JPH11255868A - Preparation of phenol aralkyl resin - Google Patents
Preparation of phenol aralkyl resinInfo
- Publication number
- JPH11255868A JPH11255868A JP5965898A JP5965898A JPH11255868A JP H11255868 A JPH11255868 A JP H11255868A JP 5965898 A JP5965898 A JP 5965898A JP 5965898 A JP5965898 A JP 5965898A JP H11255868 A JPH11255868 A JP H11255868A
- Authority
- JP
- Japan
- Prior art keywords
- phenol
- reaction
- xylylene
- resin
- aralkyl resin
- 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
Landscapes
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
Description
【0001】[0001]
【発明の属する技術分野】本発明は、各種バインダー、
コーティング材、積層材料、成形材料等に有用なフェノ
ール系重合体の製造方法に関する。特に電子材料用のエ
ポキシ硬化剤やエポキシ樹脂の原料に好適な、不純物の
少ない高純度の重合体を効率的に得る製造方法に関する
ものである。TECHNICAL FIELD The present invention relates to various binders,
The present invention relates to a method for producing a phenolic polymer useful as a coating material, a laminate material, a molding material, and the like. In particular, the present invention relates to a production method for efficiently obtaining a high-purity polymer with few impurities, which is suitable as an epoxy curing agent for an electronic material or a raw material of an epoxy resin.
【0002】[0002]
【従来の技術】フェノールホルムアルデヒド樹脂は、安
価な耐熱性樹脂として各種の用途に広く使用されてい
る。また、通常のフェノール樹脂の各特性を向上する目
的で、構造の異なる各種の樹脂が開発され、すでに公知
となっている。2. Description of the Related Art Phenol formaldehyde resin is widely used for various purposes as an inexpensive heat-resistant resin. In addition, various resins having different structures have been developed for the purpose of improving the properties of ordinary phenolic resins, and are already known.
【0003】特に、特公昭47−15111号公報など
に記載の、α,α′−ジメトキシ−p−キシレンなどの
アラルキル化合物とフェノール類との縮合反応によって
得られる重合物は、フェノールアラルキル樹脂として、
優れた耐熱性、電気特性、耐湿耐薬品性により、各種用
途に広く使用されている。更にフェノールアラルキル樹
脂は、近年ではICの高密度化、小型薄型化、表面実装
化に伴い、耐湿性が要求される封止材分野での硬化剤と
しての利用が広がっている。[0003] In particular, a polymer obtained by a condensation reaction of an aralkyl compound such as α, α'-dimethoxy-p-xylene with a phenol described in Japanese Patent Publication No. 47-15111 is a phenol aralkyl resin.
Due to its excellent heat resistance, electrical properties, and moisture and chemical resistance, it is widely used for various applications. Further, in recent years, phenol aralkyl resins have been widely used as curing agents in the field of encapsulants which require moisture resistance, as ICs are becoming denser, smaller and thinner, and being surface mounted.
【0004】上記フェノールアラルキル樹脂の製造方法
に関しては、従来より多数の方法が開示されている。最
も一般的な製造方法として、例えば特公昭47−151
11号公報や特公昭48−10960号公報では、アラ
ルキルハライドまたはアラルキルアルコール誘導体に対
し、過剰モルのフェノールを、フリーデルクラフツ型触
媒やジエチル硫酸などの存在下で反応させる方法が記載
されている。また、触媒としてp−トルエンスルホン酸
(特公昭63−238129)、メタンスルホン酸(特
公昭63−238129)なども開示されている。[0004] Regarding the method for producing the phenol aralkyl resin, many methods have been disclosed. As the most common production method, for example, Japanese Patent Publication No. 47-151
Japanese Patent Publication No. 11 and JP-B-48-10960 describe a method in which an excess mole of phenol is reacted with an aralkyl halide or an aralkyl alcohol derivative in the presence of a Friedel-Crafts catalyst or diethyl sulfate. Further, p-toluenesulfonic acid (JP-B-63-238129), methanesulfonic acid (JP-B-63-238129) and the like are also disclosed as catalysts.
【0005】[0005]
【発明が解決しようとする課題】しかしながら、これら
の公報に開示されている方法では、反応に用いる酸触媒
を反応生成物から完全に分離することは困難で、得られ
る樹脂は酸性物質を僅かに含有している。そのため、不
純物を特に嫌うような用途にはそのままでは適用でき
ず、水洗による触媒の除去などが必要である。また、残
存する酸性物質が製造過程で分子量分布の変化、粘度上
昇、フェノール類モノマーの再生などの問題を引き起こ
し、品質が安定しないという欠点を有している。However, according to the methods disclosed in these publications, it is difficult to completely separate the acid catalyst used in the reaction from the reaction product, and the obtained resin is slightly acidic. Contains. Therefore, it cannot be used as it is for applications in which impurities are particularly disliked, and it is necessary to remove the catalyst by washing with water. In addition, there is a disadvantage that the remaining acidic substance causes problems such as a change in molecular weight distribution, an increase in viscosity and a regeneration of phenolic monomers in the production process, and the quality is not stable.
【0006】この問題を解決する方法として、アラルキ
ル化合物とフェノール類とを塩酸を添加しながら反応さ
せる方法が報告されている(特開平5−247183号
公報)。これによれば残存する酸性物質による物性低下
を防ぐことは可能であるが、反応性を制御しながら樹脂
化を完結させるためには、反応中に適切な量の塩酸を連
続的に添加する必要があり、操作が煩雑である。As a method for solving this problem, a method of reacting an aralkyl compound with a phenol while adding hydrochloric acid has been reported (JP-A-5-247183). According to this, it is possible to prevent a decrease in physical properties due to remaining acidic substances, but in order to complete resinification while controlling the reactivity, it is necessary to continuously add an appropriate amount of hydrochloric acid during the reaction. And the operation is complicated.
【0007】更に特開平6−100667号公報及び化
学経済(1997年9月号P37〜41)には、フェノ
ール類とα,α’−ジクロロp−キシレンなどのアラル
キルジハライドを無触媒で反応させる方法が報告されて
いる。上記報告には無触媒で反応が進行するメカニズム
を、アラルキルジハライド自体の平衡によって説明して
いる。すなわち、70℃以上の温度では、一部のアラル
キルジハライドがベンジルカチオンとハライドイオンに
解離する平衡が存在し、ここで生じたベンジルカチオン
がフェノール類と反応し、樹脂化が進行すると説明され
ている。この方法ではアラルキルジハライドの解離によ
るベンジルカチオンの生成が前提で、これがフェノール
類と反応するので、原料のアラルキル化合物としてはア
ラルキルジハライドに限られ、アラルキルエーテル類
や、アラルキルグリコール等は使用不可能であり、上記
報告にもこれらアラルキルジハライド以外のアラルキル
化合物は一切開示されていない。Further, JP-A-6-100667 and Chemical Economics (September 1997, pp. 37-41) disclose the reaction of phenols with aralkyl dihalides such as α, α′-dichloro p-xylene without a catalyst. Methods have been reported. In the above report, the mechanism by which the reaction proceeds without a catalyst is explained by the equilibrium of aralkyl dihalide itself. That is, at a temperature of 70 ° C. or higher, there is an equilibrium in which some aralkyl dihalides dissociate into benzyl cations and halide ions, and the benzyl cations generated here react with phenols, which explains that resinification proceeds. I have. This method is based on the premise that benzyl cation is generated by dissociation of aralkyl dihalide, which reacts with phenols. Therefore, the aralkyl compound as a raw material is limited to aralkyl dihalide, and aralkyl ethers and aralkyl glycol cannot be used. The report does not disclose any aralkyl compounds other than these aralkyl dihalides.
【0008】本発明は、このような事情に鑑みなされた
もので、不純物が少なく高純度で、かつ粘度などの品質
が安定したフェノール系樹脂、フェノールアラルキル系
樹脂を効率的に得る製造方法を提供することをその目的
とする。The present invention has been made in view of the above circumstances, and provides a method for efficiently producing a phenolic resin and a phenolaralkyl-based resin having a high purity with a small amount of impurities and a stable viscosity. Its purpose is to
【0009】[0009]
【課題を解決するための手段】本発明者は、上記の目的
を達成するため、触媒種や除去方法などを鋭意検討した
結果、原料として、加水分解、及びフェノール類との縮
合反応でハロゲン化水素を発生させるキシリレン化合物
を一定量以上用い、反応開始剤として水を添加する方法
を用いることにより、酸性触媒物質の残存による物性低
下がなく、操作が簡単であり、原料キシリレン化合物の
選択の幅を広げることができ、上記の課題を解決し、高
純度でかつ品質の安定したフェノールアラルキル系樹脂
の製造法を見いだし、本発明に到達した。Means for Solving the Problems In order to achieve the above object, the present inventors have conducted intensive studies on the type of catalyst and the method of removal. By using a certain amount of xylylene compound that generates hydrogen and adding water as a reaction initiator, there is no decrease in physical properties due to the remaining acidic catalyst substance, the operation is simple, and the range of choice of raw material xylylene compound can be selected. Have been found, a method for producing a phenol aralkyl-based resin having high purity and stable quality has been achieved, and the present invention has been achieved.
【0010】すなわち本発明は、フェノール類と、下記
一般式(1)で表されるキシリレン化合物、またはこれ
と下記一般式(2)で表されるキシリレン化合物 R1 −(CH2 X)2 ・・・(1) R2 −(CH2 OR3 )2 ・・(2) (式中、R1 及び、R2 は同一または異なるフェニレン
基、アルキル置換フェニレン基、ジフェニレン基、ジフ
ェニレンオキサイド基、ナフチレン基であり、Xはハロ
ゲン原子であり、R3 は水素原子またはC1 〜C4 のア
ルキル基である。)との混合物を、酸触媒の存在下で縮
合反応させて、フェノールアラルキル樹脂を製造する方
法において、(1)/(2)のモル比が100/0から
40/60までの範囲であり、かつ反応開始剤として水
を添加し、加水分解で発生するハロゲン化水素を縮合反
応開始の触媒として用いることを特徴とする、フェノー
ルアラルキル樹脂の製造方法である。以下、本発明を詳
細に説明する。That is, the present invention relates to a phenol and a xylylene compound represented by the following general formula (1) or a xylylene compound represented by the following general formula (2) R 1- (CH 2 X) 2. ·· (1) R 2- (CH 2 OR 3 ) 2 ·· (2) (wherein R 1 and R 2 are the same or different, phenylene group, alkyl-substituted phenylene group, diphenylene group, diphenylene oxide group, A naphthylene group, X is a halogen atom, and R 3 is a hydrogen atom or a C 1 -C 4 alkyl group) in the presence of an acid catalyst to form a phenol aralkyl resin. In the production method, the molar ratio of (1) / (2) is in the range of 100/0 to 40/60, water is added as a reaction initiator, and a hydrogen halide generated by hydrolysis is subjected to a condensation reaction. Starting It is characterized by using as the medium, a method for producing a phenol aralkyl resin. Hereinafter, the present invention will be described in detail.
【0011】[0011]
【発明の実施の形態】本発明では、原料のキシリレン化
合物として一般式(1)で表されるハロメチル基を有す
るキシリレン化合物を必須成分として用い、反応開始剤
として水を添加することにより、発生するHClを酸触
媒として樹脂化を行う事を特長としている。BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, a xylylene compound having a halomethyl group represented by the general formula (1) is used as a raw material as an essential component, and is generated by adding water as a reaction initiator. It is characterized by performing resinification using HCl as an acid catalyst.
【0012】反応中に発生するHClは、最終的に系外
に揮発し除去されるため、得られた重合物は、酸性成分
の不純物をほとんど含まず高純度で、かつ粘度などの品
質が極めて安定する。The HCl generated during the reaction is finally volatilized out of the system and removed, so that the obtained polymer has little purity of acidic components, high purity, and extremely high quality such as viscosity. Stabilize.
【0013】一般式(1)で表されるキシリレン化合物
(以下単に(1)と呼ぶ)の具体例としては、ジ(クロ
ロメチル)ベンゼン、ジ(ブロモメチル)ベンゼン、ジ
(クロロメチル)ビフェニル、ジ(クロロメチル)ナフ
タリン、ジ(クロロメチル)ビフェニルエーテルなどが
挙げられる。特にジクロロメチルベンゼンが好適であ
る。ジ(クロロメチル)ベンゼンの場合の−CH2 Xの
置換位置は、オルト、メタ、パラのいずれでもよいが、
一般的に好ましいのはパラ位またはメタ位であり、メタ
位とパラ位の混合系も好ましい。Specific examples of the xylylene compound represented by the general formula (1) (hereinafter simply referred to as (1)) include di (chloromethyl) benzene, di (bromomethyl) benzene, di (chloromethyl) biphenyl, and di (chloromethyl) biphenyl. (Chloromethyl) naphthalene, di (chloromethyl) biphenyl ether and the like. Particularly, dichloromethylbenzene is preferred. Substitution position of -CH 2 X in the case of di (chloromethyl) benzene, ortho, meta, may be any of para,
Generally preferred is the para or meta position, and mixed systems of the meta and para positions are also preferred.
【0014】キシリレン化合物としては、上記ハロメチ
ル化合物(1)の他に、一般式(2)で表されるグリコ
ール類またはアルコキシ類(以下(2)と呼ぶ)を併用
して用いることが出来る。この様なキシリレン化合物と
しては、キシリレングリコール、キシリレングリコール
ジメチルエーテル、キシリレングリコールジエチルエー
テル、キシリレングリコールジプロピルエーテル、キシ
リレングリコールジブチルエーテル、キシリレングリコ
ールモノメチルエーテル、キシリレングリコールモノエ
チルエーテルなどのキシリレングリコールモノまたはジ
低級アルコールエーテルなどが挙げられる。特にキシリ
レングリコール、キシリレングリコールジメチルエーテ
ル等が好適である。上記(2)式中の−CH2 OR3 の
置換位置は、オルト、メタ、パラのいずれでもよいが、
一般的に好ましいのはパラ位またはメタ位であり、メタ
位とパラ位の混合系も好ましい。As the xylylene compound, in addition to the halomethyl compound (1), glycols or alkoxys represented by the general formula (2) (hereinafter referred to as (2)) can be used in combination. Examples of such a xylylene compound include xylylene glycol, xylylene glycol dimethyl ether, xylylene glycol diethyl ether, xylylene glycol dipropyl ether, xylylene glycol dibutyl ether, xylylene glycol monomethyl ether, and xylylene glycol monoethyl ether. Xylylene glycol mono- or di-lower alcohol ether and the like. Particularly, xylylene glycol, xylylene glycol dimethyl ether and the like are preferable. The substitution position of —CH 2 OR 3 in the above formula (2) may be any of ortho, meta and para,
Generally preferred is the para or meta position, and mixed systems of the meta and para positions are also preferred.
【0015】(1)/(2)のモル比は、100/0か
ら40/60、好ましくは80/20〜40/60であ
る。すなわち原料として(1)を単独で、または混合物
に対して40%までの(2)を含有する(1)と(2)
との混合物を用いることができる。(2)は必須成分で
はないが、(1)が固体状物質であるのに対し、(2)
は液状物質であるので、(2)を若干量含有する混合物
とした方が反応操作の面から有利であり、上記モル比を
80/20以下とするのが有利である。しかしこの比が
40/60未満の場合は反応性が相対的に低い(2)の
キシリレン化合物の官能基が一部反応しきれずに樹脂中
に取り残される。本発明においては、(1)と(2)の
混合物であっても、(1)を40%以上含有するもので
あれば、水を添加することにより発生するHClが酸触
媒として働き、(2)のキシリレン化合物もフェノール
との反応により樹脂化されるので、原料選択の自由度が
増し、目的に応じて流動性を有する混合物を原料として
用いることにより、取扱の容易な状態で反応を行うこと
ができる。The molar ratio of (1) / (2) is from 100/0 to 40/60, preferably from 80/20 to 40/60. That is, (1) alone or as a raw material, or (1) and (2) containing up to 40% of (2) with respect to the mixture.
Can be used. (2) is not an essential component, but (1) is a solid substance, whereas (2)
Is a liquid substance, it is more advantageous to use a mixture containing a small amount of (2) from the viewpoint of the reaction operation, and it is advantageous to set the above molar ratio to 80/20 or less. However, when this ratio is less than 40/60, the functional groups of the xylylene compound (2) having relatively low reactivity are not completely reacted and are left in the resin. In the present invention, even if a mixture of (1) and (2) contains 40% or more of (1), HCl generated by adding water acts as an acid catalyst, and (2) The xylylene compound is also converted into a resin by reaction with phenol, so that the degree of freedom in selecting the raw materials is increased, and by using a mixture having fluidity as a raw material according to the purpose, the reaction can be performed in an easily handled state. Can be.
【0016】本発明に用いられるフェノール類として
は、芳香族環に結合したヒドロキシル基を1個または2
個以上有する各種の単環型、多核型、または縮合多環型
芳香族化合物が使用できる。具体例としては、フェノー
ル、クレゾール、キシレノール、エチルフェノール、ブ
チルフェノール、フェニルフェノール、ハロゲン化フェ
ノールなどの置換フェノール類;レゾルシン、カテコー
ル、ジヒドロキシビフェニル、テトラメチルジヒドロキ
シビフェニル、ビスフェノールA、ビスフェノールS、
ビスフェノールFなどの2価フェノール類;α−ナフト
ールやβ−ナフトール、ナフタレンジオールなどの縮合
多環型フェノール類が挙げられ、これらを1種もしくは
2種以上使用することが出来る。これらのフェノール類
の中でも好ましくはフェノール、o−クレゾール、p−
クレゾール、p−フェニルフェノール、カテコール、
4,4′−ジヒドロキシビフェニル、α−またはβ−ナ
フトールが用いられる。The phenols used in the present invention include one or two hydroxyl groups bonded to an aromatic ring.
Various monocyclic, polynuclear, or condensed polycyclic aromatic compounds having at least one compound can be used. Specific examples include substituted phenols such as phenol, cresol, xylenol, ethylphenol, butylphenol, phenylphenol, and halogenated phenol; resorcinol, catechol, dihydroxybiphenyl, tetramethyldihydroxybiphenyl, bisphenol A, bisphenol S,
Dihydric phenols such as bisphenol F; condensed polycyclic phenols such as α-naphthol, β-naphthol, and naphthalene diol; one or more of these can be used. Of these phenols, preferably phenol, o-cresol, p-
Cresol, p-phenylphenol, catechol,
4,4'-dihydroxybiphenyl, α- or β-naphthol are used.
【0017】フェノール類に対するキシリレン化合物
は、モル比で0.1〜0.8が好ましい。このモル比が
0.1未満では、未反応のフェノール類が多くなり収率
が下がるため好ましくない。0.8を越えると生成樹脂
の分子量が増大し、軟化温度が上昇し成形時の流動性の
低下を招き易いため好ましくない。より好ましい割合は
0.2〜0.7である。The molar ratio of the xylylene compound to the phenol is preferably 0.1 to 0.8. If the molar ratio is less than 0.1, unreacted phenols increase and the yield decreases, which is not preferable. If it exceeds 0.8, the molecular weight of the produced resin increases, the softening temperature rises, and the fluidity at the time of molding tends to decrease, which is not preferable. A more desirable ratio is 0.2 to 0.7.
【0018】フェノール類とキシリレン化合物との反応
を開始させる際の反応開始剤として水を存在させる必要
がある。水の必要量はキシリレン化合物である一般式
(1)および(2)の合計量に対して、100ppm以
上が好ましい。水は、反応開始前に必要量以上を系内に
添加すれば良い。Water must be present as a reaction initiator when initiating the reaction between the phenol and the xylylene compound. The required amount of water is preferably 100 ppm or more based on the total amount of the general formulas (1) and (2), which are xylylene compounds. Water may be added to the system in a necessary amount or more before the start of the reaction.
【0019】フェノール類とキシリレン化合物との反応
は、通常80〜180℃、好ましくは110〜160℃
の温度範囲で行う。反応時間は一般に1〜10時間であ
る。The reaction between the phenols and the xylylene compound is usually carried out at 80 to 180 ° C, preferably at 110 to 160 ° C.
The temperature range is as follows. The reaction time is generally between 1 and 10 hours.
【0020】フェノール類とキシリレン化合物とを反応
させるとき、キシリレン化合物を同時に加えて反応を進
めても良く、また必要に応じて逐次添加して反応させて
もよい。When reacting a phenol with a xylylene compound, the reaction may be carried out by simultaneously adding the xylylene compound or, if necessary, by sequentially adding the xylylene compound.
【0021】この反応は、縮合によって生成するHCl
によって反応が継続進行する。縮合反応が完結した後、
系内に残ったHClを未反応のフェノール類と共に減圧
下で留去させるか、または不活性ガスを吹き込みながら
減圧蒸留するなどの適当な方法によって留去させる。This reaction is carried out by using HCl formed by condensation.
The reaction continues. After the condensation reaction is completed,
HCl remaining in the system is distilled off under reduced pressure together with unreacted phenols, or by an appropriate method such as distillation under reduced pressure while blowing in an inert gas.
【0022】本発明の方法を用いると、半導体封止用の
エポキシ樹脂硬化剤など不純物が極めて厳しく規制され
る用途においても全く問題なく適用できる。また、重合
物の熱安定化が不足し、使用の際に熱履歴を受けても、
粘度上昇、分子量分布の増大、未反応フェノールの再生
などの品質変動が全く無視できるので、品質上で極めて
安定な樹脂が得られる。The method of the present invention can be used without any problem even in applications where impurities are extremely strictly regulated, such as an epoxy resin curing agent for semiconductor encapsulation. In addition, even if the thermal stabilization of the polymer is insufficient and it receives heat history during use,
Since quality fluctuations such as an increase in viscosity, an increase in molecular weight distribution, and regeneration of unreacted phenol can be completely ignored, a resin which is extremely stable in quality can be obtained.
【0023】[0023]
【実施例】以下、実施例により本発明を具体的に説明す
る。 [実施例1]撹拌装置、コンデンサー、及び窒素ガス導
入管を備えたガラス製反応釜に、フェノール59950
重量部、水17重量部、p−キシリレングリコールジメ
チルエーテル27525重量部、1,4−ジ(クロロメ
チル)ベンゼン29017重量部を仕込み、窒素ガス気
流下、撹拌しながら加熱した。70℃から120℃まで
2時間かけて昇温しながら発生するHClおよびメタノ
ールを系外へ除去させながら反応させた。さらに140
℃で2時間の反応を行った後、50torr以下の減圧
下、窒素をバブリングさせながら110℃から150℃
まで昇温しながら6時間減圧蒸留し、系内の未反応フェ
ノールと僅かに残存するHClを除去させ69940重
量部の目的物を得た。得られたフェノールアラルキル樹
脂の性状を表1に示す。The present invention will be described below in detail with reference to examples. Example 1 Phenol 59950 was placed in a glass reactor equipped with a stirrer, a condenser, and a nitrogen gas inlet tube.
Parts by weight, 17 parts by weight of water, 27525 parts by weight of p-xylylene glycol dimethyl ether and 29017 parts by weight of 1,4-di (chloromethyl) benzene were heated while stirring under a nitrogen gas stream. The reaction was carried out while removing HCl and methanol generated from the system while raising the temperature from 70 ° C. to 120 ° C. over 2 hours. Further 140
After performing the reaction at 2 ° C. for 2 hours, the temperature was reduced from 110 ° C. to 150 ° C. while bubbling nitrogen under reduced pressure of 50 torr or less.
The mixture was distilled under reduced pressure for 6 hours while elevating the temperature to remove unreacted phenol and slightly remaining HCl in the system to obtain 69940 parts by weight of the desired product. Table 1 shows the properties of the obtained phenol aralkyl resin.
【0024】[実施例2]実施例1で用いた反応釜に、
1,4−ジ(クロロメチル)ベンゼン58035重量部
を仕込んだ後、80℃に溶融させたフェノール5995
0重量部と水23重量部を添加した。撹拌しながら窒素
ガス気流下、70℃から120℃まで2時間かけて昇温
しながら発生するHClを系外へ除去させながら反応さ
せた。さらに140℃で2時間の反応を行った後、50
torr以下の減圧下、窒素をバブリングさせながら1
10℃から150℃まで昇温しながら6時間減圧蒸留
し、系内の未反応フェノールと僅かに残存するHClを
除去させ69920重量部の目的物を得た。得られたフ
ェノールアラルキル樹脂の性状を表1に示す。Example 2 The reactor used in Example 1 was
After charging 58035 parts by weight of 1,4-di (chloromethyl) benzene, phenol 5995 melted at 80 ° C.
0 parts by weight and 23 parts by weight of water were added. The reaction was performed while removing HCl generated outside the system while heating the temperature from 70 ° C. to 120 ° C. over 2 hours under a nitrogen gas stream with stirring. After a further 2 hours of reaction at 140 ° C., 50
Under a reduced pressure of not more than torr, while bubbling nitrogen,
The mixture was distilled under reduced pressure for 6 hours while the temperature was raised from 10 ° C. to 150 ° C. to remove unreacted phenol and slightly remaining HCl in the system to obtain 69920 parts by weight of the desired product. Table 1 shows the properties of the obtained phenol aralkyl resin.
【0025】[比較例1]実施例1で用いた反応釜に、
フェノール59950重量部と、p−キシレングリコー
ルジメチルエーテル55050重量部を添加した。窒素
ガス気流下、撹拌しながら80℃でp−トルエンスルホ
ン酸1水和物230重量部を水溶液にして添加し、12
0〜140℃で発生するメタノールを系外に除去させな
がら4時間の反応を行った。その後、50torr以下
の減圧下、窒素をバブリングさせながら110℃から1
50℃まで昇温しながら6時間減圧蒸留し、系内の未反
応フェノールを除去させ69915重量部のフェノール
アラルキル樹脂を得た。得られた樹脂の性状を表1に示
す。Comparative Example 1 The reactor used in Example 1 was
59950 parts by weight of phenol and 55050 parts by weight of p-xylene glycol dimethyl ether were added. Under a nitrogen gas stream, 230 parts by weight of p-toluenesulfonic acid monohydrate was added as an aqueous solution at 80 ° C. while stirring, and 12 parts by weight were added.
The reaction was carried out for 4 hours while removing methanol generated at 0 to 140 ° C outside the system. Thereafter, under a reduced pressure of 50 torr or less, the temperature is reduced from 110 ° C. to 1 while bubbling nitrogen.
The mixture was distilled under reduced pressure for 6 hours while the temperature was raised to 50 ° C. to remove unreacted phenol in the system to obtain 69915 parts by weight of a phenol aralkyl resin. Table 1 shows the properties of the obtained resin.
【0026】[比較例2]実施例1で用いた反応釜に、
1,4−ジ(クロロメチル)ベンゼン5803重量部を
p−キシリレングリコールジメチルエーテル49545
重量部に溶解させた混合物を、仕込んだ後、80℃の溶
融させたフェノール59950重量部と水22重量部を
添加した。反応条件および減圧蒸留条件は実施例1と同
様に行い、69950重量部のフェノールアラルキル樹
脂を得た。得られたフェノールアラルキル樹脂の性状を
表1に示す。Comparative Example 2 The reactor used in Example 1 was
5803 parts by weight of 1,4-di (chloromethyl) benzene was added to p-xylylene glycol dimethyl ether 49545
After the mixture dissolved in parts by weight was charged, 59950 parts by weight of phenol melted at 80 ° C. and 22 parts by weight of water were added. The reaction conditions and the distillation conditions under reduced pressure were the same as in Example 1 to obtain 69950 parts by weight of a phenol aralkyl resin. Table 1 shows the properties of the obtained phenol aralkyl resin.
【0027】[0027]
【表1】 [Table 1]
【0028】表1に示したように、いずれの実施例で得
られた樹脂も、酸性物質や未反応キシリレン化合物など
の不純物が検出されず、高純度であった。また160℃
で10時間の熱処理を行った後も分子量分布やフェノー
ルの増加などの変化が認められず、熱安定性に優れてい
ることが判る。これに対し、触媒としてp−トルエンス
ルホン酸を用いた比較例1で得られた樹脂には、触媒の
酸性物質が残存し、抽出水のpHも低い値を示した。ま
た熱安定性にも劣り、160℃10時間の熱処理で分子
量分布が大きくなり溶融粘度が大幅に上昇し、また未反
応フェノールも3.4wt%と増加した。一方ジ(クロ
ロメチル)ベンゼン含有量の少ない混合物を原料に用い
た比較例2の樹脂には、未反応のキシリレングリコール
ジメチルエーテルが検出され、反応が完結していなかっ
た。As shown in Table 1, no impurities such as acidic substances and unreacted xylylene compounds were detected in the resins obtained in all Examples, and the resins were of high purity. 160 ° C
No change such as an increase in molecular weight distribution and phenol was observed even after the heat treatment for 10 hours, indicating that the composition was excellent in thermal stability. On the other hand, in the resin obtained in Comparative Example 1 using p-toluenesulfonic acid as the catalyst, the acidic substance of the catalyst remained, and the pH of the extraction water also showed a low value. In addition, the thermal stability was poor, and the heat treatment at 160 ° C. for 10 hours increased the molecular weight distribution, significantly increased the melt viscosity, and increased unreacted phenol to 3.4 wt%. On the other hand, unreacted xylylene glycol dimethyl ether was detected in the resin of Comparative Example 2 using a mixture containing a small amount of di (chloromethyl) benzene as a raw material, and the reaction was not completed.
【0029】[0029]
【発明の効果】本発明によれば、触媒の残存による不純
物が少なく、品質が安定し、半導体封止用のエポキシ樹
脂硬化剤などの用途に適した高純度のフェノールアラル
キル系樹脂を簡単な操作で効率的に得ることができる。
また樹脂製造のための原料キシリレン化合物も幅広く選
択することができる。According to the present invention, a simple operation of a high-purity phenol aralkyl-based resin which has a small amount of impurities due to residual catalyst, is stable in quality, and is suitable for use as an epoxy resin curing agent for semiconductor encapsulation. Can be obtained efficiently.
In addition, a raw material xylylene compound for resin production can be widely selected.
Claims (2)
されるキシリレン化合物、またはこれと下記一般式
(2)で表されるキシリレン化合物 R1 −(CH2 X)2 ・・・(1) R2 −(CH2 OR3 )2 ・・(2) (式中、R1 及び、R2 は同一または異なるフェニレン
基、アルキル置換フェニレン基、ジフェニレン基、ジフ
ェニレンオキサイド基、ナフチレン基であり、Xはハロ
ゲン原子であり、R3 は水素原子またはC1 〜C4 のア
ルキル基である。)との混合物を、酸触媒の存在下で縮
合反応させて、フェノールアラルキル樹脂を製造する方
法において、 (1)/(2)のモル比が100/0から40/60ま
での範囲であり、かつ反応開始剤として水を添加し、加
水分解で発生するハロゲン化水素を縮合反応開始の触媒
として用いることを特徴とする、フェノールアラルキル
樹脂の製造方法。1. A phenol and a xylylene compound represented by the following general formula (1), or a phenol and a xylylene compound represented by the following general formula (2): R 1 — (CH 2 X) 2. 1) R 2 — (CH 2 OR 3 ) 2 ... (2) (wherein R 1 and R 2 are the same or different phenylene groups, alkyl-substituted phenylene groups, diphenylene groups, diphenylene oxide groups, and naphthylene groups) X is a halogen atom, and R 3 is a hydrogen atom or a C 1 -C 4 alkyl group) in the presence of an acid catalyst to produce a phenol aralkyl resin. Wherein the molar ratio of (1) / (2) is in the range of 100/0 to 40/60, and water is added as a reaction initiator, and hydrogen halide generated by hydrolysis is used as a catalyst for initiating a condensation reaction. Use as Wherein the bets method for producing a phenol aralkyl resin.
式(1)及び(2)のキシリレン化合物の合計量に対し
て重量比で100ppm以上であることを特徴とする請
求項1記載のフェノールアラルキル樹脂の製造方法。2. The method according to claim 1, wherein the amount of water added as a reaction initiator is at least 100 ppm by weight based on the total amount of the xylylene compounds of the general formulas (1) and (2). A method for producing a phenol aralkyl resin.
Priority Applications (1)
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JP05965898A JP3755629B2 (en) | 1998-03-11 | 1998-03-11 | Method for producing phenol aralkyl resin |
Applications Claiming Priority (1)
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---|---|---|---|
JP05965898A JP3755629B2 (en) | 1998-03-11 | 1998-03-11 | Method for producing phenol aralkyl resin |
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JPH11255868A true JPH11255868A (en) | 1999-09-21 |
JP3755629B2 JP3755629B2 (en) | 2006-03-15 |
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ID=13119531
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Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2007063894A1 (en) * | 2005-11-30 | 2007-06-07 | Nippon Kayaku Kabushiki Kaisha | Phenolic resin, process for production thereof, epoxy resin, and use thereof |
JP2008231162A (en) * | 2007-03-16 | 2008-10-02 | Nippon Kayaku Co Ltd | Phenolic resin, epoxy resin, epoxy resin composition, and cured product thereof |
JP2009001812A (en) * | 2008-08-04 | 2009-01-08 | Nippon Steel Chem Co Ltd | Polyvalent hydroxy resin, epoxy resin, their manufacturing method, epoxy resin composition using them, and cured product |
JP2010229422A (en) * | 2010-07-21 | 2010-10-14 | Nippon Kayaku Co Ltd | Phenolaralkyl resin, epoxy resin composition and cured material thereof |
WO2010140331A1 (en) * | 2009-06-03 | 2010-12-09 | 住友ベークライト株式会社 | Resin composition for semiconductor encapsulation, and semiconductor device |
JP2015189925A (en) * | 2014-03-28 | 2015-11-02 | 新日鉄住金化学株式会社 | Vinyl benzyl ether resin, manufacturing method therefor, curable resin composition containing the same and cured product |
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1998
- 1998-03-11 JP JP05965898A patent/JP3755629B2/en not_active Expired - Fee Related
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2007063894A1 (en) * | 2005-11-30 | 2007-06-07 | Nippon Kayaku Kabushiki Kaisha | Phenolic resin, process for production thereof, epoxy resin, and use thereof |
US7968672B2 (en) | 2005-11-30 | 2011-06-28 | Nippon Kayaku Kabushiki Kaisha | Phenolic resin, process for production thereof, epoxy resin, and use thereof |
JP2008231162A (en) * | 2007-03-16 | 2008-10-02 | Nippon Kayaku Co Ltd | Phenolic resin, epoxy resin, epoxy resin composition, and cured product thereof |
JP2009001812A (en) * | 2008-08-04 | 2009-01-08 | Nippon Steel Chem Co Ltd | Polyvalent hydroxy resin, epoxy resin, their manufacturing method, epoxy resin composition using them, and cured product |
WO2010140331A1 (en) * | 2009-06-03 | 2010-12-09 | 住友ベークライト株式会社 | Resin composition for semiconductor encapsulation, and semiconductor device |
KR20120026573A (en) * | 2009-06-03 | 2012-03-19 | 스미또모 베이크라이트 가부시키가이샤 | Resin composition for semiconductor encapsulation, and semiconductor device |
US8883883B2 (en) | 2009-06-03 | 2014-11-11 | Sumitomo Bakelite Co., Ltd. | Resin composition for encapsulating semiconductor and semiconductor device |
JP2010229422A (en) * | 2010-07-21 | 2010-10-14 | Nippon Kayaku Co Ltd | Phenolaralkyl resin, epoxy resin composition and cured material thereof |
JP2015189925A (en) * | 2014-03-28 | 2015-11-02 | 新日鉄住金化学株式会社 | Vinyl benzyl ether resin, manufacturing method therefor, curable resin composition containing the same and cured product |
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