JPH1112463A - Resin composition for printed circuit board, varnish, prepreg, and laminate for printed circuit board prepared therefrom - Google Patents
Resin composition for printed circuit board, varnish, prepreg, and laminate for printed circuit board prepared therefromInfo
- Publication number
- JPH1112463A JPH1112463A JP17177497A JP17177497A JPH1112463A JP H1112463 A JPH1112463 A JP H1112463A JP 17177497 A JP17177497 A JP 17177497A JP 17177497 A JP17177497 A JP 17177497A JP H1112463 A JPH1112463 A JP H1112463A
- Authority
- JP
- Japan
- Prior art keywords
- cyanate
- printed wiring
- wiring board
- resin composition
- compound
- 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
Landscapes
- Reinforced Plastic Materials (AREA)
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Paints Or Removers (AREA)
Abstract
Description
【0001】[0001]
【発明の属する技術分野】本発明は、誘電特性や耐熱性
に優れた印刷配線板等の製造に用いられる印刷配線板用
樹脂組成物とそれを用いたワニス、プリプレグ及び印刷
配線板用積層板に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition for printed wiring boards used for producing printed wiring boards having excellent dielectric properties and heat resistance, and varnishes, prepregs and laminates for printed wiring boards using the same. About.
【0002】[0002]
【従来の技術】近年、通信分野等の高周波機器に用いら
れる印刷配線板用材料には、比誘電率及び誘電正接の低
い樹脂材料が望まれている。これに対し比誘電率や誘電
正接の低いふっ素樹脂やポリフェニレンエーテル等の熱
可塑性の樹脂材料が使用されてきたが、これらはコスト
が高く、また成形時に高温、高圧が必要という問題や寸
法安定性、金属めっきとの接着性に劣るという欠点があ
った。一方、熱硬化性樹脂材料の中で比誘電率や誘電正
接が低い樹脂として知られるシアネートエステル樹脂及
びこれをベースとしたBT(ビスマレイミドトリアジ
ン)樹脂等の樹脂材料が提案されている。しかしなが
ら、これらの樹脂材料単独では、エポキシ樹脂等と比べ
て反応性が低いため良好な誘電特性や高いガラス転移温
度(Tg)を実現するには成形時に高温を必要とすると
いう欠点がある。また,硬化物は耐燃性や吸湿後の耐熱
性に劣るという問題や、剛直な骨格のため脆く加工時等
にクラックが発生しやすいという問題が指摘されてい
る。2. Description of the Related Art In recent years, a resin material having a low relative dielectric constant and a low dielectric loss tangent has been desired as a material for a printed wiring board used for high-frequency equipment in the communication field and the like. On the other hand, thermoplastic resins such as fluororesins and polyphenylene ethers with low relative permittivity and dielectric loss tangent have been used, but these are expensive, and they require high temperatures and high pressures during molding and have dimensional stability problems. However, there is a disadvantage that the adhesiveness to metal plating is poor. On the other hand, among thermosetting resin materials, resin materials such as a cyanate ester resin known as a resin having a low relative dielectric constant and a low dielectric loss tangent, and a BT (bismaleimide triazine) resin based on the same have been proposed. However, these resin materials alone have a lower reactivity than epoxy resins and the like, and thus have the disadvantage that high temperatures are required during molding to achieve good dielectric properties and a high glass transition temperature (Tg). In addition, it has been pointed out that the cured product is inferior in flame resistance and heat resistance after moisture absorption, and that it is fragile due to its rigid skeleton and easily cracks during processing.
【0003】これらの問題の改良を目的としてBT(ビ
スマレイミドトリアジン)樹脂又はシアネートエステル
樹脂に、特開昭63−54419号公報に記載されてい
るフェノールノボラックのグリシジルエーテル化物を併
用する方法、特開平2−214741号公報に記載のフ
ェノール類付加ジシクロペンタジエン重合体のグリシジ
ルエーテル化物を併用する方法、特開平3−84040
号公報に記載のビスフェノールAのグリシジルエーテル
化物等のエポキシ樹脂、また特開平5−310673号
公報に記載のフェノール類付加ブタジエン重合体、特公
平7−47637号公報に記載のビスフェノールA等の
多価フェノール類化合物、或いは特公平4−24370
号公報に記載の臭素化ビスフェノールA及び臭素化ビス
フェノールAのヒドロキシルエーテル化物、特開平2−
286723号公報に記載の臭素化フェノールノボラッ
クのグリシジルエーテル化物、特開平5−339342
号公報に示されている臭素化ビスフェノールAのグリシ
ジルエーテル化物、特開平7−207022号公報に記
載の臭素化マレイミド類化合物等のBT(ビスマレイミ
ドトリアジン)樹脂又はシアネートエステル樹脂との反
応性を有する難燃剤を併用させる方法等が提案されてい
る。In order to improve these problems, a method of using a glycidyl etherified product of phenol novolak described in JP-A-63-54419 in combination with a BT (bismaleimide triazine) resin or a cyanate ester resin has been proposed. Japanese Patent Application Laid-Open No. 3-84040 discloses a method of using a glycidyl etherified product of a phenol-added dicyclopentadiene polymer described in JP-A-2-214474.
And phenol-added butadiene polymers described in JP-A-5-310673, and polyvalent compounds such as bisphenol A described in JP-B-7-47637. Phenol compound, or Japanese Patent Publication No. 4-24370
Patent Document 2: Brominated bisphenol A and hydroxyl etherified product of brominated bisphenol A described in
Glycidyl etherified product of brominated phenol novolak described in JP-A-286723, JP-A-5-339342
Glycidyl etherified product of brominated bisphenol A disclosed in JP-A-7-207022, and BT (bismaleimide triazine) resin or cyanate ester resin such as a brominated maleimide compound described in JP-A-7-207022. A method of using a flame retardant in combination has been proposed.
【0004】[0004]
【発明が解決しようとする課題】しかし、特開昭63−
54419号公報、特開平2−214741号公報、特
開平3−84040号公報に示されているようなエポキ
シ樹脂をシアネートエステル樹脂に併用させる方法で
は、低温での硬化性、加工性、吸湿後の耐熱性に関する
欠点は改善されるものの、Tg(ガラス転移温度)が低
下したりGHz帯域での誘電特性が悪化するため高周波
用途には不十分であった。また特開平5−310673
号公報、特公平7−47637号公報に示されているよ
うな多価フェノール類化合物を併用させる方法では、硬
化性や加工性は改善されるものの、Tgの低下や接着
性、吸湿時の耐熱性に劣るという問題、GHz帯域での
誘電特性が悪化するため高周波用途には対応できないと
いう問題があった。また特公平4−24370号公報、
特開平2−286723号公報、特開平5−33934
2号公報、特開平7−207022号公報に示されてい
るような難燃剤を併用させる方法では、耐燃性は付加で
きるものの、Tgが低下したり、吸湿時の耐熱性やGH
z帯域での誘電特性が悪化するという問題があった。こ
のようにエポキシ樹脂、多価フェノール類化合物及び反
応性難燃剤を併用する方法では、何れもGHz帯域での
誘電特性が十分ではなく、またTgも低下する。However, Japanese Patent Application Laid-Open No.
In the method of using an epoxy resin in combination with a cyanate ester resin as disclosed in JP-A-54419, JP-A-2-214474, and JP-A-3-84040, curability at low temperatures, processability, and after absorption of moisture. Although the defect relating to heat resistance is improved, Tg (glass transition temperature) is lowered and dielectric properties in the GHz band are deteriorated, so that it is insufficient for high frequency applications. Also, Japanese Patent Application Laid-Open No.
In the method using a polyhydric phenol compound as disclosed in Japanese Patent Publication No. 7-47637, the curability and processability are improved, but the Tg is lowered, the adhesive property, and the heat resistance during moisture absorption are reduced. However, there is a problem that the dielectric properties in the GHz band are deteriorated, and thus it cannot be used for high frequency applications. In addition, Japanese Patent Publication No. 4-24370,
JP-A-2-286723, JP-A-5-33934
No. 2, JP-A-7-207022 discloses a method in which a flame retardant is used in combination, although the flame resistance can be added, but the Tg is lowered, the heat resistance at the time of moisture absorption and the GH
There is a problem that the dielectric characteristics in the z band deteriorate. As described above, in the method using the epoxy resin, the polyhydric phenol compound and the reactive flame retardant in combination, the dielectric properties in the GHz band are not sufficient and the Tg is lowered.
【0005】さらに、シアネートエステル樹脂単独でも
種類により次のように問題点が異なる。シアネート基の
2−位にアルキル基等の置換基を有するシアネートエス
テルは、硬化反応時に置換基の立体的な障害を受けやす
いためシアネート基の反応性が低く、シアネートエステ
ルの中でも硬化成形に高温を要してしまう。これとは逆
に、シアネート基の2−位に置換基を有しないシアネー
トエステルは反応性は高いが、吸水率が高く吸湿時の耐
熱性等が劣るという欠点があり、また溶融粘度が低く樹
脂流れが非常に大きいため成形条件の範囲が狭いという
成形性に劣り、また、ドリル穴あけ、金型による外形打
ち抜き等の加工性がシアネート基の2−位に置換基を有
するシアネートエステルに比べて劣るという問題があ
る。[0005] Further, even if the cyanate ester resin alone is used, the problems are different depending on the kind as follows. Cyanate esters having a substituent such as an alkyl group at the 2-position of the cyanate group are susceptible to steric hindrance of the substituent during the curing reaction, and thus have low reactivity of the cyanate group. I need it. Conversely, a cyanate ester having no substituent at the 2-position of the cyanate group has high reactivity, but has a drawback that it has a high water absorption rate and is inferior in heat resistance at the time of moisture absorption, and has a low melt viscosity. Since the flow is very large, the moldability is inferior in that the range of molding conditions is narrow, and the workability such as drilling holes and punching the outer shape with a mold is inferior to the cyanate ester having a substituent at the 2-position of the cyanate group. There is a problem.
【0006】本発明は、かかる状況に鑑みなされたもの
で、Tgが低下したり、硬化性、加工性、接着性、耐燃
性、吸湿後の耐熱性等といった特性を損なうことなく、
高周波帯域での誘電特性に優れた印刷配線板用樹脂組成
物及びそれを用いたワニス、プリプレグ及び印刷配線板
用積層板を提供することを目的とした。[0006] The present invention has been made in view of such a situation, without reducing the Tg, without impairing properties such as curability, workability, adhesion, flame resistance, heat resistance after moisture absorption, and the like.
It is an object of the present invention to provide a resin composition for a printed wiring board having excellent dielectric properties in a high frequency band, and a varnish, a prepreg and a laminate for a printed wiring board using the same.
【0007】[0007]
【課題を解決するための手段】本発明は、(A)分子中
にシアネート基を2個有するシアネート類化合物または
そのプレポリマー、(B)一価フェノール類化合物及び
(C)シアネート類化合物と反応性を有しない難燃剤を
必須成分として含む樹脂組成物において、(A)分子中
にシアネート基を2個有するシアネート類化合物が、式
(1)で表されるアルキル基置換シアネート類化合物と
式(2)で表されるシアネート基の2−位に置換基を有
しないシアネート類化合物との2種類以上の混合物であ
る印刷配線板用樹脂組成物である。SUMMARY OF THE INVENTION The present invention relates to a method comprising reacting (A) a cyanate compound having two cyanate groups in a molecule or a prepolymer thereof, (B) a monohydric phenol compound and (C) a cyanate compound. In a resin composition containing a flame retardant having no property as an essential component, (A) a cyanate compound having two cyanate groups in a molecule comprises an alkyl-substituted cyanate compound represented by the formula (1) and a compound represented by the formula ( It is a resin composition for printed wiring boards, which is a mixture of two or more kinds with a cyanate compound having no substituent at the 2-position of the cyanate group represented by 2).
【化5】 Embedded image
【化6】 また、本発明は、前記印刷配線板用樹脂組成物を溶剤に
溶解ないし分散させた印刷配線板用樹脂ワニスであり、
さらに印刷配線板用ワニスを基材に含浸後、80〜20
0℃で乾燥させて得られる印刷配線板用プリプレグであ
る。さらに、本発明は、この印刷配線板用プリプレグ
を、多層プリント配線板の層間接続用プリプレグとして
使用することもでき、また、積層板用プリプレグを複数
枚重ね、さらにその外側に金属箔を積層し加熱加圧して
得られる印刷配線板用積層板である。Embedded image Further, the present invention is a resin varnish for a printed wiring board in which the resin composition for a printed wiring board is dissolved or dispersed in a solvent,
Further, after impregnating the substrate with the varnish for a printed wiring board, 80 to 20
It is a prepreg for a printed wiring board obtained by drying at 0 ° C. Furthermore, the present invention can also use this prepreg for printed wiring boards as a prepreg for interlayer connection of a multilayer printed wiring board, and also stacking a plurality of prepregs for a laminated board and further laminating a metal foil on the outside thereof. It is a laminate for printed wiring boards obtained by heating and pressing.
【0008】[0008]
【発明の実施の形態】本発明の印刷配線板用樹脂組成物
において用いられる(A)分子中にシアネート基を2個
有するシアネート類化合物またはそのプレポリマーは、
式(1)で表されるアルキル基置換シアネート類化合物
と式(2)で表されるシアネート基の2−位に置換基を
有しないシアネート類化合物との2種類以上の混合物で
あり、式(1)で表される化合物の具体例としては、ビ
ス(3,5−ジメチル−4−シアネートフェニル)メタ
ン等及びこれらのプレポリマが挙げられる。式(2)で
表される化合物の具体例としては,2,2−ビス(4−
シアネートフェニル)プロパン,ビス(4−シアネート
フェニル)エタン,2,2−ビス(4−シアネートフェ
ニル)−1,1,1,3,3,3−ヘキサフルオロプロ
パン,α,α’−ビス(4−シアネートフェニル)−m
−ジイソプロピルベンゼン,フェノール付加ジシクロペ
ンタジエン重合体のシアネートエステル化物等及びこれ
らのプレポリマが挙げられる。この中では、2,2−ビ
ス(4−シアネートフェニル)プロパン、α,α’−ビ
ス(4−シアネートフェニル)−m−ジイソプロピルベ
ンゼンが比較的低温硬化性に優れまた、硬化物の誘電特
性が特に良好であるため好ましい。BEST MODE FOR CARRYING OUT THE INVENTION (A) A cyanate compound having two cyanate groups in a molecule or a prepolymer thereof, which is used in the resin composition for a printed wiring board of the present invention, comprises:
A mixture of two or more kinds of an alkyl group-substituted cyanate compound represented by the formula (1) and a cyanate compound having no substituent at the 2-position of the cyanate group represented by the formula (2), Specific examples of the compound represented by 1) include bis (3,5-dimethyl-4-cyanatephenyl) methane and the like and prepolymers thereof. Specific examples of the compound represented by the formula (2) include 2,2-bis (4-
Cyanatephenyl) propane, bis (4-cyanatephenyl) ethane, 2,2-bis (4-cyanatephenyl) -1,1,1,3,3,3-hexafluoropropane, α, α′-bis (4 -Cyanate phenyl) -m
-Diisopropylbenzene, cyanate esterified products of phenol-added dicyclopentadiene polymers, and prepolymers thereof. Among them, 2,2-bis (4-cyanatephenyl) propane and α, α′-bis (4-cyanatephenyl) -m-diisopropylbenzene have relatively excellent low-temperature curability and the cured product has a dielectric property. It is particularly preferable because it is excellent.
【0009】上記の(A)分子中にシアネート基を2個
有するシアネート類化合物のモノマは結晶性が高く、こ
れらのモノマを溶剤でワニス化する場合、固形分濃度に
もよるがワニス中で再結晶する場合がある。そのため上
記シアネート化合物モノマをあらかじめプレポリマ化し
て用いるのが好ましい。プレポリマのシアネート基の転
化率は特に限定されるものではないが、通常は20〜6
0重量%の範囲内で転化されたプレポリマを用いること
が望ましい。The above-mentioned monomer (A) of a cyanate compound having two cyanate groups in the molecule has high crystallinity, and when these monomers are varnished with a solvent, the varnish may vary depending on the solid content concentration. May crystallize. Therefore, it is preferable to use the above-mentioned cyanate compound monomer after prepolymerization. Although the conversion of the cyanate group of the prepolymer is not particularly limited, it is usually 20 to 6%.
It is desirable to use a prepolymer converted within the range of 0% by weight.
【0010】(A)分子中にシアネート基を2個有する
シアネート類化合物またはそのプレポリマーに用いる式
(1)で表されるアルキル基置換シアネート類化合物と
式(2)で表されるシアネート基の2−位に置換基を有
しないシアネート類化合物との配合比は、式(1):式
(2)=30:70重量比〜70:30重量比とするこ
とが好ましい。式(1)の混合比が30重量比未満で
は、吸水率が高く耐熱性が低下し、混合比が70重量比
を超えると低温での硬化性が劣り、また、ガラス転移温
度が低下するため好ましくない。(A) An alkyl group-substituted cyanate compound represented by the formula (1) used for a cyanate compound having two cyanate groups in the molecule or a prepolymer thereof and a cyanate group represented by the formula (2) The compounding ratio with the cyanate compound having no substituent at the 2-position is preferably Formula (1): Formula (2) = 30: 70 weight ratio to 70:30 weight ratio. When the mixing ratio of the formula (1) is less than 30% by weight, the water absorption is high and the heat resistance is reduced. When the mixing ratio is more than 70% by weight, the curability at low temperatures is inferior and the glass transition temperature is lowered. Not preferred.
【0011】本発明の印刷配線板用樹脂組成物において
用いられる(B)一価フェノール類化合物の具体例とし
ては、p−ノニルフェノール、p−tert−ブチルフ
ェノール、p−tert−アミルフェノール、p−te
rt−オクチルフェノール等のアルキル基置換フェノー
ル類化合物及び式(3)で表される一価フェノール類化
合物等が挙げられる。式(3)で表される一価フェノー
ル類化合物としては、p−(α−クミル)フェノール等
があり、p−(α−クミル)フェノールが好ましい。ま
た(B)一価フェノール類化合物は1種類単独で用いて
もよく2種類以上を併用して用いてもよい。Specific examples of the (B) monohydric phenol compound used in the resin composition for a printed wiring board of the present invention include p-nonylphenol, p-tert-butylphenol, p-tert-amylphenol, p-te
Examples thereof include an alkyl group-substituted phenol compound such as rt-octylphenol and a monohydric phenol compound represented by the formula (3). Examples of the monohydric phenol compound represented by the formula (3) include p- (α-cumyl) phenol, and p- (α-cumyl) phenol is preferable. Further, the monohydric phenol compound (B) may be used alone or in combination of two or more.
【0012】[0012]
【化7】 (式中,R5,R6は水素原子又はメチル基を示し、それ
ぞれ同じであっても異なってもよい。またmは1〜2の
整数を表す)Embedded image (In the formula, R 5 and R 6 represent a hydrogen atom or a methyl group, and may be the same or different, and m represents an integer of 1 to 2.)
【0013】本発明における(B)一価フェノール類化
合物の配合量は、(A)分子中にシアネート基を2個有
するシアネート類化合物またはそのプレポリマー100
重量部に対して、5〜30重量部の範囲で配合すること
が好ましい。更に好ましくは7〜30重量部である。5
重量部未満の場合、誘電特性が悪化する傾向を示すため
望ましくない。30重量部を超えると、ワニス化した場
合のワニスの保存安定性が低下する傾向を示すため望ま
しくない。In the present invention, the compounding amount of the (B) monohydric phenol compound is (A) a cyanate compound having two cyanate groups in a molecule or a prepolymer thereof.
It is preferable to mix in a range of 5 to 30 parts by weight with respect to parts by weight. More preferably, it is 7 to 30 parts by weight. 5
If the amount is less than part by weight, the dielectric properties tend to deteriorate, which is not desirable. If the amount exceeds 30 parts by weight, the storage stability of the varnish when varnished tends to decrease, which is not desirable.
【0014】本発明の印刷配線板用樹脂組成物において
用いられる(C)シアネート類化合物と反応性を有しな
い難燃剤の具体例としては、1,2−ジブロモ−4−
(1,2−ジブロモエチル)シクロヘキサン,テトラブ
ロモシクロオクタン及びヘキサブロモシクロドデカン等
の脂肪族環型難燃剤があり、例示のものが好ましい。ま
た、式(4)で表される複素環型難燃剤が挙げられ、式
(4)で表される複素環型難燃剤としては、2,4,6
−トリス(トリブロモフェノキシ)−1,3,5−トリ
アジン等があり、例示のものが好ましい。この(C)シ
アネート類化合物と反応性を有しない難燃剤は、(A)
分子中にシアネート基を2個有するシアネート類化合物
またはそのプレポリマー100重量部に対し、5〜20
0重量部の範囲で配合することが好ましい。好ましく
は、5〜100重量部である。5重量部未満では、難燃
効果に乏しく、200重量部を超えると耐熱性が低下す
るので好ましくない。Specific examples of the flame retardant having no reactivity with the cyanate compound (C) used in the resin composition for a printed wiring board of the present invention include 1,2-dibromo-4-.
There are aliphatic ring-type flame retardants such as (1,2-dibromoethyl) cyclohexane, tetrabromocyclooctane, and hexabromocyclododecane, and examples are preferable. Further, a heterocyclic flame retardant represented by the formula (4) may be mentioned, and examples of the heterocyclic flame retardant represented by the formula (4) include 2,4,6
-Tris (tribromophenoxy) -1,3,5-triazine and the like, and an example is preferable. The flame retardant having no reactivity with the (C) cyanate compound is (A)
5 to 20 parts by weight based on 100 parts by weight of a cyanate compound having two cyanate groups in the molecule or a prepolymer thereof.
It is preferable to mix in a range of 0 parts by weight. Preferably, it is 5 to 100 parts by weight. If it is less than 5 parts by weight, the flame retardant effect is poor, and if it exceeds 200 parts by weight, the heat resistance is undesirably reduced.
【0015】[0015]
【化8】 (式中,l,m,nは1〜5の整数を表し,それぞれ同
じ値であっても異なってもよい)Embedded image (Where l, m, and n represent integers of 1 to 5 and may be the same or different, respectively)
【0016】本発明の印刷配線板用樹脂組成物では、硬
化反応を促進するための硬化促進剤が用いられる。その
硬化促進剤の具体例としては、コバルト,マンガン,ス
ズ,ニッケル,亜鉛,銅等の有機金属塩化合物や有機金
属錯体を用いることができる。特に、2−エチルへキサ
ン酸コバルトやナフテン酸コバルト等の有機コバルト塩
化合物が好ましい。有機金属塩化合物は1種類単独で用
いてもよく2種類以上を併用して用いてもよい。硬化促
進剤の配合量は、(A)分子中にシアネート基を2個有
するシアネート類化合物またはそのプレポリマー100
重量部に対し、配合効果と硬化物の物性を劣化させない
範囲の0.01〜3重量部であり、より好ましくは0.
02〜0.5重量部である。In the resin composition for a printed wiring board of the present invention, a curing accelerator for accelerating the curing reaction is used. Specific examples of the curing accelerator include organic metal salt compounds and organic metal complexes such as cobalt, manganese, tin, nickel, zinc, and copper. In particular, organic cobalt salt compounds such as cobalt 2-ethylhexanoate and cobalt naphthenate are preferred. The organometallic salt compounds may be used alone or in combination of two or more. The compounding amount of the curing accelerator is as follows: (A) a cyanate compound having two cyanate groups in the molecule or a prepolymer thereof.
The amount is 0.01 to 3 parts by weight, more preferably 0.1 to 3 parts by weight, within a range that does not deteriorate the mixing effect and the physical properties of the cured product.
02 to 0.5 parts by weight.
【0017】本発明の印刷配線板用樹脂組成物には、さ
らに、必要に応じて充填剤及びその他の添加剤を配合す
ることができる。充填剤としては、通常、無機充填剤が
好適に用いられ、その具体例として、溶融シリカ,ガラ
ス,アルミナ,チタニア,ジルコン,炭酸カルシウム,
珪酸カルシウム,珪酸マグネシウム,珪酸アルミニウ
ム,窒化珪素,窒化ホウ素,ベリリア,ジルコニア,チ
タン酸バリウム,チタン酸カリウム,チタン酸カルシウ
ム等が挙げられる。The resin composition for a printed wiring board of the present invention may further contain, if necessary, a filler and other additives. As the filler, usually, an inorganic filler is suitably used, and specific examples thereof include fused silica, glass, alumina, titania, zircon, calcium carbonate, and the like.
Examples thereof include calcium silicate, magnesium silicate, aluminum silicate, silicon nitride, boron nitride, beryllia, zirconia, barium titanate, potassium titanate, and calcium titanate.
【0018】本発明の印刷配線板用樹脂組成物は加熱硬
化させることにより誘電特性や耐熱性に優れた印刷配線
板の製造に供せられる。即ち本発明の印刷配線板用樹脂
組成物を溶剤に溶解、分散していったんワニス化し、ガ
ラス布等の基材に含浸し乾燥することによってプリプレ
グを作製する。次いでこのプリプレグを任意枚数と上下
又は一方の面に金属箔を重ねて加熱成形することによっ
て印刷配線板又は金属張積層板とすることができる。こ
こで乾燥は、溶剤を使用した場合には溶剤を除去するこ
と、溶剤を使用しない場合には室温での流動性がなくな
るようにすることをいう。The resin composition for a printed wiring board of the present invention is subjected to heat curing to provide a printed wiring board having excellent dielectric properties and heat resistance. That is, the resin composition for a printed wiring board of the present invention is dissolved and dispersed in a solvent to form a varnish once, impregnated into a substrate such as a glass cloth, and dried to prepare a prepreg. Next, a desired number of the prepregs are laminated with a metal foil on the upper and lower sides or on one side and heat-molded to form a printed wiring board or a metal-clad laminate. Here, drying refers to removing the solvent when a solvent is used, or eliminating fluidity at room temperature when no solvent is used.
【0019】本発明の印刷配線板用樹脂組成物をワニス
化する場合、溶剤は特に限定するものではないが、具体
例としては、アセトン,メチルエチルケトン,メチルイ
ソブチルケトン,シクロヘキサノン等のケトン類,トル
エン,キシレン等の芳香族炭化水素類,メトキシエチル
アセテート,エトキシエチルアセテート,ブトキシエチ
ルアセテート,酢酸エチル等のエステル類,N−メチル
ピロリドン,ホルムアミド,N−メチルホルムアミド,
N,N−ジメチルホルムアミド,N,N−ジメチルアセ
トアミド等のアミド類,メタノール,エタノール,エチ
レングリコール,エチレングリコールモノメチルエーテ
ル,エチレングリコールモノエチルエーテル,ジエチレ
ングリコールモノメチルエーテル,ジエチレングリコー
ルモノエチルエーテル,ジエチレングリコール,トリエ
チレングリコールモノメチルエーテル,トリエチレング
リコールモノエチルエーテル,トリエチレングリコー
ル,プロピレングリコールモノメチルエーテル,ジプロ
ピレングリコールモノメチルエーテル,プロピレングリ
コールモノプロピルエーテル,ジプロピレングリコール
モノプロピルエーテル等のアルコール類等が用いられ
る。また、これら上記溶剤は1種類単独で用いてもよ
く、2種類以上を併用して用いてもよい。When varnishing the resin composition for a printed wiring board of the present invention, the solvent is not particularly limited, but specific examples thereof include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, toluene, and the like. Aromatic hydrocarbons such as xylene, methoxyethyl acetate, ethoxyethyl acetate, butoxyethyl acetate, esters such as ethyl acetate, N-methylpyrrolidone, formamide, N-methylformamide;
Amides such as N, N-dimethylformamide, N, N-dimethylacetamide, methanol, ethanol, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol, triethylene glycol Alcohols such as monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monopropyl ether, and dipropylene glycol monopropyl ether are used. These solvents may be used alone or in combination of two or more.
【0020】上記の印刷配線板用樹脂ワニスは、ガラス
織布やガラス不織布、プラスチック織布やプラスチック
不織布、紙などの積層板に用いられている基材に含浸
後、80〜200℃で乾燥させて印刷配線板用プリプレ
グとする。多層プリント配線板の層間接着用プリプレグ
として使用する場合は、プリプレグ中の樹脂分を多めに
する。また、印刷配線板用積層板とするときは、要求さ
れる誘電特性に応じて、誘電率や誘電正接の値が小さい
ものが要求される場合は、誘電特性に優れる本発明の印
刷配線板用樹脂組成物を多くするため樹脂分を多くする
ようにする。The above-mentioned resin varnish for printed wiring boards is impregnated into a base material used for a laminated board such as glass woven fabric or glass non-woven fabric, plastic woven fabric or plastic non-woven fabric, or paper, and then dried at 80 to 200 ° C. To make a prepreg for printed wiring boards. When used as a prepreg for interlayer bonding of a multilayer printed wiring board, the resin content in the prepreg is increased. In addition, when a laminated board for a printed wiring board is required, depending on the required dielectric properties, if a value of a dielectric constant or a dielectric loss tangent is required to be small, the printed wiring board of the present invention having excellent dielectric properties is required. In order to increase the resin composition, the resin content is increased.
【0021】印刷配線板用プリプレグは、これを複数枚
重ね、さらにその外側に金属箔を積層し加熱加圧して印
刷配線板用積層板とする。A plurality of prepregs for printed wiring boards are laminated, and a metal foil is further laminated on the outside of the prepreg, and heated and pressed to form a laminated board for printed wiring boards.
【0022】一般に、樹脂硬化物の誘電特性は、分子構
造、即ち分子内の極性基の量や強さ及び分子骨格の動き
やすさ等に影響を受ける。元来、シアネートエステルの
硬化物は低極性、剛直かつ対称性構造のトリアジン骨格
を有するため低誘電率及び低誘電正接である。しかし、
成形性、硬化性、加工性及び吸湿時の耐熱性の改善や耐
燃性を付加するためシアネートエステルに多官能エポキ
シ樹脂、多価フェノール類化合物及びシアネート基との
反応性を有する反応型難燃剤等を併用する従来の樹脂組
成物では、シアネート基との反応によりトリアジン環以
外の構造で極性基の高いものが生成したり、硬化反応の
進行により流動性が失なわれ反応しきれないで残存する
官能基が多くなるため、Tgや耐熱性が低下したり、比
誘電率や誘電正接が高くなる。これに対して、本発明の
印刷配線板用樹脂組成物は、多官能エポキシ樹脂や多価
フェノール類化合物を用いないため上記のような問題が
無く、かつシアネート基の2−位に置換基を有するシア
ネート類化合物またはそのプレポリマーとシアネート基
の2−位に置換基を有しないシアネート類化合物または
そのプレポリマーとを併用することにより、立体障害に
よる硬化性の低下を少なくしつつ、かつ低吸水性や良好
な成形性、加工性を付与できる。また、本発明において
用いるフェノール類化合物は、一価のフェノール類化合
物の中でもシアネート基との反応性が高く、かつトリア
ジン環の生成を促進するフェノール類化合物である。ま
た、本発明において用いられる難燃剤は、低極性構造で
かつシアネート基に対し反応性を有しない難燃剤である
ため、トリアジン環の生成を妨げないため誘電特性を悪
化させることがなく耐燃性を付加できる。したがって、
得られた硬化物は硬化性やTgが高く、優れた成形性、
加工性、接着性、吸水性、耐熱性及び耐燃性を有し、か
つ低誘電率及び低誘電正接である。In general, the dielectric properties of a cured resin are affected by the molecular structure, that is, the amount and strength of the polar group in the molecule, the mobility of the molecular skeleton, and the like. Originally, a cured product of a cyanate ester has a low dielectric constant and a low dielectric loss tangent because it has a triazine skeleton having a low polarity, rigid and symmetric structure. But,
Reactive flame retardant with reactivity with polyfunctional epoxy resin, polyhydric phenolic compound and cyanate group to cyanate ester to improve moldability, curability, processability and heat resistance during moisture absorption and to add flame resistance In a conventional resin composition in which is used in combination, a high polar group is generated in a structure other than a triazine ring by a reaction with a cyanate group, or fluidity is lost due to the progress of a curing reaction, and the reaction is left unreacted. Since the number of functional groups increases, Tg and heat resistance decrease, and the relative dielectric constant and dielectric loss tangent increase. On the other hand, the resin composition for a printed wiring board of the present invention does not use a polyfunctional epoxy resin or a polyhydric phenol compound and thus does not have the above-described problem, and has a substituent at the 2-position of the cyanate group. Combination use of a cyanate compound having a cyanate compound or a prepolymer thereof and a cyanate compound having no substituent at the 2-position of the cyanate group or a prepolymer thereof has a reduced curability due to steric hindrance, and has low water absorption. And good moldability and workability. The phenolic compound used in the present invention is a phenolic compound having high reactivity with a cyanate group and promoting the formation of a triazine ring among monovalent phenolic compounds. In addition, the flame retardant used in the present invention is a flame retardant having a low polarity structure and having no reactivity to a cyanate group. Can be added. Therefore,
The obtained cured product has high curability and Tg, excellent moldability,
It has processability, adhesiveness, water absorption, heat resistance and flame resistance, and has a low dielectric constant and a low dielectric loss tangent.
【0023】[0023]
【実施例】以下に本発明を具体的に説明するが、本発明
はこれらに限られるものではない。The present invention will be described in detail below, but the present invention is not limited to these.
【0024】(実施例1) (A)分子中にシアネート基を2個有するシアネート類
化合物またはそのプレポリマーとして、アルキル基置換
シアネート類化合物である、ビス(3,5−ジメチル−
4−シアネートフェニル)メタンのプレポリマ(Aro
cy M−30,旭チバ株式会社製商品名)とシアネー
ト基の2−位に置換基を有しないシアネート類化合物で
ある、2,2−ビス(4−シアネートフェニル)プロパ
ンのプレポリマ(Arocy B−30,旭チバ株式会
社製商品名)、(B)一価フェノール類化合物として、
p−ノニルフェノール及び(C)シアネート類化合物と
反応性を有しない難燃剤として、1,2−ジブロモ−4
−(1,2−ジブロモエチル)シクロヘキサン(SAY
TEX BCL−462,アルベマール社製商品名)と
を表1に示す配合量でトルエンに溶解し、更に硬化促進
剤としてシアネート類化合物100重量部に対してナフ
テン酸コバルトを0.1重量部の割合で配合し、不揮発
分65重量%の印刷配線板用ワニスを作製した。Example 1 (A) As a cyanate compound having two cyanate groups in a molecule or a prepolymer thereof, an alkyl-substituted cyanate compound, bis (3,5-dimethyl-
Prepolymer of 4-cyanatephenyl) methane (Aro
cyM-30 (trade name, manufactured by Asahi Chiba Corporation) and a prepolymer of 2,2-bis (4-cyanatophenyl) propane (Arocy B-), which is a cyanate compound having no substituent at the 2-position of the cyanate group 30, Asahi Ciba Co., Ltd.), (B) monohydric phenol compounds
As a flame retardant having no reactivity with p-nonylphenol and (C) cyanate compounds, 1,2-dibromo-4
-(1,2-dibromoethyl) cyclohexane (SAY
TEX BCL-462 (trade name, manufactured by Albemarle Co., Ltd.) in toluene at the compounding amounts shown in Table 1, and 0.1 parts by weight of cobalt naphthenate with respect to 100 parts by weight of a cyanate compound as a curing accelerator. To prepare a varnish for printed wiring boards having a nonvolatile content of 65% by weight.
【0025】(実施例2)ビス(3,5−ジメチル−4
−シアネートフェニル)メタンのプレポリマと2,2−
ビス(4−シアネートフェニル)−1,1,1,3,
3,3−ヘキサフルオロプロパンのプレポリマのメチル
エチルケトン溶液(Arocy F−40S,旭チバ株
式会社製商品名)とp−tert−ブチルフェノール及
びテトラブロモシクロオクタン(SAYTEX BC−
48,アルベマール社製商品名)とを表1に示す配合量
でトルエンに溶解し、更に硬化促進剤としてシアネート
類化合物100重量部に対してナフテン酸コバルトを
0.1重量部の割合で配合し、不揮発分65重量%の印
刷配線板用ワニスを作製した。Example 2 Bis (3,5-dimethyl-4)
-Cyanatephenyl) methane prepolymer and 2,2-
Bis (4-cyanatephenyl) -1,1,1,3,
Methyl ethyl ketone solution of a prepolymer of 3,3-hexafluoropropane (Arocy F-40S, trade name, manufactured by Asahi Ciba Co., Ltd.), p-tert-butylphenol and tetrabromocyclooctane (SAYTEX BC-
48, trade name of Albemarle Co., Ltd.) in toluene at the compounding amounts shown in Table 1 and further, as a curing accelerator, 0.1 part by weight of cobalt naphthenate with respect to 100 parts by weight of a cyanate compound. A varnish for printed wiring boards having a nonvolatile content of 65% by weight was produced.
【0026】(実施例3)ビス(3,5−ジメチル−4
−シアネートフェニル)メタンのプレポリマとα,α’
−ビス(4−シアネートフェニル)−m−ジイソプロピ
ルベンゼン(RTX−366,旭チバ株式会社製商品
名)とp−tert−オクチルフェノール及びヘキサブ
ロモシクロドデカン(CD−75P,グレートレイクス
社製商品名)とを表1に示す配合量でトルエンに溶解
し、更に硬化促進剤としてシアネート類化合物100重
量部に対してナフテン酸コバルトを0.1重量部の割合
で配合し、不揮発分65重量%の印刷配線板用ワニスを
作製した。Example 3 Bis (3,5-dimethyl-4)
-Cyanate phenyl) methane prepolymer and α, α '
-Bis (4-cyanatephenyl) -m-diisopropylbenzene (RTX-366, trade name of Asahi Ciba Co., Ltd.), p-tert-octylphenol and hexabromocyclododecane (CD-75P, trade name of Great Lakes Co.) Was dissolved in toluene in the amounts shown in Table 1, and 0.1 parts by weight of cobalt naphthenate was added as a curing accelerator to 100 parts by weight of a cyanate compound to obtain a printed wiring having a nonvolatile content of 65% by weight. A plate varnish was prepared.
【0027】(実施例4)実施例1において、p−ノニ
ルフェノールをp−(α−クミル)フェノールに及び
1,2−ジブロモ−4−(1,2−ジブロモエチル)シ
クロヘキサンを臭素化トリフェニルシアヌレート(ピロ
ガードSR−245,第一工業製薬株式会社製商品名)
に代えて表1に示す配合量とした他は実施例1と同様に
して不揮発分65重量%の印刷配線板用ワニスを作製し
た。Example 4 In Example 1, p-nonylphenol was added to p- (α-cumyl) phenol and 1,2-dibromo-4- (1,2-dibromoethyl) cyclohexane was added to brominated triphenylcyan. Nurate (Piroguard SR-245, trade name of Daiichi Kogyo Seiyaku Co., Ltd.)
A varnish for printed wiring boards having a nonvolatile content of 65% by weight was prepared in the same manner as in Example 1 except that the compounding amounts shown in Table 1 were used instead.
【0028】(比較例1)実施例1において、ビス
(3,5−ジメチル−4−シアネートフェニル)メタン
のプレポリマを除き、表1に示す配合量でトルエンに溶
解した他は実施例1と同様にして不揮発分65重量%の
印刷配線板用ワニスを作製した。Comparative Example 1 The procedure of Example 1 was repeated, except that the prepolymer of bis (3,5-dimethyl-4-cyanatephenyl) methane was dissolved in toluene in the amount shown in Table 1. Thus, a varnish for printed wiring boards having a nonvolatile content of 65% by weight was produced.
【0029】(比較例2)比較例1において、2,2−
ビス(4−シアネートフェニル)プロパンのプレポリマ
をビス(3,5−ジメチル−4−シアネートフェニル)
メタンのプレポリマに代えて、表1に示す配合量でトル
エンに溶解した他は比較例1と同様にして不揮発分65
重量%の印刷配線板用ワニスを作製した。Comparative Example 2 In Comparative Example 1, 2,2-
The prepolymer of bis (4-cyanatephenyl) propane is converted to bis (3,5-dimethyl-4-cyanatephenyl)
In the same manner as in Comparative Example 1 except that the methane prepolymer was dissolved in toluene at the compounding amount shown in Table 1, the non-volatile content was 65%.
By weight, a varnish for a printed wiring board was prepared.
【0030】(比較例3)比較例1において、1,2−
ジブロモ−4−(1,2−ジブロモエチル)シクロヘキ
サンを臭素化ビスフェノールA型エポキシ樹脂(ESB
400T,住友化学工業株式会社製商品名)に代えて表
1に示す配合量でトルエンに溶解した他は比較例1と同
様にして不揮発分65重量%の印刷配線板用ワニスを作
製した。Comparative Example 3 In Comparative Example 1, 1,2-
Dibromo-4- (1,2-dibromoethyl) cyclohexane is converted to a brominated bisphenol A type epoxy resin (ESB
A varnish for a printed wiring board having a nonvolatile content of 65% by weight was prepared in the same manner as in Comparative Example 1 except that 400T (trade name, manufactured by Sumitomo Chemical Co., Ltd.) was dissolved in toluene at the compounding amount shown in Table 1.
【0031】(比較例4)比較例1において、p−ノニ
ルフェノールを除き、1,2−ジブロモ−4−(1,2
−ジブロモエチル)シクロヘキサンを臭素化ビスフェノ
ールA(TBA)に代えて表1に示す配合量でトルエン
に溶解した他は比較例1と同様にして不揮発分65重量
%の印刷配線板用ワニスを作製した。Comparative Example 4 In Comparative Example 1, except for p-nonylphenol, 1,2-dibromo-4- (1,2
A varnish for a printed wiring board having a nonvolatile content of 65% by weight was prepared in the same manner as in Comparative Example 1, except that -dibromoethyl) cyclohexane was dissolved in toluene at the compounding amount shown in Table 1 in place of brominated bisphenol A (TBA). .
【0032】(比較例5)比較例1において、p−ノニ
ルフェノールをフェノール類付加ブタジエン重合体(P
P700−300,日本石油化学株式会社製商品名)
に、1,2−ジブロモ−4−(1,2−ジブロモエチ
ル)シクロヘキサンを臭素化フェノールノボラック型エ
ポキシ樹脂(BREN−S,日本化薬株式会社製商品
名)に代えて表1に示す配合量でトルエンに溶解した他
は比較例1と同様にして不揮発分65重量%の印刷配線
板用ワニスを作製した。Comparative Example 5 In Comparative Example 1, p-nonylphenol was converted to a phenol-added butadiene polymer (P
P700-300, trade name of Nippon Petrochemical Co., Ltd.)
And 1,2-dibromo-4- (1,2-dibromoethyl) cyclohexane was replaced with a brominated phenol novolak type epoxy resin (BREN-S, trade name, manufactured by Nippon Kayaku Co., Ltd.), and the compounding amount shown in Table 1 was used. A varnish for printed wiring boards having a nonvolatile content of 65% by weight was prepared in the same manner as in Comparative Example 1 except that the varnish was dissolved in toluene.
【0033】[0033]
【表1】 [Table 1]
【0034】各実施例及び比較例で得られた印刷配線板
用ワニスを、厚み0.2mmのガラス布(Eガラス、坪
量210g/m2)に含浸し、140℃で10分加熱し
て樹脂分約41重量%の印刷配線板用プリプレグを得
た。次いで、得られた印刷配線板用プリプレグ4枚を重
ね、その両側に厚み18μmの銅箔を重ね、170℃、
60分、2.5MPaの条件でプレス成形した後、20
0℃で120分加熱処理したものと230℃で120分
加熱処理したものそれぞれについて作製し、厚み0.8
mmの印刷配線板用積層板を得た。The varnish for a printed wiring board obtained in each of Examples and Comparative Examples was impregnated into a glass cloth (E glass, basis weight 210 g / m 2 ) having a thickness of 0.2 mm, and heated at 140 ° C. for 10 minutes. A prepreg for a printed wiring board having a resin content of about 41% by weight was obtained. Next, four pieces of the obtained printed wiring board prepregs were stacked, and copper foil having a thickness of 18 μm was stacked on both sides thereof at 170 ° C.
After press molding for 60 minutes under the condition of 2.5 MPa, 20
Heat-treated at 0 ° C. for 120 minutes and heat-treated at 230 ° C. for 120 minutes.
mm was obtained.
【0035】得られた印刷配線板用積層板について、誘
電特性、はんだ耐熱性、Tg(ガラス転移温度)及び銅
箔引きはがし強さを測定した。その結果を表2に示す。
なお、誘電特性及びTg以外の測定項目の評価は、23
0℃で加熱処理した印刷配線板用積層板を用いた。The obtained laminate for a printed wiring board was measured for dielectric properties, solder heat resistance, Tg (glass transition temperature), and copper foil peeling strength. Table 2 shows the results.
The evaluation of the measurement items other than the dielectric properties and Tg was 23
A printed wiring board laminate subjected to heat treatment at 0 ° C. was used.
【0036】試験方法は以下の通りである。 ・1MHzの比誘電率(εr)及び誘電正接(tan
δ):JIS C−6481に準拠して測定した。 ・1GHzの比誘電率(εr)及び誘電正接(tan
δ):トリプレート構造直線線路共振器法により測定し
た。 ・Tg:銅箔をエッチング除去し、TMA(熱機械分
析)により測定した。 ・はんだ耐熱性:銅箔をエッチングし、PCT(121
℃,0.22MPa)中に保持した後、260℃の溶融
はんだに20秒間浸漬して、外観を調べた。表中の異常
無し個数とは、ミーズリング及びふくれの発生が無いこ
とを意味し、試験数(分母)に対する個数を(分子)で
ある。 ・耐燃性:UL−94垂直試験法に準拠して測定した。 ・銅箔引きはがし強さ:JIS C−6481に準拠し
て測定した。 ・吸水率:銅箔をエッチングして除去し、PCT処理前
後の重量変化から算出した。 ・加工性:銅箔をエッチングして除去し、金型による外
形打ち抜き後、切断部の外観を調べた。表中の良好とは
剥離、白化(クラック)及びケバ等の発生が無いことを
意味する。The test method is as follows. 1 MHz relative dielectric constant (εr) and dielectric loss tangent (tan)
δ): Measured according to JIS C-6481. A relative dielectric constant (εr) of 1 GHz and a dielectric loss tangent (tan)
δ): Measured by a triplate structure straight line resonator method. Tg: The copper foil was removed by etching and measured by TMA (thermomechanical analysis). -Solder heat resistance: PCT (121
(0.2 ° C., 0.22 MPa), and immersed in molten solder at 260 ° C. for 20 seconds to examine the appearance. The number of abnormalities in the table means that there is no occurrence of measling and blistering, and the number for the test number (denominator) is (numerator). -Flame resistance: Measured according to the UL-94 vertical test method. -Copper foil peel strength: Measured in accordance with JIS C-6481. Water absorption: The copper foil was removed by etching and calculated from the weight change before and after the PCT treatment. Workability: The copper foil was removed by etching, and after punching the outer shape with a mold, the appearance of the cut portion was examined. Good in the table means that there is no occurrence of peeling, whitening (cracks), and fluff.
【0037】[0037]
【表2】 [Table 2]
【0038】表2から明らかなように、実施例1〜4の
印刷配線板用樹脂組成物を用いた印刷配線板用積層板
は、何れも吸水率が低く、加工性、吸湿時のはんだ耐熱
性、銅箔引きはがし強さが良好である。また、1GHz
での比誘電率、誘電正接は200℃及び230℃の後加
熱処理品ともほぼ同等で低く、Tgについても200℃
及び230℃の後加熱処理品ともほぼ同等で高い値を示
し、硬化性においても優れる。As is clear from Table 2, the laminated boards for printed wiring boards using the resin compositions for printed wiring boards of Examples 1 to 4 all have low water absorption, workability, and solder heat resistance during moisture absorption. And copper foil peeling strength are good. In addition, 1GHz
Dielectric constant and dielectric loss tangent at 200 ° C. and 230 ° C. are almost the same as those of post-heat treated products, and Tg is 200 ° C.
It shows almost the same high value as that of the post-heat treated products at 230 ° C. and is excellent in curability.
【0039】これに対して、比較例1の印刷配線板用積
層板は、実施例1〜4の印刷配線板用積層板に比べ加工
性が劣り、また1GHzの比誘電率、誘電正接及び吸水
率がやや高い。比較例2の印刷配線板用積層板は、20
0℃の後加熱処理品の誘電特性及びTgが230℃の後
加熱処理品に比べやや劣り、硬化性が各実施例と比較し
て劣る。比較例3〜5の銅張積層板は、銅箔引きはがし
強さ及び吸湿時のはんだ耐熱性が低く、1GHzの比誘
電率、誘電正接及び吸水率が高い。On the other hand, the printed wiring board laminate of Comparative Example 1 is inferior in workability to the printed wiring board laminates of Examples 1 to 4, and has a relative dielectric constant of 1 GHz, a dielectric loss tangent and water absorption. The rate is somewhat high. The laminated board for a printed wiring board of Comparative Example 2 had 20
The dielectric properties and Tg of the post-heat-treated product at 0 ° C. are slightly inferior to those of the post-heat-treated product at 230 ° C., and the curability is inferior to those of the examples. The copper-clad laminates of Comparative Examples 3 to 5 have low copper foil peeling strength and low solder heat resistance during moisture absorption, and have a high relative dielectric constant, dielectric loss tangent and water absorption of 1 GHz.
【0040】[0040]
【発明の効果】以上のように、本発明の印刷配線板用樹
脂組成物、ワニスおよびそれを用いたプリプレグ、積層
板は、印刷配線板とした場合に、成形性、接着性、吸湿
時の耐熱性が良好でかつ高周波帯域での比誘電率、誘電
正接が低く、高周波信号を扱う機器に対応した印刷配線
板に用いる印刷配線板用樹脂組成物として好適である。As described above, the resin composition for a printed wiring board, the varnish, and the prepreg and laminate using the same according to the present invention, when formed into a printed wiring board, have good moldability, adhesiveness, and moisture absorption. It has good heat resistance, low relative dielectric constant and low dielectric loss tangent in a high frequency band, and is suitable as a resin composition for a printed wiring board used for a printed wiring board corresponding to a device handling a high frequency signal.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 FI C08K 5/3477 C08K 5/3477 C09D 179/00 C09D 179/00 H05K 1/03 610 H05K 1/03 610H ──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. 6 Identification code FI C08K 5/3477 C08K 5/3477 C09D 179/00 C09D 179/00 H05K 1/03 610 H05K 1/03 610H
Claims (15)
るシアネート類化合物またはそのプレポリマー、(B)
一価フェノール類化合物及び(C)シアネート類化合物
と反応性を有しない難燃剤を必須成分として含む樹脂組
成物において、(A)分子中にシアネート基を2個有す
るシアネート類化合物が、式(1)で表されるアルキル
基置換シアネート類化合物と式(2)で表されるシアネ
ート基の2−位に置換基を有しないシアネート類化合物
との2種類以上の混合物であることを特徴とする印刷配
線板用樹脂組成物。 【化1】 (式中,R1,R2は,炭素数=1〜4の低級アルキル基
を示し,それぞれ同じであっても異なってもよい。ま
た,R3は,2価の基であって,アルキレン基、ハロゲ
ン化アルキレン基、アラルキレン基、脂環式結合基を示
す。) 【化2】 (式中,R4は,2価の基であって、アルキレン基、ハ
ロゲン化アルキレン基、アラルキレン基、脂環式結合基
を示す。)(A) a cyanate compound having two cyanate groups in a molecule or a prepolymer thereof, (B)
In a resin composition containing, as an essential component, a monohydric phenol compound and a flame retardant having no reactivity with the (C) cyanate compound, the (A) cyanate compound having two cyanate groups in the molecule is represented by the formula (1) Wherein the mixture is a mixture of two or more of an alkyl group-substituted cyanate compound represented by formula (1) and a cyanate compound having no substituent at the 2-position of the cyanate group represented by formula (2). Resin composition for wiring board. Embedded image (Wherein, R 1 and R 2 each represent a lower alkyl group having 1 to 4 carbon atoms, which may be the same or different. R 3 is a divalent group and is an alkylene group. Group, a halogenated alkylene group, an aralkylene group, and an alicyclic bonding group.) (In the formula, R 4 is a divalent group, and represents an alkylene group, a halogenated alkylene group, an aralkylene group, or an alicyclic bonding group.)
るシアネート類化合物またはそのプレポリマー100重
量部に対し、(B)一価フェノール類化合物を5〜30
重量部及び(C)シアネート類化合物と反応性を有しな
い難燃剤を5〜200重量部配合することを特徴とする
請求項1に記載の印刷配線板用樹脂組成物。2. (A) 5 to 30 parts of (B) a monohydric phenol compound per 100 parts by weight of a cyanate compound having two cyanate groups in a molecule or a prepolymer thereof.
The resin composition for a printed wiring board according to claim 1, wherein 5 to 200 parts by weight of a flame retardant having no reactivity with the (C) cyanate compound is mixed.
るシアネート類化合物またはそのプレポリマーに用いる
式(1)で表されるアルキル基置換シアネート類化合物
と式(2)で表されるシアネート基の2−位に置換基を
有しないシアネート類化合物との配合比が式(1):式
(2)=30:70重量比〜70:30重量比の混合物
である請求項1または請求項2に記載の印刷配線板用樹
脂組成物。3. An alkyl-substituted cyanate compound represented by the formula (1) used for a cyanate compound having two cyanate groups in the molecule or a prepolymer thereof, and a cyanate represented by the formula (2): The compound of the formula (1): formula (2) = 30: 70 weight ratio to 70:30 weight ratio with a cyanate compound having no substituent at the 2-position of the group. 3. The resin composition for a printed wiring board according to 2.
るシアネート類化合物またはそのプレポリマーに用いる
式(1)で表されるアルキル基置換シアネート類化合物
が、ビス(3,5−ジメチル−4−シアネートフェニ
ル)メタンである請求項1ないし請求項3のいずれかに
記載の印刷配線板用樹脂組成物。4. The method according to claim 1, wherein (A) the cyanate compound having two cyanate groups in the molecule or the alkyl-substituted cyanate compound represented by the formula (1) used in the prepolymer thereof is bis (3,5-dimethyl- The resin composition for a printed wiring board according to any one of claims 1 to 3, wherein the resin composition is (4-cyanatephenyl) methane.
るシアネート類化合物またはそのプレポリマーに用いる
式(2)で表されるシアナート基の2−位に置換基を有
しないシアネート類化合物が、2,2−ビス(4−シア
ネートフェニル)プロパンである請求項1ないし請求項
4のいずれかに記載の印刷配線板用樹脂組成物。(A) a cyanate compound having two cyanate groups in the molecule or a cyanate compound having no substituent at the 2-position of the cyanate group represented by the formula (2) used in the prepolymer thereof; The resin composition for a printed wiring board according to any one of claims 1 to 4, which is 2,2-bis (4-cyanatephenyl) propane.
るシアネート類化合物またはそのプレポリマーに用いる
式(2)で表されるシアナート基の2−位に置換基を有
しないシアネート類化合物が、α,α’−ビス(4−シ
アネートフェニル)−m−ジイソプロピルベンゼンであ
る請求項1ないし請求項4のいずれかに記載の印刷配線
板用樹脂組成物。(A) a cyanate compound having two cyanate groups in the molecule or a cyanate compound having no substituent at the 2-position of the cyanate group represented by the formula (2) used for the prepolymer thereof; The resin composition for a printed wiring board according to any one of claims 1 to 4, wherein the resin composition is α, α'-bis (4-cyanatephenyl) -m-diisopropylbenzene.
キル基置換フェノール類化合物である請求項1ないし請
求項6のいずれかに記載の印刷配線板用樹脂組成物。7. The resin composition for a printed wiring board according to claim 1, wherein (B) the monohydric phenol compound is an alkyl group-substituted phenol compound.
p−ノニルフェノール、p−tert−ブチルフェノー
ル、p−tert−アミルフェノール及びp−tert
−オクチルフェノールから選ばれる1種類又は2種類以
上である請求項7に記載の印刷配線板用樹脂組成物。8. An alkyl group-substituted phenol compound,
p-nonylphenol, p-tert-butylphenol, p-tert-amylphenol and p-tert
The resin composition for a printed wiring board according to claim 7, wherein the resin composition is one kind or two or more kinds selected from octylphenol.
(3)で表される一価フェノール類化合物の1種類又は
2種類以上である請求項1ないし請求項6のいずれかに
記載の印刷配線板用樹脂組成物。 【化3】 (式中,R5,R6は水素原子又はメチル基を示し、それ
ぞれ同じであっても異なってもよい。またmは1〜2の
整数を表す)9. The method according to claim 1, wherein the monohydric phenol compound (B) is one or more monohydric phenol compounds represented by the formula (3). A resin composition for a printed wiring board. Embedded image (In the formula, R 5 and R 6 represent a hydrogen atom or a methyl group, and may be the same or different, and m represents an integer of 1 to 2.)
化合物が、p−(α−クミル)フェノールである請求項
9に記載の印刷配線板用樹脂組成物。10. The resin composition for a printed wiring board according to claim 9, wherein the monohydric phenol compound represented by the formula (3) is p- (α-cumyl) phenol.
有しない難燃剤が、1,2−ジブロモ−4−(1,2−
ジブロモエチル)シクロヘキサン、テトラブロモシクロ
オクタン及びヘキサブロモシクロドデカンから選ばれる
脂肪族環型難燃剤の1種類又は2種類以上である請求項
1ないし請求項10のいずれかに記載の印刷配線板用樹
脂組成物。11. The flame retardant having no reactivity with the cyanate compound (C) is 1,2-dibromo-4- (1,2-
The resin for a printed wiring board according to any one of claims 1 to 10, wherein the resin is at least one kind of an aliphatic cyclic flame retardant selected from dibromoethyl) cyclohexane, tetrabromocyclooctane, and hexabromocyclododecane. Composition.
有しない難燃剤が、式(4)で表される複素環型難燃剤
の1種類又は2種類以上である請求項1ないし請求項1
0のいずれかに記載の印刷配線板用樹脂組成物。 【化4】 (式中,l,m,nは1〜5の整数を表し,それぞれ同
じ値であっても異なってもよい)12. The flame retardant having no reactivity with the cyanate compound (C) is one or more heterocyclic flame retardants represented by the formula (4).
0. The resin composition for a printed wiring board according to any one of 0. Embedded image (Where l, m, and n represent integers of 1 to 5 and may be the same or different, respectively)
記載の印刷配線板用樹脂組成物を溶剤に溶解ないし分散
させた印刷配線板用樹脂ワニス。13. A resin varnish for printed wiring boards, wherein the resin composition for printed wiring boards according to any one of claims 1 to 12 is dissolved or dispersed in a solvent.
ニスを基材に含浸後、80〜200℃で乾燥させて得ら
れる印刷配線板用プリプレグ。14. A prepreg for a printed wiring board obtained by impregnating a substrate with the resin varnish for a printed wiring board according to claim 13 and drying at 80 to 200 ° C.
レグを複数枚重ね、さらにその外側に金属箔を積層し加
熱加圧して得られる印刷配線板用積層板。15. A laminate for a printed wiring board obtained by laminating a plurality of the prepregs for a printed wiring board according to claim 14, further laminating a metal foil on the outside thereof, and applying heat and pressure.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP17177497A JPH1112463A (en) | 1997-06-27 | 1997-06-27 | Resin composition for printed circuit board, varnish, prepreg, and laminate for printed circuit board prepared therefrom |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP17177497A JPH1112463A (en) | 1997-06-27 | 1997-06-27 | Resin composition for printed circuit board, varnish, prepreg, and laminate for printed circuit board prepared therefrom |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH1112463A true JPH1112463A (en) | 1999-01-19 |
Family
ID=15929438
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP17177497A Pending JPH1112463A (en) | 1997-06-27 | 1997-06-27 | Resin composition for printed circuit board, varnish, prepreg, and laminate for printed circuit board prepared therefrom |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH1112463A (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2012031428A (en) * | 2001-08-31 | 2012-02-16 | Sumitomo Bakelite Co Ltd | Prepreg with metal foil, laminated board, and semiconductor package |
EP2871918A4 (en) * | 2012-07-06 | 2016-03-16 | Nhk Spring Co Ltd | Laminate for circuit boards, metal-based circuit board, and power module |
-
1997
- 1997-06-27 JP JP17177497A patent/JPH1112463A/en active Pending
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2012031428A (en) * | 2001-08-31 | 2012-02-16 | Sumitomo Bakelite Co Ltd | Prepreg with metal foil, laminated board, and semiconductor package |
EP2871918A4 (en) * | 2012-07-06 | 2016-03-16 | Nhk Spring Co Ltd | Laminate for circuit boards, metal-based circuit board, and power module |
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