JPH0393849A - Flame-retardant phenol resin composition - Google Patents

Flame-retardant phenol resin composition

Info

Publication number
JPH0393849A
JPH0393849A JP22922989A JP22922989A JPH0393849A JP H0393849 A JPH0393849 A JP H0393849A JP 22922989 A JP22922989 A JP 22922989A JP 22922989 A JP22922989 A JP 22922989A JP H0393849 A JPH0393849 A JP H0393849A
Authority
JP
Japan
Prior art keywords
flame
phenol resin
resin
retardant
resin composition
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
Application number
JP22922989A
Other languages
Japanese (ja)
Inventor
Yutaka Matsuda
豊 松田
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sumitomo Bakelite Co Ltd
Original Assignee
Sumitomo Bakelite Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Sumitomo Bakelite Co Ltd filed Critical Sumitomo Bakelite Co Ltd
Priority to JP22922989A priority Critical patent/JPH0393849A/en
Publication of JPH0393849A publication Critical patent/JPH0393849A/en
Pending legal-status Critical Current

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  • Compositions Of Macromolecular Compounds (AREA)

Abstract

PURPOSE:To obtain the title flame-retardant composition having excellent heat resistance providing resin laminate comprising components blended good in compatibility, having excellent electric characteristics and punchability by blending a phenol resin with a specific compound. CONSTITUTION:A phenol resin is blended with a compound shown by the formula (R1 is CH2, C2H4, C3H6, C4H8, C5H10 or C6H12; R2 is H, CH3, C2H5, C3H7, C4H9 or C5H11; X is Cl or Br; n is 1-4 and m is 1-5). The amount of the phenol resin is 3-50wt% based on the phenol resin. An adduct of dibromoisopropylphenol, dibromocresol, tribromophenol or tribromocresol with an alkylene oxide may be cited as the compound.

Description

【発明の詳細な説明】 〔産業上の利用分野〕 本発明は電気的諸特性に優れ、且つ打抜加工性が良好な
樹脂積層板等に用いられる耐熱性のすぐれた難燃性フェ
ノール樹脂組戒物に関するものである. 〔従来の技術〕 最近、絶縁材料特に通信機および電子機器に使用される
積層板は加工設備の自動化、省エネルギー等の観点から
常温または、常温付近の比較的低温での打抜加工性の優
れたものが要求されている.従って、通常積層板用樹脂
としては各種のアルキルフェノールをフェノールと併用
し、乾性油等で変性したフェノール樹脂が使われている
.一方、絶縁材料に使用される積層板に対して安全性を
より重視するため難燃化の要求が強くなっている.従来
積層板の難燃化には、ハロゲンあるいはリン化合物を樹
脂中に添加する添加型難燃剤を使用する場合と、樹脂に
化学的に結合される反応型難燃剤を使用する場合とがあ
り、それぞれ一長一短である.反応型難燃剤を使用する
場合、多量に用いると可撓性が低下し、定温での打抜加
工性の低下が生じる.一方、添加型難燃剤を使用する場
合、難燃剤が製品中に未反応で残存するため、耐熱性の
低下が生じる. 〔発明が解決しようとする課題〕 本発明は電気的特性および他の諸特性を劣化させること
なく耐熱性に優れた樹脂積層板を与える難燃性フェノー
ル樹脂組或物に関するものである.〔課題を解決するた
めの手段〕 l. 本発明は、フェノール樹脂に、 (R+ : CH*,CxHa、C.H.、C 4 H
 s. C s H +。、ChHI!% Ri:H,CHs、C t H s、C.H,、C*H
w.CsH++、X : Cl,B r,n− 1〜4
、m−1〜5)なる化合物を添加することにより、上記
の各種の優れた特性を有する難燃性フェノール樹脂組底
物を提供しようとするものである. 本発明の難燃性フェノール樹脂組成物に用いられるフェ
ノール樹脂はフェノール類とパラホルム、ホルマリン水
溶液等のホルムアルデヒドと反応させたものであり、フ
ェノール類としては、フェノール、クレゾール、プロビ
ルフェノール、プチルフェノール、ノニルフェノール、
カシューダイマー等のC,〜CtOのアルキルフェノー
ルである.フェノール類とホルムアルデヒドとの反応は
触媒として酸性のものと塩基性のものとがある。酸性触
媒としては蓚酸、硫酸、パラトルエンスルホン酸等であ
り、ノボラック型フェノール樹脂が得られる.また、塩
基性触媒としては水酸化ナトリウム等の水酸化物及びア
ンモニア水7ξン頻等でこれよりレゾール型フェノール
樹脂が得られる.本発明においては、いずれも用いられ
る。又、桐油、亜麻仁油、脱水しマシ油、カシューナッ
ツ油等の油で変性された油変性フェノール樹脂をフェノ
ール樹脂として使用することも可能である.前記化合物
(I)としては、例えばジプロムイソプロピルフェノー
ル、ジプロムクレゾール、トリブロムフェノール、トリ
プロムクレゾールのアルキレンオキサイドの付加物など
である.化合物(I)の使用量は、特に以下の範囲に限
定されるという趣旨ではないが、フェノ′−ル樹脂の固
定物100重量部に対して3〜50重量部になるように
設定されることが好ましい.この使用量が3重量部を下
まわると難燃剤が不充分となる傾向があり、50重量部
を越えると電気特性等が低下の傾向を示すようになる。
[Detailed Description of the Invention] [Field of Industrial Application] The present invention provides a flame-retardant phenolic resin assembly with excellent heat resistance and excellent electrical properties and good punching workability for use in resin laminates, etc. It is related to precepts. [Prior Art] Recently, insulating materials, especially laminates used for communication equipment and electronic equipment, have been developed to have excellent punching properties at room temperature or relatively low temperatures near room temperature, from the viewpoint of automation of processing equipment and energy saving. Something is demanded. Therefore, phenolic resins modified with drying oil, etc., are usually used as resins for laminates, using various alkylphenols in combination with phenol. On the other hand, there is a growing demand for flame retardancy for laminates used as insulating materials due to increased emphasis on safety. Conventionally, laminates are made flame retardant in two ways: additive flame retardants, in which halogen or phosphorus compounds are added to the resin, and reactive flame retardants, which are chemically bonded to the resin. Each has advantages and disadvantages. When using reactive flame retardants, if they are used in large quantities, flexibility decreases and punching workability at constant temperature decreases. On the other hand, when additive flame retardants are used, the flame retardant remains unreacted in the product, resulting in a decrease in heat resistance. [Problems to be Solved by the Invention] The present invention relates to a flame-retardant phenolic resin composition that provides a resin laminate with excellent heat resistance without deteriorating electrical properties or other properties. [Means for solving the problem] l. The present invention provides phenolic resin with (R+: CH*, CxHa, C.H., C 4 H
s. C s H +. , ChHI! % Ri:H, CHs, CtHs, C. H,,C*H
w. CsH++, X: Cl, Br, n- 1-4
, m-1 to m-5) to provide a flame-retardant phenolic resin composite having the various excellent properties described above. The phenol resin used in the flame-retardant phenol resin composition of the present invention is a product made by reacting phenols with formaldehyde such as paraform and formalin aqueous solution, and examples of the phenols include phenol, cresol, propylphenol, butylphenol, nonylphenol,
C, ~CtO alkylphenol such as cashew dimer. The reaction between phenols and formaldehyde uses acidic and basic catalysts. Acidic catalysts include oxalic acid, sulfuric acid, para-toluenesulfonic acid, etc., and novolac type phenolic resins are obtained. Further, as basic catalysts, hydroxides such as sodium hydroxide and aqueous ammonia, etc., can be used to obtain resol type phenolic resins. In the present invention, any of them can be used. It is also possible to use oil-modified phenolic resins modified with oils such as tung oil, linseed oil, dehydrated mustard oil, and cashew nut oil as the phenolic resin. Examples of the compound (I) include dipromisopropylphenol, dipromcresol, tribromphenol, and alkylene oxide adducts of tripromcresol. The amount of compound (I) to be used is not limited to the following range, but it should be set at 3 to 50 parts by weight per 100 parts by weight of the phenol resin fixed material. is preferable. If the amount used is less than 3 parts by weight, the flame retardant tends to be insufficient, and if it exceeds 50 parts by weight, electrical properties etc. tend to deteriorate.

本発明において難燃剤として使用する化合物(1)はハ
ロゲンが結合しているため難燃性が優れているのはもち
ろんであるが、アルキルエーテル構造及び末端にヒドロ
キシ基を有しているので、フェノール樹脂との相溶性に
優れ、添加型難燃剤にもかかわらず、硬化物中において
も、樹脂中に均一に溶解しており、樹脂の耐熱性を低下
させることが少ない. 〔実施例〕 以下、実施例を挙げて本発明を説明する.令』l姓 桐油850 g ,メタクレゾール1200 g ,パ
ラトルエンスルホン酸2gを混合し90゜Cで90分反
応させた.次いでノニルフェノール100 g ,パラ
ホルム100g,25%アンモニア水10gを反応容器
に入れ、85゜Cで2時間反応させた。次いで減圧下で
水を除去し、溶剤を加えて樹脂ワニスを製造した. 尖旌班 合戒例のフェスに樹脂固定分に対し、トリブロムフェノ
ールのプロピレンオキサイド付加物(Br含有量57%
〉10重量部を添加した.上記ワニスをコットンリンタ
ー紙に含浸し、これを乾燥して樹脂付着分50重量部の
樹脂含浸基材を製造した.この基材を8枚重ね合わせ、
160〜165 ”C、80kg/cdの積層条件で6
0分間加熱圧着して厚さ1.6 1I1のフェノール樹
脂積層板を製造した. 且1u東L 合戒例のフェスの樹脂固形分に対し、市阪難燃剤テトラ
プロモビスフェノールA (TBA)10重量部を添加
した.以下、実施例と全く同一の方法でフェノール樹脂
積層板を製造した.比較斑1 合戒例のワニスの樹脂固形分に対し、市販難燃剤ジプロ
モクレゾールグリシジルエーテルIQ重量部を添加した
。以下、実施例と全く同一の方法でフェノール樹脂積層
板を製造した.第 1 表 積層板の特性値 以上の実施例、比較例で得られたフェノール樹脂の諸特
性を第l表に示す。
Compound (1) used as a flame retardant in the present invention not only has excellent flame retardancy because it has a halogen bonded to it, but also has an alkyl ether structure and a hydroxyl group at the end, so it has phenol It has excellent compatibility with resins, and even though it is an additive flame retardant, it is uniformly dissolved in the resin even in the cured product, so it rarely reduces the heat resistance of the resin. [Example] The present invention will be explained below with reference to Examples. 850 g of tung oil, 1200 g of metacresol, and 2 g of para-toluenesulfonic acid were mixed and reacted at 90°C for 90 minutes. Next, 100 g of nonylphenol, 100 g of paraform, and 10 g of 25% aqueous ammonia were placed in a reaction vessel and reacted at 85°C for 2 hours. Water was then removed under reduced pressure and a solvent was added to produce a resin varnish. The propylene oxide adduct of tribromophenol (Br content 57%
>10 parts by weight was added. Cotton linter paper was impregnated with the above varnish and dried to produce a resin-impregnated base material with a resin adhesion content of 50 parts by weight. Layer 8 sheets of this base material,
6 under lamination conditions of 160-165”C, 80kg/cd
A phenolic resin laminate with a thickness of 1.6 111 was produced by heat-pressing for 0 minutes. In addition, 10 parts by weight of Ichisaka's flame retardant tetrapromobisphenol A (TBA) was added to the resin solid content of the 1u East L test sheet. A phenolic resin laminate was manufactured in the same manner as in the example below. Comparative Spotting 1 Parts by weight of a commercially available flame retardant, dipromocresol glycidyl ether IQ, were added to the resin solid content of the varnish of the Comparison Example. A phenolic resin laminate was manufactured in the same manner as in the example below. Table 1 shows the various properties of the phenolic resins obtained in Examples and Comparative Examples that are higher than the characteristic values of the first front laminate.

吸水性、絶縁抵抗、耐溶剤性: JIS C 6481
による.耐 熱 性:10X10aJの積層板を230
’C、2分間加熱医ふくれの発生の有無をみる.打抜加
工性:超酎ト617  による.以上のことから明らか
なように、実施例の難燃性フェノール樹脂組戒物は難燃
性はもちろん耐熱性、打抜加工性、電気特性、耐溶剤性
等を同時に満たす特性を持ち、比較例1及び2に示した
従来のI1i燃性フェノール樹脂&ll戒物よりも格段
に優れている。
Water absorption, insulation resistance, solvent resistance: JIS C 6481
by. Heat resistance: 230 x 10x10aJ laminate
'C: Heat for 2 minutes to see if blistering occurs. Punching workability: Based on Chochuto 617. As is clear from the above, the flame-retardant phenolic resin composition of the example has properties that satisfy not only flame retardancy but also heat resistance, punching workability, electrical properties, solvent resistance, etc., and the comparative example It is much superior to the conventional I1i flammable phenolic resin shown in 1 and 2.

〔発明の効果〕〔Effect of the invention〕

本発明の難燃性フェノール樹脂&Il戒物は難燃性はも
ちろんのこと、可撓性、電気特性、耐溶剤性に優れてお
り、化粧板、戒形品、積層品等に使用可能であるが年々
要求特性が向上している積層板用の樹脂として特に好適
である. 手続補正書(自発) 平或l年10月24日
The flame-retardant phenolic resin & Il material of the present invention is not only flame-retardant, but also has excellent flexibility, electrical properties, and solvent resistance, and can be used for decorative boards, shaped products, laminated products, etc. It is particularly suitable as a resin for laminates, whose required properties are improving year by year. Procedural amendment (voluntary) October 24, 2016

Claims (1)

【特許請求の範囲】 1、フェノール樹脂に、 ▲数式、化学式、表等があります▼ (R_1:CH_2、C_2H_4、C_3H_6、C
_4H_8、C_5H_1_8、C_6H_1_2、 R_2:H、CH_3、C_2H_5、C_3H_7、
C_4H_9、C_5H_1_1、X:Cl、Br、n
=1〜4、m=1〜5)なる化合物〔 I 〕を添加する
ことを特徴とする難燃性フェノール樹脂組成物。 2、化合物〔 I 〕の添加量がフェノール樹脂に対し3
〜50重量%である請求項1記載の難燃性フェノール樹
脂組成物。
[Claims] 1. Phenolic resin has ▲mathematical formulas, chemical formulas, tables, etc.▼ (R_1: CH_2, C_2H_4, C_3H_6, C
_4H_8, C_5H_1_8, C_6H_1_2, R_2:H, CH_3, C_2H_5, C_3H_7,
C_4H_9, C_5H_1_1, X: Cl, Br, n
= 1-4, m = 1-5) A flame-retardant phenol resin composition characterized by adding a compound [I]. 2. The amount of compound [I] added is 3 to phenolic resin.
The flame retardant phenolic resin composition according to claim 1, wherein the amount is 50% by weight.
JP22922989A 1989-09-06 1989-09-06 Flame-retardant phenol resin composition Pending JPH0393849A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP22922989A JPH0393849A (en) 1989-09-06 1989-09-06 Flame-retardant phenol resin composition

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP22922989A JPH0393849A (en) 1989-09-06 1989-09-06 Flame-retardant phenol resin composition

Publications (1)

Publication Number Publication Date
JPH0393849A true JPH0393849A (en) 1991-04-18

Family

ID=16888856

Family Applications (1)

Application Number Title Priority Date Filing Date
JP22922989A Pending JPH0393849A (en) 1989-09-06 1989-09-06 Flame-retardant phenol resin composition

Country Status (1)

Country Link
JP (1) JPH0393849A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008111333A (en) * 2008-01-29 2008-05-15 Seirei Ind Co Ltd Revolving work vehicle
US8927259B2 (en) 2006-11-28 2015-01-06 Drexel University Piezoelectric microcantilever sensors for biosensing

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8927259B2 (en) 2006-11-28 2015-01-06 Drexel University Piezoelectric microcantilever sensors for biosensing
JP2008111333A (en) * 2008-01-29 2008-05-15 Seirei Ind Co Ltd Revolving work vehicle

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