JP3893648B2 - High dielectric constant resin composition, high dielectric constant prepreg, and high dielectric constant laminate - Google Patents
High dielectric constant resin composition, high dielectric constant prepreg, and high dielectric constant laminate Download PDFInfo
- Publication number
- JP3893648B2 JP3893648B2 JP28447896A JP28447896A JP3893648B2 JP 3893648 B2 JP3893648 B2 JP 3893648B2 JP 28447896 A JP28447896 A JP 28447896A JP 28447896 A JP28447896 A JP 28447896A JP 3893648 B2 JP3893648 B2 JP 3893648B2
- Authority
- JP
- Japan
- Prior art keywords
- dielectric constant
- high dielectric
- resin
- laminate
- parts
- 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.)
- Expired - Lifetime
Links
- 239000011342 resin composition Substances 0.000 title claims description 8
- 229920005989 resin Polymers 0.000 claims description 29
- 239000011347 resin Substances 0.000 claims description 29
- BGDOLELXXPTPFX-UHFFFAOYSA-N 3,4-dihydro-2h-1,2-benzoxazine Chemical group C1=CC=C2ONCCC2=C1 BGDOLELXXPTPFX-UHFFFAOYSA-N 0.000 claims description 19
- 239000000843 powder Substances 0.000 claims description 19
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 17
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 4
- 238000003825 pressing Methods 0.000 claims description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 13
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 13
- 239000000919 ceramic Substances 0.000 description 11
- 238000005553 drilling Methods 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 239000003822 epoxy resin Substances 0.000 description 6
- 229920000647 polyepoxide Polymers 0.000 description 6
- 239000004408 titanium dioxide Substances 0.000 description 6
- 239000002966 varnish Substances 0.000 description 6
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 150000003141 primary amines Chemical class 0.000 description 5
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 5
- 239000011521 glass Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000007822 coupling agent Substances 0.000 description 3
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 229920003986 novolac Polymers 0.000 description 3
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical class NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical class NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- GLTDLAUASUFHNK-UHFFFAOYSA-N n-silylaniline Chemical compound [SiH3]NC1=CC=CC=C1 GLTDLAUASUFHNK-UHFFFAOYSA-N 0.000 description 2
- 239000004745 nonwoven fabric Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- BCHZICNRHXRCHY-UHFFFAOYSA-N 2h-oxazine Chemical group N1OC=CC=C1 BCHZICNRHXRCHY-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- NOHQTLHHNIKWBA-UHFFFAOYSA-N [SiH4].NC(=O)N Chemical compound [SiH4].NC(=O)N NOHQTLHHNIKWBA-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001448 anilines Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910002115 bismuth titanate Inorganic materials 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- AOWKSNWVBZGMTJ-UHFFFAOYSA-N calcium titanate Chemical compound [Ca+2].[O-][Ti]([O-])=O AOWKSNWVBZGMTJ-UHFFFAOYSA-N 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- NKZSPGSOXYXWQA-UHFFFAOYSA-N dioxido(oxo)titanium;lead(2+) Chemical compound [Pb+2].[O-][Ti]([O-])=O NKZSPGSOXYXWQA-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical class C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- JYIZNFVTKLARKT-UHFFFAOYSA-N phenol;1,3,5-triazine-2,4,6-triamine Chemical compound OC1=CC=CC=C1.NC1=NC(N)=NC(N)=N1 JYIZNFVTKLARKT-UHFFFAOYSA-N 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 230000007261 regionalization Effects 0.000 description 1
- 229920003987 resole Polymers 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
- H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
Landscapes
- Organic Insulating Materials (AREA)
- Reinforced Plastic Materials (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、高誘電率樹脂組成物、高誘電率プリプレグ及び高誘電率積層板に関するものである。
【０００２】
【従来の技術】
近年電子技術の多様な発展にともない、電子装置に用いる絶縁材料にも多様な性能が要求されるようになってきている。特にプリント配線板は極めて広範囲の用途に使用され、プリント配線板の基板材料としての積層板に対する要求特性も益々多岐となってきている。誘電特性に関する要求についていえば、信号の高速伝搬化、高インピーダンス化、クロストークの減少などを目的として低誘電率積層板が要求され、一方、高周波、マイクロウェーブ回路における遅延回路の形成、低インピーダンス化、積層板自身にコンデンサー効果を持たせた素子の複合回路化などを目的として高誘電率積層板が要求される。
【０００３】
従来、高誘電率積層板としては、基材としてガラス布又はガラス不織布を用い、この基材に、高誘電率の無機質粉末を配合したエポキシ樹脂ワニスを含浸乾燥したプリプレグを、所要枚数重ねて加熱加圧して製造されたものが知られている。
【０００４】
【発明が解決しようとする課題】
ところが、エポキシ樹脂に配合できる高誘電率の無機質粉末の量には限度があり、したがって、積層板の誘電率を２０まで上げることができなかった。また、多量の無機質粉末を配合する必要があるため、成形性や穴あけ加工性が悪くなるという欠点があった。
本発明は、より少ない高誘電率の無機質粉末の配合量で高い誘電率の積層板を得ることができ、したがって、従来と同等の誘電率の積層板を得る場合には高誘電率の無機質粉末の配合量を少なくできるため、成形性や穴あけ加工性を改善できる高誘電率樹脂組成物、この高誘電率樹脂組成物を用いた高誘電率プリプレグ及び高誘電率積層板を提供することを目的とするものである。
【０００５】
【課題を解決するための手段】
本発明は、（ａ）分子中にジヒドロベンゾオキサジン環を有する樹脂、及び、（ｂ）ジヒドロベンゾオキサジン環とジヒドロベンゾオキサジン環が開環して生成するフェノール性水酸基のいずれかと反応性を示す化合物からなる樹脂成分、並びに、（ｃ）誘電率が１０以上の無機質粉末を必須成分として含有してなり、前記樹脂成分１００重量部に対する前記（ｃ）誘電率が１０以上の無機質粉末の配合量が８０〜２５０重量部である高誘電率樹脂組成物である。
【０００６】
また、本発明は、前記高誘電率樹脂組成物をワニスとして基材に含浸、乾燥してなる高誘電率プリプレグである。
さらに、本発明は前記の高誘電率プリプレグを加熱加圧してなる高誘電率積層板である。
【０００７】
【発明の実施の形態】
（ａ）の分子中にジヒドロベンゾオキサジン環を有する樹脂は、１５０℃以上に加熱することにより開環して重合する。この樹脂は、フェノール性水酸基を分子中に２個以上有する化合物と１級アミンとホルムアルデヒドとを反応させることによって得られる。フェノール性水酸基１モルに対して、１級アミンを０．２〜１．０モル、ホルムアルデヒドを１級アミンの２倍モル量の比で反応させるのが好ましい。１級アミンが０．２モル未満であると、ジヒドロベンゾオキサジン環の数が少なくなるので、樹脂を硬化させたとき架橋密度が小さくなって好ましくない。また、１．０モルを超えると、硬化反応において分子鎖の伸長度が小さく、架橋密度も小さくなって好ましくない。
【０００８】
フェノール性水酸基を分子中に２個以上有する化合物としては、フェノールノボラック樹脂、レゾール樹脂、フェノール変性キシレン樹脂、アルキルフェノール樹脂、メラミンフェノール樹脂、フェノール変性ポリブタジエン等が挙げられる。
【０００９】
１級アミンとしては、アニリン、置換アニリン、シクロヘキシルアミン、メチルアミン等が挙げられる。
【００１０】
（ｂ）のジヒドロベンゾオキサジン環とジヒドロベンゾオキサジン環が開環して生成するフェノール性水酸基のいずれかと反応性を示す化合物からなる樹脂成分の官能基としては、（ａ）の分子中にジヒドロベンゾオキサジン環を有する樹脂中に残存するフェノール性水酸基とも反応性を示すものであるのが好ましい。
具体的な化合物としては、フェノール性水酸基を有する化合物、２官能以上のエポキシ樹脂が挙げられる。
また、これらの化合物としては、積層板に難燃性を付与するためにハロゲン化合物、例えば、ブロム化エポキシ樹脂のようなハロゲン化樹脂を用いることもできる。
（ａ）の分子中にジヒドロベンゾオキサジン環を有する樹脂１００重量部に対する、（ｂ）のジヒドロベンゾオキサジン環及びジヒドロベンゾオキサジン環が開環して生成するフェノール性水酸基と反応性を示す化合物からなる樹脂成分の配合量は、５〜３０重量部であることが好ましい。
【００１１】
（ａ）の分子中にジヒドロベンゾオキサジン環を有する樹脂、及び、（ｂ）のジヒドロベンゾオキサジン環とジヒドロベンゾオキサジン環が開環して生成するフェノール性水酸基のいずれかと反応性を示す化合物からなる樹脂成分に、硬化剤、硬化促進剤、ジヒドロベンゾオキサジン環の開環反応を促進する化合物を配合するのが好ましい。硬化剤、硬化促進剤としては、ジシアンジアミドを単独で、又は、イミダゾール類と併用して配合するのが効果、性能及び価格の点で好ましい。配合量は、樹脂成分１００重量部に対して０．１〜５重量部とするのが好ましく、より好ましくは０．５〜１重量部とするのがさらに好ましい。
【００１２】
銅張積層板としたときの、銅はくピール強度を高めるため、必要によりカップリング剤を配合することもできる。
カップリング剤としては、シランカップリング剤が好ましく、特に尿素シラン、フェニルアミノシランが良好である。カップリング剤の配合量は樹脂成分１００重量部に対して、０．１〜２重量部とするのが好ましく、０．１〜０．５重量部とするのがより好ましい。
【００１３】
（ｃ）の高誘電率の無機質粉末としては、好ましくは、誘電率が１０以上、より好ましくは誘電率が３０以上であって、誘電正接が０．００５以下のものが用いられる。誘電率が高ければ、同じ配合量でより高い誘電率の積層板を得ることができるからである。このようなものとして例えば二酸化チタン系セラミック、チタン酸バリウム系セラミック、チタン酸鉛系セラミック、チタン酸ストロンチウム系セラミック、チタン酸カルシウム系セラミック、チタン酸ビスマス系セラミック、チタン酸マグネシウム系セラミック、ジルコン酸鉛系セラミックなどが挙げることができる。これらは、単独または２種類以上を混合して用いてもよい。
なお、前記二酸化チタン系セラミックとは、組成的には、二酸化チタンのみからなる系、又は二酸化チタンに他の少量の添加物を含む系で、主成分である二酸化チタンの結晶構造が保持されているものである。他の系のセラミックもこれと同様である。二酸化チタンは化学式がＴｉＯ２で示される物質で、種々の結晶構造を有するものがあるが、誘電体セラミックとして使用されるのは、その中のルチル構造のものである。
【００１４】
高誘電率の無機質粉末の粒子径としては、約５０μｍ以下のものを用いることができるが、好ましくは０．１〜２０μｍ、さらに好ましくは０．５〜７μｍの範囲のものが用いられる。高誘電率の無機質粉末の粒子径が５０μｍより大きいと樹脂への均一分散、混合が困難になり、また積層板の穴あけ等の成形加工性の低下をもたらす。逆に０．１未満では取り扱い性が悪くなる。
【００１５】
高誘電率の無機質粉末の樹脂成分に対する配合量は、樹脂成分１００重量部に対して、８０〜２５０重量部の範囲で、要求される誘電率によって選択される。配合量が２５０重量部を超えると、樹脂成分中への均一分散、混合が困難になり、積層後の機械的強度が低下する。また、８０重量部未満では、必要とする誘電率が得られないためである。
配合量が樹脂成分１００重量部に対して１４０重量部未満であれば、高誘電率多層プリント配線板の接着用プリプレグとしても使用可能である。
【００１６】
必要な成分を溶剤に溶解してワニスとし、基材に含浸乾燥してプリプレグとする。基材としては、ガラス繊維の織布又は不織布を用いるのが好ましい。
溶剤としては、アルコール系、エーテル系、ケトン系、アミド系、芳香族炭化水素系、エステル系、ニトリル系等が挙げられる。
【００１７】
積層板はプリプレグを必要枚数重ね合わせ積層成形することにより得られるが、このときの条件としては、温度１７０℃、圧力３ＭＰａ、で１２０分間の加熱加圧が一般的である。
【００１８】
【実施例】
実施例１
フェノール１．９ｋｇ、ホルマリン（ホルムアルデヒドの３７重量％水溶液）１．０ｋｇ、しゅう酸４ｇを５リットルフラスコに仕込み、還流温度で６時間反応させた。引き続き、フラスコ内部を７０ｈＰａ以下に減圧して未反応のフェノール及び水分を除去した。このようにして得られたフェノールノボラック樹脂１．７０ｋｇ（フェノール性水酸基として１６ｍｏｌ相当）とアニリン０．９３ｋｇ（１０ｍｏｌ）とを混合し、８０℃で５時間撹拌して均一な混合液（以下混合液Ａとする）を得た。
５リットルフラスコ中に、ホルマリン１．６２ｋｇを仕込み９０℃に加熱し、その中に混合液Ａの全量を３０分間かけて添加した。添加終了後３０分間、還流温度に保ち、然る後に１００℃で２時間７０ｈＰａ以下に減圧して縮合水を除去して、分子中にジヒドロベンゾオキサジン環を有する樹脂（以下樹脂Ａとする）を得た。樹脂Ａは、フェノールノボラック樹脂中のフェノール性水酸基のうち、７１％がジヒドロベンゾオキサジン環化されたものである。
【００１９】
樹脂Ａ８０部（重量部、以下同じ）、エポキシ当量４００、臭素含有量４８重量％のビスフェノールＡ型臭素化エポキシ樹脂（住友化学工業株式会社製、ＥＳＢ−４００（商品名）を使用した）２０部、ジシアンジアミド１部及びフェニルアミノシラン０．２５部を、メチルエチルケトン５５部、及び、ジメチルホルムアミド１５部からなる混合溶媒に溶解して溶液Ａを得た。
【００２０】
この溶液Ａに、チタン酸ストロンチウム粉末（富士チタン工業株式会社製）を２００部配合し、均一に分散させてワニスとした。このワニスを、厚さ０．１ｍｍ、重量１０４ｇ／ｍ2 のガラス布（日東紡績株式会社製、ＷＥ１１６Ｅ（商品名）を使用した）に、乾燥後の厚さが０．１５ｍｍとなるように塗布、乾燥してプリプレグを得た。
【００２１】
プリプレグを４枚重ね、温度１７０℃、圧力３ＭＰａで１２０分間、加熱加圧して厚さ０．６ｍｍの積層板を得た。
【００２２】
比較例１
エポキシ樹脂（油化シェルエポキシ株式会社製、エピコート１００１（商品名）を使用した）１００部、ジシアンジアミド１．２部（０．８当量相当）を、メチルエチルケトン５５部、及び、ジメチルホルムアミド１５部からなる混合溶媒に溶解して溶液Ｂを得た。
この溶液Ｂに、実施例１と同じチタン酸ストロンチウム粉末を２５０部配合し、均一に分散させてワニスとした。以下実施例１と同様にしてプリプレグ及び厚さ０．６ｍｍの積層板を得た。
【００２３】
実施例２
チタン酸ストロンチウム粉末の配合量を１００部としたほかは実施例１と同様にしてプリプレグ及び厚さ０．６ｍｍの積層板を得た。
【００２４】
比較例２
チタン酸ストロンチウム粉末の配合量を１５０部としたほかは比較例１と同様にしてプリプレグ及び厚さ０．６ｍｍの積層板を得た。
【００２５】
得られたプリプレグについてプリプレグ成形性を、また、積層板について誘電率、及び穴あけ加工性を以下に説明するようにして調べた。その結果を表１に示す。
誘電率：ＪＩＳ Ｃ ６４８１に準拠して、周波数１ＭＨｚで測定した。
プリプレグ成形性：厚さ０．８ｍｍ、銅はく厚さ３５μｍのガラス布基材エポキシ樹脂両面銅張積層板の片面に電源回路パターンを形成し、電源パターン形成面にプリプレグを介して厚さ３５μｍの銅はくを重ね、温度１７０℃、圧力３ＭＰａで１２０分間加熱加圧して基板を得、この基板をダイヤモンドカッターで切断し、切断面を観察してボイドの発生状況を観察した。
穴あけ加工性：直径０．９ｍｍのドリルを用いて回転数毎分６０，０００回転、送り速度３ｍ／分の条件で穴あけして調べた。穴あけ加工性の記号の意味は次の通りである。
○：良好
△：ドリル穴あけ困難
×：ドリル穴あけ不可
【００２６】
【表１】
【発明の効果】
本発明によれば、より少ない高誘電率の無機質粉末の配合量で高い誘電率の積層板を得ることができ、したがって、従来と同等の誘電率の積層板を得る場合には高誘電率の無機質粉末の配合量を少なくできるため、成形性や穴あけ加工性を改善できる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a high dielectric constant resin composition, a high dielectric constant prepreg, and a high dielectric constant laminate.
[0002]
[Prior art]
In recent years, with various developments in electronic technology, various performances have been required for insulating materials used in electronic devices. In particular, printed wiring boards are used in a very wide range of applications, and the required characteristics for laminated boards as printed circuit board materials are becoming increasingly diverse. Regarding dielectric properties, low dielectric constant laminates are required for the purpose of high-speed signal propagation, high impedance, and reduction of crosstalk. On the other hand, high-frequency, delay circuit formation in microwave circuits, low impedance High dielectric constant laminates are required for the purpose of making a composite circuit of elements in which the laminate itself has a capacitor effect.
[0003]
Conventionally, as a high dielectric constant laminate, glass cloth or glass nonwoven fabric is used as a base material, and a prepreg obtained by impregnating and drying an epoxy resin varnish mixed with a high dielectric constant inorganic powder is heated on the base material in a required number. Those manufactured by applying pressure are known.
[0004]
[Problems to be solved by the invention]
However, there is a limit to the amount of the high dielectric constant inorganic powder that can be blended in the epoxy resin, and therefore the dielectric constant of the laminate cannot be increased to 20. Moreover, since it is necessary to mix | blend a lot of inorganic powder, there existed a fault that a moldability and drilling workability worsened.
The present invention can obtain a laminate having a high dielectric constant with a smaller amount of inorganic powder having a high dielectric constant. Therefore, when obtaining a laminate having a dielectric constant equivalent to the conventional one, the inorganic powder having a high dielectric constant can be obtained. An object of the present invention is to provide a high dielectric constant resin composition that can improve moldability and drilling workability, and a high dielectric constant prepreg and a high dielectric constant laminate using the high dielectric constant resin composition. It is what.
[0005]
[Means for Solving the Problems]
The present invention relates to (a) a resin having a dihydrobenzoxazine ring in the molecule, and (b) a compound that is reactive with any of the phenolic hydroxyl groups formed by opening the dihydrobenzoxazine ring and the dihydrobenzoxazine ring. comprising a resin ingredient and, (c) Ri dielectric constant name contains as an essential component 10 or more inorganic powder, the amount of said (c) a dielectric constant of 10 or more inorganic powder to the resin component 100 parts by weight Is a high dielectric constant resin composition having a weight of 80 to 250 parts by weight .
[0006]
The present invention also provides a high dielectric constant prepreg obtained by impregnating a substrate with the high dielectric constant resin composition as a varnish and drying it.
Furthermore, the present invention is a high dielectric constant laminate obtained by heating and pressing the high dielectric constant prepreg.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
The resin having a dihydrobenzoxazine ring in the molecule (a) opens and polymerizes by heating to 150 ° C. or higher. This resin is obtained by reacting a compound having two or more phenolic hydroxyl groups in the molecule, a primary amine and formaldehyde. It is preferable to react the primary amine in a ratio of 0.2 to 1.0 mol and formaldehyde in a molar amount twice that of the primary amine with respect to 1 mol of the phenolic hydroxyl group. When the primary amine is less than 0.2 mol, the number of dihydrobenzoxazine rings is decreased, and therefore, the crosslinking density is decreased when the resin is cured, which is not preferable. On the other hand, if it exceeds 1.0 mol, the degree of elongation of the molecular chain is small in the curing reaction, and the crosslinking density is also unfavorable.
[0008]
Examples of the compound having two or more phenolic hydroxyl groups in the molecule include phenol novolac resin, resole resin, phenol-modified xylene resin, alkylphenol resin, melamine phenol resin, and phenol-modified polybutadiene.
[0009]
Examples of the primary amine include aniline, substituted aniline, cyclohexylamine, and methylamine.
[0010]
The functional group of the resin component composed of a compound that is reactive with any of the phenolic hydroxyl groups formed by the opening of the dihydrobenzoxazine ring and the dihydrobenzoxazine ring of (b) includes dihydrobenzox in the molecule of (a). It is preferable that the phenolic hydroxyl group remaining in the resin having an oxazine ring is also reactive.
Specific examples of the compound include a compound having a phenolic hydroxyl group and a bifunctional or higher functional epoxy resin.
Further, as these compounds, halogen compounds such as halogenated resins such as brominated epoxy resins can be used in order to impart flame retardancy to the laminate.
It consists of a compound that is reactive with the phenolic hydroxyl group formed by the opening of the dihydrobenzoxazine ring and dihydrobenzoxazine ring of (b) with respect to 100 parts by weight of the resin having a dihydrobenzoxazine ring in the molecule of (a). The compounding amount of the resin component is preferably 5 to 30 parts by weight.
[0011]
A resin having a dihydrobenzoxazine ring in the molecule of (a), and a compound that is reactive with any of the phenolic hydroxyl groups formed by the opening of the dihydrobenzoxazine ring and the dihydrobenzoxazine ring of (b) It is preferable to mix | blend the compound which accelerates | stimulates the ring-opening reaction of a hardening | curing agent, a hardening accelerator, and a dihydrobenzoxazine ring with a resin component. As the curing agent and curing accelerator, dicyandiamide is preferably used alone or in combination with imidazoles in view of the effect, performance and price. The blending amount is preferably 0.1 to 5 parts by weight, more preferably 0.5 to 1 part by weight with respect to 100 parts by weight of the resin component.
[0012]
In order to increase the copper peel strength when the copper-clad laminate is used, a coupling agent can be blended as necessary.
As the coupling agent, a silane coupling agent is preferable, and urea silane and phenylaminosilane are particularly preferable. The amount of the coupling agent is preferably 0.1 to 2 parts by weight, more preferably 0.1 to 0.5 parts by weight, based on 100 parts by weight of the resin component.
[0013]
As the inorganic powder having a high dielectric constant (c), those having a dielectric constant of 10 or more, more preferably a dielectric constant of 30 or more and a dielectric loss tangent of 0.005 or less are used. This is because if the dielectric constant is high, a laminate having a higher dielectric constant can be obtained with the same blending amount. For example, titanium dioxide ceramic, barium titanate ceramic, lead titanate ceramic, strontium titanate ceramic, calcium titanate ceramic, bismuth titanate ceramic , magnesium titanate ceramic , lead zirconate And ceramics. You may use these individually or in mixture of 2 or more types.
The titanium dioxide ceramic is compositionally composed of only titanium dioxide or a system containing a small amount of other additives in titanium dioxide, and the crystal structure of titanium dioxide as a main component is maintained. It is what. The same applies to other ceramics. Titanium dioxide is a substance having a chemical formula of TiO 2 and has various crystal structures, but a dielectric ceramic used is a rutile structure.
[0014]
The particle diameter of the high dielectric constant inorganic powder can be about 50 μm or less, preferably 0.1 to 20 μm, more preferably 0.5 to 7 μm. When the particle size of the inorganic powder having a high dielectric constant is larger than 50 μm, it becomes difficult to uniformly disperse and mix the resin, and the moldability such as drilling of the laminate is reduced. On the other hand, if it is less than 0.1, the handleability deteriorates.
[0015]
The blending amount of the high dielectric constant inorganic powder with respect to the resin component is selected in the range of 80 to 250 parts by weight based on the required dielectric constant with respect to 100 parts by weight of the resin component. If the blending amount exceeds 250 parts by weight, uniform dispersion and mixing in the resin component will be difficult, and the mechanical strength after lamination will decrease. Further, if it is less than 80 parts by weight, the required dielectric constant cannot be obtained.
If the blending amount is less than 140 parts by weight with respect to 100 parts by weight of the resin component, it can be used as an adhesive prepreg for a high dielectric constant multilayer printed wiring board.
[0016]
Necessary components are dissolved in a solvent to obtain a varnish, and the base material is impregnated and dried to obtain a prepreg. As a base material, it is preferable to use the woven fabric or nonwoven fabric of glass fiber.
Examples of the solvent include alcohols, ethers, ketones, amides, aromatic hydrocarbons, esters and nitriles.
[0017]
The laminate can be obtained by laminating and forming the required number of prepregs, and as a condition at this time, heating and pressurization for 120 minutes at a temperature of 170 ° C. and a pressure of 3 MPa is common.
[0018]
【Example】
Example 1
1.9 kg of phenol, 1.0 kg of formalin (37% by weight aqueous solution of formaldehyde) and 4 g of oxalic acid were charged into a 5 liter flask and reacted at reflux temperature for 6 hours. Subsequently, the pressure inside the flask was reduced to 70 hPa or less to remove unreacted phenol and moisture. 1.70 kg of phenol novolak resin thus obtained (corresponding to 16 mol as phenolic hydroxyl group) and 0.93 kg (10 mol) of aniline were mixed and stirred at 80 ° C. for 5 hours to obtain a uniform mixed solution (hereinafter referred to as “mixed solution”). A).
Into a 5-liter flask, 1.62 kg of formalin was charged and heated to 90 ° C., and the entire amount of the mixed solution A was added to the flask over 30 minutes. After completion of the addition, the temperature is maintained at the reflux temperature for 30 minutes, and then the pressure is reduced to 70 hPa or less at 100 ° C. for 2 hours to remove the condensed water, and a resin having a dihydrobenzoxazine ring in the molecule (hereinafter referred to as resin A) is obtained. Obtained. Resin A is one in which 71% of the phenolic hydroxyl groups in the phenol novolac resin are cyclized with dihydrobenzoxazine.
[0019]
Resin A 80 parts (parts by weight, the same applies hereinafter), epoxy equivalent 400, bisphenol A brominated epoxy resin having a bromine content of 48% by weight (Sumitomo Chemical Co., Ltd., ESB-400 (trade name) used) 20 parts Then, 1 part of dicyandiamide and 0.25 part of phenylaminosilane were dissolved in a mixed solvent consisting of 55 parts of methyl ethyl ketone and 15 parts of dimethylformamide to obtain a solution A.
[0020]
To this solution A, 200 parts of strontium titanate powder (Fuji Titanium Industry Co., Ltd.) was blended and uniformly dispersed to obtain a varnish. This varnish was applied to a glass cloth having a thickness of 0.1 mm and a weight of 104 g / m 2 (manufactured by Nitto Boseki Co., Ltd., using WE116E (trade name)) so that the thickness after drying was 0.15 mm. And dried to obtain a prepreg.
[0021]
Four prepregs were stacked and heated and pressed at a temperature of 170 ° C. and a pressure of 3 MPa for 120 minutes to obtain a laminate having a thickness of 0.6 mm.
[0022]
Comparative Example 1
100 parts of epoxy resin (manufactured by Yuka Shell Epoxy Co., Ltd., using Epicoat 1001 (trade name)), 1.2 parts of dicyandiamide (equivalent to 0.8 equivalent), 55 parts of methyl ethyl ketone and 15 parts of dimethylformamide Solution B was obtained by dissolving in a mixed solvent.
To this solution B, 250 parts of the same strontium titanate powder as in Example 1 was blended and uniformly dispersed to obtain a varnish. Thereafter, in the same manner as in Example 1, a prepreg and a laminated plate having a thickness of 0.6 mm were obtained.
[0023]
Example 2
A prepreg and a 0.6 mm thick laminate were obtained in the same manner as in Example 1 except that the amount of strontium titanate powder was 100 parts.
[0024]
Comparative Example 2
A prepreg and a 0.6 mm thick laminate were obtained in the same manner as in Comparative Example 1 except that the blending amount of strontium titanate powder was 150 parts.
[0025]
The prepreg moldability of the obtained prepreg and the dielectric constant and punching workability of the laminate were examined as described below. The results are shown in Table 1.
Dielectric constant: Measured at a frequency of 1 MHz in accordance with JIS C 6481.
Prepreg formability: a power circuit pattern is formed on one side of a glass cloth base epoxy resin double-sided copper-clad laminate with a thickness of 0.8 mm and a copper foil thickness of 35 μm, and the thickness of the power pattern formation surface is 35 μm via the prepreg. The copper foil was stacked and heated and pressed at a temperature of 170 ° C. and a pressure of 3 MPa for 120 minutes to obtain a substrate. This substrate was cut with a diamond cutter, and the cut surface was observed to observe the occurrence of voids.
Drilling workability: Using a drill with a diameter of 0.9 mm, drilling was performed under conditions of 60,000 rotations per minute and a feed rate of 3 m / min. The meanings of the drilling workability symbols are as follows.
○: Good △: Difficult drilling ×: Unable to drill
[Table 1]
【The invention's effect】
According to the present invention, it is possible to obtain a laminate having a high dielectric constant with a smaller amount of inorganic powder having a high dielectric constant. Therefore, when obtaining a laminate having a dielectric constant equivalent to the conventional one, a high dielectric constant is obtained. Since the blending amount of the inorganic powder can be reduced, moldability and drilling processability can be improved.
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28447896A JP3893648B2 (en) | 1996-10-25 | 1996-10-25 | High dielectric constant resin composition, high dielectric constant prepreg, and high dielectric constant laminate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28447896A JP3893648B2 (en) | 1996-10-25 | 1996-10-25 | High dielectric constant resin composition, high dielectric constant prepreg, and high dielectric constant laminate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH10130460A JPH10130460A (en) | 1998-05-19 |
| JP3893648B2 true JP3893648B2 (en) | 2007-03-14 |
Family
ID=17679047
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP28447896A Expired - Lifetime JP3893648B2 (en) | 1996-10-25 | 1996-10-25 | High dielectric constant resin composition, high dielectric constant prepreg, and high dielectric constant laminate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3893648B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4715979B2 (en) * | 2000-07-04 | 2011-07-06 | 三菱瓦斯化学株式会社 | Prepreg manufacturing method and printed wiring board using the same |
| WO2004009708A1 (en) * | 2002-07-19 | 2004-01-29 | Nippon Steel Chemical Co., Ltd. | Curable resin composition |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4501864A (en) * | 1983-12-22 | 1985-02-26 | Monsanto Company | Polymerizable compositions comprising polyamines and poly(dihydrobenzoxazines) |
| JP2814288B2 (en) * | 1990-03-29 | 1998-10-22 | 大塚化学 株式会社 | High dielectric resin composition |
| JP3429090B2 (en) * | 1994-12-28 | 2003-07-22 | 日立化成工業株式会社 | Thermosetting resin composition and cured product thereof |
-
1996
- 1996-10-25 JP JP28447896A patent/JP3893648B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH10130460A (en) | 1998-05-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101677736B1 (en) | Thermosetting resin composition for semiconductor package and Prepreg and Metal Clad laminate using the same | |
| JP5338187B2 (en) | Inorganic filler-containing resin composition, prepreg, laminate and wiring board | |
| KR102077867B1 (en) | Thermosetting epoxy resin composition, adhesive film for forming insulating layer and multilayer printed wiring board | |
| JP4926811B2 (en) | Resin composition, prepreg, laminate and wiring board | |
| WO2005023933A1 (en) | Thermosetting resin composition for high speed transmission circuit board | |
| WO2004102589A1 (en) | Insulating material, film, circuit board and method for manufacture thereof | |
| KR101013074B1 (en) | Epoxy resin composition and an adhesive film for a printed wiring boards prepared using the same | |
| US6544652B2 (en) | Cyanate ester-containing insulating composition, insulating film made therefrom and multilayer printed circuit board having the film | |
| JP3371916B2 (en) | Epoxy resin composition | |
| KR100632862B1 (en) | Resin composition, prepreg and laminate using the composition | |
| JP3893648B2 (en) | High dielectric constant resin composition, high dielectric constant prepreg, and high dielectric constant laminate | |
| KR102136861B1 (en) | Thermosetting resin composition for semiconductor pakage and preprege using the same | |
| JP2008106106A (en) | Resin composition having high permittivity, prepreg and laminated plate used for printed wiring board | |
| JP2692508B2 (en) | Manufacturing method of laminated board | |
| JP2001347600A (en) | Laminated sheet | |
| JP3529088B2 (en) | Epoxy resin composition, prepreg and laminate using the same | |
| JP2004315653A (en) | Resin composition and its use | |
| JP2002145994A (en) | Prepreg for printed circuit board and laminate | |
| JP3089522B2 (en) | Method for producing prepreg for electric laminate, electric laminate using the prepreg, and printed wiring board using the laminate | |
| JP2004059704A (en) | Epoxy resin composition for printed wiring board, prepreg and laminate | |
| JPS62169828A (en) | Production of substrate for printed circuit | |
| JP2003020407A (en) | Varnish composition, prepreg and metal foil-clad laminate using the same | |
| JP2002241521A (en) | Epoxy resin prepreg, epoxy resin copper-clad board, epoxy resin printed circuit board and epoxy resin multilayer printed circuit board | |
| JPH08103984A (en) | Copper-clad laminated plate | |
| JPH09157496A (en) | Thermosetting resin composition, cured product therefrom, prepreg and metallic foil-laminated plate using the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20050325 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20060516 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20060718 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20060808 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20061121 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20061204 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20101222 Year of fee payment: 4 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20101222 Year of fee payment: 4 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20111222 Year of fee payment: 5 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20111222 Year of fee payment: 5 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20121222 Year of fee payment: 6 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20121222 Year of fee payment: 6 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20131222 Year of fee payment: 7 |
|
| S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
| S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20131222 Year of fee payment: 7 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| EXPY | Cancellation because of completion of term |