JPH0564992B2 - - Google Patents
Info
- Publication number
- JPH0564992B2 JPH0564992B2 JP63072887A JP7288788A JPH0564992B2 JP H0564992 B2 JPH0564992 B2 JP H0564992B2 JP 63072887 A JP63072887 A JP 63072887A JP 7288788 A JP7288788 A JP 7288788A JP H0564992 B2 JPH0564992 B2 JP H0564992B2
- Authority
- JP
- Japan
- Prior art keywords
- composite oxide
- impregnation
- dispersed
- particle size
- solution
- 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
- 239000002245 particle Substances 0.000 claims description 40
- 229920005989 resin Polymers 0.000 claims description 31
- 239000011347 resin Substances 0.000 claims description 30
- 238000005470 impregnation Methods 0.000 claims description 27
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 21
- 229920006380 polyphenylene oxide Polymers 0.000 claims description 21
- 239000000463 material Substances 0.000 claims description 20
- 239000002905 metal composite material Substances 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 20
- 239000000843 powder Substances 0.000 claims description 13
- 239000000178 monomer Substances 0.000 claims description 9
- 229920000642 polymer Polymers 0.000 claims description 8
- 239000002131 composite material Substances 0.000 claims description 7
- 239000000919 ceramic Substances 0.000 claims description 6
- 229910052574 oxide ceramic Inorganic materials 0.000 claims description 6
- 239000011224 oxide ceramic Substances 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 229910052779 Neodymium Inorganic materials 0.000 claims description 2
- 239000011812 mixed powder Substances 0.000 claims description 2
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 2
- 239000010955 niobium Substances 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 2
- 239000000243 solution Substances 0.000 description 29
- 239000004744 fabric Substances 0.000 description 11
- 239000010954 inorganic particle Substances 0.000 description 10
- 239000011521 glass Substances 0.000 description 9
- 239000011342 resin composition Substances 0.000 description 9
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 7
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 5
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 4
- -1 poly(2,6-dimethyl -1,4-phenylene oxide) Polymers 0.000 description 4
- 229920003048 styrene butadiene rubber Polymers 0.000 description 4
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910002113 barium titanate Inorganic materials 0.000 description 3
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 239000012456 homogeneous solution Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 239000000123 paper Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 238000004062 sedimentation Methods 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229920013623 Solprene Polymers 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- YKTNISGZEGZHIS-UHFFFAOYSA-N 2-$l^{1}-oxidanyloxy-2-methylpropane Chemical group CC(C)(C)O[O] YKTNISGZEGZHIS-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- 229910002115 bismuth titanate Inorganic materials 0.000 description 1
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 0.000 description 1
- AOWKSNWVBZGMTJ-UHFFFAOYSA-N calcium titanate Chemical compound [Ca+2].[O-][Ti]([O-])=O AOWKSNWVBZGMTJ-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000000805 composite resin Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000003989 dielectric material 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
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical class OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000002655 kraft paper Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920002852 poly(2,6-dimethyl-1,4-phenylene oxide) polymer Polymers 0.000 description 1
- 229920002589 poly(vinylethylene) polymer Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- QCTJRYGLPAFRMS-UHFFFAOYSA-N prop-2-enoic acid;1,3,5-triazine-2,4,6-triamine Chemical class OC(=O)C=C.NC1=NC(N)=NC(N)=N1 QCTJRYGLPAFRMS-UHFFFAOYSA-N 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene 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
- Compositions Of Macromolecular Compounds (AREA)
- Graft Or Block Polymers (AREA)
- Reinforced Plastic Materials (AREA)
Description
(産業上の利用分野)
この発明は、無機物粒子分散樹脂の含浸方法に
関するものである。さらに詳しくは、この発明
は、積層板等の基材への含浸に有用な、均一な含
浸が可能であつて、プリプレグ特性の向上を図る
ことのできる、無機物粒子を分散させた樹脂溶液
の含浸方法に関するものである。
(従来の技術)
積層板の絶縁性、誘電特性、強度等の性能を改
善するために、無機物粒子を分散含有させた樹脂
溶液を用いて基材を含浸処理することが従来より
広く行われている。
この含浸処理においては、エポキシ樹脂、ポリ
エステル、フエノール樹脂、ポリアミド、ポリイ
ミド等の樹脂にシリカ、アルミナ、マグネシアな
どの無機物の粒子を分散させ、ガラスクロス、ガ
ラスシート、ガラスマツト、紙などの基材に含浸
することが一般的な方法として採用されてきてい
る。
(発明が解決しようとする課題)
しかしながら、この従来の樹脂溶液の含浸方法
においては、溶液に分散させる無機物粒子によつ
て、基材への含浸が不均一になり、かつ基材の性
能にも大きく影響するという問題があり、この問
題は依然として未解決なまま残されていた。
特に、積層板の特性を左右する無機物粒子を樹
脂とともに含浸させる場合には、このような含浸
の不均一さによる影響は無視できないものであつ
た。
このような含浸の不均一性は、この発明の発明
者の検討による無機物粒子の径の大きさに起因す
るものであり、粒子径が大きいと含浸工程中に沈
降し、含浸処理の開始時と終了時とでは無機物粒
子の樹脂溶液中への含有率が大きく異なつてく
る。
また一方で、粒径があまり小さいと、無機物粒
子、ひいては含浸基材の物性を所要のものとする
ことはできず、粒子の粉砕にともなうコスト増の
原因となる。
このため、均一な無機物粒子分散樹脂の含浸が
可能で、基材あるいは積層板の性能向上に寄与す
ることのできる適切な含浸方法の実現が望まれて
いた。
(課題を解決するための手段)
この発明は、以上の通りの事情に鑑みてなされ
たものであり、従来の樹脂含浸方法の欠点を改善
し、無機物粒子を分散させた樹脂溶液の含浸処理
において、これら無機物粒子の均一な含浸を可能
とする改善された方法を提供することを目的とし
ている。
この発明は、このため、平均粒径2μm以下で、
最大粒径7μm以下の金属複合酸化物系誘電体粉
末を、ポリフエニレンオキサイドと架橋性のポリ
マーおよびモノマーとの混合樹脂溶液に分散させ
た誘電体分散樹脂溶液を基材に含浸させることを
特徴としている。また、特に、この発明の含浸方
法は、高誘電特性の積層板製造等に好適である。
上記の樹脂溶液中の金属複合酸化物系誘電体粒
子の沈降を防ぐには、その粒子の平均粒径が2μ
m以下であり、かつ、その最大粒径が7μm以下
とすることが必要である。粒径は小さいほど安定
性はよいが、含浸基材の物性、粒子物性、粉砕コ
スト等の面から、あまり微小にすることは有利で
はない。
金属複合酸化物系誘電体粒子の沈降は樹脂溶液
の粘度にも関係することから、この粘度を適宜に
調整することが好ましい。一般的には粘度は大き
い方がよいが、あまり大きすぎると含浸時の浸透
速度が遅くなり、乾燥処理までに充分な含浸が得
られない。基材としてガラスクロスを用いる場合
には、約100〜700csp程度の粘度とするのが好ま
しい。100csp以下では、基材への樹脂付着量が少
なくなり、しかも金属複合酸化物系誘電体粒子の
沈降も速くなる。
また、金属複合酸化物系誘電体粒子の溶液中の
安定性には、粒子の比重、溶液の比重も関係する
が、通常の粉末(ρ<7)と溶液比重(d<1.5)
では、上記の粒径の範囲とすることで充分であ
る。
この発明の含浸方法は、前記の通り、ポリフエ
ニレンオキサイド(PPO)と架橋性ポリマーお
よびモノマーとの混合溶液に金属複合酸化物系誘
電体粉末を分散させた樹脂溶液の含浸に用いられ
るものである。金属複合酸化物系誘導体粉末とし
ては、たとえばチタン酸バリウム系、チタン酸鉛
系、チタン酸カルシウム系、チタン酸マグネシウ
ム系、チタン酸ビスマス系等のチタン酸金属系セ
ラミツク、ジルコン酸鉛系、ジルコン酸バリウム
系等のジルコン酸金属系セラミツク、K2O−PbO
−SiO2系等の鉛複合酸化物系セラミツク、Baf0.5
Pb0.5Nd2Ti5O14系、BaNd2Ti5O14系等のネオジ
ウム複合酸化物系セラミツク、またはBa(Zn1/2
Nb2/3)O3系等のニオブ複合酸化物系セラミツク
の粉末、あるいはこれらの2種以上の混合粉末が
示される。これらの無機物粒子によつて、誘電特
性に優れた含浸基材とそれを用いた積層板が得ら
れる。
ポリフエニレンオキサイドは、たとえば、次の
化学式(1)
(Rは水素または炭素数1〜3の炭化水素基を表
し、各Rは同じであつても異なつてもよい)で表
されるものがあり、その一例としては、ポリ
(2,6−ジメチル−1,4−フエニレンオキサ
イド)をあげることができる。
架橋性ポリマーとしては、たとえば、1,2−
ポリブタジエン、1,4−ポリブタジエン、スチ
レンブタジエンコポリマー、変性1,2−ポリブ
タジエン(マレイン変性、アクリル変性、エポキ
シ変性)、ゴム類などがあげられ、それぞれ、単
独でまたは2つ以上併せて用いることができる。
これらのポリマーの状態はエラストマーでもラバ
ーでもよい。
また、架橋性モノマーとしては、たとえばエ
ステルアクリレート類、エポキシアクリレート
類、ウレタンアクリレート類、エーテルアクリレ
ート類、メラミンアクリレート類、アルキドアク
リレート類、シリコンアクリレート類などのアク
リレート類、トリアリルシアヌレート、トリア
リルイソシアヌレート、エチレングリコールジメ
タクリレート、ジビニルベンゼン、ジアリルフタ
レートなどの多官能モノマー、ビニルトルエ
ン、エチルビニルベンゼン、スチレン、パラメチ
ルスチレンなどの単官能モノマー、多官能エポ
キシ類などがあげられ、それぞれ、単独であるい
は2つ以上併せて用いることができる。このう
ち、トリアリルシアヌレートおよび/またはトリ
アリルイソシアヌレートが、ポリフエニレンオキ
サイドと相溶性がよく、成膜性、架橋性、耐熱性
および誘電特性を向上させるので好ましい。
このトリアリルシアヌレートとトリアリルイソ
シアヌレートとは、化学構造的には異性体の関係
にあり、ほぼ同様の成膜性、相溶性、溶解性、反
応性などを有するもので、いずれか一方または両
方ともに同様に使用することができる。
以上のような架橋性ポリマーおよびモノマーと
金属複合酸化物系誘電体とをポリフエニレンオキ
サイドに含有させるに際しては、さらに開始剤を
用いることができる。
開始剤としては、ポリフエニレンオキサイド樹
脂組成物を紫外線硬化型かまたは熱硬化型にする
かにより適宜なものを選ぶことができる。
ポリフエニレンオキサイド系樹脂溶液に金属複
合酸化物系誘電体粒子を分散させたものを含浸に
用いるこの発明の方法においては、通常、樹脂の
組成物を溶剤に溶かして分散させ、混合する。こ
の場合の溶剤には適宜なものを使用することがで
き、たとえば、トリクロロエチレン、トリクロロ
エタン、クロロホルム、塩化メチレン、クロロベ
ンゼンなどのハロゲン化炭化水素、ベンゼン、ト
ルエン、キシレンなどの芳香族炭化水素、アセト
ン、四塩化炭素などを使用でき、特にトリクロロ
エチレンが好ましい。これらは、それぞれ単独で
または2つ以上混合して用いることができる。
金属複合酸化物系誘電体粒子を分散させた混合
樹脂溶液を基材に含浸させるための方法として
は、従来公知のものをはじめとして適宜な方法を
採用することができる。一般的には、たとえば、
金属複合酸化物系誘電体粒子をはじめとする樹脂
組成物を溶剤分散させ、その溶剤溶液中に基材を
浸漬(デイツピング)するなどして、含浸させ付
着させる。そして乾燥などにより溶剤を除去する
か、あるいは半硬化させてBステージにすること
ができる。基材は、ガラスクロス、アラミドクロ
ス、ポリエステルクロス、ナイロンクロス等樹脂
含浸可能なクロス状物および/または不織布など
の繊維状物、クラフト紙、リンター紙などの紙な
どを用いることができ、またこれらに限定される
ことはない。このようにして、プリプレグを作製
すれば、樹脂を溶融させなくてもよいので、比較
的低温で容易に行うことができる。
樹脂および金属複合酸化物系誘電体粒子を含浸
した基材は、たとえば通常の方法によつて、金属
箔と積層一体化することにより、プリント配線板
用積層板とすることができる。
(作用)
前記金属複合酸化物系誘電体粒子の平均粒径を
2μm以下に、また最大粒径を7μm以下とするこ
とにより、これら粒子を含有するポリフエニレン
オキサイドと架橋性ポリマーおよびモノマーとの
混合樹脂溶液は、金属複合酸化物系誘電体粒子の
沈降を抑えて基材の均一な含浸を可能とする。放
熱性、寸法安定性、誘電特性等のために樹脂溶液
に混合した金属複合酸化物系誘電体粒子は、樹脂
とともに安定的に、均一に含浸される。この方法
により、高誘電特性の樹脂含浸基材を得ることが
可能となる。
以下、この発明の実施例を示し、さらに詳しく
この発明について説明する。
実施例 1
21の減圧装置付反応器にポリフエニレンオキサ
イド(PPO)100g、スチレンブタジエンコポリ
マー(旭化成工業(株):ソルプレンT406)30g、
トリアリルイソシアヌレート(日本化成(株):
TAIC)40g、2,5−ジメチル−2,5−ジ−
(tert−ブチルパーオキシ)ヘキシン−3(日本油
脂(株):パーヘキシン25B)2gを加え、さらにト
リクロロエチレン(東亜合成化学工業(株):トリク
レン)750gを加えて、均一溶液になるまで充分
攪拌した。この後、平均粒径1〜2μmのチタン
酸バリウム(BaTiO3)系セラミツク粉末150g
を加え、ボールミルで約24時間攪拌し、均一に分
散させた。その後、脱泡を行い、得られたPPO
系樹脂組成物にガラスクロス(100g/m2)を浸
漬してこの溶液に含浸させてから取り出し、50℃
で約10分間、130℃で約20分間乾燥させ、プリプ
レグを得た。得られたプリプレグ4枚を積層し、
成形プレスにより195℃、10Kg/cm2で成形し、積
層板を得た。
表1に示した通り、樹脂溶液は安定性に優れ、
粒子の沈降もなく、均一な含浸がなされた。
実施例 2〜12
表1に示した配合で、実施例1と同様にして含
浸させた。
実施例5、7および8は、2種類以上の複合酸
化物の混合物を用いた。いずれの場合も樹脂溶液
は安定していた。
実施例 13
21の減圧装置付反応器に800gのトリクロロエ
チレン(東亜合成化学工業(株):トリクレン)中
に、PPO40g、スチレンブタジエンコポリマー
40g、トリアリルイソシアヌレート120g、2,
5−ジメチル−2,5−ジ−(tert−ブチルパー
オキシ)ヘキシン−3(日本油脂(株):パーヘキシ
ン25B)6gを加え、均一溶液になるまで充分攪
拌した。次に、チタン酸バリウム(BaTiO3)系
セラミツク粉末130gを加え、さらに攪拌して均
一に分散して、脱泡を行つた。得られたPPO系
樹脂組成物にガラスクロス(100g/m2)を浸漬
してこの溶液に含浸させてから取り出し、50℃で
約10分間、130℃で約20分間乾燥させ、プリプレ
グを得た。得られたプリプレグ4枚を積層し、成
形プレスにより195℃、10Kg/cm2で成形し、積層
板を得た。
実施例 14〜25
表1に示した配合において、実施例13と同様に
して積層板を作製した。
含浸は均一に行われた。
実施例 26
実施例1のPPO系樹脂組成物溶液中にガラス
クロスをしばらく浸漬させた後、これを溶液から
取り出して50℃で約10分間、130℃で約20分間乾
燥させ、トリクロロエチレンを完全に除去して
PPO系樹脂組成物が含浸したガラスクロス(プ
リプレグ)を得た。このプリプレグ2枚と実施例
6のシート3枚を、シート、プリプレグの順次積
層し、実施例1の条件で加熱圧締して積層板を作
製した。
(Industrial Application Field) The present invention relates to a method for impregnating an inorganic particle-dispersed resin. More specifically, the present invention is directed to impregnation with a resin solution in which inorganic particles are dispersed, which is useful for impregnating base materials such as laminates, enables uniform impregnation, and improves prepreg properties. It is about the method. (Prior art) In order to improve the performance of laminates, such as their insulation properties, dielectric properties, and strength, it has been widely practiced to impregnate a base material with a resin solution containing dispersed inorganic particles. There is. In this impregnation process, particles of inorganic substances such as silica, alumina, and magnesia are dispersed in resins such as epoxy resins, polyesters, phenolic resins, polyamides, and polyimides, and are impregnated into base materials such as glass cloth, glass sheets, glass mats, and paper. has been adopted as a general method. (Problems to be Solved by the Invention) However, in this conventional resin solution impregnation method, the inorganic particles dispersed in the solution result in non-uniform impregnation of the base material and also affect the performance of the base material. This issue remained unresolved due to its significant impact. In particular, when inorganic particles that affect the properties of the laminate are impregnated together with a resin, the influence of such non-uniform impregnation cannot be ignored. Such non-uniformity of impregnation is due to the size of the inorganic particles as determined by the inventors of the present invention.If the particle size is large, they will settle during the impregnation process, and the particles will settle at the beginning of the impregnation process. The content of inorganic particles in the resin solution differs greatly between the end and the end. On the other hand, if the particle size is too small, the physical properties of the inorganic particles and, by extension, the impregnated base material cannot be achieved as required, leading to increased costs associated with pulverization of the particles. Therefore, it has been desired to realize an appropriate impregnation method that can uniformly impregnate inorganic particle-dispersed resin and contribute to improving the performance of the base material or laminate. (Means for Solving the Problems) This invention was made in view of the above circumstances, and improves the drawbacks of the conventional resin impregnation method, and provides an impregnation treatment for a resin solution in which inorganic particles are dispersed. , the aim is to provide an improved method that allows uniform impregnation of these inorganic particles. Therefore, this invention has an average particle size of 2 μm or less,
The feature is that the base material is impregnated with a dielectric dispersed resin solution in which metal composite oxide dielectric powder with a maximum particle size of 7 μm or less is dispersed in a mixed resin solution of polyphenylene oxide, crosslinkable polymer, and monomer. It is said that Furthermore, the impregnation method of the present invention is particularly suitable for manufacturing laminates with high dielectric properties. In order to prevent the metal composite oxide dielectric particles from settling in the above resin solution, the average particle size of the particles must be 2 μm.
m or less, and the maximum particle size must be 7 μm or less. Although the smaller the particle size, the better the stability, it is not advantageous to make the particle size too small in terms of physical properties of the impregnated base material, particle physical properties, pulverization cost, etc. Since the precipitation of metal composite oxide dielectric particles is also related to the viscosity of the resin solution, it is preferable to adjust this viscosity appropriately. Generally, the higher the viscosity, the better; however, if the viscosity is too large, the permeation rate during impregnation will be slow, and sufficient impregnation will not be achieved before drying. When glass cloth is used as the base material, it is preferable to have a viscosity of about 100 to 700 csp. If it is less than 100 csp, the amount of resin adhering to the base material will be small, and the metal composite oxide dielectric particles will also settle quickly. In addition, the stability of metal composite oxide dielectric particles in solution is also related to the specific gravity of the particles and the specific gravity of the solution.
In this case, it is sufficient to have the particle size within the above range. As mentioned above, the impregnation method of the present invention is used to impregnate a resin solution in which metal composite oxide dielectric powder is dispersed in a mixed solution of polyphenylene oxide (PPO), a crosslinkable polymer, and a monomer. be. Examples of metal composite oxide derivative powders include metal titanate ceramics such as barium titanate, lead titanate, calcium titanate, magnesium titanate, and bismuth titanate, lead zirconate, and zirconate. Zirconate metal ceramics such as barium type, K 2 O−PbO
−Lead composite oxide ceramics such as SiO 2 type, Baf 0.5
Neodymium composite oxide ceramics such as Pb 0.5 Nd 2 Ti 5 O 14 series, BaNd 2 Ti 5 O 14 series, or Ba(Zn 1/2
Examples include powders of niobium composite oxide ceramics such as Nb 2/3 ) O 3 series, or mixed powders of two or more of these. These inorganic particles provide an impregnated base material with excellent dielectric properties and a laminate using the same. For example, polyphenylene oxide has the following chemical formula (1) (R represents hydrogen or a hydrocarbon group having 1 to 3 carbon atoms, and each R may be the same or different.) One example is poly(2,6-dimethyl -1,4-phenylene oxide). Examples of crosslinkable polymers include 1,2-
Examples include polybutadiene, 1,4-polybutadiene, styrene-butadiene copolymer, modified 1,2-polybutadiene (malein-modified, acrylic-modified, epoxy-modified), rubbers, etc., and each can be used alone or in combination of two or more. .
These polymers may be in the form of elastomers or rubbers. Examples of crosslinking monomers include acrylates such as ester acrylates, epoxy acrylates, urethane acrylates, ether acrylates, melamine acrylates, alkyd acrylates, and silicone acrylates, triallyl cyanurate, and triallyl isocyanurate. , polyfunctional monomers such as ethylene glycol dimethacrylate, divinylbenzene, diallyl phthalate, monofunctional monomers such as vinyltoluene, ethylvinylbenzene, styrene, paramethylstyrene, and polyfunctional epoxies. Two or more can be used together. Among these, triallyl cyanurate and/or triallyl isocyanurate are preferred because they have good compatibility with polyphenylene oxide and improve film-forming properties, crosslinking properties, heat resistance, and dielectric properties. Triallyl cyanurate and triallyl isocyanurate are chemically structurally isomers and have almost the same film-forming properties, compatibility, solubility, reactivity, etc., and either one or Both can be used equally. An initiator can further be used when the polyphenylene oxide is made to contain the crosslinkable polymer, monomer, and metal composite oxide dielectric as described above. An appropriate initiator can be selected depending on whether the polyphenylene oxide resin composition is of an ultraviolet curing type or a thermosetting type. In the method of the present invention in which metal composite oxide dielectric particles are dispersed in a polyphenylene oxide resin solution for impregnation, the resin composition is usually dissolved in a solvent, dispersed, and mixed. In this case, an appropriate solvent can be used, such as halogenated hydrocarbons such as trichloroethylene, trichloroethane, chloroform, methylene chloride, and chlorobenzene, aromatic hydrocarbons such as benzene, toluene, and xylene, acetone, Carbon chloride and the like can be used, with trichlorethylene being particularly preferred. These can be used alone or in combination of two or more. As a method for impregnating a base material with a mixed resin solution in which metal composite oxide-based dielectric particles are dispersed, any suitable method including conventionally known methods can be employed. Generally, for example,
A resin composition including metal composite oxide-based dielectric particles is dispersed in a solvent, and a substrate is impregnated and adhered by dipping (dipping) in the solvent solution. Then, the solvent can be removed by drying or the like, or it can be semi-cured to bring it to the B stage. As the base material, resin-impregnated cloth materials such as glass cloth, aramid cloth, polyester cloth, and nylon cloth and/or fibrous materials such as nonwoven fabrics, paper such as kraft paper and linter paper, etc. can be used. It is not limited to. If the prepreg is produced in this way, it is not necessary to melt the resin, so it can be easily carried out at a relatively low temperature. A base material impregnated with resin and metal composite oxide-based dielectric particles can be laminated and integrated with a metal foil, for example, by a conventional method to form a laminate for a printed wiring board. (Function) The average particle size of the metal composite oxide dielectric particles is
By setting the particle size to 2 μm or less and the maximum particle size to 7 μm or less, the mixed resin solution of polyphenylene oxide, crosslinkable polymer, and monomer containing these particles can suppress the sedimentation of metal composite oxide dielectric particles. This enables uniform impregnation of the substrate. Metal composite oxide dielectric particles mixed into a resin solution for heat dissipation, dimensional stability, dielectric properties, etc. are stably and uniformly impregnated with the resin. This method makes it possible to obtain a resin-impregnated base material with high dielectric properties. Hereinafter, examples of the present invention will be shown and the present invention will be explained in more detail. Example 1 100g of polyphenylene oxide (PPO), 30g of styrene-butadiene copolymer (Asahi Kasei Corporation: Solprene T406),
Triallylisocyanurate (Nippon Kasei Co., Ltd.:
TAIC) 40g, 2,5-dimethyl-2,5-di-
2 g of (tert-butylperoxy)hexine-3 (Nippon Oil & Fats Co., Ltd.: Perhexine 25B) was added, followed by 750 g of trichlorethylene (Toagosei Chemical Co., Ltd.: Trichlene) and stirred thoroughly until a homogeneous solution was obtained. . After this, 150 g of barium titanate (BaTiO 3 ) ceramic powder with an average particle size of 1 to 2 μm was prepared.
was added and stirred using a ball mill for about 24 hours to uniformly disperse the mixture. After that, defoaming is performed and the obtained PPO
A glass cloth (100 g/m 2 ) was immersed in the resin composition, then taken out and heated at 50°C.
The prepreg was dried at 130°C for about 10 minutes and at 130°C for about 20 minutes. The four prepregs obtained were laminated,
A laminate was obtained by molding at 195° C. and 10 Kg/cm 2 using a molding press. As shown in Table 1, the resin solution has excellent stability;
Uniform impregnation was achieved without particles settling. Examples 2 to 12 Impregnation was carried out in the same manner as in Example 1 using the formulations shown in Table 1. Examples 5, 7, and 8 used a mixture of two or more types of composite oxides. The resin solution was stable in both cases. Example 13 40 g of PPO and styrene-butadiene copolymer were placed in 800 g of trichlorethylene (Toagosei Kagaku Kogyo Co., Ltd.: Trichlene) in a 21 reactor equipped with a pressure reduction device.
40g, triallyl isocyanurate 120g, 2,
6 g of 5-dimethyl-2,5-di-(tert-butylperoxy)hexyne-3 (Nippon Oil Co., Ltd.: Perhexin 25B) was added and thoroughly stirred until a homogeneous solution was obtained. Next, 130 g of barium titanate (BaTiO 3 ) ceramic powder was added and further stirred to uniformly disperse and defoam. A glass cloth (100 g/m 2 ) was immersed in the resulting PPO resin composition to be impregnated with this solution, taken out, and dried at 50°C for about 10 minutes and at 130°C for about 20 minutes to obtain a prepreg. . Four sheets of the obtained prepreg were laminated and molded using a molding press at 195° C. and 10 kg/cm 2 to obtain a laminate. Examples 14-25 Laminated plates were produced in the same manner as in Example 13 using the formulations shown in Table 1. Impregnation was uniform. Example 26 After immersing a glass cloth in the PPO resin composition solution of Example 1 for a while, it was taken out from the solution and dried at 50°C for about 10 minutes and at 130°C for about 20 minutes to completely remove the trichlorethylene. remove it
A glass cloth (prepreg) impregnated with a PPO resin composition was obtained. Two sheets of this prepreg and three sheets of Example 6 were laminated in this order: sheet and prepreg, and heat-pressed under the conditions of Example 1 to produce a laminate.
【表】【table】
【表】【table】
【表】【table】
【表】
比較例 1
31の減圧装置付反応器にPPO140g、スチレン
ブタジエンコポリマー(旭化成工業(株):ソルプレ
ンT406)40g、トリアリルイソシアヌレート
(日本化成(株):TATIC)40g、ジクミルパーオ
キサイド3gを加え、さらにトリクロロエチレン
(東亜合成化学工業(株):トリクレン)850gを加え
て、均一溶液になるまで充分攪拌した。この後、
平均粒径5〜6μmの酸化アルミニウム粉末(住
友アルミニウム製錬(株):酸化アルミニウムAM−
21)280gを加え、さらに攪拌して均一に分散さ
せた。その後、脱泡を行い、得られたPPO系樹
脂組成物溶液を、実施例1と同様にして含浸に用
い、積層板を作製した。表2に示した通り、無機
物の酸化アルミニウム粉末は沈降し、均一な含浸
とはならなかつた。
また、プリプレグの外観もこの不均一性によつ
てあまり良好ではなかつた。
比較例 2〜5
表2に示す配合において、実施例1と同じよう
にして積層板を作製した。溶液は不安定であつ
た。
なお、上記各プリプレグのPPO系樹脂組成物
含有量は、30〜80重量%であつた。
この発明の樹脂溶液による含浸はいずれも溶液
が安定しており、粒子の沈降はなく、均一な含浸
が行われた。
なお、実施例1〜26および比較例1〜5の各金
属複合酸化物系誘電体、酸化アルミニウムおよび
二酸化チタン粉末は、それぞれ、表3に示す条件
で焼成を行つて得たものを用いた。各粉末の平均
粒度および粒度分布、種類も表3に示した。[Table] Comparative Example 1 140 g of PPO, 40 g of styrene-butadiene copolymer (Asahi Kasei Corporation: Solprene T406), 40 g of triallyl isocyanurate (TATIC, Nippon Kasei Corporation), and dicumyl peroxide were placed in a 31 reactor equipped with a pressure reduction device. Then, 850 g of trichlorethylene (Toagosei Kagaku Kogyo Co., Ltd.: Trichlene) was added, and the mixture was thoroughly stirred until a homogeneous solution was obtained. After this,
Aluminum oxide powder with an average particle size of 5 to 6 μm (Sumitomo Aluminum Smelting Co., Ltd.: Aluminum oxide AM-
21) 280g was added and further stirred to uniformly disperse. Thereafter, defoaming was performed, and the resulting PPO-based resin composition solution was used for impregnation in the same manner as in Example 1 to produce a laminate. As shown in Table 2, the inorganic aluminum oxide powder precipitated and was not uniformly impregnated. Also, the appearance of the prepreg was not very good due to this non-uniformity. Comparative Examples 2 to 5 Laminated plates were produced in the same manner as in Example 1 using the formulations shown in Table 2. The solution was unstable. The content of the PPO resin composition in each of the above prepregs was 30 to 80% by weight. In all cases of impregnation with the resin solution of this invention, the solution was stable, there was no sedimentation of particles, and uniform impregnation was performed. The metal composite oxide dielectrics, aluminum oxide, and titanium dioxide powders of Examples 1 to 26 and Comparative Examples 1 to 5 were obtained by firing under the conditions shown in Table 3, respectively. The average particle size, particle size distribution, and type of each powder are also shown in Table 3.
【表】【table】
【表】【table】
【表】【table】
【表】【table】
【表】
(発明の効果)
この発明により、以上詳しく説明した通り、金
属複合酸化物系誘電体粒子を含有するポリフエニ
レンオキサイドと架橋性ポリマーおよびモノマー
との混合樹脂溶液の安定した、かつ均一な基材へ
の含浸が可能となる。金属複合酸化物系誘電体粒
子の沈降のない、効果的含浸が行われる。
誘電特性に優れた樹脂含浸基材が得られる。[Table] (Effects of the Invention) As explained in detail above, the present invention provides a stable and uniform solution of a mixed resin solution of polyphenylene oxide containing metal composite oxide dielectric particles, a crosslinkable polymer, and a monomer. It is possible to impregnate various base materials. Effective impregnation of metal composite oxide dielectric particles without sedimentation is achieved. A resin-impregnated base material with excellent dielectric properties can be obtained.
Claims (1)
金属複合酸化物系誘電体粉末を、ポリフエニレン
オキサイドと架橋性のポリマーおよびモノマーと
の混合樹脂溶液に分散させた誘電体分散樹脂溶液
を基材に含浸させることを特徴とする無機物粒子
分散樹脂の含浸方法。 2 金属複合酸化物系誘電体粉末が、チタン酸金
属系セラミツク、ジルコン酸金属系セラミツク、
鉛複合酸化物系セラミツク、ネオジウム複合酸化
物系セラミツク、またはニオブ複合酸化物系セラ
ミツクの粉末、あるいはこれらの2種以上の混合
粉末である請求項1記載の無機物粒子分散樹脂の
含浸方法。[Claims] 1. A metal composite oxide dielectric powder having an average particle size of 2 μm or less and a maximum particle size of 7 μm or less is dispersed in a mixed resin solution of polyphenylene oxide, a crosslinkable polymer, and a monomer. A method for impregnating an inorganic particle-dispersed resin, the method comprising impregnating a base material with a dielectric-dispersed resin solution. 2. The metal composite oxide dielectric powder is a metal titanate ceramic, a metal zirconate ceramic,
2. The method for impregnating an inorganic particle-dispersed resin according to claim 1, wherein the impregnation method is a powder of lead composite oxide ceramic, neodymium composite oxide ceramic, or niobium composite oxide ceramic, or a mixed powder of two or more of these.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP7288788A JPH01245038A (en) | 1988-03-27 | 1988-03-27 | Method for impregnating resin containing inorganic substance particle dispersed therein |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP7288788A JPH01245038A (en) | 1988-03-27 | 1988-03-27 | Method for impregnating resin containing inorganic substance particle dispersed therein |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH01245038A JPH01245038A (en) | 1989-09-29 |
JPH0564992B2 true JPH0564992B2 (en) | 1993-09-16 |
Family
ID=13502301
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP7288788A Granted JPH01245038A (en) | 1988-03-27 | 1988-03-27 | Method for impregnating resin containing inorganic substance particle dispersed therein |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH01245038A (en) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1457515A4 (en) * | 2001-08-31 | 2004-11-24 | Sumitomo Bakelite Co | Resin composition prepreg laminated sheet and semiconductor package |
JP5288581B2 (en) * | 2006-03-03 | 2013-09-11 | 株式会社半導体エネルギー研究所 | Method for manufacturing semiconductor device |
US8173519B2 (en) | 2006-03-03 | 2012-05-08 | Semiconductor Energy Laboratory Co., Ltd. | Method for manufacturing semiconductor device |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5894461A (en) * | 1981-12-01 | 1983-06-04 | 松下電工株式会社 | White epoxy resin laminated board |
JPS5894449A (en) * | 1981-12-01 | 1983-06-04 | 松下電工株式会社 | Flame-retarded laminated board |
JPS63165446A (en) * | 1986-12-27 | 1988-07-08 | Toyo Electric Mfg Co Ltd | Resin curing accelerator |
JPH01115965A (en) * | 1987-10-28 | 1989-05-09 | Chuo Hatsumei Kenkyusho:Kk | Monomer inorganic colloidal sol impregnating agent and production thereof |
-
1988
- 1988-03-27 JP JP7288788A patent/JPH01245038A/en active Granted
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5894461A (en) * | 1981-12-01 | 1983-06-04 | 松下電工株式会社 | White epoxy resin laminated board |
JPS5894449A (en) * | 1981-12-01 | 1983-06-04 | 松下電工株式会社 | Flame-retarded laminated board |
JPS63165446A (en) * | 1986-12-27 | 1988-07-08 | Toyo Electric Mfg Co Ltd | Resin curing accelerator |
JPH01115965A (en) * | 1987-10-28 | 1989-05-09 | Chuo Hatsumei Kenkyusho:Kk | Monomer inorganic colloidal sol impregnating agent and production thereof |
Also Published As
Publication number | Publication date |
---|---|
JPH01245038A (en) | 1989-09-29 |
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