JP2002138199A - Resin composition for laminate, prepreg using the same and laminate - Google Patents
Resin composition for laminate, prepreg using the same and laminateInfo
- Publication number
- JP2002138199A JP2002138199A JP2001330965A JP2001330965A JP2002138199A JP 2002138199 A JP2002138199 A JP 2002138199A JP 2001330965 A JP2001330965 A JP 2001330965A JP 2001330965 A JP2001330965 A JP 2001330965A JP 2002138199 A JP2002138199 A JP 2002138199A
- Authority
- JP
- Japan
- Prior art keywords
- resin composition
- laminate
- component
- laminate according
- cyanate
- 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
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
に優れた積層板として有用な積層板用樹脂組成物、該組
成物を用いた積層板用プリプレグ及び金属張り積層板に
関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition for a laminate useful as a laminate having excellent dielectric properties and heat resistance, a prepreg for a laminate using the composition, and a metal-clad laminate.
【０００２】[0002]
【従来の技術】近年、通信分野等の高周波機器に用いら
れるプリント配線板材料には、誘電率及び誘電正接の低
い積層板用樹脂が望まれている。これに対し誘電率や誘
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やポリフェニレンエーテルにエポキ
シ樹脂、シアネートエステル樹脂及びＢＴ（ビスマレイ
ミドトリアジン）樹脂等の熱硬化性樹脂を併用した樹脂
材料が提案されているが、これらは融点や軟化点が高い
ことから成形に高温、高圧が必要で成形性に劣るという
問題や金属箔や金属めっきとの接着性に劣るというに問
題があった。一方、上記熱可塑性樹脂を併用しなくとも
誘電率や誘電正接が低い樹脂材料として知られるシアネ
ートエステル樹脂単独では、硬化物の脆さに伴う加工
性、耐燃性及び吸湿時の耐熱性に問題があった。2. Description of the Related Art In recent years, as a printed wiring board material used for high-frequency equipment in the communication field and the like, a resin for a laminate having a low dielectric constant and a low dielectric loss tangent has been desired. On the other hand, a fluororesin having a low dielectric constant or a dielectric loss tangent, a thermoplastic resin material such as polyphenylene ether, or a resin obtained by using a thermosetting resin such as an epoxy resin, a cyanate ester resin and a BT (bismaleimide triazine) resin in combination with polyphenylene ether. Materials have been proposed, but these have problems in that high melting points and softening points require high temperatures and high pressures for molding, resulting in poor moldability and poor adhesion to metal foils and metal plating. . On the other hand, the cyanate ester resin alone, which is known as a resin material having a low dielectric constant and a low dielectric loss tangent without using the above thermoplastic resin alone, has problems in workability due to brittleness of the cured product, flame resistance, and heat resistance during moisture absorption. there were.
【０００３】上記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２−２８
６７２３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
報に記載の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。For the purpose of improving the above-mentioned problems, a method in which a glycidyl etherified product of phenol novolak described in JP-A-63-54419 is used in combination with a BT (bismaleimide triazine) resin or a cyanate ester resin. JP-A-2144741, a method using a glycidyl etherified product of a phenol-added dicyclopentadiene polymer in combination, an epoxy resin such as a glycidyl etherified product of bisphenol A described in JP-A-3-84040, and JP-A-5-214. Phenol-added butadiene polymer described in JP-A-310673;
-Polyphenol compounds such as bisphenol A described in JP-B-47637, or brominated bisphenol A and hydroxyl etherified product of brominated bisphenol A described in JP-B-4-24370, JP-A-2-28
No. 6723, a glycidyl etherified product of a brominated phenol novolak, a glycidyl etherified product of a brominated bisphenol A described in JP-A-5-339342, a brominated maleimide compound described in JP-A-7-207022, and the like. And a method of using a flame retardant having reactivity with a BT (bismaleimide triazine) resin or a cyanate ester resin.
【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、成形性、加工性、接着性、耐熱性、耐燃性に関する
欠点は改善されるものの、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、成形性や加工性は改善されるものの、接着
性や吸湿時の耐熱性に劣るという問題や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５−３３９３４２
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
るものの前述同様吸湿時の耐熱性やGHz帯域での誘電特
性が悪化するという問題があった。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, moldability, workability, adhesiveness, heat resistance, Although the disadvantages related to the flame resistance were improved, the dielectric properties in the GHz band deteriorated, and were insufficient for high frequency applications. Also, Japanese Patent Application Laid-Open
In the method of using a polyhydric phenol compound as disclosed in JP-A-310673 and JP-B-7-47637, moldability and processability are improved, but adhesiveness and heat resistance during moisture absorption are improved. There is a problem that it is inferior and that it cannot be used for high frequency applications due to deterioration of dielectric properties in the GHz band. Japanese Patent Publication No. Hei 4-24370, Japanese Patent Laid-Open No. 2-286723, Japanese Patent Laid-Open No. 5-339342.
In the method of using a flame retardant as disclosed in JP-A-7-207022, the flame resistance can be added, but the heat resistance at the time of moisture absorption and the dielectric characteristics in the GHz band deteriorate as described above. was there.
【０００５】本発明は、成形性、加工性、接着性、耐熱
性、耐燃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積層板用樹脂組成物及び該組成
物を用いた積層板用樹脂ワニス、積層板用プリプレグ、
金属張り積層板を提供するものである。[0005] The present invention provides a resin composition for a laminate having excellent dielectric properties in a high frequency band without impairing properties such as moldability, workability, adhesiveness, heat resistance, and flame resistance. Resin varnish for laminated board, prepreg for laminated board,
A metal-clad laminate is provided.
【０００６】[0006]
【課題を解決するための手段】本発明は、（Ａ）（Ｉ）
式で表される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の１種以上と、
（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
積層板用樹脂組成物である。また、本発明は、前記積層
板用樹脂組成物を溶剤に溶解ないし分散させた積層板用
樹脂ワニスを基材に含浸後、８０〜２００℃で乾燥させ
て得られる積層板用プリプレグである。さらに、本発明
は、この積層板用プリプレグを、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金属張り積層板
である。The present invention provides (A) and (I)
One or more cyanate compounds having two cyanate groups in the molecule represented by the formula or a prepolymer thereof,
It is a resin composition for laminated boards which contains a flame retardant which does not react with (B) a monohydric phenol compound and (C) a cyanate compound as essential components. Further, the present invention is a prepreg for a laminate obtained by impregnating a base material with a resin varnish for a laminate obtained by dissolving or dispersing the resin composition for a laminate in a solvent, and then drying at 80 to 200 ° C. Further, in the present invention, the prepreg for a laminate can be used as a prepreg for interlayer connection of a multilayer printed wiring board, and a plurality of prepregs for a laminate are laminated, and a metal foil is further laminated on the outside of the prepreg for heating. It is a metal-clad laminate obtained by pressing.
【０００７】[0007]
【発明の実施の形態】本発明の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
の材料は、（Ｉ）式で表され、少なくとも１種以上を用
いる。（Ｉ）式で表される化合物として、その具体例と
しては、ビス（４−シアネートフェニル）エタン、ビス
（３，５−ジメチル−４−シアネートフェニル）メタ
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それらのプレポ
リマが挙げられる。この中では、ビス（３,５−ジメチ
ル−４−シアネートフェニル）メタン、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である
と硬化物の誘電特性が特に良好であるためより好まし
い。BEST MODE FOR CARRYING OUT THE INVENTION A cyanate compound having two cyanate groups in a molecule of the present invention or a material of a prepolymer thereof is represented by the formula (I), and at least one kind is used. Specific examples of the compound represented by the formula (I) include bis (4-cyanatephenyl) ethane, bis (3,5-dimethyl-4-cyanatephenyl) methane, 2,2-bis (4-cyanate) Phenyl) -1,
1,1,3,3,3-hexafluoropropane, α,
α'-bis (4-cyanatephenyl) -m-diisopropylbenzene, cyanate esterified phenol-added dicyclopentadiene polymer, and prepolymers thereof. Among them, bis (3,5-dimethyl-4-cyanatephenyl) methane, 2,2-bis (4-cyanatephenyl) -1,1,1,3,3,3
-Hexafluoropropane and α, α'-bis (4-cyanatephenyl) -m-diisopropylbenzene are more preferred because the cured product has particularly good dielectric properties.
【０００８】[0008]
【化３】 Embedded image
【０００９】上記の（Ａ）（Ｉ）式で表される分子中に
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
じめプレポリマー化して用いるのが好ましい。プレポリ
マー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２０〜６０重量％の範囲内で転化された
プレポリマーを用いることが望ましい。また（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一種類単独で用いてもよく、二種
類以上を混合して用いてもよい。A monomer of a cyanate compound having two cyanate groups in the molecule represented by the above formulas (A) and (I) has high crystallinity, and when these monomers are varnished with a solvent, the solid content concentration is high. Depending on the case, recrystallization may occur in the varnish. Therefore, it is preferable to use the cyanate compound monomer in a prepolymerized state. Although the conversion of the cyanate group of the prepolymer is not particularly limited, it is usually desirable to use the prepolymer converted within the range of 20 to 60% by weight. Further, (A) a cyanate compound having two cyanate groups in a molecule or a prepolymer thereof may be used singly or as a mixture of two or more.
【００１０】本発明の積層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、（Ｂ）一価フェ
ノール類化合物を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。The (B) monohydric phenol compound used in the resin composition for a laminate of the present invention is based on (A) a cyanate compound having two cyanate groups in a molecule or 100 parts by weight of a prepolymer thereof. It is preferable to blend (B) the monohydric phenol compound in the range of 5 to 30 parts by weight. More preferably, it is 7 to 30 parts by weight.
If the amount is less than 5 parts 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.
【００１１】本発明で使用する（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−tert−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（II）式で表される一価フェノ
ール類化合物等が挙げられる。（II）式で表される一価
フェノール類化合物としては、ｐ−（α−クミル）フェ
ノールが好ましい。また（Ｂ）一価フェノール類化合物
は一種類単独で用いてもよく、二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 present invention include p-nonylphenol and p-nonylphenol.
Examples include alkyl-substituted phenol compounds such as tert-butylphenol, p-tert-amylphenol, and p-tert-octylphenol, and monohydric phenol compounds represented by the formula (II). As the monohydric phenol compound represented by the formula (II), 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４】 Embedded image
【００１３】本発明の積層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及
び（III）式で表される複素環型難燃剤が挙げられる。
（III）式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、５〜２００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、２０
０重量部を越えると耐熱性が低下するので好ましくな
い。The flame retardant having no reactivity with the cyanate compound (C) used in the resin composition for a laminate of the present invention includes 1,2-dibromo-4- (1,2-dibromoethyl) cyclohexane, Aliphatic ring flame retardants such as tetrabromooctane and hexabromocyclododecane and heterocyclic flame retardants represented by the formula (III) are mentioned.
As the heterocyclic flame retardant represented by the formula (III),
4,6-tris (tribromophenoxy) -1,3,5
-Triazines are preferred. The flame retardant having no reactivity with the (C) cyanate compound is in the range of 5 to 200 parts by weight based on 100 parts by weight of the (A) cyanate compound having two cyanate groups in the molecule or a prepolymer thereof. It is preferable to mix them. 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
Exceeding 0 parts by weight is not preferred because heat resistance is reduced.
【００１４】[0014]
【化５】 Embedded image
【００１５】本発明の積層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を挙げること
ができる。特に２−エチルヘ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
機金属塩化合物は一種類単独で用いてもよく、二種類以
上を混合して用いてもよい。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 laminate of the present invention, a curing accelerator for accelerating the curing reaction is used. Specific examples of the curing accelerator include cobalt, manganese, tin,
Organic metal salt compounds such as nickel, zinc, and copper can be mentioned. Particularly, organic cobalt salt compounds such as cobalt 2-ethylhexanoate and cobalt naphthenate are preferred. The organometallic salt compounds may be used alone or in a combination of two or more. The amount of the curing accelerator is
(A) 100 parts by weight of a cyanate compound having two cyanate groups in the molecule or a prepolymer thereof in an amount of from 0.01 to 0.01 in a range that does not deteriorate the mixing effect and the physical properties of the cured product.
It is 3 parts by weight, more preferably 0.02 to 0.5 part by weight.
【００１６】本発明の積層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 laminate of the present invention may further contain a filler and other additives as necessary. As the filler, usually, an inorganic filler is suitably used, and specific examples thereof include fused silica, glass, alumina, titania, zircon, calcium carbonate,
Examples thereof include calcium silicate, magnesium silicate, aluminum silicate, silicon nitride, boron nitride, beryllia, zirconia, barium titanate, potassium titanate, and calcium titanate.
【００１７】本発明の積層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積層板の製造
に供せられる。即ち本発明の積層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まずプリプレグを作製
する。次いでこのプリプレグを任意枚数とその上下又は
一方の面に金属箔を重ねて加熱成形することによって積
層板とすることができる。The resin composition for a laminate of the present invention can be subjected to heat curing to provide a laminate having excellent dielectric properties and heat resistance. That is, the resin composition for a laminated 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 and a metal foil are laminated on the upper and lower sides or on one side thereof, and heat-molded to form a laminate.
【００１８】本発明の積層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系、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、これら上記溶剤は一種類単独で用いてもよ
く、又は二種類以上を混合して用いてもよい。When the resin composition for a laminate of the present invention is varnished, the solvent is not particularly limited, but specific examples thereof include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, toluene, and xylene. Aromatic hydrocarbons such as, methoxyethyl acetate, ethoxyethyl acetate, butoxyethyl acetate, ester 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 singly or as a mixture of two or more.
【００１９】上記の積層板用樹脂ワニスは、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、８
０〜２００℃で乾燥させて積層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、金属張り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積層板用樹脂組
成物を多くするため樹脂分を多くするようにする。The resin varnish for a laminate described above is impregnated into a base material used for a laminate such as a glass woven fabric, a glass nonwoven fabric, a plastic woven fabric, a plastic nonwoven fabric, and paper.
It is dried at 0 to 200 ° C. to obtain a prepreg for a laminate.
When used as a prepreg for interlayer bonding of a multilayer printed wiring board, the resin content in the prepreg is increased. Further, when a metal-clad laminate is used, a resin composition for a laminate of the present invention having excellent dielectric properties is required when a material having a small value of dielectric constant or dielectric loss tangent is required according to required dielectric properties. To increase the amount of resin.
【００２０】積層板用プリプレグは、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金属
張り積層板とする。A plurality of prepregs for a laminate are stacked, and a metal foil is further laminated on the outside of the prepreg, and heated and pressed to form a metal-clad laminate.
【００２１】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樹
脂の硬化物は低極性、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、吸湿時の耐熱性や耐燃性を改善するためシアネート
エステル樹脂にエポキシ樹脂、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の併
用といった従来の方法では、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、反応（硬化）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、耐熱性が
低下したり誘電率や誘電正接が高くなる。これに対し
て、本発明の積層板用樹脂組成物において用いられるフ
ェノール類化合物は、一価のフェノール類化合物である
ため上記のような問題が無く、さらに一価のフェノール
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、本発明の積層板用樹脂組成物において用いら
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
を妨げなことから誘電特性を悪化させることなく耐燃性
を付加することができる。したがって、得られる樹脂硬
化物は高耐熱性、高耐燃性であり誘電率や誘電正接の値
が低く誘電特性に優れたものとなる。以下実施例によ
り、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。In general, the dielectric properties of a cured resin are affected by the molecular structure, that is, the amount and strength of polar groups in the molecule, the mobility of the molecular skeleton, and the like. Originally, a cured product of a cyanate ester resin 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. However, in order to improve the heat resistance and flame resistance during moisture absorption, in the conventional method such as a combination of a cyanate ester resin and an epoxy resin, a polyhydric phenol compound and a reactive flame retardant having reactivity with a cyanate group, the cyanate group is used. The reaction produces a structure other than a triazine ring with a high polar group, or the progress of the reaction (curing) causes loss of fluidity and the number of remaining functional groups that cannot be reacted increases, reducing heat resistance. And the dielectric constant and dielectric tangent increase. On the other hand, the phenolic compound used in the resin composition for a laminate of the present invention is a monovalent phenolic compound and thus does not have the above-described problems. It is a phenolic compound having high reactivity with and promoting the formation of a triazine ring. Further, since the flame retardant used in the resin composition for a laminate of the present invention is a flame retardant having a low polarity structure and no reactivity to cyanate groups, it does not hinder the formation of a triazine ring and thus has a dielectric property. Flame resistance can be added without deterioration. Therefore, the obtained cured resin has high heat resistance and high flame resistance, and has low dielectric constant and dielectric loss tangent, and has excellent dielectric properties. Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited thereto.
【００２２】[0022]
【実施例】（実施例１）分子中にシアネート基を２個以
上有するシアネート類化合物としてビス（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
（Ａｒｏｃｙ Ｍ−３０、旭チバ株式会社製商品名）、
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（ＳＡＹＴＥＸ 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及
びメチルエチルケトン（メチルエチルケトンの含有率４
０重量％）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％の積
層板用樹脂ワニスを作製した。(Example 1) As a cyanate compound having two or more cyanate groups in a molecule, a prepolymer of bis (3,5-dimethyl-4-cyanatephenyl) methane (Arocy M-30, manufactured by Asahi Chiba Corporation) Product name),
1,2-dibromo-4- (1,2-dibromoethyl) cyclohexane (SAYTEX BCL-462, a trade name of Albemarle) as a flame retardant having no reactivity with p-nonylphenol and cyanate compounds as monohydric phenol compounds ) And toluene and methyl ethyl ketone (content of methyl ethyl ketone 4
0% by weight), and 0.1 part by weight of cobalt naphthenate is added to 100 parts by weight of a cyanate compound as a curing accelerator to prepare a resin varnish for laminates having a nonvolatile content of 65% by weight. did.
【００２３】（実施例２）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（Ａ
ｒｏｃｙ 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に示す配合量で配合した他は、実施例１
と同様にして不揮発分６５重量％の積層板用樹脂ワニス
を作製した。Example 2 Methyl ethyl ketone solution of a prepolymer of 2,2-bis (4-cyanatephenyl) -1,1,1,3,3,3-hexafluoropropane (A
rocy F-40S, trade name, manufactured by Asahi Ciba Co., Ltd.) and p
Example 1 except that -tert-butylphenol and tetrabromocyclooctane (SAYTEX BC-48, trade name of Albemarle) were blended in the amounts shown in Table 1.
In the same manner as in the above, a resin varnish for laminate having a nonvolatile content of 65% by weight was produced.
【００２４】（実施例３）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
す配合量で配合した他は、実施例１と同様にして不揮発
分６５重量％の積層板用樹脂ワニスを作製した。Example 3 α, α'-bis (4-cyanatephenyl) -m-diisopropylbenzene (RTX
-366, trade name of Asahi Ciba Co., Ltd.) and p-tert-octylphenol and hexabromocyclododecane (CD
A resin varnish for a laminated board having a nonvolatile content of 65% by weight was prepared in the same manner as in Example 1 except that -75P (trade name, manufactured by Great Lakes Co.) was blended in the amount shown in Table 1.
【００２５】（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（ＳＡＹＴＥＸ ＢＣＬ−４６２）を臭素
化トリフェニルシアヌレート（ピロガードＳＲ−２４
５、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％の積層板用樹脂ワニスを作製した。Example 4 In Example 1, p-nonylphenol was replaced with p- (α-cumyl) phenol and 1,2-dibromo-4- (1,2-dibromoethyl) cyclohexane (SAYTEX BCL-462). ) With brominated triphenyl cyanurate (Pyroguard SR-24)
5, a non-volatile content of 65 in the same manner as in Example 1 except that the compounding amount shown in Table 1 was used in place of Daiichi Kogyo Seiyaku Co., Ltd.
By weight, a resin varnish for a laminate was prepared.
【００２６】（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
のプレポリマー（Ａｒｏｃｙ Ｍ−３０）を２，２−ビ
ス（４−シアネートフェニル）プロパンのプレポリマー
（Ａｒｏｃｙ Ｂ−３０、旭チバ株式会社製商品名）
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（ＳＡＹＴＥＸ ＢＣＬ−４６
２）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実施例１と同
様にして不揮発分６５重量％の積層板用樹脂ワニスを作
製した。Comparative Example 1 In Example 1, a prepolymer (Arocy M-30) of bis (3,5-dimethyl-4-cyanatephenyl) methane was replaced with 2,2-bis (4-cyanatephenyl) propane. Prepolymer (Arocy B-30, trade name, manufactured by Asahi Chiba Corporation)
And 1,2-dibromo-4- (1,2-dibromoethyl) cyclohexane (SAYTEX BCL-46)
2) is a brominated bisphenol A type epoxy resin (ESB
A resin varnish for a laminated board having a nonvolatile content of 65% by weight was prepared in the same manner as in 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.
【００２７】（比較例２）実施例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（ＳＡＹＴＥＸ ＢＣＬ−４６２）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実施例１と同様にして不揮発分６５
重量％の積層板用樹脂ワニスを作製した。Comparative Example 2 In Example 1, 1,2-
Dibromo-4- (1,2-dibromoethyl) cyclohexane (SAYTEX BCL-462) was replaced with a brominated phenol novolak type epoxy resin (BREN-S, trade name, manufactured by Nippon Kayaku Co., Ltd.), and the amount shown in Table 1 And dissolved in toluene in the same manner as in Example 1.
By weight, a resin varnish for a laminate was prepared.
【００２８】（比較例３）比較例１において、ｐ−ノニ
ルフェノールを除き、臭素化ビスフェノールＡ型エポキ
シ樹脂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％の積層板用樹脂ワニスを作
製した。(Comparative Example 3) In Comparative Example 1, except that p-nonylphenol was used and brominated bisphenol A type epoxy resin was replaced with brominated bisphenol A (TBA) and dissolved in toluene at the compounding amount shown in Table 1, In the same manner as in Comparative Example 1, a resin varnish for a laminate having a nonvolatile content of 65% by weight was produced.
【００２９】（比較例４）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、及び臭素化ビスフェノールＡ型エポキシ樹脂を臭素
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％の積層板用樹脂ワニスを作製した。Comparative Example 4 In Comparative Example 1, p-nonylphenol was replaced with a phenol-added butadiene polymer (P
P700-300, trade name of Nippon Petrochemical Co., Ltd.)
And a brominated bisphenol A type epoxy resin was dissolved in toluene at the compounding amount shown in Table 1 in place of brominated bisphenol A (TBA). A resin varnish was prepared.
【００３０】[0030]
【表１】 [Table 1]
【００３１】各実施例及び比較例で得られた積層板用樹
脂ワニスを、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％となるように積層板用プリプレグを得
た。次いで、得られた積層板用プリプレグ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、２３０℃で
１２０分加熱処理し厚み０．８mmの銅張り積層板を作製
した。The resin varnish for a laminate obtained in each of the 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 laminate was obtained so as to have a resin content of about 41% by weight. Then, the obtained four prepregs for a laminated board are stacked,
Laminate 18μm thick copper foil on both sides,
After press-forming under the conditions of 2.5 MPa for 2.5 minutes, a heat treatment was performed at 230 ° C. for 120 minutes to produce a copper-clad laminate having a thickness of 0.8 mm.
【００３２】得られたプリプレグについて、表面の外観
を目視で、内部を顕微鏡で観察した。また、得られた銅
張り積層板について、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。The appearance of the surface of the obtained prepreg was visually observed, and the inside was observed with a microscope. In addition, the obtained copper-clad laminate had dielectric properties, solder heat resistance, and Tg.
(Glass transition temperature) and peel strength of the copper foil were measured. Table 2 shows the results.
【００３３】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（tanδ）：Ｊ
ＩＳ−Ｃ−６４８１に準拠して測定。 ・１GHzの比誘電率（εr）及び誘電正接（tanδ）：ト
リプレート構造直線線路共振器法により測定。 ・Ｔｇ：銅箔をエッチングし、ＴＭＡ（熱機械分析）に
より測定。 ・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。 ・銅箔引きはがし強さ：ＪＩＳ−Ｃ−６４８１に準拠し
て測定。 ・加工性：銅箔をエッチングし、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、ケ
バの発生が無いことを意味する。The test method is as follows.・ Relative permittivity (εr) and dielectric loss tangent (tanδ) of 1 MHz: J
Measured according to IS-C-6481.・ Relative permittivity (εr) and dielectric loss tangent (tanδ) at 1 GHz: Measured by a triplate structure straight line resonator method. Tg: Copper foil is etched and measured by TMA (thermomechanical analysis). -Solder heat resistance: PCT (121
After being held at 0.22 MPa), it was immersed in molten solder at 260 ° C. for 20 seconds, and its appearance was examined. 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 according to JIS-C-6481. Workability: After etching the copper foil and punching the outer shape with a mold, the appearance of the cut portion was examined. Good in the table means that there is no peeling or fluffing.
【００３４】[0034]
【表２】 [Table 2]
【００３５】表２から明らかなように、実施例１〜４の
樹脂組成物を用いた銅張積層板は、何れもＴｇが高く、
加工性、吸湿時のはんだ耐熱性、銅箔引きはがし強さが
良好でかつ１GHzでの比誘電率、誘電正接が低い。これ
に対して、各比較例の銅張積層板は、１GHzの比誘電率
及び誘電正接が高く、吸湿時のはんだ耐熱性及び銅箔引
きはがし強さが低い。As is clear from Table 2, the copper clad laminates using the resin compositions of Examples 1 to 4 all have high Tg,
Good workability, heat resistance to soldering when absorbing moisture, and peeling strength of copper foil, and low relative dielectric constant and dielectric loss tangent at 1 GHz. On the other hand, the copper clad laminate of each comparative example has a high relative dielectric constant and a dielectric loss tangent of 1 GHz, low solder heat resistance when absorbing moisture, and low copper foil peeling strength.
【００３６】[0036]
【発明の効果】以上のように本発明の積層板用樹脂組成
物は、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積層板用樹脂組成
物として好適である。As described above, the resin composition for laminates of the present invention has good moldability, adhesiveness, heat resistance when absorbing moisture, and has a low dielectric constant and dielectric loss tangent in a high frequency band, and has a high frequency signal. It is suitable as a resin composition for a laminate used for a printed wiring board corresponding to a device to be handled.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｃ０８Ｋ 5/3492 Ｃ０８Ｋ 5/3492 (72)発明者 栗谷 弘之 茨城県下館市大字小川1500番地 日立化成 工業株式会社下館研究所内 Ｆターム(参考） 4F072 AA04 AA07 AB02 AB09 AB28 AB29 AD11 AE07 AF15 AF20 AF25 AG03 AG17 AG19 AH02 AH21 AK05 AL09 AL12 AL13 4J002 CM021 EB097 EJ016 EU197 FD137 FD206 GF00 GQ01 GQ05 4J043 PA02 PB23 QC23 RA47 SA13 SB01 TA02 TB01 UA051 UA131 UA141 UB011 UB021 UB061 VA021 VA031 VA041 ZA02 ZA12 ZA43 ZA60 ZB02 ZB50 ZB59 ──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. 7 Identification FI FI Theme Court ゛ (Reference) C08K 5/3492 C08K 5/3492 (72) Inventor Hiroyuki Kuriya 1500 Ogawa Oji, Shimodate City, Ibaraki Prefecture Hitachi Chemical Co., Ltd. F-term in the Shimodate Research Laboratories (reference) 4F072 AA04 AA07 AB02 AB09 AB28 AB29 AD11 AE07 AF15 AF20 AF25 AG03 AG17 AG19 AH02 AH21 AK05 AL09 AL12 AL13 4J002 CM021 EB097 EJ016 EU197 FD137 FD206 GF00 GQ01 GQ05 4J043 PA02 TA02 UA131 UA141 UB011 UB021 UB061 VA021 VA031 VA041 ZA02 ZA12 ZA43 ZA60 ZB02 ZB50 ZB59
Claims (13)
るシアネート化合物またはそのプレポリマーの１種以
上、（Ｂ）一価フェノール化合物、及び（Ｃ）前記成分
（Ａ）と反応性を有しない難燃剤を含む積層板用樹脂組
成物。(A) a reactive compound with at least one of a cyanate compound having two cyanate groups in a molecule or a prepolymer thereof, (B) a monohydric phenol compound, and (C) a component (A). Laminate resin composition containing non-flame retardant.
記成分（Ｂ）が５〜３０重量部である、請求項１記載の
積層板用樹脂組成物。2. The resin composition for a laminate according to claim 1, wherein the component (B) is 5 to 30 parts by weight based on 100 parts by weight of the component (A).
チルー４−シアネートフェニル）メタン又はそのプレポ
リマーである、請求項１又は２記載の積層板用樹脂組成
物。3. The resin composition for a laminate according to claim 1, wherein the component (A) is bis (3,5-dimethyl-4-cyanatephenyl) methane or a prepolymer thereof.
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又はそのプレポリマーである、請求
項１又は２記載の積層板用樹脂組成物。4. The method according to claim 1, wherein the component (A) is 2,2-bis (4-
The resin composition for a laminate according to claim 1, which is (cyanate phenyl) -1,1,1,3,3,3-hexafluoropropane or a prepolymer thereof.
−シアネートフェニル）−ｍ−ジイソプロピルベンゼン
又はそのプレポリマーである、請求項１又は２記載の積
層板用樹脂組成物。5. The composition according to claim 1, wherein said component (A) is α, α′-bis (4
3. The resin composition for a laminate according to claim 1, wherein the resin composition is (cyanate phenyl) -m-diisopropylbenzene or a prepolymer thereof. 4.
フェノール化合物である、請求項１〜５のいずれか１項
記載の積層板用樹脂組成物。6. The resin composition for a laminate according to claim 1, wherein the component (B) is an alkyl group-substituted monohydric phenol compound.
物が、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種以上である、請求項６
に記載の積層板用樹脂組成物。7. The alkyl group monovalent substituted phenol compound is one or more selected from P-nonylphenol, P-tert-butylphenol, p-tert-amylphenol and p-tert-octylphenol.
5. The resin composition for a laminate according to item 1.
（II）式で表される一価フェノール化合物を少なくとも
１種含む、請求項１〜５のいずれか１項記載の積層板用
樹脂組成物。 【化１】 8. The (B) monohydric phenol compound,
The resin composition for a laminate according to any one of claims 1 to 5, comprising at least one monohydric phenol compound represented by the formula (II). Embedded image
フェノールである、請求項８に記載の積層板用樹脂組成
物。9. The composition according to claim 1, wherein the component (B) is p- (α-cumyl)
The resin composition for a laminate according to claim 8, which is phenol.
−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種以上である、
請求項１〜９のいずれか１項記載の積層板用樹脂組成
物。10. An aliphatic cyclic flame retardant wherein the component (C) is selected from 1,2-dibromo-4- (1,2-dibromoethyl) cyclohexane, tetrabromocyclooctane and hexabromocyclododecane. More than a species,
The resin composition for a laminate according to any one of claims 1 to 9.
れる複素環型難燃剤、少なくとも１種を含む、請求項１
〜９のいずれかに記載の積層板用樹脂組成物。 【化２】 11. The composition according to claim 1, wherein the component (C) contains at least one heterocyclic flame retardant represented by the formula (III).
A resin composition for a laminate according to any one of claims 1 to 9. Embedded image
積層板用樹脂組成物を溶剤に溶解、分散しワニスとし、
このワニスを基材に含浸後、８０〜２００℃で乾燥させ
て得られる積層板用プリプレグ。12. The resin composition for a laminate according to any one of claims 1 to 11, which is dissolved and dispersed in a solvent to form a varnish.
A prepreg for a laminate obtained by impregnating a substrate with this varnish and drying at 80 to 200 ° C.
グを複数枚重ね、さらにその外側に金属箔を積層し加熱
加圧して得られる金属張り積層板。13. A metal-clad laminate obtained by laminating a plurality of the prepregs for a laminate according to claim 12, further laminating a metal foil on the outside thereof, and applying heat and pressure.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001330965A JP2002138199A (en) | 2001-10-29 | 2001-10-29 | Resin composition for laminate, prepreg using the same and laminate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001330965A JP2002138199A (en) | 2001-10-29 | 2001-10-29 | Resin composition for laminate, prepreg using the same and laminate |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8003397A Division JP3261061B2 (en) | 1997-03-31 | 1997-03-31 | Resin composition for laminate, prepreg and laminate using the composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2002138199A true JP2002138199A (en) | 2002-05-14 |
Family
ID=19146611
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2001330965A Pending JP2002138199A (en) | 2001-10-29 | 2001-10-29 | Resin composition for laminate, prepreg using the same and laminate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2002138199A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20180090739A (en) | 2017-02-03 | 2018-08-13 | 토요잉크Sc홀딩스주식회사 | Printed wiring board with protective sheet, thermosetting adhesive sheet with sheet-like substrate, manufacturing methods thereof and thermosetting adhesive sheet |
-
2001
- 2001-10-29 JP JP2001330965A patent/JP2002138199A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20180090739A (en) | 2017-02-03 | 2018-08-13 | 토요잉크Sc홀딩스주식회사 | Printed wiring board with protective sheet, thermosetting adhesive sheet with sheet-like substrate, manufacturing methods thereof and thermosetting adhesive sheet |
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