JPH0455462A - Phenolic resin composition for laminate - Google Patents
Phenolic resin composition for laminateInfo
- Publication number
- JPH0455462A JPH0455462A JP16645190A JP16645190A JPH0455462A JP H0455462 A JPH0455462 A JP H0455462A JP 16645190 A JP16645190 A JP 16645190A JP 16645190 A JP16645190 A JP 16645190A JP H0455462 A JPH0455462 A JP H0455462A
- Authority
- JP
- Japan
- Prior art keywords
- phenolic resin
- resin composition
- amine
- epoxy resin
- curing agent
- 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
- 239000005011 phenolic resin Substances 0.000 title claims abstract description 29
- 239000000203 mixture Substances 0.000 title claims abstract description 26
- 229920001568 phenolic resin Polymers 0.000 title claims abstract description 20
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 239000003822 epoxy resin Substances 0.000 claims abstract description 12
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 12
- 150000001412 amines Chemical class 0.000 claims abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
- 239000003063 flame retardant Substances 0.000 claims abstract description 9
- 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 abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 8
- 125000005270 trialkylamine group Chemical group 0.000 abstract description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 abstract 3
- 239000004593 Epoxy Substances 0.000 abstract 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract 1
- 125000003700 epoxy group Chemical group 0.000 abstract 1
- 229910052739 hydrogen Inorganic materials 0.000 abstract 1
- 239000001257 hydrogen Substances 0.000 abstract 1
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 239000002966 varnish Substances 0.000 description 4
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical class C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 3
- 239000000123 paper Substances 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- -1 amine compounds Chemical class 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 125000005265 dialkylamine group Chemical group 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000002655 kraft paper Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 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 1
- 239000002383 tung oil 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
- H05K1/032—Organic insulating material consisting of one material
- H05K1/0326—Organic insulating material consisting of one material containing O
Landscapes
- Reinforced Plastic Materials (AREA)
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
- Paints Or Removers (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
この発明は、積層板用フェノール樹脂組成物に関するも
のである。さらに詳しくは、この発明は、耐水性、耐湿
性および耐熱性を向上させることのできる、紙・フェノ
ール樹脂積層板等に有用なフェノール樹脂組成物に関す
るものである。DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) This invention relates to a phenolic resin composition for laminates. More specifically, the present invention relates to a phenolic resin composition useful for paper/phenolic resin laminates, etc., which can improve water resistance, moisture resistance, and heat resistance.
（従来の技術）
従来より、電気・電子機器等に用いられ配線板用の積層
板として、紙基材等にフェノール樹脂を含浸させたフェ
ノール樹脂積層板が知られている。(Prior Art) Phenol resin laminates, in which a paper base material or the like is impregnated with phenol resin, have been known as laminates for wiring boards used in electrical and electronic devices.
これら積層板、たとえば紙・フェノール樹脂積層板用の
フェノール樹脂組成物には、通常、反応型難燃剤として
臭素化エポキシ樹脂が配合され、その耐熱性の向上を図
ってもいる。The phenolic resin compositions for these laminates, such as paper/phenolic resin laminates, usually contain a brominated epoxy resin as a reactive flame retardant to improve their heat resistance.
（発明が解決しようとする課題）
しかしながら、従来の積層板用フェノール樹脂の場合に
は、他の充填材等とともに添加配合する上記の反応型難
燃剤としての臭素化エポキシ樹脂の反応が必ずしも充分
でなく、未反応成分として残存してしまうという欠点が
あった。このため、残存する臭素化エポキシ樹脂が、配
線板用積層板の特性に悪影響を及ぼし、特に、耐湿性、
耐水性、耐熱性等を低下させるという問題が避けられな
かった。(Problem to be solved by the invention) However, in the case of conventional phenolic resins for laminates, the reaction of the brominated epoxy resin as a reactive flame retardant added and blended with other fillers etc. is not necessarily sufficient. However, there was a drawback that it remained as an unreacted component. Therefore, the remaining brominated epoxy resin has a negative effect on the properties of the wiring board laminate, especially its moisture resistance and
The problem of deterioration of water resistance, heat resistance, etc. was unavoidable.
この発明は、このような事情に鑑みてなされたものであ
り、従来の積層板用フェノール樹脂組成物の欠点を改善
し、耐湿、耐水、さらに耐熱性等の特性向上を図ること
のできる新しいフェノール樹脂組成物を提供することを
目的としている。This invention was made in view of the above circumstances, and is a new phenol that can improve the shortcomings of conventional phenolic resin compositions for laminates and improve properties such as moisture resistance, water resistance, and heat resistance. The purpose is to provide a resin composition.
（課題を解決するための手段）
この発明は、上記の課題を解決するものとして、反応型
難燃剤としての臭素化エポキシ樹脂を含有するフェノー
ル樹脂組成物に、アミン系エポキシ樹脂硬化剤を配合し
てなることを特徴とする積層板用フェノール樹脂組成物
を提供する。(Means for Solving the Problems) This invention solves the above problems by blending an amine-based epoxy resin curing agent into a phenol resin composition containing a brominated epoxy resin as a reactive flame retardant. A phenolic resin composition for laminates is provided.
（作 用）
この発明の積層板用のフェノール樹脂組成物においては
、反応型難燃剤としての臭素化エポキシ樹脂を充分に反
応硬化させるためのアミン系硬化剤を添加配合するため
、この添加によって樹脂の架橋密度が向上し、配線板用
積層板の耐湿性、耐水性、耐熱性が大きく向上する。(Function) In the phenolic resin composition for laminates of the present invention, an amine curing agent is added to sufficiently reaction-cure the brominated epoxy resin as a reactive flame retardant. The crosslinking density of the laminate is improved, and the moisture resistance, water resistance, and heat resistance of the laminate for wiring boards are greatly improved.
〈実施例）
以下、実施例を示し、さらに詳しくこの発明のフェノー
ル樹脂組成物について説明する。<Examples> Hereinafter, the phenol resin composition of the present invention will be described in more detail with reference to Examples.
ベース樹脂としてのフェノール樹脂としては、これまで
に知られている各種のものが使用でき、フェノール、レ
ゾルシン、クレゾール等を原料とした種々の樹脂を用い
ることができる。臭素化エポキシ樹脂についても同様で
ある。As the phenol resin as the base resin, various known ones can be used, and various resins made from phenol, resorcinol, cresol, etc. can be used. The same applies to brominated epoxy resins.
フェノール樹脂に対して、この反応型難燃剤としての臭
素化エポキシ樹脂は、その重量比として、フェノール樹
脂量に対して１００ ： １０〜１００：５０程度の割
合で使用することができる。このような割合で配合する
臭素化エポキシ樹脂については、上記した通りのアミン
系硬化剤を、アミンの活性水素／エポキシ基のモル比が
１．０以下の割合で添加するのが一般的に好ましい。The brominated epoxy resin as a reactive flame retardant can be used in a weight ratio of about 100:10 to 100:50 to the amount of phenol resin. For brominated epoxy resins blended in such proportions, it is generally preferable to add the amine-based curing agent as described above at a ratio where the molar ratio of amine active hydrogen/epoxy group is 1.0 or less. .
この場合のアミン系硬化剤としては、アルキルアミン、
ジアルキルアミン、トリアルキルアミン、アルキルボリ
アミシ、イミダゾール類、トリアゾール類、その他各種
のアミン化合物を用いることができる。In this case, the amine curing agent includes alkylamine,
Dialkylamines, trialkylamines, alkylboriamic acids, imidazoles, triazoles, and other various amine compounds can be used.
もちろん、この発明は、さらに他の、トリフェニルフォ
スフェートや酸化アンチモン等の難燃剤、無機充填材、
その他の各種の添加剤を適宜に配合したフェノール樹脂
組成物をも対象とすることができる。Of course, this invention also includes other flame retardants such as triphenyl phosphate and antimony oxide, inorganic fillers,
Phenol resin compositions suitably blended with various other additives can also be used.
以下、この発明の組成物について具体的に説明する。The composition of the present invention will be specifically explained below.
実施例１〜５
（Ａ）ベース樹脂の合成
攪拌機、冷却器、温度計を備えた５ｊのフラスコに桐油
１，２００ ｇ、フェノール１，５００ｇ、パラトルエ
ンスルホン酸８ｇを配合し、８０℃の温度で２時間反応
させた。Examples 1 to 5 (A) Synthesis of base resin 1,200 g of tung oil, 1,500 g of phenol, and 8 g of p-toluenesulfonic acid were mixed into a 5J flask equipped with a stirrer, a cooler, and a thermometer, and the mixture was heated to a temperature of 80°C. The mixture was allowed to react for 2 hours.
次いで、この反応液に５０％ホルマリン９０Ｇ 、、２
５％アンモニア水５０ｍ１を加え、８０℃の温度で４時
間反応させた。Next, 50% formalin 90G was added to this reaction solution.
50 ml of 5% aqueous ammonia was added, and the mixture was reacted at a temperature of 80° C. for 4 hours.
縮合水を留去し、反応物の１６０℃熱盤上でのゲルタイ
ムが２分となった点を終点とし、ベース樹脂とした。The condensation water was distilled off, and the point at which the reaction product gelled for 2 minutes on a 160° C. heating plate was defined as the end point, and a base resin was obtained.
（Ｂ）フェノール樹脂ワニスの配合
上記の方法によって製造したフェノール樹脂を用い、臭
素化エポキシ樹脂をはじめとする難燃剤、およびアミン
系硬化剤を含有する５種の組成物を調整して樹脂ワニス
とした。(B) Formulation of phenolic resin varnish Using the phenolic resin produced by the method described above, five types of compositions containing flame retardants including brominated epoxy resins and amine curing agents were prepared to form a resin varnish. did.
その配合割合を示したものが表１である。Table 1 shows the blending ratio.
なお、比較のためにアミン系硬化剤を含有しないものに
ついてもワニスを訳整した。For comparison, varnishes that do not contain amine hardeners were also prepared.
（Ｃ） 積層板の製造
表１の配合のフェノール樹脂ワニスについて、その各々
をクラフト紙に含浸し、樹脂含有量５０％のプリプレグ
とした。(C) Production of laminates Kraft paper was impregnated with each of the phenolic resin varnishes having the formulations shown in Table 1 to prepare prepregs with a resin content of 50%.
このプリプレグ８枚と接着剤付銅箔を上下１枚づつ重ね
合せ、所定の温度、圧力で成形し、厚さ１．６ ｗｍの
銅張積層板を製造した。Eight sheets of this prepreg and one sheet of adhesive-coated copper foil were stacked one on top of the other, and molded at a predetermined temperature and pressure to produce a copper-clad laminate having a thickness of 1.6 wm.
温度は１３０〜１８０℃、圧カフ０〜１５０眩／−の範
囲としな。The temperature should be in the range of 130 to 180°C, and the pressure cuff should be in the range of 0 to 150 dazzles/-.
（Ｄ＞特性の評価
上記方法により製造した積層板について、耐熱限界温度
と、吸水率および吸湿性について評価した。その結果を
示したものが表２である。この表２から明らかなように
、この発明のフェノール樹脂組成物から製造した積層板
の場合には、いずれの特性も大きく向上していることが
確認された。(D> Evaluation of Properties The laminates produced by the above method were evaluated for heat resistance limit temperature, water absorption rate, and hygroscopicity. Table 2 shows the results. As is clear from Table 2, In the case of the laminate produced from the phenolic resin composition of the present invention, it was confirmed that all properties were greatly improved.
（発明の効果）
以上詳しく説明した通り、この発明のフェノール樹脂組
成物により、耐湿性、耐水性、そして耐熱性を大きく向
上させることのできるプリント配線板用の積層板が得ら
れる。(Effects of the Invention) As explained in detail above, the phenol resin composition of the present invention provides a laminate for printed wiring boards that can greatly improve moisture resistance, water resistance, and heat resistance.
Claims (2)
するフェノール樹脂組成物に、アミン系エポキシ樹脂硬
化剤を配合してなることを特徴とする積層板用フェノー
ル樹脂組成物。(1) A phenolic resin composition for a laminate, comprising a phenol resin composition containing a brominated epoxy resin as a reactive flame retardant, and an amine-based epoxy resin curing agent.
のフェノール樹脂組成物。(2) A phenolic resin composition for a paper/phenolic resin laminate according to claim (1).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2166451A JPH07119354B2 (en) | 1990-06-25 | 1990-06-25 | Phenolic resin composition for laminated board |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2166451A JPH07119354B2 (en) | 1990-06-25 | 1990-06-25 | Phenolic resin composition for laminated board |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0455462A true JPH0455462A (en) | 1992-02-24 |
| JPH07119354B2 JPH07119354B2 (en) | 1995-12-20 |
Family
ID=15831650
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2166451A Expired - Fee Related JPH07119354B2 (en) | 1990-06-25 | 1990-06-25 | Phenolic resin composition for laminated board |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07119354B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| USH1975H1 (en) | 1999-09-23 | 2001-07-03 | General Electric Co. | Thermoplastic article having a metallic flake appearance |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60260618A (en) * | 1984-06-06 | 1985-12-23 | Toshiba Chem Corp | Flame-retarding epoxy resin composition |
-
1990
- 1990-06-25 JP JP2166451A patent/JPH07119354B2/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60260618A (en) * | 1984-06-06 | 1985-12-23 | Toshiba Chem Corp | Flame-retarding epoxy resin composition |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| USH1975H1 (en) | 1999-09-23 | 2001-07-03 | General Electric Co. | Thermoplastic article having a metallic flake appearance |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH07119354B2 (en) | 1995-12-20 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |