JPS5869242A - Flame-retardant phenolic resin composition - Google Patents
Flame-retardant phenolic resin compositionInfo
- Publication number
- JPS5869242A JPS5869242A JP56169287A JP16928781A JPS5869242A JP S5869242 A JPS5869242 A JP S5869242A JP 56169287 A JP56169287 A JP 56169287A JP 16928781 A JP16928781 A JP 16928781A JP S5869242 A JPS5869242 A JP S5869242A
- Authority
- JP
- Japan
- Prior art keywords
- resin
- flame
- retardant
- weight
- epoxy
- 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.)
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- Compositions Of Macromolecular Compounds (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は、難燃性、耐熱性、寸法安定性及び打抜き加工
性に優れた積層板用難燃性フェノール樹脂組成物に関す
る。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a flame-retardant phenolic resin composition for laminates that has excellent flame retardancy, heat resistance, dimensional stability, and punching workability.
最近、印刷配線板の製造加工工程の大幅な進歩に伴い高
度の寸法安定性、耐熱性を備えた積層板が要望されてい
る。チップ部品搭載用積層板もその一例である。チップ
部品搭載用積層板の特性としては、その加工工程中の処
理条件を勘案すると従来品以上の耐熱性、加熱時の寸法
安定性が要求される。また、一方では、通常部品との併
用、回路の高密度化という点から、打抜加工性も要求さ
れる。さらに、最終製品の輸出依存度が大きいことより
、今後一層基板の難燃化の比率は増加するものと考えら
れる。Recently, with significant progress in the manufacturing process of printed wiring boards, there has been a demand for laminates with high dimensional stability and heat resistance. One example is a laminate for mounting chip components. Considering the processing conditions during the processing process, the characteristics of a laminate for mounting chip components are required to have better heat resistance and dimensional stability during heating than conventional products. On the other hand, punching workability is also required from the viewpoint of use with ordinary parts and high density circuits. Furthermore, given the heavy dependence on export of final products, it is thought that the proportion of flame-retardant substrates will further increase in the future.
しかし、通常、難燃性と耐熱性、寸法安定性、打抜き加
工性及び電気的緒特性、耐湿性は相反するものである。However, flame retardancy and heat resistance, dimensional stability, punching workability, electrical characteristics, and moisture resistance are usually contradictory.
基板の難燃化に従来広く用いられている方法は、難燃剤
と可塑剤を兼用させる形であり、ブロム化エポキシ樹脂
単独、ブロム化エポキシ樹脂とテトラブロモビスフェノ
ールA(以下TBAと略す)との反応物、エポキシ化植
物油とTRAの反応物等のブロム化合物と二酸化アンチ
モン併用系である。また、さらに、可塑化効果を出すた
めに、リン化合物、窒素化合物の併用系も用いられる。Conventionally widely used methods for making substrates flame retardant use both a flame retardant and a plasticizer, such as brominated epoxy resin alone, brominated epoxy resin and tetrabromobisphenol A (hereinafter abbreviated as TBA). It is a system that uses a bromine compound such as a reactant, an epoxidized vegetable oil, and a reactant of TRA in combination with antimony dioxide. Further, in order to produce a plasticizing effect, a combination system of a phosphorus compound and a nitrogen compound is also used.
しかし、従来方法の欠点は、ブロム化エポキシ樹脂を使
用する場合、反応性の高いものを利用すると、しばしば
積層板が硬く、もろくなり打抜き加工性に劣り、さらに
積層材料の可使時間が極端に短くなる傾向がある。また
、ブロム化エポキシ樹脂とTBAの反応物を使用する場
合反応が不充分であると、前記のプロふ化エポキシ樹脂
を単独で用いた場合の欠点の他に、残存するTDAによ
り、耐熱性、打抜き加工性、電気的特性、耐湿性に劣る
。そこで反応を逸め、既暴と活性エポキシ基を消失した
ものを用いると、基板中番ζ、架橋反応に関与しないま
ま残存し、単純な添加型可塑剤としての効果しか示さず
、耐熱性、耐薬品性、電気特性、寸法安定性、打抜き加
工性に劣る。However, the disadvantages of conventional methods are that the highly reactive brominated epoxy resins often result in laminates that are hard and brittle, resulting in poor die-cutting properties, and that the pot life of the laminate material is extremely short. It tends to be shorter. In addition, if the reaction is insufficient when using a reaction product of brominated epoxy resin and TBA, in addition to the disadvantages of using a brominated epoxy resin alone, residual TDA may cause heat resistance, punching, etc. Poor workability, electrical properties, and moisture resistance. If the reaction is diverted and the active epoxy groups are used, the substrate will remain uninvolved in the crosslinking reaction and will only show the effect as a simple additive plasticizer, resulting in heat resistance, Poor chemical resistance, electrical properties, dimensional stability, and punching workability.
従って、難燃性、耐熱性、寸法安定性、打抜き加工性に
ついて、総合的に向上させるためには、硬化反応の過程
で架橋反応に関与し得る活性点を持ち、かつ、未反応の
低分子物を含まない難燃性の反応型可塑剤が必要である
。Therefore, in order to comprehensively improve flame retardancy, heat resistance, dimensional stability, and punching workability, it is necessary to use low-molecular-weight molecules that have active sites that can participate in the crosslinking reaction during the curing reaction and that have unreacted Reactive plasticizers that are free of flame retardants are needed.
本発明は、以上の点よりエポキシ樹脂とTDAとの変成
反応後のブロム化エポキシ樹脂に、OH基との反応性の
よいインシネート化合物R−(CNO)nを予め反応さ
せ、これを桐油変性フェノール樹脂と混合しておくこと
により、硬化する際に、難燃剤を硬化反応番こ関与させ
、単純な添加型難燃剤となることを防ぎ、積層板の緒特
性を向上させるものである。ここで、Rは、フェニル基
、アルキル基又は水素のうちの1種又は2種以上Iこよ
り置換されたフェニレン基、′N1
ジフェニルメタン核基、又はアルキレン基を示し、nは
、2乃至4の正の整数を示す。In view of the above points, the present invention allows the brominated epoxy resin after the modification reaction between the epoxy resin and TDA to react in advance with the insinate compound R-(CNO)n, which has good reactivity with OH groups, and converts it into tung oil-modified phenol. By mixing the flame retardant with the resin, the flame retardant takes part in the curing reaction during curing, prevents the flame retardant from becoming a simple additive type flame retardant, and improves the strength properties of the laminate. Here, R represents a phenyl group, an alkyl group, a phenylene group substituted with one or more types of hydrogen, a 'N1 diphenylmethane nuclear group, or an alkylene group, and n is a positive 2 to 4 group. indicates an integer.
本発明を実施するにあたり、TEAと反応させるエポキ
シ樹脂としては、通常のビスフェノール型エポキシ樹脂
、ブロム化エポキシ樹脂、エポキシ化植物油が使用でき
る。価格の点からは、相対的1(安価で、ブロム含有率
の高い18人を多く使用することが望ましく、積層板特
性の点からは、残存TBAをできるだけ少くすることが
望ましい。従って、本発明は、18人と前記エポキシ樹
脂を充分反応させた後、エポキシ基とTBAの反応Iこ
よって生ずる分子内のOH基と1−(NCO)nを反応
させ゛1反応活性点を新しく作り出すことにより反応型
難燃性樹脂とし、桐油変性フェノール樹脂との硬化反応
薯こ関与させるものである。In carrying out the present invention, ordinary bisphenol type epoxy resins, brominated epoxy resins, and epoxidized vegetable oils can be used as the epoxy resins to be reacted with TEA. From the point of view of price, it is desirable to use a large amount of relative 1 (18, which is inexpensive and has a high bromine content), and from the point of view of laminate properties, it is desirable to reduce the residual TBA as much as possible. Therefore, the present invention After fully reacting the epoxy resin with 18 people, 1-(NCO)n was reacted with the OH group in the molecule resulting from the reaction between the epoxy group and TBA. It is a reactive flame-retardant resin that undergoes a curing reaction with tung oil-modified phenolic resin.
一般に、R−(NCO)nは、OH基との反応性に富み
、水、アルコール性OH基等と容易に反応する。触媒と
しては、第三級アミン(ベン今
ジルジメ貫ルアミン、トリエチレンシアミン等)を用い
る。R−(NCO)nを用い(あたり、NCO当量/エ
ポキシ当量比が、0.1以上であると、生成した反応型
llI燃性樹脂は常温硬化し、工業的な使用に耐えず、
また架橋密度の増加により積層板が硬くなる傾向があり
、実用上当量比(N C,O当量/エポキシ当量)で0
0.1〜005が有効である。Generally, R-(NCO)n has high reactivity with OH groups and easily reacts with water, alcoholic OH groups, and the like. As a catalyst, a tertiary amine (benzyldimetinylamine, triethylenecyamine, etc.) is used. When R-(NCO)n is used and the NCO equivalent/epoxy equivalent ratio is 0.1 or more, the generated reactive type III flammable resin hardens at room temperature and cannot withstand industrial use.
In addition, the laminate tends to become harder due to the increase in crosslinking density, and in practical terms, the equivalent ratio (NC,O equivalent/epoxy equivalent) is 0.
0.1-005 is valid.
本発明では、E記反応型lll燃性樹脂を積層板の可塑
効果より、桐油変性フェノール樹脂に配合する。その含
有量は樹脂固型換算で10〜500〜50重量部が適当
である。10重量%未満では規定の難燃効果が出ず、5
00重量部越えると積層板が硬く、もろくなり、打抜き
加工性が低下する。In the present invention, the E-reaction type lll flammable resin is blended with the tung oil-modified phenolic resin due to the plasticizing effect of the laminate. The content thereof is suitably 10 to 500 to 50 parts by weight in terms of solid resin. If it is less than 10% by weight, the specified flame retardant effect will not be achieved;
If the amount exceeds 0.00 parts by weight, the laminate will become hard and brittle, resulting in poor punching workability.
実施例1
テトラブロモビスフェノールAのジグリシジルエーテル
で、エポキシ当量400のエポキシ樹脂120重量部に
TBA80重量部を加え、トルエンで70重重量法液に
した後、この溶液にベンジルジメチルアミンを1重量部
加え90℃で6時間反応させた(フェスA)。その後、
2.4−ジイソシアン酸トリレン(以下2.4−TD■
と略す)05重量部を加え、さらに90〜゛で2時間反
応させ、160°C,でのゲル化時間8分のワニスBを
得た。Example 1 80 parts by weight of TBA was added to 120 parts by weight of an epoxy resin with an epoxy equivalent of 400 using diglycidyl ether of tetrabromobisphenol A, and the solution was made up to 70 parts by weight with toluene, and 1 part by weight of benzyldimethylamine was added to this solution. The mixture was added and reacted at 90°C for 6 hours (Fest A). after that,
2.4-Tolylene diisocyanate (hereinafter referred to as 2.4-TD■
05 parts by weight was added thereto, and the reaction was further carried out at 90°C for 2 hours to obtain varnish B having a gelation time of 8 minutes at 160°C.
一方、桐油変性フェノール樹脂は次の樺に調製した。メ
タクレゾール100重量部、桐油120重量部、パラト
ル、エンスルホン酸0.15重量部を反応容器に入れ8
0°Cで1時間反応させ、さらにフェノール90重量部
、85係パラホルムアルデヒド77重量部、25−アン
モニア水45重量部を添加し、80℃で反応を進め分子
量3000〜4000の高分子鳳声が反応物中の100
重量部達した時点で脱水を行い、樹脂固型が555重量
部なる様トルエンを加え、160℃でのゲル化時間が5
分の桐油変性フェノール樹脂ワニスを得た。On the other hand, tung oil modified phenolic resin was prepared in the following birch. Put 100 parts by weight of metacresol, 120 parts by weight of tung oil, 0.15 parts by weight of paratol and ensulfonic acid into a reaction container.
The reaction was carried out at 0°C for 1 hour, and further 90 parts by weight of phenol, 77 parts by weight of 85% paraformaldehyde, and 45 parts by weight of 25-ammonia water were added, and the reaction was continued at 80°C to form a polymer with a molecular weight of 3,000 to 4,000. 100 in the reactant
When the weight reaches 555 parts by weight, dehydration is performed, toluene is added so that the resin solid becomes 555 parts by weight, and the gelation time at 160°C is 5.
A tung oil-modified phenolic resin varnish was obtained.
その後、上記桐油変性フェノール樹脂ワニスを樹脂固型
で60重量部、前記ワニスiBlを樹脂固型で40重量
部配合して難燃性フェノール樹脂組成物を得た。これを
、厚さlOミルスのクラフト紙に含浸乾燥し、樹脂含量
500重量部プリプレグを得た。該プリプレグを9枚重
ねて圧力1000/cd、温度160℃で60分間加熱
、加圧積層成形し、厚さ16謔の積層板を得た。Thereafter, 60 parts by weight of the tung oil-modified phenolic resin varnish in solid resin form and 40 parts by weight of the varnish iBl in solid resin form were blended to obtain a flame-retardant phenol resin composition. This was impregnated into kraft paper having a thickness of 10 mils and dried to obtain a prepreg having a resin content of 500 parts by weight. Nine sheets of the prepreg were stacked and heated at a pressure of 1000/cd and a temperature of 160° C. for 60 minutes to form a laminated sheet under pressure to obtain a laminate having a thickness of 16 cm.
実施例2
エポキシ当量が250であるエポキシ化大豆油100重
量部に、TBA 100重量部を加え、トルエンで10
重量%溶液にした後、この溶液に1. s−ジアザビシ
クロ〔5,4,0)−7−ウンデセン1重量部を添加し
901゛で6時間反応させた。次いで、2.4−TDI
を0.5重量部加え、さらに90ヤで3時間反応させて
160℃でのゲル化時間9分のワニスCを得た。Example 2 To 100 parts by weight of epoxidized soybean oil with an epoxy equivalent of 250, 100 parts by weight of TBA was added, and the mixture was diluted with toluene to 100 parts by weight.
After making a weight% solution, add 1. 1 part by weight of s-diazabicyclo[5,4,0)-7-undecene was added and reacted at 901° for 6 hours. Then 2.4-TDI
0.5 part by weight was added thereto, and the mixture was further reacted at 90°C for 3 hours to obtain Varnish C having a gelation time of 9 minutes at 160°C.
実施例1で用いた桐油変性フェノール樹脂ワニス樹脂固
型で60重量部、前記ワニスCを樹脂固型で40重量部
配合して、難燃性フェノール樹脂組成物を調製し、以下
実施例1と同様に厚さ1.6mの積層板を得た。A flame-retardant phenol resin composition was prepared by blending 60 parts by weight of the tung oil-modified phenolic resin varnish resin solid used in Example 1 and 40 parts by weight of the varnish C in resin solid form. Similarly, a laminate with a thickness of 1.6 m was obtained.
比較例1
実施例1で得たワニスA(ブロム化エポキシ樹脂)を樹
脂固型で30重量部、実施例1で用いた桐油変性フェノ
ール樹脂ワニス樹脂固型で70重量部配合し、これを用
いて実施例1と同一方法で厚さ1.6111mの積層板
を得た。Comparative Example 1 Varnish A (brominated epoxy resin) obtained in Example 1 was blended with 30 parts by weight in solid resin form and 70 parts by weight in solid form of the tung oil-modified phenolic resin varnish resin used in Example 1. A laminate with a thickness of 1.6111 m was obtained in the same manner as in Example 1.
以上の実施例、比較例で得た積層板につき、特性試験を
行い第1表の結果を得た。また、実施例2で得た積層板
および比較例1で得た積層板の粘弾性特性を第1図に示
す。Characteristic tests were conducted on the laminates obtained in the above Examples and Comparative Examples, and the results shown in Table 1 were obtained. Further, the viscoelastic properties of the laminate obtained in Example 2 and the laminate obtained in Comparative Example 1 are shown in FIG.
第 1 表
第1表より、実施例1.2により作製した積層板は、比
較例の積層板より吸湿後の電気的特性、打抜き加工性、
耐熱安定性、寸法安定性に優れていることがわかる。ま
た、図の粘弾性特性より、実施例2の積層板(曲線2)
は比較例1の積層板(曲線l)のような特定の温度域を
境界としての急激な機械的性質の変化がなく、耐熱安定
性、寸法安定性を保持していることを証明している。Table 1 From Table 1, the laminate produced in Example 1.2 had better electrical properties after moisture absorption, punching workability, and better punching properties than the laminate of the comparative example.
It can be seen that it has excellent heat resistance stability and dimensional stability. Also, from the viscoelastic properties in the figure, the laminate of Example 2 (curve 2)
This proves that unlike the laminate of Comparative Example 1 (curve l), there is no sudden change in mechanical properties across a specific temperature range, and the material maintains heat resistance stability and dimensional stability. .
以上のように、本発明は、使用する離燃剤を主成分の桐
油変性フェノール樹脂の硬化反応に関与させることによ
り、単純添加型の難燃剤の欠点を克服し、広い温度範囲
にわたって、高度な品質安定性を備えた難燃性積層板を
提供できる点、その工業的価値は極めて大なるものであ
る。As described above, the present invention overcomes the drawbacks of simply added flame retardants by involving the flame retardant used in the curing reaction of the main component, tung oil-modified phenolic resin, and achieves high quality over a wide temperature range. Its industrial value is extremely great in that it can provide a flame-retardant laminate with stability.
図面は、本発明で得た積層板の自由減衰型ねじり振動法
による粘弾性特性を、比較例と共に示した曲線図である
。
特許出願人
□温叉じC)The drawing is a curve diagram showing the viscoelastic properties of the laminate obtained according to the present invention measured by a free damping type torsional vibration method together with a comparative example. Patent applicant □Warm C)
Claims (1)
キシ樹脂とテトラブロモビスフェノールムとの反応物に
、一般式R−(NGO)n(Rはフェニル基、アルキル
基、又は水素のうちの1種又は2種以上により置換され
たフェニレン基、ジフェニルメタンam、又aアルキレ
ン基を示し、nは2乃至4の正の整数を示す)で示され
る化合物を反応させて得られる反応型難燃性樹脂を桐油
変性フェノール樹脂に配合し樹脂固型換算で前記反応型
難燃性樹脂の含有量をlO〜50重量パーセントとして
なる難燃性フェノール樹脂組成物。 2 エポキシ樹脂がプロふ化エポキシ樹脂である特許請
求の範囲第1項記載の離燃性フェノール樹脂組成物。 & エポキシ樹脂が、エポキシ化植物油である特許請求
の範囲第1項記載の難燃性フェノール樹脂組成物。[Claims] 1. A reaction product of an epoxy resin having at least one epoxy group in the molecule and tetrabromobisphenol has the general formula R-(NGO)n (R is a phenyl group, an alkyl group, or a phenylene group substituted with one or more types of hydrogen, diphenylmethane am, or a alkylene group, n is a positive integer from 2 to 4) obtained by reacting the compound represented by A flame-retardant phenol resin composition comprising a reactive flame-retardant resin mixed with a tung oil-modified phenol resin so that the content of the reactive flame-retardant resin is 10 to 50 weight percent in terms of solid resin. 2. The flame-retardant phenolic resin composition according to claim 1, wherein the epoxy resin is a profluorinated epoxy resin. & The flame-retardant phenolic resin composition according to claim 1, wherein the epoxy resin is an epoxidized vegetable oil.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP56169287A JPS6033140B2 (en) | 1981-10-22 | 1981-10-22 | Flame retardant phenolic resin composition |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP56169287A JPS6033140B2 (en) | 1981-10-22 | 1981-10-22 | Flame retardant phenolic resin composition |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS5869242A true JPS5869242A (en) | 1983-04-25 |
JPS6033140B2 JPS6033140B2 (en) | 1985-08-01 |
Family
ID=15883714
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP56169287A Expired JPS6033140B2 (en) | 1981-10-22 | 1981-10-22 | Flame retardant phenolic resin composition |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS6033140B2 (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6289309U (en) * | 1985-11-26 | 1987-06-08 |
-
1981
- 1981-10-22 JP JP56169287A patent/JPS6033140B2/en not_active Expired
Also Published As
Publication number | Publication date |
---|---|
JPS6033140B2 (en) | 1985-08-01 |
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