JP4997664B2 - Flame retardant resin composition, prepreg and laminate using the same - Google Patents
Flame retardant resin composition, prepreg and laminate using the same Download PDFInfo
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- JP4997664B2 JP4997664B2 JP2001001995A JP2001001995A JP4997664B2 JP 4997664 B2 JP4997664 B2 JP 4997664B2 JP 2001001995 A JP2001001995 A JP 2001001995A JP 2001001995 A JP2001001995 A JP 2001001995A JP 4997664 B2 JP4997664 B2 JP 4997664B2
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- 239000003063 flame retardant Substances 0.000 title claims description 22
- 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 title claims description 20
- 239000011342 resin composition Substances 0.000 title claims description 17
- 229920005989 resin Polymers 0.000 claims description 35
- 239000011347 resin Substances 0.000 claims description 35
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 claims description 19
- 229920003986 novolac Polymers 0.000 claims description 18
- 239000004695 Polyether sulfone Substances 0.000 claims description 15
- 229920006393 polyether sulfone Polymers 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000003825 pressing Methods 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 description 13
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 7
- 229910052698 phosphorus Inorganic materials 0.000 description 7
- 239000011574 phosphorus Substances 0.000 description 7
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 6
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 6
- 229910052794 bromium Inorganic materials 0.000 description 6
- 239000011889 copper foil Substances 0.000 description 5
- 239000004744 fabric Substances 0.000 description 5
- 229910000679 solder Inorganic materials 0.000 description 5
- 239000002966 varnish Substances 0.000 description 5
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-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
- 239000011521 glass Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- LIAWCKFOFPPVGF-UHFFFAOYSA-N 2-ethyladamantane Chemical compound C1C(C2)CC3CC1C(CC)C2C3 LIAWCKFOFPPVGF-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 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 2
- SZKXDURZBIICCF-UHFFFAOYSA-N cobalt;pentane-2,4-dione Chemical compound [Co].CC(=O)CC(C)=O SZKXDURZBIICCF-UHFFFAOYSA-N 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- -1 curing accelerators Substances 0.000 description 2
- TXCDCPKCNAJMEE-UHFFFAOYSA-N dibenzofuran Chemical compound C1=CC=C2C3=CC=CC=C3OC2=C1 TXCDCPKCNAJMEE-UHFFFAOYSA-N 0.000 description 2
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 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
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000006243 chemical reaction 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
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229940120693 copper naphthenate Drugs 0.000 description 1
- SEVNKWFHTNVOLD-UHFFFAOYSA-L copper;3-(4-ethylcyclohexyl)propanoate;3-(3-ethylcyclopentyl)propanoate Chemical compound [Cu+2].CCC1CCC(CCC([O-])=O)C1.CCC1CCC(CCC([O-])=O)CC1 SEVNKWFHTNVOLD-UHFFFAOYSA-L 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- SGGOJYZMTYGPCH-UHFFFAOYSA-L manganese(2+);naphthalene-2-carboxylate Chemical compound [Mn+2].C1=CC=CC2=CC(C(=O)[O-])=CC=C21.C1=CC=CC2=CC(C(=O)[O-])=CC=C21 SGGOJYZMTYGPCH-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000000465 moulding Methods 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
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000013034 phenoxy resin Substances 0.000 description 1
- 229920006287 phenoxy resin Polymers 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 229920003208 poly(ethylene sulfide) Polymers 0.000 description 1
- 238000000197 pyrolysis Methods 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
- 238000003860 storage Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 238000005829 trimerization reaction Methods 0.000 description 1
- 239000002699 waste material Substances 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
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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- Reinforced Plastic Materials (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、ハロゲン系難燃剤、リン系難燃剤を使用しなくても優れた難燃性を有する樹脂組成物、プリプレグ及び積層板に関するものである。本発明の樹脂組成物、プリプレグ及び積層板は、例えば、回路基板の用途に好適に用いられる。
【０００２】
【従来の技術】
熱硬化性樹脂はその優れた特性から電気及び電子機器部品等に広く使用されており、火災に対する安全性を確保するため難燃性が付与されている場合が多い。これらの樹脂の難燃化はハロゲン含有化合物（特に、臭素含有化合物）を用いることが一般的であった。臭素含有化合物は高度な難燃性を有するが、芳香族臭素含有化合物は熱分解で腐食性の臭素、臭化水素を分離するだけでなく、酸素存在下で分解した場合に毒性の高いポリブロモジベンゾフラン、及びポリジブロモベンゾオキシンを形成する可能性がある。また、臭素を含有する老朽廃材の処分は極めて困難である。このような理由から臭素含有化合物に代わる難燃剤としてリン含有化合物や窒素含有化合物が検討されている。リン含有化合物には、トリフェニルホスフェート、クレジルジフェニルホスフェート、赤リン等が挙げられ、窒素含有化合物には、メラミン、グアニジン等が挙げられる。
【０００３】
しかし、トリフェニルホスフェート、クレジルジフェニルホスフェート、赤リン等のリン含有化合物は毒性が高いものも多く、埋め立て処分が困難な場合もある。また、燃焼時にホスフィンガスの発生も懸念されており、安全性に疑問が生じている。従って、リン含有化合物も使用しないで難燃性を向上することが要求されている。また、メラミン、グアニジン等の窒素含有化合物単独では、難燃性が不十分であった。
【０００４】
【発明が解決しようとする課題】
本発明の課題は、ハロゲン系難燃剤、リン系難燃剤を使用しなくても優れた難燃性を有する難燃性樹脂組成物、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。
【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）で表されるノボラックシアネート樹脂、
【化２】
（Ｂ）ポリエーテルスルホン樹脂
を必須成分としてなる難燃性樹脂組成物を基材に含浸させてなるプリプレグを１枚又は２枚以上重ね合わせ加熱加圧してなる銅張積層板であって、前記（Ｂ）ポリエーテルスルホン樹脂を、難燃性樹脂組成物成分１００重量部中、１０〜５０重量部含有することを特徴とする銅張積層板。
【０００６】
【発明の実施の形態】
本発明の難燃性樹脂組成物では、下記一般式（Ｉ）で表されるノボラックシアネート樹脂を用いることを特徴とする。
【化３】
ノボラックシアネート樹脂は硬化反応によって難燃効果の大きいトリアジン環を生じるため難燃性に優れているからである。また、ノボラックシアネート樹脂は芳香環含有率も高く、ガラス転移温度も高いため、特に難燃剤を使用しなくても十分な難燃性を有するからである。
本発明で用いるノボラックシアネート樹脂には、前記一般式（１）においてｎ＝２〜１０のプレポリマーを用いても構わない。
また、ノボラックシアネート樹脂とプレポリマーを併用しても構わない。プレポリマーを併用することで流動性が向上するからである。ノボラックシアネート樹脂にプレポリマーを併用する場合、プレポリマーはノボラックシアネート樹脂の３０％以下が樹脂の流動性が特に向上する点で好ましい。
プレポリマー化は、通常加熱溶融して行われる。
ノボラックシアネート樹脂は樹脂成分１００重量部中、５０〜９０重量部が好ましい。５０重量部未満では耐熱性が十分でなく、また９０重量部を越えると銅箔との密着性が悪化し好ましくない。
【０００７】
本発明の難燃性樹脂組成物では、ポリエーテルスルホン樹脂（以下、ＰＥＳと略す）を前記ノボラックシアネート樹脂と併用することを特徴とする。
芳香環含有率が高いＰＥＳは、十分な難燃性を有している。また、ＰＥＳは分子中に硫黄原子を含み、銅箔との密着性に優れている。そして、前記ノボラックシアネート樹脂とＰＥＳとを併用することで、両樹脂のそれぞれの特性が発現する、即ち、高度の難燃性を有し、かつノボラックシアネート樹脂単独では不十分であった銅箔との密着性を顕著に向上させることができる。更に、高いガラス転移点を有するＰＥＳは、ノボラックシアネート樹脂と併用しても、樹脂の耐熱性を低下させることがない。
【０００８】
本発明で用いるＰＥＳは、分子量５，０００〜１００，０００が好ましく、更に好ましくは、８，０００〜１５，０００である。分子量が５，０００未満であると密着性向上の効果が十分でない傾向があり、１００，０００を越えるとプリプレグ製造時の含浸性が悪化する傾向がある。
ＰＥＳは樹脂成分１００重量部中、１０〜５０重量部が好ましい。１０重量部未満では密着性が十分でなく、また５０重量部を越えると耐熱性が悪化し好ましくない。更に好ましくは、１５〜３０重量部である。かかる範囲で難燃性を維持したまま、樹脂組成物と銅箔との密着性が顕著に向上するからである。
【０００９】
本発明では、前記の難燃性樹脂組成物を基材に含浸させてプリプレグを得ることを特徴とする。本発明で得られるプリプレグは、良好な成形性と長期保存性を有する。ここで、基材は特に限定されるものではなく、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を使用することができる。これらの中でもガラス織布が強度、低吸水率の点で好ましい。
本発明の難燃性樹脂組成物を、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される。用いられる溶剤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。
【００１０】
本発明では、例えば、得られた難燃性樹脂組成物を溶剤に溶解して得られるワニスを基材に塗布、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。
本発明では、前記プリプレグを１枚又は２枚以上重ね合わせ加熱加圧して難燃性積層板又は銅張積層板を得ることを特徴とする。本発明においてプリプレグを加熱加圧する条件は、通常の積層板等を成形する条件を用いることができる。
【００１１】
本発明の難燃性樹脂組成物は、上述したノボラックシアネート樹脂とポリエーテルスルホン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、その他の成分を添加することは差し支えない。硬化促進剤として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、ナフテン酸亜鉛等の亜鉛含有化合物、ナフテン酸マンガン等のマンガン含有化合物、ナフテン酸銅等の銅含有化合物が好ましい。
【００１２】
【実施例】
以下、本発明の実施例を説明する。
【００１３】
（実施例１）
フェノールノボラックシアネート樹脂（軟化点６０℃、ロンザ社製ＰＴ−６０）８０重量部、ポリエーテルスルホン樹脂（住友化学社製スミカエクセル５００３Ｐ）２０重量部、コバルトアセチルアセトン錯体０．０８重量部にジメチルホルムアミドを加え、不揮発分濃度６０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。
【００１４】
（実施例２〜３、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。
【００１５】
得られた銅張積層板については半田耐熱性およびピール強度を測定した。半田耐熱性、ピール強度についてはＪＩＳ Ｃ ６４８１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ＵＬ−９４規格に従い垂直法により評価した。評価結果を表１に示す。実施例で得られた銅張積層板はいずれも、耐燃性、半田耐熱性、密着性にすぐれていることがわかる。
【００１６】
【表１】
【００１７】
【表２】
【００１８】
表の注
（１）フェノールノボラックシアネート樹脂（ロンザ製 ＰＴ−６０：軟化点６０℃）
（２）フェノールノボラックシアネート樹脂（ロンザ製 ＰＴ−３０：軟化点３０℃）
（３）ポリエーテルスルホン樹脂（住友化学工業製 スミカエクセル５００３Ｐ：分子量１００００）
（４）コバルトアセチルアセトナート（コバルトアセチルアセトン錯体）
（５）ビスフェノールＡシアネート樹脂（チバガイギー製 Ｂ−４０Ｓ：プレポリマー化３量化率４０％）
（６）ビスフェノールＡフェノキシ樹脂（東都化成製 フェノトートＹＰ−５０：分子量１４０００）
【００１９】
【発明の効果】
本発明の難燃性樹脂組成物は、ハロゲン化合物、リン化合物を含有しなくとも高度な難燃性を有し、十分な密着性、耐熱性を有する熱硬化性樹脂組成物であり、特にプリント配線板用の積層板等に好適に使用されるものである。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a resin composition, a prepreg, and a laminate having excellent flame retardancy without using a halogen-based flame retardant or a phosphorus-based flame retardant. The resin composition, prepreg, and laminate of the present invention are suitably used for, for example, circuit board applications.
[0002]
[Prior art]
Thermosetting resins are widely used in electrical and electronic equipment parts due to their excellent characteristics, and are often provided with flame retardancy in order to ensure safety against fire. In general, flame retardants for these resins use halogen-containing compounds (particularly bromine-containing compounds). Bromine-containing compounds have a high degree of flame retardancy, but aromatic bromine-containing compounds not only separate bromine and hydrogen bromide that are thermally decomposed by pyrolysis, but are also highly toxic polybromo when decomposed in the presence of oxygen. Dibenzofuran and polydibromobenzoxine can be formed. Also, it is extremely difficult to dispose of obsolete waste containing bromine. For these reasons, phosphorus-containing compounds and nitrogen-containing compounds have been studied as flame retardants to replace bromine-containing compounds. Examples of phosphorus-containing compounds include triphenyl phosphate, cresyl diphenyl phosphate, and red phosphorus. Examples of nitrogen-containing compounds include melamine and guanidine.
[0003]
However, many phosphorus-containing compounds such as triphenyl phosphate, cresyl diphenyl phosphate, and red phosphorus are highly toxic and may be difficult to dispose of in landfills. There is also concern about the generation of phosphine gas during combustion, raising questions about safety. Therefore, it is required to improve flame retardancy without using a phosphorus-containing compound. Moreover, the flame retardance was insufficient only with nitrogen-containing compounds such as melamine and guanidine.
[0004]
[Problems to be solved by the invention]
An object of the present invention is to provide a flame retardant resin composition having excellent flame retardancy without using a halogen flame retardant or a phosphorus flame retardant, a prepreg, and a laminate obtained from the prepreg. .
[0005]
[Means for Solving the Problems]
The present invention
(1) (A) a novolak cyanate resin represented by the following general formula (I):
[Chemical formula 2]
(B) A copper-clad laminate obtained by heating and pressing one or more prepregs obtained by impregnating a base material with a flame retardant resin composition comprising a polyethersulfone resin as an essential component, (B) A copper-clad laminate comprising 10 to 50 parts by weight of a polyethersulfone resin in 100 parts by weight of a flame retardant resin composition component .
[0006]
DETAILED DESCRIPTION OF THE INVENTION
The flame retardant resin composition of the present invention is characterized by using a novolak cyanate resin represented by the following general formula (I).
[Chemical 3]
This is because the novolak cyanate resin is excellent in flame retardancy because a triazine ring having a large flame retardant effect is produced by the curing reaction. In addition, the novolac cyanate resin has a high aromatic ring content and a high glass transition temperature, and therefore has sufficient flame retardancy even without using a flame retardant.
In the novolac cyanate resin used in the present invention, a prepolymer of n = 2 to 10 in the general formula (1) may be used.
Moreover, you may use together novolak cyanate resin and a prepolymer. It is because fluidity | liquidity improves by using a prepolymer together. When the prepolymer is used in combination with the novolak cyanate resin, the prepolymer is preferably 30% or less of the novolak cyanate resin in that the fluidity of the resin is particularly improved.
The prepolymerization is usually performed by heating and melting.
The novolak cyanate resin is preferably 50 to 90 parts by weight per 100 parts by weight of the resin component. If it is less than 50 parts by weight, the heat resistance is not sufficient, and if it exceeds 90 parts by weight, the adhesion with the copper foil is deteriorated.
[0007]
The flame retardant resin composition of the present invention is characterized in that a polyethersulfone resin (hereinafter abbreviated as PES) is used in combination with the novolac cyanate resin.
PES having a high aromatic ring content has sufficient flame retardancy. Moreover, PES contains a sulfur atom in the molecule and is excellent in adhesiveness with copper foil. And, by using the novolac cyanate resin and PES in combination, the respective characteristics of both resins are expressed, that is, copper foil having high flame retardancy and novolac cyanate resin alone is insufficient. Can be improved significantly. Furthermore, PES having a high glass transition point does not lower the heat resistance of the resin even when used in combination with a novolac cyanate resin.
[0008]
PES used in the present invention preferably has a molecular weight of 5,000 to 100,000, and more preferably 8,000 to 15,000. If the molecular weight is less than 5,000, the effect of improving the adhesion tends to be insufficient, and if it exceeds 100,000, the impregnation property during prepreg production tends to deteriorate.
PES is preferably 10 to 50 parts by weight per 100 parts by weight of the resin component. If it is less than 10 parts by weight, the adhesion is not sufficient, and if it exceeds 50 parts by weight, the heat resistance is deteriorated, which is not preferable. More preferably, it is 15-30 weight part. This is because the adhesiveness between the resin composition and the copper foil is remarkably improved while maintaining the flame retardancy within such a range.
[0009]
In the present invention, a prepreg is obtained by impregnating a base material with the flame retardant resin composition. The prepreg obtained by the present invention has good moldability and long-term storage. Here, the substrate is not particularly limited, and a glass fabric, a glass fabric, a fabric having a component other than glass, a fabric, or the like can be used. Among these, a glass woven fabric is preferable in terms of strength and low water absorption.
When the base material is impregnated with the flame retardant resin composition of the present invention, it is usually used in the form of a varnish dissolved in a solvent. Although it is desirable that the solvent used has good solubility in the composition, a poor solvent may be used as long as it does not adversely affect the composition.
[0010]
In the present invention, for example, a prepreg can be obtained by applying and impregnating a base material with a varnish obtained by dissolving the obtained flame-retardant resin composition in a solvent and drying at 80 to 200 ° C.
In the present invention, one or more prepregs are stacked and heated and pressed to obtain a flame-retardant laminate or a copper-clad laminate. In the present invention, the conditions for heating and pressurizing the prepreg may be the conditions for forming a normal laminated sheet or the like.
[0011]
The flame-retardant resin composition of the present invention contains the above-described novolak cyanate resin and polyethersulfone resin as essential components, but other resins, curing accelerators, and coupling agents within the scope not departing from the object of the present invention. It is possible to add other components. As the curing accelerator, cobalt-containing compounds such as cobalt acetylacetonate and cobalt naphthenate, zinc-containing compounds such as zinc naphthenate, manganese-containing compounds such as manganese naphthenate, and copper-containing compounds such as copper naphthenate are preferable.
[0012]
【Example】
Examples of the present invention will be described below.
[0013]
Example 1
Dimethylformamide was added to 80 parts by weight of phenol novolac cyanate resin (softening point 60 ° C., PT-60 manufactured by Lonza), 20 parts by weight of polyethersulfone resin (Sumika Excel 5003P manufactured by Sumitomo Chemical Co., Ltd.), and 0.08 parts by weight of cobalt acetylacetone complex. In addition, the varnish was adjusted to have a nonvolatile content concentration of 60% by weight.
Using this varnish, 100 parts by weight of glass fiber cloth (thickness 0.18 mm, manufactured by Nitto Boseki Co., Ltd.) was impregnated with 80 parts by weight of varnish solids, and dried in a dryer oven at 150 ° C. for 5 minutes, A prepreg having a content of 44.4% was prepared.
6 sheets of the above prepreg are stacked, and 35 μm thick electrolytic copper foils are stacked on the top and bottom. The pressure is 40 kgf / cm 2 , the temperature is 200 ° C. for 120 minutes, and the heat and pressure molding is performed at 220 ° C. for 60 minutes. A double-sided copper-clad laminate was obtained.
[0014]
(Examples 2-3 and Comparative Examples 1-3)
A double-sided copper-clad laminate was prepared in the same manner as in Example 1 except for the formulation shown in Table 1.
[0015]
The obtained copper-clad laminate was measured for solder heat resistance and peel strength. Solder heat resistance and peel strength were measured in accordance with JIS C 6481. Solder heat resistance was determined by checking for abnormal appearance after immersion in a solder bath at 260 ° C. for 120 seconds after performing a moisture absorption treatment for 2 hours at boiling. Examined. Flame retardancy was evaluated by the vertical method according to UL-94 standards. The evaluation results are shown in Table 1. It can be seen that the copper clad laminates obtained in the examples are all excellent in flame resistance, solder heat resistance, and adhesion.
[0016]
[Table 1]
[0017]
[Table 2]
[0018]
Notes to table (1) Phenol novolac cyanate resin (Lonza PT-60: softening point 60 ° C.)
(2) Phenol novolac cyanate resin (Lonza PT-30: softening point 30 ° C.)
(3) Polyether sulfone resin (Sumitomo Chemical Industries Sumika Excel 5003P: molecular weight 10,000)
(4) Cobalt acetylacetonate (cobalt acetylacetone complex)
(5) Bisphenol A cyanate resin (B-40S manufactured by Ciba Geigy: prepolymerization trimerization rate 40%)
(6) Bisphenol A phenoxy resin (manufactured by Toto Kasei Phenototo YP-50: molecular weight 14000)
[0019]
【Effect of the invention】
The flame retardant resin composition of the present invention is a thermosetting resin composition having a high degree of flame retardancy even without containing a halogen compound or a phosphorus compound, and having sufficient adhesion and heat resistance. It is suitably used for laminated boards for wiring boards.
Claims (1)
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| JP2001001995A JP4997664B2 (en) | 2001-01-10 | 2001-01-10 | Flame retardant resin composition, prepreg and laminate using the same |
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| JP2001001995A JP4997664B2 (en) | 2001-01-10 | 2001-01-10 | Flame retardant resin composition, prepreg and laminate using the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP5150991B2 (en) * | 2001-07-27 | 2013-02-27 | 住友ベークライト株式会社 | Resin composition, prepreg and circuit board |
| JP2005097524A (en) * | 2003-09-05 | 2005-04-14 | Sumitomo Bakelite Co Ltd | Resin composition, prepreg and laminate |
| US20050182203A1 (en) | 2004-02-18 | 2005-08-18 | Yuuichi Sugano | Novel cyanate ester compound, flame-retardant resin composition, and cured product thereof |
| US9169356B2 (en) | 2005-10-25 | 2015-10-27 | Mitsubishi Gas Chemical Company, Inc. | Cyanate ester polymer |
| TW201026763A (en) * | 2008-12-08 | 2010-07-16 | Albemarle Corp | Phosphorus flame retardants and applications therefor |
| US10155835B2 (en) | 2011-08-09 | 2018-12-18 | Mitsubishi Gas Chemical Company, Inc. | Cyanate ester compound and method for producing the same, and curable resin composition comprising the compound, and cured product thereof composition |
| EP2789637A4 (en) | 2011-12-07 | 2015-07-22 | Mitsubishi Gas Chemical Co | Resin composition, prepreg, and laminate |
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| EP0801110A2 (en) * | 1990-11-13 | 1997-10-15 | Ici Composites Inc. | Resin bodies comprising a combination of thermoplastic and thermoset resin |
| JPH11124433A (en) * | 1997-10-22 | 1999-05-11 | Mitsubishi Gas Chem Co Inc | Phenol novolak type cyanate prepolymer |
| JP3915853B2 (en) * | 1997-10-22 | 2007-05-16 | 三菱瓦斯化学株式会社 | Heat resistant cyanate ester coprepolymer |
| JP2002305378A (en) * | 2000-07-06 | 2002-10-18 | Sumitomo Bakelite Co Ltd | Multilayer wiring board, method for manufacturing the same, and semiconductor device |
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