JP2002309085A - Heat resistant resin composition, prepreg using the same and laminate - Google Patents
Heat resistant resin composition, prepreg using the same and laminateInfo
- Publication number
- JP2002309085A JP2002309085A JP2001115584A JP2001115584A JP2002309085A JP 2002309085 A JP2002309085 A JP 2002309085A JP 2001115584 A JP2001115584 A JP 2001115584A JP 2001115584 A JP2001115584 A JP 2001115584A JP 2002309085 A JP2002309085 A JP 2002309085A
- Authority
- JP
- Japan
- Prior art keywords
- resin
- epoxy resin
- resin composition
- general formula
- prepreg
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000011342 resin composition Substances 0.000 title claims abstract description 14
- 229920006015 heat resistant resin Polymers 0.000 title claims abstract description 5
- 229920005989 resin Polymers 0.000 claims abstract description 34
- 239000011347 resin Substances 0.000 claims abstract description 34
- 239000003822 epoxy resin Substances 0.000 claims abstract description 29
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 29
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 claims abstract description 25
- 239000003063 flame retardant Substances 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 4
- 238000010521 absorption reaction Methods 0.000 abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 15
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 abstract description 13
- 235000010290 biphenyl Nutrition 0.000 abstract description 12
- 239000004305 biphenyl Substances 0.000 abstract description 12
- 239000004615 ingredient Substances 0.000 abstract 1
- 229910000679 solder Inorganic materials 0.000 description 12
- 239000004593 Epoxy Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 6
- 239000011521 glass Substances 0.000 description 5
- 239000002966 varnish Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 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 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 239000004744 fabric Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000005829 trimerization reaction Methods 0.000 description 4
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- FJDJVBXSSLDNJB-LNTINUHCSA-N cobalt;(z)-4-hydroxypent-3-en-2-one Chemical compound [Co].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FJDJVBXSSLDNJB-LNTINUHCSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 230000010365 information processing Effects 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 238000005470 impregnation Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- 101100407151 Arabidopsis thaliana PBL6 gene Proteins 0.000 description 1
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- SZKXDURZBIICCF-UHFFFAOYSA-N cobalt;pentane-2,4-dione Chemical compound [Co].CC(=O)CC(C)=O SZKXDURZBIICCF-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- WSFQLUVWDKCYSW-UHFFFAOYSA-M sodium;2-hydroxy-3-morpholin-4-ylpropane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CC(O)CN1CCOCC1 WSFQLUVWDKCYSW-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
Landscapes
- Reinforced Plastic Materials (AREA)
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、耐熱性に優れ、誘
電特性に優れた樹脂組成物、プリプレグ及び積層板に関
するものである。特に、高周波用回路基板の用途に好適
に用いられるものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition, a prepreg, and a laminate having excellent heat resistance and excellent dielectric properties. In particular, it is suitably used for high frequency circuit boards.
【０００２】ノート型パーソナルコンピューターや携帯
電話等の情報処理機器は小型化が求められている。ＬＳ
Ｉ等の電子部品を搭載するプリント配線板においても小
型軽量化の要求は強くなっている。小型軽量化のために
は配線幅を小さくすることや、スルーホール径を小さく
しメッキ厚を薄くすることが必要である。メッキ厚を薄
くすると熱衝撃時にメッキクラックが発生するおそれが
あり、耐熱性が要求される。また同時にこれらの情報処
理用危機の高速化も要求されておりＣＰＵクロック周波
数が高くなっている。そのため信号伝搬速度の高速化が
要求されており、高速化に有利な誘電率、誘電正接の低
いプリント板であることが必要とされる。Information processing devices such as notebook personal computers and mobile phones are required to be miniaturized. LS
There is a strong demand for smaller and lighter printed wiring boards on which electronic components such as I are mounted. In order to reduce the size and weight, it is necessary to reduce the wiring width and to reduce the through hole diameter and the plating thickness. If the plating thickness is reduced, plating cracks may occur at the time of thermal shock, and heat resistance is required. At the same time, speeding up of these information processing crises is also required, and the CPU clock frequency is increasing. Therefore, a higher signal propagation speed is required, and a printed board having a low dielectric constant and a low dielectric loss tangent, which is advantageous for the high speed, is required.
【０００３】耐熱性に優れ、誘電特性に優れた樹脂とし
てシアネート樹脂が用いられる（例えば、特開平８−８
５０１号公報）。シアネート樹脂は硬化反応によって水
酸基などの分極の大きい反応基が生じることがないた
め、誘電特性が非常に優れている。しかしながら窒素原
子を多く含むため吸水率が高い欠点がある。A cyanate resin is used as a resin having excellent heat resistance and excellent dielectric properties (for example, see JP-A-8-8).
No. 501). The cyanate resin does not generate a highly polarized reactive group such as a hydroxyl group by a curing reaction, and thus has a very excellent dielectric property. However, there is a drawback that the water absorption rate is high because it contains many nitrogen atoms.
【０００４】[0004]
【発明が解決しようとする課題】本発明は、このような
問題を解決すべく検討結果なされたものであり、シアネ
ート樹脂とフェノールアラルキルエポキシ樹脂又はビフ
ェニルアラルキルエポキシ樹脂を併用することで耐熱
性、誘電特性、吸水率に優れた樹脂組成物、プリプレグ
及びプリプレグから得られた積層板を提供するものであ
る。DISCLOSURE OF THE INVENTION The present invention has been made to solve the above problems, and has been developed by using a cyanate resin and a phenol aralkyl epoxy resin or a biphenyl aralkyl epoxy resin in combination. An object of the present invention is to provide a resin composition excellent in properties and water absorption, a prepreg, and a laminate obtained from the prepreg.
【０００５】[0005]
【課題を解決するための手段】本発明は （１）（Ａ）下記一般式（Ｉ）で表されるシアネート樹
脂又はそのプレポリマー、及びThe present invention provides (1) (A) a cyanate resin represented by the following general formula (I) or a prepolymer thereof, and
【化３】 （Ｂ１）下記一般式（ＩＩ）で表されるビフェニルアラ
ルキルエポキシ樹脂、又は（Ｂ２）下記一般式（ＩＩ
Ｉ）で表されるフェノールアラルキルエポキシ樹脂Embedded image (B1) a biphenylaralkyl epoxy resin represented by the following general formula (II), or (B2) a following general formula (II)
Phenol aralkyl epoxy resin represented by I)
【化４】 を必須成分として含有してなることを特徴とする耐熱性
樹脂組成物、（２）第（１）項記載の樹脂組成物を基材
に含浸させてなることを特徴とするプリプレグ、（３）
第（２）項記載のプリプレグを１枚又は２枚以上重ね合
わせ加熱加圧してなることを特徴とする難燃性積層板又
は銅張積層板、である。Embedded image (2) a prepreg, wherein a base material is impregnated with the resin composition described in (1), (3) a heat-resistant resin composition comprising:
A flame-retardant laminate or a copper-clad laminate obtained by laminating one or more prepregs according to the item (2) and heating and pressing them.
【０００６】[0006]
【発明の実施の形態】本発明で用いる（Ａ）成分のシア
ネート樹脂は下記一般式（Ｉ）で示される。BEST MODE FOR CARRYING OUT THE INVENTION The cyanate resin of the component (A) used in the present invention is represented by the following general formula (I).
【化５】 また、かかる一般式を有するシアネート樹脂をプレポリ
マー化したものも成形性、流動性を調整するために好ま
しく使用され、本発明の（Ａ）成分に含まれるものであ
る。プレポリマー化は、通常加熱溶融して行われる。本
発明でプレポリマーとは、３量化率２０〜５０％のもの
をいう。３量化率は赤外分光分析装置を用いて求めるこ
とができる。なお、シアネート樹脂とシアネート樹脂を
プレポリマー化したものとを併用しても構わない。シア
ネート樹脂は樹脂成分１００重量部中、５０〜８０重量
部が好ましい。５０重量部未満では２６０℃の半田耐熱
性が十分でなく、また８０重量部を越えると吸水率が悪
化し好ましくない。本発明におけるシアネート樹脂のＲ
１のアルキル基は炭素数１〜６が好ましく、アリール基
は炭素数は２〜６が好ましい。また、同様にＲ２のアル
キル基は炭素数１〜４が好ましく、アリール基は炭素数
１〜３が好ましい。Embedded image Further, those obtained by prepolymerizing a cyanate resin having such a general formula are also preferably used for adjusting moldability and fluidity, and are included in the component (A) of the present invention. The prepolymerization is usually performed by heating and melting. In the present invention, the term "prepolymer" refers to a prepolymer having a trimerization ratio of 20 to 50%. The trimerization ratio can be determined using an infrared spectrometer. Note that a cyanate resin and a prepolymerized cyanate resin may be used in combination. The content of the cyanate resin is preferably 50 to 80 parts by weight based on 100 parts by weight of the resin component. If it is less than 50 parts by weight, the solder heat resistance at 260 ° C. is not sufficient, and if it exceeds 80 parts by weight, the water absorption is undesirably deteriorated. R of the cyanate resin in the present invention
One alkyl group preferably has 1 to 6 carbon atoms, and the aryl group preferably has 2 to 6 carbon atoms. Similarly, the alkyl group of R2 preferably has 1 to 4 carbon atoms, and the aryl group preferably has 1 to 3 carbon atoms.
【０００７】本発明で用いる（Ｂ１）成分のビフェニル
アラルキル樹脂は下記一般式（ＩＩ）で示される。ま
た、（Ｂ２）成分のフェノールアラルキルエポキシ樹脂
は、下記一般式（ＩＩＩ）で示される。The biphenyl aralkyl resin of the component (B1) used in the present invention is represented by the following general formula (II). The phenol aralkyl epoxy resin of the component (B2) is represented by the following general formula (III).
【化６】 フェノールアラルキルエポキシ樹脂又はビフェニルアラ
ルキルエポキシ樹脂は樹脂成分１００重量部中、２０〜
５０重量部が好ましい。２０重量部未満では低吸水化が
十分でなく、また５０重量部を越えると２６０℃の半田
耐熱性が悪化し好ましくない。両者の中でもビフェニル
アラルキルエポキシ樹脂が、エポキシ当量が大きく低吸
水化の効果が大きい点で好ましい。また、本発明でビフ
ェニルアラルキル樹脂のｎは２〜７が２６０℃の半田耐
熱性の点で好ましい。ｎが２未満であると架橋密度が低
下する傾向があり２６０℃での半田耐熱性が悪化する場
合があり、７を超えるとシアネート樹脂との相溶性が悪
化する場合がある。また、フェノールアラルキルエポキ
シ樹脂のｍは２〜７が２６０℃の半田耐熱性の点で特に
好ましい。ｍが２未満であると架橋密度が低下する傾向
があり２６０℃での半田耐熱性が悪化する場合があり、
７を超えるとシアネート樹脂との相溶性が悪化する場合
がある。Embedded image Phenol aralkyl epoxy resin or biphenyl aralkyl epoxy resin is 20 to 20 parts by weight of the resin component.
50 parts by weight are preferred. If the amount is less than 20 parts by weight, the water absorption is not sufficiently reduced, and if it exceeds 50 parts by weight, the solder heat resistance at 260 ° C is undesirably deteriorated. Among them, biphenylaralkyl epoxy resin is preferred because it has a large epoxy equivalent and a large effect of reducing water absorption. In the present invention, n of the biphenyl aralkyl resin is preferably 2 to 7 from the viewpoint of the solder heat resistance at 260 ° C. When n is less than 2, the crosslink density tends to decrease, and the solder heat resistance at 260 ° C. may deteriorate. When n exceeds 7, the compatibility with the cyanate resin may deteriorate. In addition, m of the phenol aralkyl epoxy resin is particularly preferably 2 to 7 in view of solder heat resistance at 260 ° C. When m is less than 2, the crosslinking density tends to decrease, and the solder heat resistance at 260 ° C. may deteriorate,
If it exceeds 7, the compatibility with the cyanate resin may deteriorate.
【０００８】前述のように、シアネート樹脂は硬化反応
によってトリアジン環を生じるが、トリアジン環は対称
性に優れているため分極が小さく誘電特性が非常に優れ
ている。更に、トリアジン環は窒素を含む剛直構造であ
るため難燃性に優れている特徴がある。しかし、シアネ
ート樹脂は、窒素含有率が高いため、吸水率が高い欠点
がある。吸水率を低下させるためには、エラストマーや
ジシクロペンタジエン樹脂などの低吸水樹脂を添加する
方法があるが、これらの樹脂は燃焼しやすい欠点があ
る。本発明ではこの問題を解決するため、シアネート樹
脂にフェノールアラルキルエポキシ樹脂又はビフェニル
アラルキルエポキシ樹脂を併用する。フェノールアラル
キルエポキシ樹脂、ビフェニルアラルキルエポキシ樹脂
はエポキシ当量が大きく、硬化物中のエポキシ基濃度が
小さくなるため誘電特性に優れている。また分子中のベ
ンゼン環によって疎水性が高く吸水率も低い。また、フ
ェノールアラルキルエポキシ樹脂、ビフェニルアラルキ
ルエポキシ樹脂は、ベンゼン環含有率が高く炭化しやす
いため、燃焼しにくくシアネート樹脂の優れた耐燃性を
悪化させない。さらにエポキシ基はシアネート基と反応
するため、樹脂骨格中に組み込むことができるためシア
ネート樹脂の優れた耐熱性を低下させない。As described above, a cyanate resin generates a triazine ring by a curing reaction. However, the triazine ring has excellent symmetry and thus has small polarization and very excellent dielectric properties. Furthermore, the triazine ring has a feature of excellent flame retardancy because of its rigid structure containing nitrogen. However, the cyanate resin has a disadvantage that it has a high water absorption due to its high nitrogen content. In order to reduce the water absorption, there is a method of adding a low water absorption resin such as an elastomer or dicyclopentadiene resin, but these resins have a disadvantage that they are easily burned. In the present invention, in order to solve this problem, a phenol aralkyl epoxy resin or a biphenyl aralkyl epoxy resin is used in combination with the cyanate resin. A phenol aralkyl epoxy resin and a biphenyl aralkyl epoxy resin have a large epoxy equivalent and a low epoxy group concentration in a cured product, and thus have excellent dielectric properties. In addition, the benzene ring in the molecule has high hydrophobicity and low water absorption. In addition, phenol aralkyl epoxy resins and biphenyl aralkyl epoxy resins have a high benzene ring content and are easily carbonized, so that they do not easily burn and do not deteriorate the excellent flame resistance of the cyanate resin. Further, since the epoxy group reacts with the cyanate group, it can be incorporated into the resin skeleton, so that the excellent heat resistance of the cyanate resin is not reduced.
【０００９】本発明で用いる基材としては、ガラス繊
布、ガラス不繊布、あるいはガラス以外を成分とする繊
布又は不繊布等が挙げられる。これら基材の中でも強
度、吸水率の点でガラス織布が好ましい。Examples of the substrate used in the present invention include glass woven cloth, glass non-woven cloth, and woven or non-woven cloth containing components other than glass. Among these substrates, a glass woven fabric is preferable in terms of strength and water absorption.
【００１０】本発明で得られる樹脂組成物を基材に含浸
させる方法には、含浸塗布設備等を用いる。本発明にお
いては、基材に含浸する際には通常溶剤に溶解したワニ
スの形で使用することが含浸性の点で好ましい。用いら
れる溶媒は組成に対して良好な溶解性を示すことが望ま
しいが、悪影響を及ぼさない範囲で貧溶媒を使用しても
構わない。良好な溶解性を示す溶媒としては、メチルエ
チルケトン、シクロヘキサノン等が挙げられる。本発明
の樹脂組成物を溶剤に溶解して得られるワニスを、基材
に含浸させ、８０〜２００℃で乾燥させることによりプ
リプレグを得ることが出来る。The method of impregnating the base material with the resin composition obtained by the present invention uses an impregnation coating facility or the like. In the present invention, when impregnating the substrate, it is usually preferable to use it in the form of a varnish dissolved in a solvent from the viewpoint of impregnation. It is desirable that the solvent used has good solubility in the composition, but a poor solvent may be used as long as the solvent is not adversely affected. Solvents exhibiting good solubility include methyl ethyl ketone, cyclohexanone and the like. A prepreg can be obtained by impregnating a base material with a varnish obtained by dissolving the resin composition of the present invention in a solvent and drying at 80 to 200 ° C.
【００１１】本発明で得られたプリプレグを１枚又は２
枚以上重合わせ、１５０〜２００℃で加熱加圧して積層
板又は銅張積層板を得ることができる。[0011] One or two prepregs obtained by the present invention
Laminates or copper-clad laminates can be obtained by stacking more than one sheet and heating and pressing at 150 to 200 ° C.
【００１２】本発明の樹脂組成物は、上述したシアネー
ト樹脂とフェノールアラルキルエポキシ樹脂又はビフェ
ニルアラルキルエポキシ樹脂を必須成分として含有する
が、本発明の目的に反しない範囲において、その他の樹
脂、硬化促進剤、カップリング剤、難燃剤、その他の成
分を添加することは差し支えない。難燃剤として、臭素
化エポキシ樹脂を用いると、エポキシ基とシアネート基
が反応し、難燃剤を樹脂骨格中に組み込むことができる
ため、樹脂の特性を悪化させず好ましい。硬化促進剤と
してはコバルトアセチルアセトナート、ナフテン酸コバ
ルト等のコバルト含有化合物、塩化亜鉛、ナフテン酸亜
鉛等の亜鉛含有化合物、塩化銅等の銅含有化合物が好ま
しい。The resin composition of the present invention contains the above-mentioned cyanate resin and phenol aralkyl epoxy resin or biphenyl aralkyl epoxy resin as essential components, but other resins and curing accelerators within a range not inconsistent with the object of the present invention. , Coupling agents, flame retardants and other components may be added. When a brominated epoxy resin is used as the flame retardant, the epoxy group and the cyanate group react with each other, and the flame retardant can be incorporated into the resin skeleton. As the curing accelerator, a cobalt-containing compound such as cobalt acetylacetonate and cobalt naphthenate, a zinc-containing compound such as zinc chloride and zinc naphthenate, and a copper-containing compound such as copper chloride are preferable.
【００１３】[0013]
【実施例】（実施例１）ビスフェノールＡシアネート樹
脂（プレポリマー化したもの、３量化率４０％、チバガ
イギー社製Ｂ−４０）７０重量部、ビフェニルアラルキ
ルエポキシ樹脂（エポキシ当量２８０、日本化薬社製Ｎ
Ｃ−３０００Ｓ）３０重量部、コバルトアセチルアセト
ン錯体０．１０重量部にジメチルセルソルブを加え、不
揮発分濃度５５重量％となるようにワニスを調整した。
このワニスを用いて、ガラス繊布（厚さ０．１８ｍｍ、
日東紡績（株）製）１００重量部にワニス固形分で８０
重量部含浸させて、１５０℃の乾燥機炉で５分乾燥さ
せ、樹脂含有量４４．４％のプリプレグを作成した。上
記プリプレグを６枚重ね、上下に厚さ３５μｍの電解銅
箔を重ねて、圧力４０ｋｇｆ／ｃｍ2 、温度２００℃で
１２０分、２２０℃で６０分加熱加圧成形を行い、厚さ
１．２ｍｍの両面銅張積層板を得た。EXAMPLES Example 1 70 parts by weight of bisphenol A cyanate resin (prepolymerized, trimerization rate 40%, C-40, B-40 manufactured by Ciba Geigy), biphenyl aralkyl epoxy resin (epoxy equivalent 280, Nippon Kayaku Co., Ltd.) Made N
C-3000S) Dimethylcellosolve was added to 30 parts by weight and 0.10 part by weight of a cobalt acetylacetone complex to prepare a varnish so that the non-volatile content concentration became 55% by weight.
Using this varnish, a glass fabric (0.18 mm thick,
80 parts by weight of varnish solids in 100 parts by weight of Nitto Boseki Co., Ltd.
Part by weight was impregnated and dried in a dryer oven at 150 ° C. for 5 minutes to prepare a prepreg having a resin content of 44.4%. Six sheets of the above prepreg were stacked, and an electrolytic copper foil having a thickness of 35 μm was stacked on the upper and lower sides, and heated and pressed under a pressure of 40 kgf / cm 2 , a temperature of 200 ° C. for 120 minutes, and a temperature of 220 ° C. for 60 minutes, and a thickness of 1.2 mm. Was obtained.
【００１４】（実施例２〜５、及び比較例１〜３）表１
に示した配合処方で、これ以外は全て実施例１と同様の
方法で両面銅張積層板を作成した。(Examples 2 to 5 and Comparative Examples 1 to 3)
, A double-sided copper-clad laminate was prepared in the same manner as in Example 1 except for the above formulation.
【００１５】得られた銅張積層板については難燃性、半
田耐熱性、ピール強度および吸水率を測定した。半田耐
熱性、ピール強度、吸水率についてはＪＩＳ Ｃ ６４８
１に準じて測定し、半田耐熱性は煮沸２時間の吸湿処理
を行った後、２６０℃の半田槽に１２０秒浸漬した後の
外観の異常の有無を調べた。難燃性は１ｍｍ厚のサンプ
ルをＵＬ−９４規格に従い垂直法で評価した。ガラス転
移点はレオメトリックス製 ＲＤＳ−７７００を用い
て、昇温速度３℃／ｍｉｎ、周波数１Ｈｚで測定した。
誘電率、誘電正接の測定はＪＩＳ Ｃ ６４８１に準じて
行い、周波数１ＭＨｚの静電容量を測定して求めた。評
価結果を表１に示す。実施例に示す銅張積層板はいずれ
も誘電率、誘電正接が低く、耐熱性、半田耐熱性、吸水
率に優れていることがわかる。The obtained copper-clad laminate was measured for flame retardancy, solder heat resistance, peel strength and water absorption. For solder heat resistance, peel strength, and water absorption, refer to JIS C648.
The solder heat resistance was measured according to No. 1 and the appearance of the solder was checked for abnormalities after immersion in a solder bath at 260 ° C. for 120 seconds after performing a moisture absorption treatment for 2 hours. The flame retardancy was evaluated by a vertical method for a sample having a thickness of 1 mm according to the UL-94 standard. The glass transition point was measured at a heating rate of 3 ° C./min and a frequency of 1 Hz using RDS-7700 manufactured by Rheometrics.
The dielectric constant and the dielectric loss tangent were measured in accordance with JIS C 6481, and were determined by measuring the capacitance at a frequency of 1 MHz. Table 1 shows the evaluation results. It can be seen that all of the copper-clad laminates shown in Examples have a low dielectric constant and a low dielectric loss tangent, and are excellent in heat resistance, solder heat resistance and water absorption.
【００１６】[0016]
【表１】 [Table 1]
【００１７】[0017]
【表２】 [Table 2]
【００１８】表の注 （１）ビスフェノールＡシアネート（プレポリマー化：
３量化率４０％、商品名：チバガイギー社製Ｂ−４０） （２）ビフェニルアラルキルエポキシ樹脂（エポキシ当
量２８０、商品名：日本化薬社製ＮＣ−３０００Ｓ） （３）フェノールアラルキルエポキシ樹脂（エポキシ当
量２３５、商品名：三井化学社製Ｅ−ＸＬ−３Ｌ） （４）臭素化エポキシ樹脂（エポキシ当量４００、臭素
化率４８％、大日本インキ化学工業社製エピクロン１５
３） （５）コバルトアセチルアセトナート （６）フェノールノボラックエポキシ樹脂（エポキシ当
量１９０、大日本インキ化学工業社製エピクロンＮ−７
７０）Notes to Table (1) Bisphenol A cyanate (prepolymerized:
Trimerization rate 40%, trade name: B-40 manufactured by Ciba Geigy Co., Ltd. (2) Biphenyl aralkyl epoxy resin (epoxy equivalent 280, trade name: NC-3000S manufactured by Nippon Kayaku Co., Ltd.) (3) phenol aralkyl epoxy resin (epoxy equivalent) 235, trade name: E-XL-3L, manufactured by Mitsui Chemicals, Inc. (4) Brominated epoxy resin (epoxy equivalent: 400, bromination ratio: 48%, Epicron 15 manufactured by Dainippon Ink and Chemicals, Inc.)
3) (5) Cobalt acetylacetonate (6) Phenol novolak epoxy resin (epoxy equivalent 190, Epicron N-7 manufactured by Dainippon Ink and Chemicals, Inc.)
70)
【００１９】[0019]
【発明の効果】本発明の耐熱性樹脂組成物は、プリント
配線板材料に適用された場合、高耐熱性を有し、誘電率
が低い特性を有し、かつ吸水率に優れた特性を有してい
る。従って、今後、小型情報処理用危機のプリント配線
板に最適な樹脂組成物を提供するものである。The heat-resistant resin composition of the present invention, when applied to a printed wiring board material, has characteristics of high heat resistance, low dielectric constant, and excellent water absorption. are doing. Therefore, in the future, the present invention provides a resin composition which is most suitable for a printed wiring board in crisis for small information processing.
───────────────────────────────────────────────────── フロントページの続き Ｆターム(参考） 4F072 AA04 AA07 AB09 AB28 AD27 AD45 AG03 AH25 AK14 AL12 4F100 AB17C AG00 AK51A AK51B BA02 BA03 BA04 BA05 BA06 BA07 BA10A BA10B BA10C EJ172 EJ422 GB43 JG05 JJ03 JJ07 4J002 CD03W CM02X ER006 FD066 GF00 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4F072 AA04 AA07 AB09 AB28 AD27 AD45 AG03 AH25 AK14 AL12 4F100 AB17C AG00 AK51A AK51B BA02 BA03 BA04 BA05 BA06 BA07 BA10A BA10B BA10C EJ172 EJ422 GB43 JG05 JJ03 002
Claims (3)
ネート樹脂又はそのプレポリマー、及び 【化１】 （Ｂ１）下記一般式（ＩＩ）で表されるビフェニルアラ
ルキルエポキシ樹脂、又は（Ｂ２）下記一般式（ＩＩ
Ｉ）で表されるフェノールアラルキルエポキシ樹脂、 【化２】 を必須成分として含有してなることを特徴とする耐熱性
樹脂組成物。(A) a cyanate resin represented by the following general formula (I) or a prepolymer thereof, and (B1) a biphenylaralkyl epoxy resin represented by the following general formula (II), or (B2) a following general formula (II)
A phenol aralkyl epoxy resin represented by I) A heat-resistant resin composition characterized by containing as an essential component.
させてなることを特徴とするプリプレグ。2. A prepreg obtained by impregnating a base material with the resin composition according to claim 1.
枚以上重ね合わせ加熱加圧してなることを特徴とする難
燃性積層板又は銅張積層板。3. One or two prepregs according to claim 2
A flame-retardant laminate or a copper-clad laminate, characterized by being laminated and heated and pressed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001115584A JP4738622B2 (en) | 2001-04-13 | 2001-04-13 | Heat resistant resin composition, prepreg and laminate using the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001115584A JP4738622B2 (en) | 2001-04-13 | 2001-04-13 | Heat resistant resin composition, prepreg and laminate using the same |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2006134981A Division JP2006307227A (en) | 2006-05-15 | 2006-05-15 | Heat-resistant resin composition, prepreg and laminate using the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2002309085A true JP2002309085A (en) | 2002-10-23 |
| JP4738622B2 JP4738622B2 (en) | 2011-08-03 |
Family
ID=18966456
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2001115584A Expired - Lifetime JP4738622B2 (en) | 2001-04-13 | 2001-04-13 | Heat resistant resin composition, prepreg and laminate using the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4738622B2 (en) |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003018675A1 (en) * | 2001-08-31 | 2003-03-06 | Sumitomo Bakelite Company Limited | Resin composition, prepreg, laminated sheet and semiconductor package |
| WO2004029127A1 (en) * | 2002-09-30 | 2004-04-08 | Hitachi Chemical Co., Ltd. | Resin composition for printed wiring board, and vanish, prepreg and metal-clad laminate using same |
| JP2005248147A (en) * | 2004-02-04 | 2005-09-15 | Hitachi Chem Co Ltd | Thermosetting resin composition, and prepreg, metal-laminated lamination plate and printed wire board using the same |
| WO2006090662A1 (en) * | 2005-02-25 | 2006-08-31 | Nippon Kayaku Kabushiki Kaisha | Epoxy resin, hardenable resin composition containing the same and use thereof |
| JP2008074934A (en) * | 2006-09-20 | 2008-04-03 | Mitsubishi Gas Chem Co Inc | Manufacturing method of prepreg |
| JP2008088400A (en) * | 2006-02-24 | 2008-04-17 | Mitsubishi Gas Chem Co Inc | Resin composition, prepreg and metal foil-clad laminate |
| JP2009155654A (en) * | 2009-04-03 | 2009-07-16 | Hitachi Chem Co Ltd | Thermosetting resin composition, and prepreg, metal-clad laminate, and printed wiring board, using the same |
| JPWO2008126825A1 (en) * | 2007-04-10 | 2010-07-22 | 住友ベークライト株式会社 | Resin composition, prepreg, laminate, multilayer printed wiring board, and semiconductor device |
| JP2011006683A (en) * | 2004-02-04 | 2011-01-13 | Hitachi Chem Co Ltd | Thermosetting resin composition and prepreg, metal-clad laminate, printed wiring board using the same |
| US7968672B2 (en) | 2005-11-30 | 2011-06-28 | Nippon Kayaku Kabushiki Kaisha | Phenolic resin, process for production thereof, epoxy resin, and use thereof |
| KR101047924B1 (en) | 2007-12-28 | 2011-07-08 | 주식회사 엘지화학 | Curing composition and cured product prepared using the same |
| WO2012018126A1 (en) | 2010-08-06 | 2012-02-09 | 日立化成工業株式会社 | Process for producing compatibilized resin, thermosetting resin composition, prepreg, and laminate |
| JP2013010970A (en) * | 2012-10-16 | 2013-01-17 | Mitsubishi Gas Chemical Co Inc | Method for producing prepreg |
-
2001
- 2001-04-13 JP JP2001115584A patent/JP4738622B2/en not_active Expired - Lifetime
Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003018675A1 (en) * | 2001-08-31 | 2003-03-06 | Sumitomo Bakelite Company Limited | Resin composition, prepreg, laminated sheet and semiconductor package |
| US7816430B2 (en) | 2002-09-30 | 2010-10-19 | Hitachi Chemical Company, Ltd. | Composition of polycyanate ester and biphenyl epoxy resin |
| WO2004029127A1 (en) * | 2002-09-30 | 2004-04-08 | Hitachi Chemical Co., Ltd. | Resin composition for printed wiring board, and vanish, prepreg and metal-clad laminate using same |
| JPWO2004029127A1 (en) * | 2002-09-30 | 2006-01-26 | 日立化成工業株式会社 | Resin composition for printed wiring board and varnish, prepreg and metal-clad laminate using the same |
| JP4639806B2 (en) * | 2002-09-30 | 2011-02-23 | 日立化成工業株式会社 | Resin composition for printed wiring board and varnish, prepreg and metal-clad laminate using the same |
| JP2011006685A (en) * | 2002-09-30 | 2011-01-13 | Hitachi Chem Co Ltd | Resin composition for printed wiring board, and vanish, prepreg and metal-clad laminated sheet using the same |
| JP2005248147A (en) * | 2004-02-04 | 2005-09-15 | Hitachi Chem Co Ltd | Thermosetting resin composition, and prepreg, metal-laminated lamination plate and printed wire board using the same |
| JP2011006683A (en) * | 2004-02-04 | 2011-01-13 | Hitachi Chem Co Ltd | Thermosetting resin composition and prepreg, metal-clad laminate, printed wiring board using the same |
| WO2006090662A1 (en) * | 2005-02-25 | 2006-08-31 | Nippon Kayaku Kabushiki Kaisha | Epoxy resin, hardenable resin composition containing the same and use thereof |
| JP5180583B2 (en) * | 2005-02-25 | 2013-04-10 | 日本化薬株式会社 | Epoxy resin, curable resin composition containing the same, and use thereof |
| US7968672B2 (en) | 2005-11-30 | 2011-06-28 | Nippon Kayaku Kabushiki Kaisha | Phenolic resin, process for production thereof, epoxy resin, and use thereof |
| JP2008088400A (en) * | 2006-02-24 | 2008-04-17 | Mitsubishi Gas Chem Co Inc | Resin composition, prepreg and metal foil-clad laminate |
| JP2008074934A (en) * | 2006-09-20 | 2008-04-03 | Mitsubishi Gas Chem Co Inc | Manufacturing method of prepreg |
| JPWO2008126825A1 (en) * | 2007-04-10 | 2010-07-22 | 住友ベークライト株式会社 | Resin composition, prepreg, laminate, multilayer printed wiring board, and semiconductor device |
| US8294268B2 (en) | 2007-04-10 | 2012-10-23 | Sumitomo Bakelite Company, Ltd. | Resin composition, prepreg, laminated board, multilayer printed wiring board and semiconductor device |
| KR101047924B1 (en) | 2007-12-28 | 2011-07-08 | 주식회사 엘지화학 | Curing composition and cured product prepared using the same |
| JP2009155654A (en) * | 2009-04-03 | 2009-07-16 | Hitachi Chem Co Ltd | Thermosetting resin composition, and prepreg, metal-clad laminate, and printed wiring board, using the same |
| WO2012018126A1 (en) | 2010-08-06 | 2012-02-09 | 日立化成工業株式会社 | Process for producing compatibilized resin, thermosetting resin composition, prepreg, and laminate |
| JP2013010970A (en) * | 2012-10-16 | 2013-01-17 | Mitsubishi Gas Chemical Co Inc | Method for producing prepreg |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4738622B2 (en) | 2011-08-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4738622B2 (en) | Heat resistant resin composition, prepreg and laminate using the same | |
| JP4159902B2 (en) | Resin composition, prepreg and laminate | |
| JP3592056B2 (en) | Epoxy resin composition, prepreg and laminate | |
| JP4783988B2 (en) | Heat resistant resin composition, prepreg and laminate using the same | |
| JP3981251B2 (en) | Heat resistant resin composition, prepreg and laminate using the same | |
| JP2003238681A (en) | Resin composition, prepreg, and laminate | |
| EP2103652A1 (en) | Resin composition, prepreg and laminate | |
| JP2002226680A (en) | Heat resistant resin composition and prepreg and laminate each using the same | |
| JP2007254746A (en) | Heat resistant resin composition, prepreg and laminated board made by using it | |
| JP4736367B2 (en) | Resin composition, prepreg and laminate | |
| JP3529088B2 (en) | Epoxy resin composition, prepreg and laminate using the same | |
| JP2004018615A (en) | Resin composition, prepreg and laminate | |
| JP2002179790A (en) | Heat resistant resin composition and prepreg and laminate using the composition | |
| JP2003221457A (en) | Resin composition, prepreg and laminate | |
| JP2004224817A (en) | Resin composition and prepreg and laminated sheet using the same | |
| JP5098226B2 (en) | Metal-clad laminate | |
| JP2003020327A (en) | Resin composition, prepreg and laminate using it | |
| JP4742426B2 (en) | Heat resistant resin composition, prepreg and laminate using the same | |
| JP2006307227A (en) | Heat-resistant resin composition, prepreg and laminate using the same | |
| JP2004059836A (en) | Resin composition, prepreg and laminated sheet | |
| JP3326862B2 (en) | Manufacturing method of prepreg | |
| JP4496591B2 (en) | Epoxy resin composition, prepreg and laminate using the same | |
| JP2003128765A (en) | Heat-resistant resin composition, prepreg using the same and laminate | |
| JP5292942B2 (en) | Circuit board resin composition, prepreg and laminate | |
| JP2004067968A (en) | Resin composition, prepreg, and laminated plate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20040406 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20060301 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20060314 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20060515 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20060607 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20070508 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20070709 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20071009 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20071206 |
|
| A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20080311 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20080507 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20080523 |
|
| A911 | Transfer to examiner for re-examination before appeal (zenchi) |
Free format text: JAPANESE INTERMEDIATE CODE: A911 Effective date: 20080623 |
|
| A912 | Re-examination (zenchi) completed and case transferred to appeal board |
Free format text: JAPANESE INTERMEDIATE CODE: A912 Effective date: 20080711 |
|
| RD02 | Notification of acceptance of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7422 Effective date: 20090817 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20110427 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 4738622 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140513 Year of fee payment: 3 |
|
| EXPY | Cancellation because of completion of term |