JPH08183855A - Thermosetting resin composition and cured material thereof - Google Patents
Thermosetting resin composition and cured material thereofInfo
- Publication number
- JPH08183855A JPH08183855A JP32684494A JP32684494A JPH08183855A JP H08183855 A JPH08183855 A JP H08183855A JP 32684494 A JP32684494 A JP 32684494A JP 32684494 A JP32684494 A JP 32684494A JP H08183855 A JPH08183855 A JP H08183855A
- Authority
- JP
- Japan
- Prior art keywords
- thermosetting resin
- group
- structural unit
- resin composition
- composition according
- 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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Links
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- Compositions Of Macromolecular Compounds (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
Description
【0001】[0001]
【産業上の利用分野】本発明は、耐熱性・難燃性等に優
れる高機能成形材料・塗料・コーティング材・接着剤・
封止材・積層板・FRP及び炭素製品原料に用いるジヒ
ドロベンゾオキサジン系熱硬化性樹脂組成物に関する。[Industrial field of application] The present invention is a highly functional molding material, paint, coating material, adhesive, which has excellent heat resistance and flame retardancy.
The present invention relates to a dihydrobenzoxazine-based thermosetting resin composition used as a sealing material, a laminated plate, an FRP and a raw material for carbon products.
【0002】[0002]
【従来の技術】フェノール樹脂、メラミン樹脂、エポキ
シ樹脂、不飽和ポリエステル樹脂、ビスマレイミド樹脂
等の熱硬化性樹脂は、その熱硬化性という性質に基づく
耐熱性、信頼性により多くの産業分野で用いられてい
る。しかし、フェノール樹脂やメラミン樹脂は硬化時に
揮発性副生成物を発生し、エポキシ樹脂や不飽和ポリエ
ステル樹脂は難燃性に劣り、ビスマレイミド樹脂は非常
に高価である等それぞれ固有の問題点が存在し、現実に
は用途に応じて適宜妥協して使用されている。そこで、
これらの欠点を有しない新規な熱硬化性樹脂の開発が従
来より進められてきた。Thermosetting resins such as phenolic resins, melamine resins, epoxy resins, unsaturated polyester resins and bismaleimide resins are used in many industrial fields due to their heat resistance and reliability due to their thermosetting properties. Has been. However, phenolic resins and melamine resins generate volatile by-products during curing, epoxy resins and unsaturated polyester resins have poor flame retardancy, and bismaleimide resins are very expensive. However, in reality, it is appropriately compromised depending on the application. Therefore,
The development of new thermosetting resins that do not have these drawbacks has been progressing from the past.
【0003】その一つとしてジヒドロベンゾオキサジン
化合物がある(特開昭49−47387号公報、米国特
許第5152939号明細書参照)。この化合物の硬化
は、ジヒドロベンゾオキサジン環の開環重合反応を利用
するものであるため、揮発分の発生を殆ど伴わずに熱硬
化する。One of them is a dihydrobenzoxazine compound (see JP-A-49-47387 and US Pat. No. 5,152,939). Since the curing of this compound utilizes the ring-opening polymerization reaction of the dihydrobenzoxazine ring, it is thermally cured with almost no generation of volatile components.
【0004】[0004]
【発明が解決しようとする課題】この開環重合反応は通
常のフェノール樹脂の硬化反応と比べて硬化に長時間を
要するという欠点があり、生産性の点で産業上の用途が
限定されるという問題も知られている。この問題を解決
するため硬化剤の添加が試みられているが、機械特性の
低下、残留硬化剤の分解による揮発分の発生など実用化
には至っていない。This ring-opening polymerization reaction has the drawback that it takes a longer time to cure than the ordinary phenol resin curing reaction, and its industrial use is limited in terms of productivity. The problem is also known. Attempts have been made to add a curing agent to solve this problem, but they have not been put to practical use such as deterioration of mechanical properties and generation of volatile components due to decomposition of the residual curing agent.
【0005】本発明は機械的特性の低下等、諸特性を低
下させずに硬化性を向上させたジヒドロベンゾオキサジ
ン環を有する熱硬化性樹脂組成物及びその硬化物を提供
することを目的とする。An object of the present invention is to provide a thermosetting resin composition having a dihydrobenzoxazine ring having improved curability without deteriorating various properties such as deterioration of mechanical properties, and a cured product thereof. .
【0006】[0006]
【課題を解決するための手段】本発明者らは前記目的を
達成するために鋭意研究を重ねた結果、ジヒドロベンゾ
オキサジン環を有する熱硬化性樹脂にフェノール樹脂を
硬化剤として用いることにより、機械特性等諸特性を低
下させずに硬化性を向上させることができることを見い
だし本発明を完成するに至った。Means for Solving the Problems As a result of intensive studies to achieve the above-mentioned object, the present inventors have found that a thermosetting resin having a dihydrobenzoxazine ring can be used as a curing agent by using a phenol resin as a curing agent. The inventors have found that the curability can be improved without deteriorating various characteristics such as characteristics, and have completed the present invention.
【0007】すなわち本発明はジヒドロベンゾオキサジ
ン環を有する熱硬化性樹脂とフェノール樹脂からなるこ
とを特徴とする熱硬化性樹脂組成物を提供するものであ
る。That is, the present invention provides a thermosetting resin composition comprising a thermosetting resin having a dihydrobenzoxazine ring and a phenol resin.
【0008】ジヒドロベンゾオキサジン環を有する熱硬
化性樹脂とフェノール樹脂の配合割合はジヒドロベンゾ
オキサジン環を有する熱硬化性樹脂30〜97重量%と
フェノール樹脂3〜70重量%とすることが好ましい。The mixing ratio of the thermosetting resin having a dihydrobenzoxazine ring and the phenol resin is preferably 30 to 97% by weight of the thermosetting resin having a dihydrobenzoxazine ring and 3 to 70% by weight of the phenol resin.
【0009】ジヒドロベンゾオキサジン環を有する熱硬
化性樹脂としては、下記式(A)で表される構造単位A
及び下記式(B)で表される構造単位Bを有し、構造単
位Aと構造単位Bのモル比(A/B)が1/0.25〜
1/9であり、各構造単位が直接に又は有機の基を介し
て結合している樹脂が好ましく用いられる。The thermosetting resin having a dihydrobenzoxazine ring is a structural unit A represented by the following formula (A).
And a structural unit B represented by the following formula (B), and the molar ratio (A / B) of the structural unit A and the structural unit B is 1 / 0.25 to
It is 1/9, and a resin in which each structural unit is bonded directly or via an organic group is preferably used.
【0010】[0010]
【化3】 (但し、R1は、メチル基、シクロヘキシル基、フェニ
ル基又はメチル置換等のアルキル置換、メトキシ置換な
どの置換フェニル基であり、構造単位A及び構造単位B
の芳香環の水素は、構造単位Aのヒドロキシル基のオル
ト位の一つを除き、任意の置換基で置換されてもよ
い。) 各構造単位の数は、特に制限はないが、1分子中に含ま
れる構造単位(A)の数をm、構造単位(B)の数をn
としたときm≧1、n≧1かつ10≧m+n≧2である
ことが好ましく、10≧m+n≧3であれば更に好まし
い。Embedded image (However, R 1 is a methyl group, a cyclohexyl group, a phenyl group or a substituted phenyl group such as a methyl-substituted alkyl-substituted methoxy group, a structural unit A and a structural unit B
The hydrogen of the aromatic ring of may be substituted with any substituent except one of the ortho positions of the hydroxyl group of the structural unit A. The number of each structural unit is not particularly limited, but the number of structural units (A) contained in one molecule is m, and the number of structural units (B) is n.
Then, m ≧ 1, n ≧ 1, and 10 ≧ m + n ≧ 2 are preferable, and 10 ≧ m + n ≧ 3 is more preferable.
【0011】その理由は、構造単位(A)、(B)間が
あらかじめ安定な結合によって適切な鎖長が形成されて
いると、硬化物の特性が良好となるためである。The reason for this is that if a suitable chain length is previously formed between the structural units (A) and (B) by a stable bond, the properties of the cured product will be good.
【0012】各構造単位は、直接に結合していてもよ
く、有機の基を介して結合していてもよい。有機の基と
してはアルキレン基、キシリレン基などが挙げられ、ア
ルキレン基としては、例えば下記式(C)で表される
基、炭素数5以上の長鎖アルキレン基などが挙げられ
る。Each structural unit may be directly bonded or may be bonded via an organic group. Examples of the organic group include an alkylene group and a xylylene group, and examples of the alkylene group include a group represented by the following formula (C) and a long-chain alkylene group having 5 or more carbon atoms.
【0013】[0013]
【化4】 (但し、R2は、水素、メチル基、エチル基、プロピル
基、イソプロピル基、フェニル基又はメチル置換等のア
ルキル置換、メトキシ置換などの置換フェニル基を表
す。) 本発明の熱硬化性樹脂組成物のジヒドロベンゾオキサジ
ン環を有する熱硬化性樹脂は、ヒドロキシル基のオルト
位の少なくとも一つが水素であるヒドロキシフェニレン
基を、1分子中に2以上有する化合物と、1級アミンと
ホルムアルデヒド類とを前記ヒドロキシフェニレン基の
オルト位の少なくとも一つが水素であるヒドロキシル基
1モルに対し、1級アミンを0.2〜0.9モル、及び
ホルムアルデヒド類を1級アミンの2倍モル量以上の比
で反応させることによって製造される。[Chemical 4] (However, R 2 represents hydrogen, a methyl group, an ethyl group, a propyl group, an isopropyl group, a phenyl group or a substituted phenyl group such as a methyl-substituted alkyl-substituted methoxy group.) The thermosetting resin composition of the present invention The thermosetting resin having a dihydrobenzoxazine ring is a compound having two or more hydroxyphenylene groups in which at least one ortho-position of a hydroxyl group is hydrogen in one molecule, a primary amine and formaldehydes. Reaction of primary amine in an amount of 0.2 to 0.9 mol, and formaldehydes in a molar ratio of at least twice as much as the primary amine, relative to 1 mol of a hydroxyl group in which at least one of the ortho positions of the hydroxyphenylene group is hydrogen. It is manufactured by
【0014】具体的には、ヒドロキシル基のオルト位の
少なくとも一つが水素であるヒドロキシフェニレン基
を、1分子中に2以上有する化合物(以下、反応し得る
ヒドロキシフェニレン基を有する化合物という)と、1
級アミンとの混合物を、70℃以上に加熱したホルムア
ルデヒド類中に添加して、70〜110℃、好ましく
は、90〜100℃で、20分〜2時間反応させ、その
後、120℃以下の温度で減圧乾燥することによって目
的とする熱硬化性樹脂が得られる。Specifically, a compound having two or more hydroxyphenylene groups in which at least one ortho-position of a hydroxyl group is hydrogen in one molecule (hereinafter, referred to as a compound having a reactive hydroxyphenylene group) and 1
The mixture with the primary amine is added to formaldehydes heated to 70 ° C. or higher, and the reaction is performed at 70 to 110 ° C., preferably 90 to 100 ° C. for 20 minutes to 2 hours, and then the temperature is 120 ° C. or lower. The desired thermosetting resin is obtained by drying under reduced pressure.
【0015】反応し得るヒドロキシフェニレン基を有す
る化合物のヒドロキシル基1モルに対し、1級アミンを
0.2〜0.9モル、及び、ホルムアルデヒド類を1級
アミンの2倍モル以上の比で反応させることが肝要であ
る。1級アミンが0.2モルより少ないと、ジヒドロベ
ンゾオキサジン環の数が少なくなるので、得られた熱硬
化性樹脂を硬化させたとき、架橋密度が小さく、強度が
小さい硬化物しか得られない。また、0.9モルより多
いと挙動が従来知られているジヒドロベンゾオキサジン
化合物類似となり好ましくない。The primary amine is reacted in an amount of 0.2 to 0.9 mol, and the formaldehydes are reacted in a ratio of at least twice the molar amount of the primary amine, relative to 1 mol of the hydroxyl group of the compound having a reactive hydroxyphenylene group. It is essential to let them do it. When the amount of the primary amine is less than 0.2 mol, the number of dihydrobenzoxazine rings will be small, so that when the obtained thermosetting resin is cured, only a cured product having a low crosslink density and a low strength can be obtained. . Further, if it exceeds 0.9 mol, the behavior becomes similar to the conventionally known dihydrobenzoxazine compound, which is not preferable.
【0016】反応し得るヒドロキシフェニレン基を有す
る化合物に対する1級アミンの配合量は、次のようにし
て求めることができる。すなわち、ヒドロキシフェニレ
ン基を有する化合物の全ヒドロキシル量と同モル量の1
級アミンを反応させて、実際に得られた生成物の重量か
ら反応したヒドロキシル基量、すなわち、ヒドロキシフ
ェニレン基を有する化合物中の反応し得るヒドロキシル
基量を見積もり、これに対する前記のモル比として算出
する。The blending amount of the primary amine with respect to the compound having a reactive hydroxyphenylene group can be determined as follows. That is, 1 mol of the same molar amount as the total hydroxyl amount of the compound having a hydroxyphenylene group
The amount of the reacted hydroxyl group, that is, the amount of the reactable hydroxyl group in the compound having a hydroxyphenylene group is estimated from the weight of the product actually obtained by reacting the primary amine, and calculated as the above molar ratio. To do.
【0017】1分子中に2以上の反応し得るヒドロキシ
フェニレン基を有する化合物としては、部分的にフェノ
ール核を有する種々の化合物を用いることができる。具
体的にはフェノールノボラック樹脂、レゾール樹脂、フ
ェノール変性キシレン樹脂、アルキルフェノール樹脂、
メラミンフェノール樹脂、フェノール変性ポリブタジエ
ン等が挙げられる。これらは特に限定するものではない
が架橋点となるヒドロキシル基のオルト位が無置換であ
るものが硬化特性の点で望ましく、そのため例えばフェ
ノールノボラック樹脂の場合は、オルト率が小さく、比
較的分子量の小さいいわゆるランダムノボラックを用い
ることが好ましい。As the compound having two or more reactive hydroxyphenylene groups in one molecule, various compounds partially having a phenol nucleus can be used. Specifically, phenol novolac resin, resol resin, phenol-modified xylene resin, alkylphenol resin,
Examples include melamine phenol resin and phenol-modified polybutadiene. These are not particularly limited, but those in which the ortho position of the hydroxyl group serving as a crosslinking point is unsubstituted are desirable in terms of curing characteristics. Therefore, for example, in the case of phenol novolac resin, the ortho ratio is small and the ortho position is relatively low. It is preferred to use small so-called random novolacs.
【0018】上記の樹脂は、1分子中の反応しうるヒド
ロキシフェニレン基の数が異なった化合物の集合であ
り、製造中に生成した熱硬化性化合物の一部が互いに重
合する。従って、得られる本発明の熱硬化性化合物は、
m及びnが異なった化合物の集合体となる。m及びnが
異なった化合物を単離することは、現状では不可能であ
る。The above-mentioned resin is a set of compounds having different numbers of hydroxyphenylene groups capable of reacting in one molecule, and a part of the thermosetting compound produced during the production is polymerized with each other. Therefore, the obtained thermosetting compound of the present invention is
It is an aggregate of compounds in which m and n are different. Isolation of compounds with different m and n is currently not possible.
【0019】1級アミンとしては具体的にはメチルアミ
ン、シクロヘキシルアミン、アニリン、トルイジン、ア
ニシジンなどの置換アニリン等が挙げられる。Specific examples of primary amines include substituted anilines such as methylamine, cyclohexylamine, aniline, toluidine and anisidine.
【0020】脂肪族アミンであると、得られたジヒドロ
ベンゾオキサジン環を有する熱硬化性樹脂の硬化が速い
が硬化物の耐熱性がやや劣り、アニリンのような芳香族
アミンであると、得られた熱硬化性化合物を硬化させた
硬化物の耐熱性はよいが硬化が遅くなる。When the aliphatic amine is used, the resulting thermosetting resin having a dihydrobenzoxazine ring cures quickly, but the heat resistance of the cured product is slightly inferior, and when it is an aromatic amine such as aniline, it is obtained. The heat resistance of the cured product obtained by curing the thermosetting compound is good, but the curing is slow.
【0021】このジヒドロベンゾオキサジン環を有する
熱硬化性樹脂は、150℃以上、望ましくは、170〜
220℃に加熱することにより、触媒や硬化剤を用いな
いで、副生成物を生じることなく硬化する。The thermosetting resin having a dihydrobenzoxazine ring is 150 ° C. or higher, preferably 170 to
By heating to 220 ° C., curing is performed without using a catalyst or a curing agent and without producing a by-product.
【0022】これらのジヒドロベンゾオキサジン環を有
する熱硬化性樹脂は2種以上を組み合わせて用いること
もできる。またこれらの多官能ジヒドロベンゾオキサジ
ン環を有する熱硬化性樹脂をあらかじめ80〜180
℃、好ましくは120〜160℃で処理することによ
り、その一部を予備重合させ成形時の硬化速度や溶融粘
度を調節することもできる。Two or more of these thermosetting resins having a dihydrobenzoxazine ring can be used in combination. Further, a thermosetting resin having these polyfunctional dihydrobenzoxazine rings is previously added to 80 to 180
It is also possible to pre-polymerize a part of the mixture by treating at a temperature of 120 ° C., preferably 120 to 160 ° C. to control the curing rate and melt viscosity during molding.
【0023】フェノール樹脂としては、ノボラック樹
脂、レゾール樹脂を用いることができる。ノボラック樹
脂としてはフェノールノボラック樹脂やビスフェノール
ノボラック樹脂、フェノール変性キシレン樹脂、アルキ
ルフェノール樹脂等が挙げられる。レゾール樹脂として
は液状、固形レゾール、ジメチレンエーテル型レゾー
ル、メチロール型レゾール等が挙げられる。As the phenol resin, novolac resin and resol resin can be used. Examples of novolac resins include phenol novolac resins, bisphenol novolac resins, phenol-modified xylene resins, and alkylphenol resins. Examples of the resole resin include liquid, solid resole, dimethylene ether type resole, and methylol type resole.
【0024】ノボラック樹脂を用いた場合、ジヒドロベ
ンゾオキサジン環を有する熱硬化性樹脂単独の場合より
も機械特性が低下することがあるためレゾール樹脂を用
いるのが好ましい。レゾール樹脂のうちでも固形のジメ
チレンエーテル型レゾール樹脂を用いることにより機械
特性を低下させずに硬化性を向上させることができる。When a novolac resin is used, mechanical properties may be deteriorated as compared with the case of using a thermosetting resin having a dihydrobenzoxazine ring alone. Therefore, it is preferable to use a resole resin. By using a solid dimethylene ether type resole resin among the resole resins, curability can be improved without lowering mechanical properties.
【0025】ジメチレンエーテル型レゾール樹脂等のフ
ェノール樹脂の添加量が3重量%未満になると硬化性を
向上させることが難しくなる。70重量%を超えると硬
化性が向上しにくく、機械特性が低下することがある。
フェノール樹脂の添加量を3〜70重量%にすることに
より機械特性等の諸特性を低下させずに硬化性を向上さ
せることができる。If the amount of the phenol resin such as dimethylene ether type resole resin added is less than 3% by weight, it becomes difficult to improve the curability. If it exceeds 70% by weight, the curability is difficult to improve and the mechanical properties may deteriorate.
By setting the addition amount of the phenol resin to 3 to 70% by weight, curability can be improved without deteriorating various characteristics such as mechanical characteristics.
【0026】またヘキサメチレンテトラミンや水酸化カ
ルシウム等のフェノール樹脂用の硬化剤を必要に応じて
用いることができる。If desired, a curing agent for phenol resin such as hexamethylenetetramine or calcium hydroxide can be used.
【0027】ジヒドロベンゾオキサジン環を有する熱硬
化性樹脂とフェノール樹脂は両者をミキサー等で微粉砕
した後、粉体混合してもよいが、加熱ロール等で溶融混
合することが好ましい。The thermosetting resin having a dihydrobenzoxazine ring and the phenol resin may be finely pulverized with a mixer or the like and then powder-mixed, but it is preferable to melt-mix with a heating roll or the like.
【0028】また、上記組成物には必要に応じて充填
剤、強化繊維、着色剤、接着剤等を添加することもでき
る。If desired, a filler, a reinforcing fiber, a coloring agent, an adhesive agent, etc. may be added to the above composition.
【0029】[0029]
【作用】本発明は上記樹脂組成物とその硬化物を提供す
るものである。ジヒドロベンゾオキサジン環を有する熱
硬化性樹脂とフェノール樹脂との樹脂組成物とすること
によりジヒドロベンゾオキサジン環を有する熱硬化性樹
脂単独より硬化性が向上し、更に機械特性や難燃性が良
好な硬化物を得ることができる。これらは上記樹脂組成
物を加熱ロール等により混練し然る後に180〜220
℃、成形圧20〜70kgf/cm2で3〜10分間圧
成形又は移送成形することにより得られ、更に180〜
220℃で5〜120分間硬化させることにより、より
良好な特性を有する硬化物が得られる。The present invention provides the above resin composition and a cured product thereof. By using a resin composition of a thermosetting resin having a dihydrobenzoxazine ring and a phenol resin, the curability is improved as compared with a thermosetting resin having a dihydrobenzoxazine ring alone, and the mechanical properties and flame retardancy are good. A cured product can be obtained. These are 180 to 220 after kneading the above resin composition by a heating roll or the like.
It is obtained by pressure molding or transfer molding for 3 to 10 minutes at a molding temperature of 20 to 70 kgf / cm 2 at 180 ° C.
By curing at 220 ° C. for 5 to 120 minutes, a cured product having better properties can be obtained.
【0030】[0030]
【実施例】以下に本発明の具体的な実施例を示すが、本
発明はこれらに限定されるものではない。EXAMPLES Specific examples of the present invention are shown below, but the present invention is not limited thereto.
【0031】実施例1〜11、比較例1〜5 ジヒドロベンゾオキサジン環を有する熱硬化性樹脂の合
成(I) (1)フェノールノボラック樹脂の合成 フェノール1.9kg、ホルマリン(37%水溶液)
1.15kg、しゅう酸4gを5リットルフラスコに仕
込み、還流温度で6時間反応させた。引き続き、内部を
6666.1Pa以下に減圧して未反応のフェノール及
び水を除去した。得られた樹脂は軟化点89℃(環球
法)、3〜多角体/2核体比89/11(ゲルパーミエ
ーションクロマトグラフィーによるピーク面積比)であ
った。Examples 1 to 11 and Comparative Examples 1 to 5 Synthesis of thermosetting resin having dihydrobenzoxazine ring (I) (1) Synthesis of phenol novolac resin 1.9 kg of phenol, formalin (37% aqueous solution)
1.15 kg and 4 g of oxalic acid were charged in a 5 liter flask and reacted at reflux temperature for 6 hours. Subsequently, the inside pressure was reduced to 6666.1 Pa or less to remove unreacted phenol and water. The obtained resin had a softening point of 89 ° C. (ring and ball method) and a 3-polyhedron / 2 nucleus ratio of 89/11 (peak area ratio by gel permeation chromatography).
【0032】(2)ジヒドロベンゾオキサジン環の導入 上記により合成したフェノールノボラック樹脂1.7k
g(ヒドロキシル基16mol相当)をアニリン0.9
3kg(10mol相当)と混合し80℃で5時間攪拌
し、均一な混合溶液を調製した。5リットルフラスコ中
に、ホルマリン1.62kgを仕込み90℃に加熱し、
ここへノボラック/アニリン混合溶液を30分間かけて
少しずつ添加した。添加終了後30分間、還流温度に保
ち、然る後に100℃で2時間6666.1Pa以下に
減圧して縮合水を除去し、反応し得るヒドロキシル基の
75%がジヒドロベンゾオキサジン化されたジヒドロベ
ンゾオキサジン環を有する熱硬化性樹脂を得た。(2) Introduction of dihydrobenzoxazine ring Phenol novolac resin 1.7k synthesized above
aniline 0.9 g (corresponding to 16 mol of hydroxyl group)
The mixture was mixed with 3 kg (corresponding to 10 mol) and stirred at 80 ° C. for 5 hours to prepare a uniform mixed solution. Into a 5 liter flask, charge 1.62 kg of formalin and heat to 90 ° C.
The novolak / aniline mixed solution was added little by little over 30 minutes. After the completion of the addition, the reflux temperature was maintained for 30 minutes, and then the water of condensation was removed by reducing the pressure to 6666.1 Pa or less at 100 ° C. for 2 hours to remove 75% of the reactive hydroxyl groups. A thermosetting resin having an oxazine ring was obtained.
【0033】ジヒドロベンゾオキサジン化合物の合成
(II) (1)フェノールノボラック樹脂の合成 フェノール1.9kg、ホルマリン(37%水溶液)
1.10kg、しゅう酸4gを5リットルフラスコに仕
込み、ジヒドロベンゾオキサジン化合物の合成(I)と
同様にしてフェノールノボラック樹脂を合成した。得ら
れた樹脂は軟化点84℃(環球法)、3〜多核体/2核
体比82/18(ゲルパーミエーションクロマトグラフ
ィーによるピーク面積比)であった。 (2)ジヒドロベンゾオキサジン環の導入 以下ジヒドロベンゾオキサジン環を有する熱硬化性樹脂
の合成(I)と同様にしてジヒドロベンゾオキサジン環
を導入した。得られた熱硬化性樹脂組成物は、フェノー
ルノボラック樹脂の、反応しうるヒドロキシル基の71
%にジヒドロベンゾオキサジン環が導入されたものであ
った。Synthesis of dihydrobenzoxazine compound (II) (1) Synthesis of phenol novolac resin 1.9 kg of phenol, formalin (37% aqueous solution)
1.10 kg and 4 g of oxalic acid were charged into a 5 liter flask, and a phenol novolac resin was synthesized in the same manner as in the synthesis (I) of dihydrobenzoxazine compound. The obtained resin had a softening point of 84 ° C. (ring and ball method) and a ratio of 3 to polynuclear bodies / 2 binuclear bodies of 82/18 (peak area ratio by gel permeation chromatography). (2) Introduction of dihydrobenzoxazine ring A dihydrobenzoxazine ring was introduced in the same manner as in Synthesis (I) of thermosetting resin having a dihydrobenzoxazine ring. The resulting thermosetting resin composition has 71% of the reactive hydroxyl groups of the phenol novolac resin.
% Of which a dihydrobenzoxazine ring was introduced.
【0034】ジヒドロベンゾオキサジン環を有する熱硬
化性樹脂の合成(III) キシリレン変性フェノール樹脂(三井東圧化学株式会社
製商品名ミレックスXL−225−3L)1.70kg
(ヒドロキシル基10mol相当)、アニリン0.52
kg(5.6mol)、ホルマリン(37%水溶液)
0.91kgの配合で上記合成法と同様に反応しうるヒ
ドロキシル基の71%にジヒドロベンゾオキサジン環が
導入された熱硬化性樹脂を合成した。Synthesis of Thermosetting Resin Having Dihydrobenzoxazine Ring (III) 1.70 kg of xylylene-modified phenolic resin (trade name Milex XL-225-3L manufactured by Mitsui Toatsu Chemicals, Inc.)
(Equivalent to hydroxyl group 10 mol), aniline 0.52
kg (5.6 mol), formalin (37% aqueous solution)
A thermosetting resin having a dihydrobenzoxazine ring introduced into 71% of hydroxyl groups capable of reacting in the same manner as in the above-mentioned synthetic method was synthesized with a composition of 0.91 kg.
【0035】ジメチレンエーテル型レゾール樹脂の合成 フェノール2kg、ホルマリン(37%水溶液)0.3
8kg、パラホルムアルデヒド0.78kgを5リット
ルフラスコに仕込み還流温度で6時間反応させた。引き
続き内部を6666.1Pa以下に減圧し、水蒸気蒸留
により未反応のフェノール及び水を除去した。得られた
樹脂は軟化点77℃であった。Synthesis of dimethylene ether type resole resin 2 kg phenol, formalin (37% aqueous solution) 0.3
8 kg and 0.78 kg of paraformaldehyde were charged into a 5 liter flask and reacted at a reflux temperature for 6 hours. Subsequently, the inside pressure was reduced to 6666.1 Pa or less, and unreacted phenol and water were removed by steam distillation. The obtained resin had a softening point of 77 ° C.
【0036】フェノールノボラック樹脂の合成 フェノール1.9kg、ホルマリン(37%水溶液)
1.15kg、しゅう酸4gを5リットルフラスコに仕
込み、還流温度で6時間反応させた。引き続き、内部を
6666.1Pa以下に減圧して未反応のフェノール及
び水を除去した。得られた樹脂は軟化点84℃(環球
法)、3〜多核体/2核体比82/18(ゲルパーミエ
ーションクロマトグラフィーによるピーク面積比)であ
った。Synthesis of phenol novolac resin 1.9 kg phenol, formalin (37% aqueous solution)
1.15 kg and 4 g of oxalic acid were charged in a 5 liter flask and reacted at reflux temperature for 6 hours. Subsequently, the inside pressure was reduced to 6666.1 Pa or less to remove unreacted phenol and water. The obtained resin had a softening point of 84 ° C. (ring and ball method) and a ratio of 3 to polynuclear bodies / 2 binuclear bodies of 82/18 (peak area ratio by gel permeation chromatography).
【0037】フェノール樹脂をフラスコに仕込み、11
0〜120℃に加熱して樹脂を溶解し、ここにジヒドロ
ベンゾオキサジン環を有する熱硬化性樹脂を加え、均一
になるまで10分間攪拌した。Phenol resin was charged into a flask, and 11
The resin was dissolved by heating to 0 to 120 ° C., a thermosetting resin having a dihydrobenzoxazine ring was added thereto, and the mixture was stirred for 10 minutes until it became uniform.
【0038】上記の樹脂を表1、表2の割合で混合した
樹脂組成物を粉砕し、内径120×80×4mmの金型
内に充填し180℃、1.96MPaで10分間加熱加
圧して硬化物を作製した。樹脂組成物の特性は、ゲルタ
イムについては樹脂組成物0.3gを180℃に加温し
たゲルタイマー上で1回/秒で攪拌し続け糸引きがなく
なるまでの時間とした。A resin composition prepared by mixing the above resins in the ratios shown in Tables 1 and 2 was crushed, filled in a mold having an inner diameter of 120 × 80 × 4 mm, and heated and pressed at 180 ° C. and 1.96 MPa for 10 minutes. A cured product was produced. Regarding the characteristics of the resin composition, the gel time was the time until the stringing disappeared by continuously stirring 0.3 g of the resin composition on the gel timer heated at 180 ° C. once / second.
【0039】硬化物の特性は、曲げ強さ及び曲げ弾性率
はJISK6911に準じ、23℃、曲げ速度2mm/
分で評価した。難燃性についてはUL−94に準じ、
3.6mm厚さで評価した。The characteristics of the cured product are bending strength and bending elastic modulus according to JIS K6911, 23 ° C., bending speed 2 mm /
Evaluated in minutes. Flame retardance is based on UL-94,
Evaluation was made with a thickness of 3.6 mm.
【0040】以下この結果を3〜6に示す。The results are shown in 3-6 below.
【0041】[0041]
【表1】 [Table 1]
【0042】[0042]
【表2】 [Table 2]
【0043】[0043]
【表3】 [Table 3]
【0044】[0044]
【表4】 [Table 4]
【0045】[0045]
【表5】 [Table 5]
【0046】[0046]
【表6】 [Table 6]
【0047】[0047]
【発明の効果】本発明の熱硬化性樹脂組成物は速硬化で
あり、その硬化物は良好な機械特性、難燃性を備えてい
る。したがって、本発明の熱硬化性樹脂組成物は高機能
性成形材料、塗料、コーティング材、接着剤、封止材、
積層板、FRP及び炭素製品原料などとして有用であ
る。The thermosetting resin composition of the present invention is fast-curing, and the cured product has good mechanical properties and flame retardancy. Therefore, the thermosetting resin composition of the present invention is a highly functional molding material, paint, coating material, adhesive, sealing material,
It is useful as a laminated plate, FRP, and raw material for carbon products.
Claims (10)
硬化性樹脂とフェノール樹脂からなることを特徴とする
熱硬化性樹脂組成物。1. A thermosetting resin composition comprising a thermosetting resin having a dihydrobenzoxazine ring and a phenol resin.
硬化性樹脂が30〜97重量%及びフェノール樹脂が3
〜70重量%からなる請求項1記載の熱硬化性樹脂組成
物。2. A thermosetting resin having a dihydrobenzoxazine ring in an amount of 30 to 97% by weight and a phenol resin in an amount of 3%.
The thermosetting resin composition according to claim 1, which comprises ˜70% by weight.
硬化性樹脂が下記式(A)で表される構造単位A及び下
記式(B)で表される構造単位Bを有し、構造単位Aと
構造単位Bのモル比(A/B)が1/0.25〜1/9
であり、各構造単位が直接に又は有機の基を介して結合
している樹脂であり、フェノール樹脂がノボラック型又
はレゾール型フェノール樹脂である請求項1又は2記載
の熱硬化性樹脂組成物。 【化1】 (但し、R1は、メチル基、シクロヘキシル基、フェニ
ル基又は置換フェニル基であり、構造単位A及び構造単
位Bの芳香環の水素は、構造単位Aのヒドロキシル基の
オルト位の一つを除き、任意の置換基で置換されてもよ
い。)3. A thermosetting resin having a dihydrobenzoxazine ring has a structural unit A represented by the following formula (A) and a structural unit B represented by the following formula (B). The molar ratio (A / B) of the unit B is 1 / 0.25 to 1/9
The thermosetting resin composition according to claim 1 or 2, wherein each structural unit is a resin bonded directly or via an organic group, and the phenol resin is a novolac type or resol type phenol resin. Embedded image (However, R 1 is a methyl group, a cyclohexyl group, a phenyl group or a substituted phenyl group, and hydrogen of the aromatic ring of the structural unit A and the structural unit B excludes one of the ortho positions of the hydroxyl group of the structural unit A. , May be substituted with any substituent.)
ン環を有する熱硬化性樹脂が構造単位Aの数をm、構造
単位Bの数をnとしたときm≧1,n≧1かつ10≧m
+n≧2である請求項3記載の熱硬化性樹脂組成物。4. The thermosetting resin having a dihydrobenzoxazine ring according to claim 3, wherein m ≧ 1, n ≧ 1 and 10 ≧ m, where m is the number of structural units A and n is the number of structural units B.
The thermosetting resin composition according to claim 3, wherein + n ≧ 2.
がアルキレン基を介して結合している請求項3記載の熱
硬化性樹脂組成物。5. Structural unit A and structural unit B of thermosetting resin
The thermosetting resin composition according to claim 3, wherein is bonded via an alkylene group.
が下記式(C)で表される基を介して結合している請求
項3記載の熱硬化性樹脂組成物。 【化2】 (但し、R2は、水素、メチル基、エチル基、プロピル
基、イソプロピル基、フェニル基又は置換フェニル基を
表す。)6. A thermosetting resin structural unit A and structural unit B
The thermosetting resin composition according to claim 3, wherein is bonded via a group represented by the following formula (C). Embedded image (However, R 2 represents hydrogen, a methyl group, an ethyl group, a propyl group, an isopropyl group, a phenyl group or a substituted phenyl group.)
がキシリレン基を介して結合している請求項3記載の熱
硬化性樹脂組成物。7. A thermosetting resin structural unit A and structural unit B
The thermosetting resin composition according to claim 3, wherein is bonded via a xylylene group.
樹脂である請求項1ないし7いずれか記載の熱硬化性樹
脂組成物。8. The thermosetting resin composition according to claim 1, wherein the phenol resin is a resol type phenol resin.
エーテル型レゾール樹脂である請求項1ないし7いずれ
か記載の熱硬化性樹脂組成物。9. The thermosetting resin composition according to claim 1, wherein the resol type phenol resin is a dimethylene ether type resol resin.
化性樹脂組成物を硬化させてなる硬化物。10. A cured product obtained by curing the thermosetting resin composition according to claim 1.
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JP32684494A JP3429090B2 (en) | 1994-12-28 | 1994-12-28 | Thermosetting resin composition and cured product thereof |
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Family
ID=18192351
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0789056A3 (en) * | 1996-02-09 | 1997-12-29 | Hitachi Chemical Co., Ltd. | Thermosetting resin composition, cured product, prepreg, metal-clad laminate and wiring board |
JPH10130460A (en) * | 1996-10-25 | 1998-05-19 | Hitachi Chem Co Ltd | High-permittivity resin composition, high-permittivity prepreg, and high-pertmittivity laminate |
WO2005005541A1 (en) * | 2003-07-10 | 2005-01-20 | Asahi Organic Chemicals Industry Co., Ltd. | Phenol resin composition |
CN100415826C (en) * | 2003-07-10 | 2008-09-03 | 旭有机材工业株式会社 | Phenol resin composition |
-
1994
- 1994-12-28 JP JP32684494A patent/JP3429090B2/en not_active Expired - Lifetime
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0789056A3 (en) * | 1996-02-09 | 1997-12-29 | Hitachi Chemical Co., Ltd. | Thermosetting resin composition, cured product, prepreg, metal-clad laminate and wiring board |
US5945222A (en) * | 1996-02-09 | 1999-08-31 | Hitachi Chemical Company, Ltd. | Thermosetting resin composition, cured product, prepreg, metal-clad laminate and wiring board |
JPH10130460A (en) * | 1996-10-25 | 1998-05-19 | Hitachi Chem Co Ltd | High-permittivity resin composition, high-permittivity prepreg, and high-pertmittivity laminate |
WO2005005541A1 (en) * | 2003-07-10 | 2005-01-20 | Asahi Organic Chemicals Industry Co., Ltd. | Phenol resin composition |
CN100415826C (en) * | 2003-07-10 | 2008-09-03 | 旭有机材工业株式会社 | Phenol resin composition |
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