a surface temperature of 40 ° C. when drilling holes with a pitch of 1.78 mm and a hole diameter of 0.7 mm using an 80-ton press. In Table 1, the evaluation of the punching workability was as follows.
〇: good, △: slightly bad, ×: bad. Solder heat resistance (JIS C 6481): The test piece was floated in a solder bath heated to 260 ° C., and the time required for blistering was measured. Insulation resistance (JIS C 6481): 60 ° C, 90% R
The insulation resistance between the two electrodes after being exposed to the H atmosphere for 96 hours was measured.
【００２６】[0026]
【発明の効果】本発明における紙基材プリプレグ、これ
を用いて得られる銅張積層板及びプリント配線板は、耐
熱性、耐湿性、打抜加工性に優れる。The paper base prepreg of the present invention, and the copper-clad laminate and printed wiring board obtained using the same have excellent heat resistance, moisture resistance and punching workability.
───────────────────────────────────────────────────── フロントページの続き Ｆターム(参考） 4F072 AB03 AB09 AB29 AB31 AD17 AG03 AH02 AH21 AJ04 AL09 4J033 CA01 CA02 CA03 CA05 CA11 CA12 CA13 CA19 CA31 CA37 CB02 CB14 CC02 CC07 HA02 HA13 HB01 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4F072 AB03 AB09 AB29 AB31 AD17 AG03 AH02 AH21 AJ04 AL09 4J033 CA01 CA02 CA03 CA05 CA11 CA12 CA13 CA19 CA31 CA37 CB02 CB14 CC02 CC07 HA02 HA13 HB01
Claims (2)
含浸し、加熱乾燥させてなるプリプレグにおいて、乾性
油変性フェノール樹脂が、フェノール若しくはフェノー
ルと改質樹脂の反応物と乾性油との反応物であって、重
量平均分子量が５，０００〜２２，０００であるものに
ホルムアルデヒドを反応させて得られるものであるプリ
プレグ。1. A prepreg obtained by impregnating a substrate with a drying oil-modified phenol resin varnish and drying by heating, wherein the drying oil-modified phenol resin is a reaction product of phenol or a reaction product of phenol and a modified resin with a drying oil. A prepreg obtained by reacting formaldehyde with a compound having a weight average molecular weight of 5,000 to 22,000.
ね、その片面若しくは両面に銅はくを重ね併せ、加熱加
圧成形してなる銅張積層板。2. A copper-clad laminate obtained by laminating a plurality of prepregs according to claim 1, laminating copper foil on one or both sides thereof, and forming the laminate under heat and pressure.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP37338199A JP2001181417A (en) | 1999-12-28 | 1999-12-28 | Prepreg and copper-clad laminate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP37338199A JP2001181417A (en) | 1999-12-28 | 1999-12-28 | Prepreg and copper-clad laminate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2001181417A true JP2001181417A (en) | 2001-07-03 |
Family
ID=18502065
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP37338199A Withdrawn JP2001181417A (en) | 1999-12-28 | 1999-12-28 | Prepreg and copper-clad laminate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2001181417A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102002140A (en) * | 2010-10-27 | 2011-04-06 | 山东圣泉化工股份有限公司 | Synthesis method for phenolic resin for coated abrasive polyester fabric treatment |
| KR101245195B1 (en) * | 2011-09-06 | 2013-03-19 | 주식회사 유원 | Entry board for drilling pcb and method for manufacturing the same |
| KR101348731B1 (en) | 2012-04-03 | 2014-01-08 | 주식회사 유원 | Method for producing of laminate board having excellent heat resistance |
-
1999
- 1999-12-28 JP JP37338199A patent/JP2001181417A/en not_active Withdrawn
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102002140A (en) * | 2010-10-27 | 2011-04-06 | 山东圣泉化工股份有限公司 | Synthesis method for phenolic resin for coated abrasive polyester fabric treatment |
| CN102002140B (en) * | 2010-10-27 | 2012-07-25 | 山东圣泉化工股份有限公司 | Synthesis method for phenolic resin for coated abrasive polyester fabric treatment |
| KR101245195B1 (en) * | 2011-09-06 | 2013-03-19 | 주식회사 유원 | Entry board for drilling pcb and method for manufacturing the same |
| KR101348731B1 (en) | 2012-04-03 | 2014-01-08 | 주식회사 유원 | Method for producing of laminate board having excellent heat resistance |
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