JPS6333415A - Resin composition for flame-retardant laminates - Google Patents
Resin composition for flame-retardant laminatesInfo
- Publication number
- JPS6333415A JPS6333415A JP17746186A JP17746186A JPS6333415A JP S6333415 A JPS6333415 A JP S6333415A JP 17746186 A JP17746186 A JP 17746186A JP 17746186 A JP17746186 A JP 17746186A JP S6333415 A JPS6333415 A JP S6333415A
- Authority
- JP
- Japan
- Prior art keywords
- resin composition
- flame
- epoxy resin
- compound
- laminates
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000011342 resin composition Substances 0.000 title claims description 12
- 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 8
- 239000003063 flame retardant Substances 0.000 title claims description 8
- 239000003822 epoxy resin Substances 0.000 claims abstract description 10
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 10
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims abstract description 8
- 150000001875 compounds Chemical class 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 239000002075 main ingredient Substances 0.000 claims description 6
- 230000001588 bifunctional effect Effects 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims 1
- 239000000758 substrate Substances 0.000 abstract description 3
- 239000004848 polyfunctional curative Substances 0.000 abstract 2
- 239000000463 material Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 238000004080 punching Methods 0.000 description 3
- 238000005476 soldering Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 229920003986 novolac Polymers 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000002759 woven fabric Substances 0.000 description 2
- CMQUQOHNANGDOR-UHFFFAOYSA-N 2,3-dibromo-4-(2,4-dibromo-5-hydroxyphenyl)phenol Chemical compound BrC1=C(Br)C(O)=CC=C1C1=CC(O)=C(Br)C=C1Br CMQUQOHNANGDOR-UHFFFAOYSA-N 0.000 description 1
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241000257465 Echinoidea Species 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- KYPYTERUKNKOLP-UHFFFAOYSA-N Tetrachlorobisphenol A Chemical compound C=1C(Cl)=C(O)C(Cl)=CC=1C(C)(C)C1=CC(Cl)=C(O)C(Cl)=C1 KYPYTERUKNKOLP-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Landscapes
- Reinforced Plastic Materials (AREA)
- Epoxy Resins (AREA)
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は、基材への塗工作業性に優れ、かつ耐熱性、耐
衝撃性の良好な積層板を提供できる難燃性積層板用樹脂
組成物に関する。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention provides a resin composition for flame-retardant laminates that has excellent workability in coating onto base materials and can provide laminates with good heat resistance and impact resistance. relating to things.
従来の技術
電子機器の小型軽量化に伴なって、回路を形成した絶縁
基板に搭載される各種部品も、チップ部品やフラッドパ
ッケージLSIが多用されている。絶縁基板としては、
紙や布、ガラス織布、ガラス不織布等の基材に熱硬化性
樹脂を含浸乾燥しで得たプリプレグを#i層成形してな
る積層板が用いられ、前記のような状況から、積層板の
耐熱性、耐湿性、耐ミーズリング性等の特性の向上が望
まれている。2. Description of the Related Art As electronic devices become smaller and lighter, chip components and flat package LSIs are increasingly being used for various components mounted on insulating substrates on which circuits are formed. As an insulating substrate,
A laminate is used, which is formed by forming an #i layer of prepreg obtained by impregnating and drying a thermosetting resin on a base material such as paper, cloth, glass woven fabric, or glass nonwoven fabric. It is desired to improve properties such as heat resistance, moisture resistance, and measling resistance.
このようケ積層板を提供するための難燃性積層板用樹脂
組成物とし゛〔、エポキシ樹脂と2価フェノール類のハ
ロゲン化物を主剤とし、硬化剤としてフェノールノボラ
ック樹脂を配合した樹脂組成物が提案されている(特開
昭58−89614号公報)。このものは、樹脂組成物
を基材に含浸するとき、基材への濡れ性を改良して前記
各特性を満足しようとするものである。As a flame-retardant resin composition for laminates to provide such laminates, a resin composition containing an epoxy resin and a halide of dihydric phenols as main ingredients and a phenol novolak resin as a curing agent has been proposed. (Japanese Unexamined Patent Publication No. 58-89614). This is intended to improve the wettability to the base material when impregnating the resin composition into the base material, thereby satisfying each of the above-mentioned properties.
発明が解決しようとする問題点
しかし、近年、積層板には、特にフラットパッケージL
SI搭載に伴なう耐熱性の向上と共に打抜加工に伴なう
耐衝撃性の向上が望まれている。耐熱性と耐衝撃性は相
反する特性であり、両者を同時に向上させることは困難
な問題であった。Problems to be Solved by the Invention However, in recent years, laminates have been used especially for flat packages.
It is desired to improve the heat resistance associated with SI mounting as well as the impact resistance associated with punching. Heat resistance and impact resistance are contradictory properties, and it has been difficult to improve both at the same time.
本発明は、上記の点に鑑み、基材への塗工作業性、濡れ
性が良好で、耐熱性および耐衝撃性の良好な積層板を提
供できる難燃性積層板用樹脂組成物を提供するものであ
る。In view of the above points, the present invention provides a resin composition for a flame-retardant laminate that has good coating workability and wettability to a base material, and can provide a laminate with good heat resistance and impact resistance. It is something to do.
問題点を解決するための手段
上記目的を達成するために、本発明は、分子ff150
0以下の二官能エポキシ樹脂とハロゲン化ビスフェノー
ルAの混合物を主剤とし、硬化剤として次の一般式で示
される化合物■(但し、n≧1)
を配合したものである。Means for Solving the Problems In order to achieve the above objects, the present invention provides the molecule ff150
The main ingredient is a mixture of a bifunctional epoxy resin of 0 or less and halogenated bisphenol A, and a compound (2) represented by the following general formula (where n≧1) is blended as a curing agent.
作用
上記化合物Iを硬化剤として使用することにより、この
組成物を基材に含浸し乾燥する工程において、エポキシ
樹脂とハロゲン化ビスフェノールAとの反応を選択的に
行なうことができる。この結果、積層板の耐熱性、耐湿
性、耐溶剤性を向上させ、かつ硬化物の架橋密度を著し
く低下させることな(可撓性を付与できるため耐衝撃性
の向上を図ることかできる。Effect: By using the above compound I as a curing agent, the reaction between the epoxy resin and the halogenated bisphenol A can be selectively carried out in the step of impregnating the base material with this composition and drying it. As a result, the heat resistance, moisture resistance, and solvent resistance of the laminate are improved, and the crosslink density of the cured product is not significantly reduced (flexibility can be imparted, so impact resistance can be improved).
実施例
本発明に使用される二官能エポキシ樹脂は、ビスフェノ
ールA系で分子量500以下であれハ特に限定しない。Examples The bifunctional epoxy resin used in the present invention is not particularly limited as long as it is bisphenol A type and has a molecular weight of 500 or less.
ハロゲン化ビスフェノールAは、−紋穴
たはハロゲンで、少なくとも1つはハロゲン)で表わさ
れ、テトラブロモビスフェノールA。A halogenated bisphenol A is represented by a halogen or a halogen, at least one of which is a halogen, and is a tetrabromobisphenol A.
テトラクロロビスフェノールA等である。ハロゲンは、
一般にブロムである方が熱安定性がよいが−特に限定し
ない。Tetrachlorobisphenol A and the like. Halogen is
Generally, bromine has better thermal stability, but there is no particular limitation.
また、本発明の樹脂組成物は、硬化促進剤として第三級
アミン系、イミダゾール系等を併用してもよい。無機充
填剤を含ませることは、積層板の寸法安定性が良好とな
り好ましい。Furthermore, the resin composition of the present invention may also contain a tertiary amine type, imidazole type, etc. as a curing accelerator. It is preferable to include an inorganic filler because the dimensional stability of the laminate becomes good.
実施例1
二官能エポキシ樹脂(分子ff1370.エポキシ当i
dl 86) l 00重ffi部、テトラブロモビス
フェノールA40重量部を主剤とし、化合ウニ(この場
合nm2、水酸基当[161)30重量部、2−エチル
−4−メチルイミダゾール0.4重量部を配合して難燃
性積層板用樹脂組成積層し、両表面に銅箔を配置後、加
熱・加圧して1.211aw厚みの両面銅張積層板を得
た。Example 1 Bifunctional epoxy resin (molecule ff1370.epoxy
dl 86) l 00 parts by weight ffi, 40 parts by weight of tetrabromobisphenol A as main ingredients, 30 parts by weight of compound sea urchin (in this case nm2, hydroxyl group [161)], and 0.4 parts by weight of 2-ethyl-4-methylimidazole. The resin composition for a flame-retardant laminate was laminated, copper foil was placed on both surfaces, and then heated and pressed to obtain a double-sided copper-clad laminate having a thickness of 1.211 aw.
実施例2
実施例1において、化合物Iとしてnx4のものを20
重社部配合し、他は実施例1と同様にして1.2種厚み
の両面銅張積層板を得た。Example 2 In Example 1, nx4 was used as compound I at 20
A double-sided copper-clad laminate with a thickness of 1.2 was obtained in the same manner as in Example 1, except that the above ingredients were mixed.
従来例1
実施例1において、化合物Iの代りにフェノールノボラ
ック樹脂(水酸基当量103)20重it部を配合し、
他は実施例1と同様にして、1.2fl厚みの両面銅張
積層板を得た。Conventional Example 1 In Example 1, 20 parts by weight of phenol novolac resin (hydroxyl equivalent: 103) was blended instead of Compound I,
Otherwise, a double-sided copper-clad laminate having a thickness of 1.2 fl was obtained in the same manner as in Example 1.
比較例1
エポキシ当11500の難燃性エポキシ樹脂(商品名エ
ポン1045、油化シェル製)100重社部を主剤とし
、(テトラブロモビスフェノールAは配合せず)、他は
実施例1と同様にして1.2fi厚みの両面銅張積層板
を得た。Comparative Example 1 A flame-retardant epoxy resin (trade name: Epon 1045, manufactured by Yuka Shell Co., Ltd.) with an epoxy weight of 11,500% was used as the main ingredient (tetrabromobisphenol A was not blended), and the other conditions were the same as in Example 1. A double-sided copper-clad laminate having a thickness of 1.2 fi was obtained.
比較例2
二官能エポキシ樹脂(分子fi680、エポキシ当量3
40)100重量部、テトラブロモビスフェノールA4
0重量部を主剤とし、池は実施例1と同様にして1.2
闘厚みの両面銅張積層板を得た。Comparative Example 2 Bifunctional epoxy resin (molecule fi680, epoxy equivalent 3
40) 100 parts by weight, tetrabromobisphenol A4
0 parts by weight was used as the main ingredient, and the pond was prepared in the same manner as in Example 1 to 1.2 parts by weight.
A thick double-sided copper-clad laminate was obtained.
比較例3
実施例1において化合物■の代りにジシアンジアミド4
重量部を配合し、他は実施例1と同様にして1.21厚
みの両面鋼張積層板を得た。Comparative Example 3 In Example 1, dicyandiamide 4 was used instead of compound ①.
A double-sided steel clad laminate having a thickness of 1.21 mm was obtained in the same manner as in Example 1 except that the weight parts were blended.
実施例1.2、従来例1.比較例1〜31こおける積層
板の特性を第【表に示す。Example 1.2, Conventional Example 1. The properties of the laminates in Comparative Examples 1 to 31 are shown in Table 1.
第 1 表
11 含浸性ニガラス織布基材より径25mの小片を
切り出し、これを温度
20゛Cの樹脂組成物に浮かべて
完全に濡れるまでの時間を測定。Table 1: A small piece with a diameter of 25 m was cut from an impregnable Nigarasu woven fabric base material, and the time required for the piece to be completely wetted by floating it on a resin composition at a temperature of 20°C was measured.
なお、樹脂組成物中の不揮発分 含有重量は、アセトンで654 に調整した。In addition, the nonvolatile content in the resin composition Content weight is 654 in acetone Adjusted to.
*2 はんだ耐熱性:120″C12気圧の飽和水蒸気
の中で12時間処理した
後、270”Cのはんだ槽に浮か
べてフクレが発生するまでの時
間を測定。*2 Soldering heat resistance: After processing in saturated steam at 120"C and 12 atmospheres for 12 hours, float it in a soldering bath at 270"C and measure the time until blistering occurs.
木3 離燃性:UL−94法に準拠した。Wood 3 Flammability: Compliant with UL-94 law.
*4 打抜加工性: DIN規洛で使用される金型で打
抜きを行ない、クラック
の発生状態を観察。*4 Punching workability: Punching was performed using the mold used by DIN Kiraku, and the state of crack occurrence was observed.
O:クラックなし
△:クラック若干あり
×:クラックが全面にみえる
*5 耐ミーズリング性:120’C,2気圧の飽和水
蒸気の中で4時間処理し
た後、270″Cのはんだ槽に
30秒間浮かべ、ミーズリング
の発生状態をみる。O: No cracks △: Some cracks ×: Cracks visible on the entire surface *5 Measling resistance: Processed in saturated steam at 120'C and 2 atm for 4 hours, then placed in a soldering bath at 270'C for 30 seconds Float it to see if measling is forming.
○:ミーズリングなし
△:ミーズリング若干あり
×:ミーズリングが著るしい
発明の効果
第1表から明らかな様に、本発明は、塗工作業性、基材
への濡れ性が良好で、かつ耐熱性、耐衝撃性が良好な積
層板を得られる難燃性積層板用樹脂組成物を提供できる
点において、その工業的価値は甚大である。○: No measling △: Some measling present ×: Significant measling Effects of the invention As is clear from Table 1, the present invention has good coating workability and wettability to the base material. Moreover, its industrial value is enormous in that it can provide a flame-retardant resin composition for laminates that can yield laminates with good heat resistance and impact resistance.
Claims (1)
ビスフェノールAの混合物を主剤とし、硬化剤として次
の一般式で示される化合物I▲数式、化学式、表等があ
ります▼ (但し、n≧1) を配合した難燃性積層板用樹脂組成物。[Claims] Compound I, whose main ingredient is a mixture of bifunctional epoxy resin with a molecular weight of 500 or less and halogenated bisphenol A, and which is represented by the following general formula as a curing agent ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (However, A resin composition for flame-retardant laminates containing n≧1).
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP17746186A JPS6333415A (en) | 1986-07-28 | 1986-07-28 | Resin composition for flame-retardant laminates |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP17746186A JPS6333415A (en) | 1986-07-28 | 1986-07-28 | Resin composition for flame-retardant laminates |
Publications (1)
Publication Number | Publication Date |
---|---|
JPS6333415A true JPS6333415A (en) | 1988-02-13 |
Family
ID=16031337
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP17746186A Pending JPS6333415A (en) | 1986-07-28 | 1986-07-28 | Resin composition for flame-retardant laminates |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS6333415A (en) |
-
1986
- 1986-07-28 JP JP17746186A patent/JPS6333415A/en active Pending
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